JP2013026042A - Nonaqueous electrolyte, nonaqueous electrolyte battery, battery pack using nonaqueous electrolyte battery, electronic device, electrically-operated vehicle, condenser, and electric power system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both the effect of suppressing the end-of-charging voltage by an electrochemical reaction, and the effect of uniformizing the discharge capacity in a nonaqueous electrolyte battery.SOLUTION: The nonaqueous electrolyte takes a liquid or gel form and comprises: a nonaqueous solvent; an electrolytic salt; an overcharge-control agent such that an oxidation-reduction reaction is caused at a predetermined potential; and at least one compound selected from the group consisting of the additive compounds (1)-(4). In the compounds, R21 and R23 are independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic ring group, or an alkyl group, an alkenyl group or an alkynyl group which is substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group, or a halogenated group thereof, and R22 is a straight or branched chain of an alkylene group, an arylene group, a divalent group including an arylene group and an alkylene group, or a halogenated group thereof.

Description

  The present technology relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery using the non-aqueous electrolyte, and in particular, a non-aqueous electrolyte capable of suppressing an end-of-charge voltage by an electrochemical reaction and thereby uniforming a discharge capacity, and the same. The present invention relates to a non-aqueous electrolyte battery. In addition, the present invention relates to a battery pack, an electronic device, an electric vehicle, a power storage device, and a power system using such a nonaqueous electrolyte battery.

  In recent years, portable electronic devices such as a video camera, a digital still camera, a mobile phone, or a laptop computer have been widely used, and there is a strong demand for miniaturization, weight reduction, and long life. Accordingly, as a power source, development of a battery, in particular, a secondary battery that is small and lightweight and capable of obtaining a high energy density is in progress.

  In particular, lithium ion secondary batteries that use the insertion and extraction of lithium ions for charge / discharge reactions, lithium metal secondary batteries that use precipitation and dissolution of lithium metal, and the like are highly expected. This is because an energy density higher than that of a lead battery or a nickel cadmium battery can be obtained.

  By the way, the lithium ion secondary battery or the lithium metal secondary battery has a very high energy density per unit volume, and uses a flammable organic solvent as a non-aqueous electrolyte. In a nonaqueous electrolyte secondary battery using an organic solvent, ensuring safety is one of the most important issues, and overcharge protection is particularly important. For example, in a nickel-cadmium battery, when the charging voltage rises during overcharging, an overcharge prevention mechanism works due to the consumption of charging energy due to the chemical reaction of water contained in the electrolyte. On the other hand, a non-aqueous lithium secondary battery does not consume charging energy due to a chemical reaction of water, and requires another mechanism instead.

  As an overcharge prevention mechanism in a nonaqueous electrolyte battery, a method using a chemical reaction and a method using an electronic circuit have been proposed, and the latter is mainly used practically. However, the method using an electronic circuit not only increases the cost, but also causes various restrictions on product design.

  In view of this, in non-aqueous electrolyte batteries, development of technology for preventing overcharge using a chemical reaction is underway. Among them, as one of chemical overcharge protection means, a method of adding an appropriate redox reagent to the electrolytic solution has been attempted. According to this method, when the reversibility of the oxidation-reduction reagent is good, a protection mechanism is established in the battery that reciprocates between the positive and negative electrodes and consumes an overcharge current.

  As an example using such a redox reagent, for example, the following Patent Document 1 can be cited. Patent Document 1 describes the use of a fluorine ester / ether and an aromatic compound having a silyl group. Patent Document 2 describes the use of a nitroxide compound. Patent Document 3 describes the use of a triphenylamine compound. Patent Document 4 describes using vinylene carbonate or sultone in combination with anisole compounds. Patent Document 5 describes the use of an N-oxide compound. Patent Document 6 describes the use of cyclable compounds including aromatic compounds. Patent Document 7 describes a battery including a plurality of series-connected rechargeable lithium ion batteries each including an electrolyte containing a redox reagent.

Japanese Patent No. 351201 JP 2010-521050 A JP 2009-527096 A JP 2009-514149 A JP 2008-541041 A JP 2007-531972 A JP 2007-53970 A

  However, when the present inventor applied an oxidation-reduction reagent as described in the above-mentioned patent document to an actual lithium ion battery, the end-of-charge voltage was suppressed by an electrochemical reaction, and the discharge capacity was thereby made uniform. It was found that the effect was insufficient.

  The present technology provides a non-aqueous electrolyte, a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery that are capable of solving the above-described problems and realizing both suppression of an end-of-charge voltage by electrochemical reaction and uniform discharge capacity. It is an object of the present invention to provide a used battery pack, electronic device, electric vehicle, power storage device, and electric power system.

（式中、Ｒ２１およびＲ２３は、それぞれ独立して、アルキル基、アルケニル基、アルキニル基、アリール基または複素環基であり、または、芳香族炭化水素基または脂環式炭化水素基により置換されたアルキル基、アルケニル基またはアルキニル基であり、または、それらがハロゲン化された基である。Ｒ２２は、直鎖状または分岐状のアルキレン基、アリーレン基、アリーレン基とアルキレン基とを含む２価の基、または、それらがハロゲン化された基である。）

（式中、Ｒ２１およびＲ２３、ならびにＲ２２は上記添加化合物（１）と同様である。）

In order to solve the above-mentioned problem, the nonaqueous electrolyte of the present technology includes a nonaqueous solvent, an electrolyte salt, an overcharge control agent that causes a redox reaction at a predetermined potential, and the following additive compounds (1) to And at least one selected from the compound (4).

(Wherein R21 and R23 are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group) An alkyl group, an alkenyl group or an alkynyl group, or a group in which they are halogenated R22 is a linear or branched alkylene group, an arylene group, a divalent group containing an arylene group and an alkylene group; Or a group in which they are halogenated.)

(In the formula, R21, R23, and R22 are the same as those in the additive compound (1).)

  Moreover, the nonaqueous electrolyte battery of this technique is equipped with the electrode group containing a positive electrode and a negative electrode, and the said nonaqueous electrolyte.

  As in the present technology, there are at least one additive compound (1) to additive compound (4) and an overcharge control agent that electrochemically suppresses a voltage increase during charging by an oxidation-reduction reaction that occurs at a predetermined potential. By using the nonaqueous electrolyte contained together, the mobility between the electrodes of the compound that electrochemically suppresses the voltage increase during overcharge can be ensured. For this reason, the reaction current of the compound can be sufficiently increased with respect to the current density during charging.

  Furthermore, the battery pack, the electronic device, the electric vehicle, the power storage device, and the power system of the present technology include the above-described nonaqueous electrolyte battery.

  By applying the nonaqueous electrolyte of the present technology to a nonaqueous electrolyte battery, both the effect of suppressing the end-of-charge voltage due to an electrochemical reaction of a compound that causes a redox reaction at a predetermined potential and the uniform discharge capacity are achieved. Can be realized.

It is sectional drawing which shows the structure of the nonaqueous electrolyte battery concerning the 2nd Embodiment of this technique. It is sectional drawing which expands and shows a part of winding electrode body concerning the nonaqueous electrolyte battery shown in FIG. It is a disassembled perspective view which shows the structure of the nonaqueous electrolyte battery concerning the 3rd Embodiment of this technique. It is sectional drawing showing the cross-sectional structure along the II line | wire of the winding electrode body shown in FIG. It is a block diagram which shows the structural example of the battery pack by embodiment of this technique. It is the schematic which shows the example applied to the electrical storage system for houses using the nonaqueous electrolyte battery of this technique. It is a schematic diagram showing roughly an example of composition of a hybrid vehicle which adopts a series hybrid system to which this art is applied. It is a graph which shows the analysis result which analyzed the SnCoC containing material obtained in Example 2-1-1 to Example 2-129 by XPS.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
1. 1st Embodiment (example of nonaqueous electrolyte of this technique)
2. Second Embodiment (Example of a cylindrical nonaqueous electrolyte battery using the nonaqueous electrolyte of the present technology)
3. Third Embodiment (Example of Laminated Film Type Nonaqueous Electrolyte Battery Using Nonaqueous Electrolyte of the Present Technology)
4). Fourth embodiment (example of battery pack using non-aqueous electrolyte battery of the present technology)
5. Fifth embodiment (an example of a power storage system using the nonaqueous electrolyte battery of the present technology)

1. 1st Embodiment In 1st Embodiment, the structure and manufacturing method of a nonaqueous electrolyte and a gel-like nonaqueous electrolyte (henceforth a gel electrolyte suitably) are demonstrated.

(1-1) Nonaqueous Electrolytic Solution The first embodiment is a nonaqueous electrolytic solution used for a nonaqueous electrolyte battery. The nonaqueous electrolytic solution is a liquid nonaqueous electrolyte.

  The nonaqueous electrolytic solution of the present technology includes a compound (hereinafter appropriately referred to as an overcharge control agent) that electrochemically suppresses a voltage increase during overcharge, together with a nonaqueous solvent and an electrolyte salt. In addition, the non-aqueous electrolyte of the present technology further includes a compound of the present technology (hereinafter referred to as an additive compound) in order to obtain a uniform effect on the end-of-charge voltage due to an electrochemical reaction of the overcharge control agent and a uniform effect on the discharge capacity. As appropriate).

[Overcharge control agent]
The non-aqueous electrolyte of the present technology includes an overcharge control agent as an essential component in order to electrochemically suppress a voltage increase during charging. Hereinafter, the overcharge control agent will be described.

  The overcharge control agent is made of, for example, a material that causes a redox reaction at a potential slightly higher than the positive electrode potential when the nonaqueous electrolyte battery is fully charged. Note that the potential at which the oxidation-reduction reaction of the overcharge control agent occurs is not limited to the above potential, and a material that causes the oxidation-reduction reaction at a potential lower than the positive electrode potential at the time of full charge may be used as the overcharge control agent. . The fully charged state of the nonaqueous electrolyte battery refers to a state in which the battery voltage becomes the voltage set as the end-of-charge voltage. That is, when a non-aqueous electrolyte battery containing an overcharge control agent is overcharged beyond a predetermined potential, the overcharge control agent causes an oxidation-reduction reaction due to the oxidation activity of the positive electrode surface, and the non-aqueous electrolyte battery Increase in the voltage (positive electrode potential) can be suppressed. Specifically, the overcharge control agent is oxidized and diffused to the negative electrode side when it reaches a predetermined positive electrode potential, and is repeatedly reduced and diffused to the positive electrode side on the negative electrode side, It is an oxidizable and reducible material that can repeatedly transport charges between the positive and negative electrodes.

  By using such an overcharge control agent, it is possible to suppress variations in discharge capacity due to overcharge of the nonaqueous electrolyte battery. Moreover, since decomposition | disassembly etc. of the non-aqueous electrolyte resulting from overcharge becoming a positive electrode potential too high are suppressed, the gas generation inside a battery can be suppressed.

  As the overcharge control agent, for example, the following overcharge control agent (1) to overcharge control agent (12) can be used. The overcharge control agent is a mixture of one or more of the compounds represented by the overcharge control agent (1) to the overcharge control agent (12).

（式中、Ｒａは直鎖状もしくは分岐状のアルキル基であり、またはそれらが部分的に、もしくはすべてがハロゲン化された基である。Ｒ１〜Ｒ５は独立してアルコキシ基、ハロゲン基、ニトリル基もしくは直鎖状もしくは分岐状のアルキル基であり、またはそれらが部分的に、もしくはすべてがハロゲン化された基であり、または、ＲａおよびＲ１〜Ｒ５が隣り合う基と互いに連結された基である。ただし、ＲａおよびＲ１〜Ｒ５の連結は、Ｒ１〜Ｒ５すべてがアルコキシ基である場合を除く。）

(In the formula, Ra is a linear or branched alkyl group, or a group in which they are partially or entirely halogenated. R1 to R5 are independently an alkoxy group, a halogen group, or a nitrile. A group or a linear or branched alkyl group, or a group that is partially or wholly halogenated, or a group in which Ra and R1 to R5 are linked to each other with an adjacent group. (However, Ra and R1 to R5 are linked except when all of R1 to R5 are alkoxy groups.)

（式中、Ｒｂは直鎖状もしくは分岐状のアルキル基であり、またはそれらが部分的に、もしくはすべてがハロゲン化された基である。Ｒ１〜Ｒ７は独立してアルコキシ基、ハロゲン基、または直鎖状もしくは分岐状のアルキル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、ＲｂおよびＲ１〜Ｒ７が隣り合う基と互いに連結された基である。ただし、ＲｂおよびＲ１〜Ｒ７の連結は、Ｒ１〜Ｒ７すべてがアルコキシ基である場合を除く。）

(Wherein Rb is a linear or branched alkyl group, or a group in which they are partially or wholly halogenated. R1 to R7 are independently an alkoxy group, a halogen group, or A linear or branched alkyl group, a group in which they are partially or fully halogenated, or a group in which Rb and R1 to R7 are linked to each other, provided that Rb And R1 to R7 are connected except when R1 to R7 are all alkoxy groups.)

（式中、ＲｂおよびＲ１〜Ｒ７は、上記過充電制御剤（２）と同様である。）

(In the formula, Rb and R1 to R7 are the same as the overcharge control agent (2).)

（式中、Ｍは遷移金属元素、または長周期型周期表における１３族元素、１４族元素もしくは１５族元素である。Ｒｃはアリール基あるいは複素環基であり、またはそれらが部分的にもしくはすべてがハロゲン化された基である。Ｒ１〜Ｒ４は独立してアルコキシ基、ハロゲン基、または直鎖状もしくは分岐状のアルキル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、Ｒ１〜Ｒ４が隣り合う基と互いに連結された基である。）

(In the formula, M is a transition metal element, or a group 13 element, group 14 element or group 15 element in the long-period periodic table. Rc is an aryl group or a heterocyclic group, or they are partially or completely. R1 to R4 are independently an alkoxy group, a halogen group, or a linear or branched alkyl group, a group in which they are partially or wholly halogenated, Or, R1 to R4 are groups connected to adjacent groups.)

（式中、Ｒ１〜Ｒ４は独立してアルコキシ基、ハロゲン基、または直鎖状もしくは分岐状のアルキル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、Ｒ１〜Ｒ４が隣り合う基と互いに連結された基である。Ｒ５およびＲ６はアルコキシ基、ハロゲン基、または直鎖状もしくは分岐状のアルキル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、Ｒ５およびＲ６が互いに連結された基である。Ｒ５およびＲ６が互いに連結された基は、アルキレン基、部分的にまたはすべてがハロゲン化されたアルキレン基または下記一般式（Ａ）で示される連結基である。

一般式（Ａ）中、l₁およびl₂はそれぞれ独立して０〜２の整数である。Ａは炭素数０〜２のアルキレン基であり、またはそれらが部分的に、もしくはすべてがハロゲン化されたアルキレン基を示す。）

Wherein R1 to R4 are independently an alkoxy group, a halogen group, or a linear or branched alkyl group, a group in which they are partially or fully halogenated, or R1 to R4 And R5 and R6 are alkoxy groups, halogen groups, or linear or branched alkyl groups, which are partially or all halogenated groups. Or a group in which R5 and R6 are linked to each other, the group to which R5 and R6 are linked to each other is an alkylene group, an alkylene group partially or wholly halogenated, or a group represented by the following general formula (A): A linking group.

In the general formula (A), l ₁ and l ₂ are each independently represent an integer of 0 to 2. A is an alkylene group having 0 to 2 carbon atoms, or an alkylene group in which they are partially or wholly halogenated. )

（式中、ＸはＮ−オキシドまたはＮ−オキソ基を示す。Ｙは酸素原子または硫黄原子である。Ｒ８〜Ｒ１１は独立してアルキル基、アルケニル基、アルキニル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、Ｒ８とＲ９、Ｒ１０とＲ１１が互いに連結された基である。Ｒ１２は、水素基、水酸基、アルキル基、アルケニル基、アルキニル基、アリール基もしくは複素環基であり、または、ニトリル基、複素環基、芳香族炭化水素基もしくは脂環式炭化水素基により置換されたアルキル基、アルケニル基もしくはアルキニル基であり、または、それらがハロゲン化された基、エーテル基、アミド基、カルボン酸エステル基、リン酸エステル基、チオエステル基、環状エーテルもしくは鎖状エーテルで置換されたアルキル基である。）

(In the formula, X represents an N-oxide or N-oxo group. Y represents an oxygen atom or a sulfur atom. R8 to R11 independently represent an alkyl group, an alkenyl group, an alkynyl group, or a partial or All are halogenated groups, or R8 and R9, and R10 and R11 are linked to each other R12 is a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic ring A nitrile group, a heterocyclic group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, an alkenyl group or an alkynyl group, or a group in which they are halogenated, Ether group, amide group, carboxylic ester group, phosphoric ester group, thioester group, cyclic ether or chain ether substituted A kill group.)

（式中、Ｘ、ＹおよびＲ８〜Ｒ１１は、上記過充電制御剤（６）と同様である。なお、Ｙが酸素原子の場合Ｒ１４、Ｒ１５は非共有電子対を示し、Ｙが硫黄原子の場合、Ｒ１４、Ｒ１５は独立して非共有電子対またはオキソ基を示す。Ｒ１３は、水素基、水酸基、アルキル基、アルケニル基、アルキニル基、アリール基もしくは複素環基であり、または、芳香族炭化水素基もしくは脂環式炭化水素基により置換されたアルキル基、アルケニル基もしくはアルキニル基であり、または、それらがハロゲン化された基、エーテル基、アミド基、カルボン酸エステル基、リン酸エステル基、チオエステル基、環状エーテルもしくは鎖状エーテルで置換されたアルキル基である。）

(In the formula, X, Y, and R8 to R11 are the same as the overcharge control agent (6). When Y is an oxygen atom, R14 and R15 represent a lone pair, and Y is a sulfur atom. In this case, R14 and R15 independently represent an unshared electron pair or an oxo group, and R13 represents a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or an aromatic carbonized group. An alkyl group, an alkenyl group or an alkynyl group substituted by a hydrogen group or an alicyclic hydrocarbon group, or a group in which they are halogenated, an ether group, an amide group, a carboxylate group, a phosphate group, (It is an alkyl group substituted with a thioester group, a cyclic ether or a chain ether.)

（式中、ＸおよびＲ８〜Ｒ１１は、上記過充電制御剤（６）と同様である。Ｒ１２は、水素基、水酸基、アルキル基、アルケニル基、アルキニル基、アリール基もしくは複素環基であり、または、芳香族炭化水素基もしくは脂環式炭化水素基により置換されたアルキル基、アルケニル基もしくはアルキニル基であり、または、それらがハロゲン化された基、エーテル基、アミド基、カルボン酸エステル基、リン酸エステル基、チオエステル基、環状エーテルもしくは鎖状エーテルで置換されたアルキル基である。）

(In the formula, X and R8 to R11 are the same as the overcharge control agent (6). R12 is a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Or an alkyl group, an alkenyl group or an alkynyl group substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group, or a group in which they are halogenated, an ether group, an amide group, a carboxylic acid ester group, (It is an alkyl group substituted with a phosphate ester group, a thioester group, a cyclic ether or a chain ether.)

（式中、Ｘ、Ｒ８〜Ｒ１１およびＲ１２は、上記過充電制御剤（８）と同様である。Ｒ１６およびＲ１７は、独立してアルキル基、アルケニル基、アルキニル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、Ｒ１６とＲ１７が互いに連結された基である。）

(Wherein X, R8 to R11 and R12 are the same as the overcharge control agent (8). R16 and R17 independently represent an alkyl group, an alkenyl group, an alkynyl group, or a partial or All are halogenated groups, or R16 and R17 are groups linked together.)

（式中、ＸおよびＲ８〜Ｒ１１は、上記過充電制御剤（８）と同様である。Ｚは、下記一般式（Ｂ１）〜一般式（Ｂ６）のいずれかである。

（一般式（Ｂ１）〜一般式（Ｂ６）中、Ｒ１２は上記過充電制御剤（８）と同様である。Ｒ１８は独立してアルキル基、アルケニル基、アルキニル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、Ｒ１８とＲ１９が互いに連結された基である。Ｒ１９は水素基、水酸基、アルキル基、アリール基、アラルキル基、シクロアルキル基またはエーテル基である。Ｒ２０は独立して水素基、アルキル基、アリール基、アラルキル基、アルケニル基、アルキニル基、シクロアルキル基またはグリシジル基である。））

(In formula, X and R8-R11 are the same as that of the said overcharge control agent (8). Z is either of the following general formula (B1)-general formula (B6).

(In General Formula (B1) to General Formula (B6), R12 is the same as the overcharge control agent (8). R18 is independently an alkyl group, an alkenyl group, an alkynyl group, or a part thereof, or All are halogenated groups, or groups in which R18 and R19 are connected to each other, and R19 is a hydrogen group, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, or an ether group. Are independently a hydrogen group, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or a glycidyl group.))

（式中、Ｘは上記過充電制御剤（８）と同様である。Ｒ８〜Ｒ１１は独立してアルキル基、アルケニル基、アルキニル基、カルボン酸エステル基、それらが部分的に、もしくはすべてがハロゲン化された基であり、または、Ｒ８とＲ９、Ｒ１０とＲ１１が互いに連結された基である。）

(In the formula, X is the same as the above-described overcharge control agent (8). R8 to R11 are independently an alkyl group, an alkenyl group, an alkynyl group, a carboxylic acid ester group, a partial or all of them being halogen. Or a group in which R8 and R9, and R10 and R11 are linked to each other.)

（式中、ｓは平均で４以上１２以下であり、Ｄが水素、塩素または臭素である。）

(In the formula, s is 4 or more and 12 or less on average, and D is hydrogen, chlorine or bromine.)

  Examples of the compound of the overcharge control agent (1) include the following overcharge control agents (1-1) to overcharge control agents (1-81). Similarly, as the compound of the overcharge control agent (2) to the overcharge control agent (12), for example, the overcharge control agent (2-1) to the overcharge control agent (2-2), the overcharge control Agent (3-1) to Overcharge Control Agent (3-7), Overcharge Control Agent (4-1) to Overcharge Control Agent (4-75), Overcharge Control Agent (5-1) to Overcharge Control Agent (5-6), overcharge control agent (6-1) to overcharge control agent (6-13), overcharge control agent (7-1) to overcharge control agent (7-2), overcharge control Agent (8-1) to Overcharge Control Agent (8-5), Overcharge Control Agent (9-1) to Overcharge Control Agent (9-12), Overcharge Control Agent (10-1) to Overcharge Control Agents (10-7), overcharge control agents (11-1) to overcharge control agents (11-6), and overcharge control agents (12-1) to overcharge control agents (12-2). It is done. However, as long as it has any structure shown in General Formula (1) to General Formula (12), other compounds may be used.

  The content of the overcharge control agent in the non-aqueous electrolyte is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less. This is because the effect of suppressing the voltage rise during charging is sufficiently exhibited. In addition, above-described content is applied also in any case where a non-aqueous electrolyte contains 1 type, or 2 or more types of overcharge control agents.

[Additive compounds]
By adding the additive compound to the non-aqueous electrolyte, it is possible to obtain a uniform effect on the end-of-charge voltage due to the electrochemical reaction of the overcharge control agent and a uniform effect on the discharge capacity. Hereinafter, the additive compound will be described.

  As the additive compound, for example, the following additive compound (1) to additive compound (4) can be used. As the additive compound, one or two or more of the compounds represented by additive compound (1) to additive compound (4) may be mixed and used.

（式中、Ｒ２１およびＲ２３は、それぞれ独立して、アルキル基、アルケニル基、アルキニル基、アリール基または複素環基であり、または、芳香族炭化水素基または脂環式炭化水素基により置換されたアルキル基、アルケニル基またはアルキニル基であり、または、それらがハロゲン化された基である。Ｒ２２は、直鎖状または分岐状のアルキレン基、アリーレン基、アリーレン基とアルキレン基とを含む２価の基、または、それらがハロゲン化された基である。）

(Wherein R21 and R23 are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group) An alkyl group, an alkenyl group or an alkynyl group, or a group in which they are halogenated R22 is a linear or branched alkylene group, an arylene group, a divalent group containing an arylene group and an alkylene group; Or a group in which they are halogenated.)

（式中、Ｒ２１およびＲ２３、ならびにＲ２２は上記添加化合物（１）と同様である。）

(In the formula, R21, R23, and R22 are the same as those in the additive compound (1).)

  By using such an additive compound, the effect obtained by adding the above-described overcharge control agent to the non-aqueous electrolyte can be further enhanced. That is, compared with the case where the overcharge control agent is added alone to the non-aqueous electrolyte, the non-aqueous electrolyte using the overcharge control agent and the additive compound of the present technology in combination between the electrodes of the overcharge control agent. The mobility can be made higher. For this reason, the reaction current of the compound can be sufficiently increased with respect to the current density at the time of charging, and the protection mechanism that consumes the overcharge current by reciprocating between the positive and negative electrodes becomes easier to work. It becomes easy to obtain the effect of suppressing voltage rise during overcharging. Therefore, the combined use of the overcharge control agent of the present technology and the additive compound can suppress gas generation due to variations in discharge capacity, decomposition of the non-aqueous electrolyte, and the like.

  The content of the additive compound is preferably more than 0% by mass and less than 20% by mass with respect to the content of the overcharge control agent in the nonaqueous electrolytic solution. When the content is small outside the above range, the uniform effect of the end-of-charge voltage and the resulting uniform effect of the discharge capacity are reduced. This is because when the content is larger than the above range, the viscosity of the solvent increases and sufficient ionic conductivity cannot be realized.

  When at least one of the additive compound (1) and the additive compound (2) is used, the content of the additive compound exceeds 0% by mass with respect to the content of the overcharge control agent in the non-aqueous electrolyte. It is preferable that it is less than 6.0 mass%. Further, when at least one of the additive compound (3) and the additive compound (4) is used, the content of the additive compound is 0.001 mass relative to the content of the overcharge control agent in the non-aqueous electrolyte. % Or more and 3.0% by mass or less is preferable. When at least one of the compound of additive compound (1) and additive compound (2) and at least one of compound of additive compound (3) and additive compound (4) are mixed and used, 0.001% by mass or more 6 It is preferable that it is 0.0 mass% or less.

  Examples of the alkyl group of R21 and R23 of the additive compound (1) include a methyl group, an ethyl group, an n (normal) -propyl group, an isopropyl group, an n-butyl group or an isobutyl group, a sec (secondary) -butyl group, Examples include tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, and n-hexyl group.

  Examples of the alkenyl group of R21 and R23 of the additive compound (1) include an n-heptyl group, vinyl group, 2-methylvinyl group, 2,2-dimethylvinyl group, butene-2,4-diyl group or allyl group. Is mentioned.

  Examples of the alkynyl group of R21 and R23 of the additive compound (1) include an ethynyl group.

  Although carbon number, such as the above-mentioned alkyl group, an alkenyl group, or an alkynyl group, is not specifically limited, 1-20 are preferable especially, 1-7 are more preferable, and 1-4 are more preferable. This is because excellent solubility and compatibility can be obtained.

  Examples of the aryl group of R21 and R23 of the additive compound (1) include a phenyl group.

  Regarding the alkyl group substituted by the aromatic hydrocarbon group or alicyclic hydrocarbon group of R21 and R23 of the additive compound (1), examples of the aromatic hydrocarbon group include a phenyl group. Moreover, as an alicyclic hydrocarbon group, a cyclohexyl group is mentioned, for example. Among these, examples of the alkyl group (aralkyl group) substituted with a phenyl group include a benzyl group and a 2-phenylethyl group (phenethyl group).

  The halogenated alkyl group of R21 and R23 of the additive compound (1) is not particularly limited, and among these, fluorine (F), chlorine (Cl) or bromine (Br) is preferable, and fluorine is More preferred. Examples of the halogenated alkyl group include a fluorinated alkyl group. Examples of the fluorinated alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluoroethyl group. The “halogenated group” is a group in which a part or all of hydrogen groups (—H) such as alkyl groups are substituted with halogen groups (—F, etc.).

  Among them, a group substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group is preferable to a halogenated group, and a group not substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group is preferred. More preferred. In the group substituted by the aromatic hydrocarbon group or the alicyclic hydrocarbon group, the number of carbon atoms is not particularly limited. The total number of carbon atoms of the aromatic hydrocarbon group or alicyclic hydrocarbon group and the carbon number of the alkyl group is preferably 20 or less, and more preferably 7 or less.

  R21 and R23 may be derivatives such as the above-described alkyl groups. This derivative is a group in which one or more substituents are introduced into an alkyl group or the like, and the substituent may be a hydrocarbon group or other group.

    The number of carbon atoms of a group such as a linear or branched alkylene group constituting R22 of the additive compound (1) is not particularly limited, but is preferably 2 to 10, more preferably 2 to 6, and 2 to 4 Is more preferable. This is because excellent solubility and compatibility can be obtained. The divalent group containing an arylene group and an alkylene group may be a group in which one arylene group and one alkylene group are linked, or a group in which two alkylene groups are linked via an arylene group ( An aralkylene group).

  Such R22 includes a linear alkylene group represented by additive compound (R22-1) to additive compound (R22-7), or additive compound (R22-8) to additive compound (R22-16). It is represented by a branched alkylene group, an arylene group represented by an additive compound (R22-17) to an additive compound (R22-19), or an additive compound (R22-20) to an additive compound (R22-22). And a divalent group (benzylidene group) containing an arylene group and an alkylene group.

  The divalent group having 2 to 12 carbon atoms including an ether bond and an alkylene group is preferably a group in which at least two alkylene groups are connected via an ether bond and both ends are carbon atoms. . The number of carbon atoms in such a group is preferably 4-12. This is because excellent solubility and compatibility can be obtained. The number of ether bonds and the connecting order of ether bonds and alkylene groups are arbitrary.

  Examples of R2 include groups represented by additive compound (R22-23) to additive compound (R22-25). In addition, when the divalent group shown in additive compound (R22-23) to additive compound (R22-25) is fluorinated, for example, additive compound (R22-26) to additive compound (R22-28) The group etc. which are represented by these are mentioned. Especially, the structure of carbon number m = 1-3 of the group shown to the additional compound (R22-24) is preferable.

（式中、炭素数ｍは１以上の整数であり、炭素数ｍ＝１〜５が好ましい。）

(In the formula, carbon number m is an integer of 1 or more, and carbon number m = 1 to 5 is preferable.)

（式中、炭素数ｎは１以上の整数であり、炭素数ｎ＝１〜３が好ましい。）

(In the formula, carbon number n is an integer of 1 or more, and carbon number n = 1 to 3 is preferable.)

  R22 may be a derivative such as the above-described alkylene group, as described for R21 and R23.

  The molecular weight of the overcharge control agent (1) is not particularly limited, but 200 to 800 is preferable, 200 to 600 is more preferable, and 200 to 450 is more preferable. This is because excellent solubility and compatibility can be obtained.

  Specific examples of the overcharge control agent (1) include compounds represented by the overcharge control agent (1-1) to the overcharge control agent (1-12). This is because sufficient solubility and compatibility are obtained, and the chemical stability of the electrolytic solution is sufficiently improved. However, compounds other than the compounds shown in the overcharge control agent (1-1) to the overcharge control agent (1-12) may be used.

  About the compound shown to the overcharge control agent (2), it has the group similar to an overcharge control agent (1). The molecular weight of the overcharge control agent is not particularly limited, but is preferably 162 to 1000, more preferably 162 to 500, and still more preferably 162 to 300. This is because excellent dissolution and compatibility can be obtained.

  Specific examples of the compound shown in the overcharge control agent (2) include compounds represented by the overcharge control agent (2-1) to the overcharge control agent (2-17). This is because sufficient solubility and compatibility are obtained, and the chemical stability of the electrolytic solution is sufficiently improved. However, compounds other than the compounds shown in the overcharge control agent (2-1) to the overcharge control agent (2-17) may be used.

[Nonaqueous solvent]
The nonaqueous solvent contains at least one organic solvent described below. In addition, suppose that the material shown with additive compound (1) and additive compound (2) among the additive compounds mentioned above is removed from the nonaqueous solvent demonstrated below.

  Examples of the non-aqueous solvent include the following compounds. Ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane or tetrahydrofuran. 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane or 1,4-dioxane. Methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylacetate or ethyl trimethylacetate. N, N-dimethylformamide, N-methylpyrrolidone or N-methyloxazolidinone. N, N'-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate or dimethyl sulfoxide. This is because in a nonaqueous electrolyte battery using a nonaqueous electrolyte, excellent battery capacity, cycle characteristics, storage characteristics, and the like can be obtained.

  Among these, at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is preferable. This is because excellent battery capacity, cycle characteristics, storage characteristics, and the like can be obtained. In this case, a high viscosity (high dielectric constant) solvent such as ethylene carbonate or propylene carbonate (for example, a relative dielectric constant ε ≧ 30) and a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate (for example, viscosity ≦ 1 mPas). -A combination with s) is more preferred. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.

  In particular, the non-aqueous solvent preferably contains at least one of unsaturated carbon-bonded cyclic carbonates represented by formulas (1) to (3). This is because a stable protective film is formed on the surface of the electrode at the time of charge / discharge of the nonaqueous electrolyte battery, so that the decomposition reaction of the nonaqueous electrolyte is suppressed. This unsaturated carbon bond cyclic carbonate is a cyclic carbonate having one or more unsaturated carbon bonds. R31 and R32 may be the same type of group or different types of groups. The same applies to R33 to R36. The content of the unsaturated carbon bond cyclic carbonate in the non-aqueous solvent is, for example, 0.01% by mass or more and 10% by mass or less. However, the unsaturated carbon bond cyclic carbonate is not limited to the compounds described below, and may be other compounds.

（式中、Ｒ３１およびＲ３２は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基である。）

(In the formula, R 31 and R 32 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group.)

（式中、Ｒ３３〜Ｒ３６は、それぞれ独立して、水素基、アルキル基、ビニル基またはアリル基であり、それらのうちの少なくとも１つはビニル基またはアリル基である。）

(Wherein R33 to R36 are each independently a hydrogen group, an alkyl group, a vinyl group or an allyl group, and at least one of them is a vinyl group or an allyl group.)

（式中、Ｒ３７はアルキレン基である。）

(In the formula, R37 is an alkylene group.)

  The unsaturated carbon bond cyclic ester carbonate represented by the formula (1) is a vinylene carbonate compound. Examples of this vinylene carbonate compound include the following compounds. Vinylene carbonate, methyl vinylene carbonate or ethyl vinylene carbonate. 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4-fluoro-1,3-dioxol-2-one or 4-trifluoro Methyl-1,3-dioxol-2-one. Among these, vinylene carbonate is preferable. This is because it can be easily obtained and a high effect can be obtained.

  The unsaturated carbon-bonded cyclic ester carbonate represented by the formula (2) is a vinyl ethylene carbonate compound. The following compounds etc. are mentioned as an example of this vinyl carbonate-type compound. Vinylethylene carbonate, 4-methyl-4-vinyl-1,3-dioxolan-2-one or 4-ethyl-4-vinyl-1,3-dioxolan-2-one. 4-n-propyl-4-vinyl-1,3-dioxolan-2-one, 5-methyl-4-vinyl-1,3-dioxolan-2-one, 4,4-divinyl-1,3-dioxolane- 2-one or 4,5-divinyl-1,3-dioxolan-2-one. Of these, vinyl ethylene carbonate is preferred. This is because it can be easily obtained and a high effect can be obtained. Of course, as R33 to R36, all may be vinyl groups, all may be allyl groups, or vinyl groups and allyl groups may be mixed.

  The unsaturated carbon bond cyclic carbonate represented by the formula (3) is a methylene ethylene carbonate compound. The following compounds etc. are mentioned as an example of this methylene ethylene carbonate type compound. 4-methylene-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one or 4,4-diethyl-5-methylene-1,3-dioxolane- 2-one. The methylene ethylene carbonate compound may be a compound having one methylene group as shown in the formula (3) or a compound having two methylene groups.

  The unsaturated carbon-bonded cyclic ester carbonate may be catechol carbonate having a benzene ring in addition to the compounds represented by the formulas (1) to (3).

  The nonaqueous solvent preferably contains at least one of a halogenated chain carbonate represented by the formula (4) and a halogenated cyclic carbonate represented by the formula (5). This is because a stable protective film is formed on the surface of the electrode at the time of charge / discharge of the nonaqueous electrolyte battery, so that the decomposition reaction of the nonaqueous electrolyte is suppressed. The halogenated chain carbonate ester is a chain carbonate ester containing halogen as a constituent element, and the halogenated cyclic carbonate ester is a cyclic carbonate ester containing halogen as a constituent element. In addition, R41-R46 in Formula (4) may be the same type of group, or may be a different type of group. The same applies to R47 to R50 in the formula (5). The content of the halogenated chain carbonate and the halogenated cyclic carbonate in the non-aqueous solvent is, for example, 0.01% by mass or more and 50% by mass or less. However, the halogenated chain carbonic acid ester or the halogenated cyclic carbonic acid ester is not limited to the compounds described below, and may be other compounds.

（式中、Ｒ４１〜Ｒ４６は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、それらのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。）

(Wherein R41 to R46 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)

（式中、Ｒ４７〜Ｒ５０は、それぞれ独立して、水素基、ハロゲン基、アルキル基またはハロゲン化アルキル基であり、それらのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。）

(In the formula, R47 to R50 are each independently a hydrogen group, a halogen group, an alkyl group or a halogenated alkyl group, and at least one of them is a halogen group or a halogenated alkyl group.)

  The kind of halogen is not particularly limited, but among them, fluorine, chlorine or bromine is preferable, and fluorine is more preferable. This is because an effect higher than that of other halogens can be obtained. However, the number of halogens is preferably two rather than one, and may be three or more. When a non-aqueous electrolyte is used in a non-aqueous electrolyte battery, the ability to form a protective film on the surface of the electrode during the electrode reaction increases, and a stronger and more stable protective film is formed. This is because the decomposition reaction of the liquid is further suppressed.

  Examples of the halogenated chain carbonate ester include fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, difluoromethyl methyl carbonate, and the like.

  Examples of the halogenated cyclic carbonate include compounds represented by formula (5-1) to formula (5-21). That is, 4-fluoro-1,3-dioxolan-2-one of formula (5-1), 4-chloro-1,3-dioxolan-2-one of formula (5-2), or formula (5-3) 4,5-difluoro-1,3-dioxolan-2-one. Tetrafluoro-1,3-dioxolan-2-one of formula (5-4), 4-chloro-5-fluoro-1,3-dioxolan-2-one of formula (5-5) or formula (5-6) ) Of 4,5-dichloro-1,3-dioxolan-2-one. Tetrachloro-1,3-dioxolan-2-one of formula (5-7), 4,5-bistrifluoromethyl-1,3-dioxolan-2-one of formula (5-8) or formula (5-9) ) 4-trifluoromethyl-1,3-dioxolan-2-one. 4,5-difluoro-4,5-dimethyl-1,3-dioxolan-2-one of formula (5-10) or 4,4-difluoro-5-methyl-1,3- of formula (5-11) Dioxolan-2-one. 4-ethyl-5,5-difluoro-1,3-dioxolan-2-one of formula (5-12), 4-fluoro-5-trifluoromethyl-1,3-dioxolane of formula (5-13) 2-one or 4-methyl-5-trifluoromethyl-1,3-dioxolan-2-one of formula (5-14). 4-fluoro-4,5-dimethyl-1,3-dioxolan-2-one of formula (5-15) or 5- (1,1-difluoroethyl) -4,4-difluoro of formula (5-16) -1,3-dioxolan-2-one. 4,5-dichloro-4,5-dimethyl-1,3-dioxolan-2-one of formula (5-17), 4-ethyl-5-fluoro-1,3-dioxolane- of formula (5-18) 2-one or 4-ethyl-4,5-difluoro-1,3-dioxolan-2-one of formula (5-19). 4-ethyl-4,5,5-trifluoro-1,3-dioxolan-2-one of formula (5-20) or 4-fluoro-4-methyl-1,3-dioxolane of formula (5-21) -2-one.

  This halogenated cyclic carbonate includes geometric isomers. Among them, 4-fluoro-1,3-dioxolan-2-one represented by the formula (5-1) or 4,5-difluoro-1,3-dioxolan-2-one represented by the formula (5-3) is preferred. The latter is preferred and the latter is more preferred. In particular, in 4,5-difluoro-1,3-dioxolan-2-one, the trans isomer is preferable to the cis isomer. This is because it can be easily obtained and a high effect can be obtained.

  The non-aqueous solvent preferably contains sultone (cyclic sulfonic acid ester). This is because the chemical stability of the non-aqueous electrolyte is further improved. Examples of the sultone include propane sultone and propene sultone. The content of sultone in the non-aqueous solvent is, for example, 0.5% by mass or more and 5% by mass or less. However, the sultone is not limited to the compounds described above, and may be other compounds.

  Further, the non-aqueous solvent preferably contains an acid anhydride. This is because the chemical stability of the non-aqueous electrolyte is further improved. Examples of the acid anhydride include a carboxylic acid anhydride, a disulfonic acid anhydride, and an anhydride of a carboxylic acid and a sulfonic acid. Examples of the carboxylic acid anhydride include succinic anhydride, glutaric anhydride, and maleic anhydride. Examples of the disulfonic anhydride include ethane disulfonic anhydride and propane disulfonic anhydride. Examples of the anhydride of carboxylic acid and sulfonic acid include anhydrous sulfobenzoic acid, anhydrous sulfopropionic acid, and anhydrous sulfobutyric acid. The content of the acid anhydride in the non-aqueous solvent is, for example, 0.5% by mass or more and 5% by mass or less. However, the acid anhydride is not limited to the compounds described above, and may be other compounds.

  Similarly, the non-aqueous solvent preferably contains a nitrile compound. This is because the chemical stability of the non-aqueous electrolyte is further improved. Examples of the nitrile compound include succinonitrile, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, and 3-methoxypropionitrile. The content of the nitrile compound in the non-aqueous solvent is, for example, 0.5% by mass or more and 5% by mass or less. However, the nitrile compound is not limited to the above-described compounds, and may be other compounds.

[Electrolyte salt]
The electrolyte salt includes, for example, at least one of lithium salts described below. However, the electrolyte salt may contain, for example, a salt other than the lithium salt (for example, a light metal salt other than the lithium salt).

Examples of the lithium salt include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium perchlorate (LiClO ₄ ), and lithium hexafluoroarsenate (LiAsF ₆ ). . Lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ) or lithium tetrachloroaluminate (LiAlCl ₄ ) . Examples thereof include dilithium hexafluorosilicate (Li ₂ SiF ₆ ), lithium chloride (LiCl), and lithium bromide (LiBr). This is because in a nonaqueous electrolyte battery using an electrolytic solution, excellent battery capacity, cycle characteristics, storage characteristics, and the like can be obtained. However, the lithium salt is not limited to the above-described compounds, and may be other compounds.

  Among these, at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, and lithium hexafluoroarsenate is preferable, and lithium hexafluorophosphate is more preferable. This is because the internal resistance is lowered and a higher effect of improving battery characteristics can be obtained.

  In particular, the electrolyte salt preferably contains at least one of the compounds represented by the formulas (6) to (11). This is because a higher effect can be obtained. In addition, R61 in Formula (6) may be the same or different. The same applies to R71 to R73 in formula (7) and R81 and R82 in formula (8). However, the compounds shown in Formula (6) to Formula (11) are not limited to the compounds described below, and may be other compounds.

（Ｘ６１は長周期型周期表における１族元素または２族元素、またはアルミニウムである。Ｍ６１は遷移金属元素、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒ６１はハロゲン基である。Ｙ６１は−Ｃ（＝Ｏ）−Ｒ６２−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｃ（Ｒ６３）₂−または−Ｃ（＝Ｏ）−Ｃ（＝Ｏ）−である。ただし、Ｒ６２はアルキレン基、ハロゲン化アルキレン基、アリーレン基またはハロゲン化アリーレン基である。Ｒ６３はアルキル基、ハロゲン化アルキル基、アリール基またはハロゲン化アリール基である。なお、ａ６は１〜４の整数であり、ｂ６は０、２または４であり、ｃ６、ｄ６、ｍ６およびｎ６は１〜３の整数である。）

(X61 is a group 1 element or group 2 element in the long-period periodic table, or aluminum. M61 is a transition metal element, or a group 13, element, or group 15 element in the long-period periodic table. R61 Y61 is —C (═O) —R62—C (═O) —, —C (═O) —C (R63) ₂ — or —C (═O) —C (═O) Where R62 is an alkylene group, a halogenated alkylene group, an arylene group or a halogenated arylene group, and R63 is an alkyl group, a halogenated alkyl group, an aryl group or a halogenated aryl group, wherein a6 is (It is an integer of 1 to 4, b6 is 0, 2 or 4, and c6, d6, m6 and n6 are integers of 1 to 3.)

（Ｘ７１は長周期型周期表における１族元素または２族元素である。Ｍ７１は遷移金属元素、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｙ７１は−Ｃ（＝Ｏ）−（Ｃ（Ｒ７１）₂）_b7−Ｃ（＝Ｏ）−、−（Ｒ７３）₂Ｃ−（Ｃ（Ｒ７２）₂）_c7−Ｃ（＝Ｏ）−、−（Ｒ７３）₂Ｃ−（Ｃ（Ｒ７２）₂）_c7−Ｃ（Ｒ７３）₂−、−（Ｒ７３）₂Ｃ−（Ｃ（Ｒ７２）₂）_c7−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（Ｃ（Ｒ７２）₂）_d7−Ｓ（＝Ｏ）₂−または−Ｃ（＝Ｏ）−（Ｃ（Ｒ７２）₂）_d7−Ｓ（＝Ｏ）₂−である。ただし、Ｒ７１およびＲ７３は、それぞれ独立して、水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、それぞれのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。Ｒ７２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。なお、ａ７、ｅ７およびｎ７は１または２であり、ｂ７およびｄ７は１〜４の整数であり、ｃ７は０〜４の整数であり、ｆ７およびｍ７は１〜３の整数である。）

(X71 is a group 1 element or group 2 element in the long-period periodic table. M71 is a transition metal element, or a group 13, element, or group 15 element in the long-period periodic table. Y71 is -C. (= O) - (C ( R71) 2) b7 -C (= O) -, - (R73) 2 C- (C (R72) 2) c7 -C (= O) -, - (R73) 2 C _{- (C (R72) 2)} c7 -C (R73) 2 -, - (R73) 2 C- (C (R72) 2) c7 -S (= O) 2 -, - S (= O) 2 - ( C (R72) ₂ ) _d7- S (= O) _2- or -C (= O)-(C (R72) ₂ ) _d7- S (= O) _2- , where R71 and R73 are each Independently a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, at least one of each being a halogen group or R72 is a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, wherein a7, e7 and n7 are 1 or 2, and b7 and d7 are integers of 1 to 4. C7 is an integer of 0 to 4, and f7 and m7 are integers of 1 to 3.)

（Ｘ８１は長周期型周期表における１族元素または２族元素である。Ｍ８１は遷移金属元素、または長周期型周期表における１３族元素、１４族元素または１５族元素である。Ｒｆはフッ素化アルキル基またはフッ素化アリール基であり、いずれの炭素数も１〜１０である。Ｙ８１は−Ｃ（＝Ｏ）−（Ｃ（Ｒ８１）₂）_d8−Ｃ（＝Ｏ）−、−（Ｒ８２）₂Ｃ−（Ｃ（Ｒ８１）₂）_d8−Ｃ（＝Ｏ）−、−（Ｒ８２）₂Ｃ−（Ｃ（Ｒ８１）₂）_d8−Ｃ（Ｒ８２）₂−、−（Ｒ８２）₂Ｃ−（Ｃ（Ｒ８１）₂）_d8−Ｓ（＝Ｏ）₂−、−Ｓ（＝Ｏ）₂−（Ｃ（Ｒ８１）₂）_e8−Ｓ（＝Ｏ）₂−または−Ｃ（＝Ｏ）−（Ｃ（Ｒ８１）₂）_e8−Ｓ（＝Ｏ）₂−である。ただし、Ｒ８１は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基である。Ｒ８２は水素基、アルキル基、ハロゲン基またはハロゲン化アルキル基であり、そのうちの少なくとも１つはハロゲン基またはハロゲン化アルキル基である。なお、ａ８、ｆ８およびｎ８は１または２であり、ｂ８、ｃ８およびｅ８は１〜４の整数であり、ｄ８は０〜４の整数であり、ｇ８およびｍ８は１〜３の整数である。）

(X81 is a group 1 element or group 2 element in the long-period periodic table. M81 is a transition metal element, or a group 13, element or group 15 element in the long-period periodic table. Rf is fluorinated. An alkyl group or a fluorinated aryl group, each having 1 to 10 carbon atoms, Y81 is —C (═O) — (C (R81) ₂ ) _d8 —C (═O) —, — (R82) ₂ C- (C (R81) ₂ ) _d8 -C (= O)-,-(R82) ₂ C- (C (R81) ₂ ) _d8 -C (R82) ₂ -,-(R82) ₂ C- ( _{C (R81) 2) d8 -S} (= O) 2 -, - S (= O) 2 - (C (R81) 2) e8 -S (= O) 2 - or -C (= O) - (C _{(R81) 2) e8 -S (} = O) 2 -. is, however, R81 is a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group R82 is a hydrogen group, an alkyl group, a halogen group or a halogenated alkyl group, at least one of which is a halogen group or a halogenated alkyl group, wherein a8, f8 and n8 are 1 or 2. b8, c8 and e8 are integers of 1 to 4, d8 is an integer of 0 to 4, and g8 and m8 are integers of 1 to 3.)

  Note that group 1 elements in the long-period periodic table are hydrogen (H), lithium (Li) sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Group 2 elements are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). Group 13 elements are boron, aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). The group 14 elements are carbon, silicon, germanium (Ge), tin (Sn), and lead (Pb). Group 15 elements are nitrogen, phosphorus, arsenic (As), antimony (Sb), and bismuth (Bi).

  As a compound shown in Formula (6), the compound etc. which are represented by Formula (6-1)-Formula (6-6) are mentioned, for example. Examples of the compound represented by the formula (7) include compounds represented by the formula (7-1) to the formula (7-8). As a compound shown to Formula (8), the compound etc. which are represented by Formula (8-1) are mentioned, for example.

  Moreover, it is more preferable that the electrolyte salt contains at least one of the compounds represented by the formulas (9) to (11). This is because a higher effect can be obtained.

_{LiN (C m F 2m + 1} SO 2) (C n F 2n + 1 SO 2) ... (9)
(In the formula, m and n are each independently an integer of 1 or more.)

（式中、Ｒ９１は炭素数＝２〜４の直鎖状または分岐状のパーフルオロアルキレン基である。）

(In the formula, R91 is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms.)

LiC (C _p F _{2p + 1} SO ₂ ) (C _q F _{2q + 1} SO ₂ ) (C _r F _{2r + 1} SO ₂ ) (11)
(In the formula, p, q and r are each independently an integer of 1 or more.)

The compound shown in Formula (9) is a chain imide compound. Examples of the compound include bis (trifluoromethanesulfonyl) imide lithium (LiN (CF ₃ SO ₂ ) ₂ : LITFSI), bis (pentafluoroethanesulfonyl) imide lithium (LiN (C ₂ F ₅ SO ₂ ) ₂ ), (Trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) imide lithium (LiN (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ )), (trifluoromethanesulfonyl) (heptafluoropropanesulfonyl) imide lithium (LiN (CF ₃ SO _{2) (C 3 F 7 SO} 2)), it includes (trifluoromethanesulfonyl) (nonafluorobutanesulfonyl) imide _{(LiN (CF 3 SO 2)} (C 4 F 9 SO 2)).

  The compound shown in Formula (10) is a cyclic imide compound. Examples of this compound include compounds represented by formula (10-1) to formula (10-4). That is, 1,2-perfluoroethanedisulfonylimide lithium of formula (10-1), 1,3-perfluoropropane disulfonylimide lithium of formula (10-2), 1,3 of formula (10-3) -Perfluorobutanedisulfonylimide lithium or 1,4-perfluorobutanedisulfonylimide lithium of the formula (10-4).

The compound represented by the formula (11) is a chain methide compound. Examples of this compound include lithium tris (trifluoromethanesulfonyl) methide (LiC (CF ₃ SO ₂ ) ₃ ).

  The content of the electrolyte salt is preferably 0.3 mol / kg to 3.0 mol / kg with respect to the non-aqueous solvent. This is because high ionic conductivity is obtained.

(1-2) Gel electrolyte As another configuration, a gel electrolyte in which the above-described nonaqueous electrolytic solution is held in a polymer compound to form a gel can be used.

[Polymer compound]
The polymer compound may be any one that gels upon absorption of a solvent. For example, a fluorine-based polymer compound such as polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropropylene, polyethylene oxide or polyethylene oxide. And ether-based polymer compounds such as crosslinked products containing polyacrylonitrile, polypropylene oxide, or polymethyl methacrylate as repeating units. Any one of these polymer compounds may be used alone, or two or more thereof may be mixed and used.

  In particular, from the viewpoint of redox stability, a fluorine-based polymer compound is desirable, and among them, a copolymer containing vinylidene fluoride and hexafluoropropylene as components is preferable. Furthermore, this copolymer contains monoesters of unsaturated dibasic acids such as monomethylmaleic acid ester, halogenated ethylenes such as ethylene trifluorochloride, cyclic carbonates of unsaturated compounds such as vinylene carbonate, or epoxy group-containing compounds. An acrylic vinyl monomer may be included as a component. This is because higher characteristics can be obtained.

  The method for forming the gel electrolyte layer will be described later.

〔effect〕
When the nonaqueous electrolyte of the first embodiment is applied to a nonaqueous electrolyte battery, the end-of-charge voltage is suppressed and the discharge capacity is uniformized due to an electrochemical reaction during charging of the nonaqueous electrolyte battery. High effects can be obtained for both.

2. Second Embodiment In a second embodiment, a cylindrical non-aqueous electrolyte battery using the non-aqueous electrolyte or gel electrolyte in the first embodiment will be described.

(2-1) Configuration of Nonaqueous Electrolyte Battery FIG. 1 shows a cross-sectional structure of a nonaqueous electrolyte battery according to the second embodiment. This nonaqueous electrolyte battery is, for example, a lithium ion secondary battery.

  This non-aqueous electrolyte battery is a so-called cylindrical type, and a pair of strip-like positive electrode 21 and strip-like negative electrode 22 are wound through a separator 23 in a substantially hollow cylindrical battery can 11. A wound electrode body 20 is provided. The battery can 11 is made of, for example, iron plated with nickel, and has one end closed and the other end open. Inside the battery can 11, a pair of insulating plates 12 and 13 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.

  At the open end of the battery can 11, a battery lid 14, a safety valve mechanism 15 provided inside the battery lid 14 and a heat sensitive resistance element (Positive Temperature Coefficient; PTC element) 16 are interposed via a gasket 17. It is attached by caulking, and the inside of the battery can 11 is sealed. The battery lid 14 is made of, for example, the same material as the battery can 11. The safety valve mechanism 15 is electrically connected to the battery lid 14 via the heat sensitive resistance element 16, and the disk plate 15A is reversed when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating. Thus, the electrical connection between the battery lid 14 and the wound electrode body 20 is cut off. When the temperature rises, the heat sensitive resistance element 16 limits the current by increasing the resistance value and prevents abnormal heat generation due to a large current. The gasket 17 is made of, for example, an insulating material, and asphalt is applied to the surface.

  For example, a center pin 24 is inserted in the center of the wound electrode body 20. A positive electrode lead 25 made of aluminum or the like is connected to the positive electrode 21 of the spirally wound electrode body 20, and a negative electrode lead 26 made of nickel or the like is connected to the negative electrode 22. The positive electrode lead 25 is electrically connected to the battery lid 14 by being welded to the safety valve mechanism 15, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.

  FIG. 2 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. In the second embodiment, the positive electrode active material of the first embodiment can be used as the positive electrode active material. Hereinafter, the positive electrode 21, the negative electrode 22, and the separator 23 will be described in detail.

[Positive electrode]
The positive electrode 21 has, for example, a structure in which a positive electrode active material layer 21B is provided on both surfaces of a positive electrode current collector 21A having a pair of opposed surfaces. Although not shown, the positive electrode active material layer 21B may be provided only on one surface of the positive electrode current collector 21A. The positive electrode current collector 21A is made of, for example, a metal foil such as an aluminum foil.

  The positive electrode active material layer 21B includes, for example, a positive electrode active material, a conductive agent, and a binder. The positive electrode active material includes any one or more positive electrode materials capable of inserting and extracting lithium as the positive electrode active material. Other materials may be included.

As the positive electrode material capable of inserting and extracting lithium, for example, lithium-containing compounds such as lithium oxide, lithium phosphorus oxide, lithium sulfide, or an intercalation compound containing lithium are suitable, and two or more of these are used. May be used in combination. In order to increase the energy density, a lithium-containing compound containing lithium, a transition metal element, and oxygen (O) is preferable. Examples of such lithium-containing compounds include lithium composite oxides having a layered rock salt structure shown in (Chemical Formula I), lithium composite phosphates having an olivine type structure shown in (Chemical Formula II), and the like. Can be mentioned. It is more preferable that the lithium-containing compound includes at least one member selected from the group consisting of cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe) as a transition metal element. Examples of such lithium-containing compounds include lithium composite oxides having a layered rock salt type structure shown in (Chemical III), (Chemical IV) or (Chemical V), and spinel type compounds shown in (Chemical VI). Examples thereof include a lithium composite oxide having a structure, or a lithium composite phosphate having an olivine type structure shown in (Chemical Formula VII). Specifically, LiNi _0.50 Co _0.20 Mn _0.30 O ₂ , Li _a CoO ₂ (A≈1), Li _b NiO ₂ (b≈1), Li _c1 Ni _c2 Co _1-c2 O ₂ (c1≈1, 0 <c2 <1), Li _d Mn ₂ O ₄ (d≈1) or Li _e FePO ₄ (e≈1).

(Chemical I)
_{Li p Ni (1-qr)} Mn q M1 r O (2-y) X z
(In the formula, M1 represents at least one element selected from Group 2 to Group 15 excluding nickel (Ni) and manganese (Mn). X represents Group 16 element and Group 17 element other than oxygen (O). P, q, y, and z are 0 ≦ p ≦ 1.5, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.0, −0.10 ≦ y ≦ 0. (20, 0 ≦ z ≦ 0.2)

(Chemical II)
Li _a M2 _b PO ₄
(In the formula, M2 represents at least one element selected from Groups 2 to 15. a and b are values in the range of 0 ≦ a ≦ 2.0 and 0.5 ≦ b ≦ 2.0. .)

(Chemical III)
Li _f Mn _(1-gh) Ni _g M3 _h O _(2-j) F _k
(In the formula, M3 is cobalt (Co), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu ), Zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). g, h, j and k are 0.8 ≦ f ≦ 1.2, 0 <g <0.5, 0 ≦ h ≦ 0.5, g + h <1, −0.1 ≦ j ≦ 0.2, (The value is in the range of 0 ≦ k ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of f represents a value in a fully discharged state.)

(Chemical IV)
Li _m Ni _(1-n) M4 _n O _(2-p) F _q
(Wherein M4 is cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), at least one selected from the group consisting of m, n, p and q are values within the range of 0.8 ≦ m ≦ 1.2, 0.005 ≦ n ≦ 0.5, −0.1 ≦ p ≦ 0.2, 0 ≦ q ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of m represents a value in a fully discharged state.)

(Chemical V)
Li _r Co _(1-s) M5 _s O _{(2-t) Fu}
(In the formula, M5 is nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), at least one kind. s, t, and u are values within the ranges of 0.8 ≦ r ≦ 1.2, 0 ≦ s <0.5, −0.1 ≦ t ≦ 0.2, and 0 ≦ u ≦ 0.1. (Note that the composition of lithium varies depending on the state of charge and discharge, and the value of r represents the value in a fully discharged state.)

(Chemical VI)
Li _v Mn _(2-w) M6 _w O _x F _y
(In the formula, M6 represents cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr) and tungsten (W), at least one selected from the group consisting of v, w, x, and y are values within the range of 0.9 ≦ v ≦ 1.1, 0 ≦ w ≦ 0.6, 3.7 ≦ x ≦ 4.1, and 0 ≦ y ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of v represents the value in a fully discharged state.)

(Chemical VII)
Li _z M7PO ₄
(Wherein M7 is cobalt (Co), manganese (Mn), iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V ), Niobium (Nb), copper (Cu), zinc (Zn), molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W) and zirconium (Zr) Z is a value in a range of 0.9 ≦ z ≦ 1.1, wherein the composition of lithium varies depending on the state of charge and discharge, and the value of z represents a value in a complete discharge state. )

  Furthermore, as a composite particle in which the surface of the core particle made of any of the above lithium-containing compounds is coated with fine particles made of any of the other lithium-containing compounds, from the viewpoint that higher electrode filling properties and cycle characteristics can be obtained. Also good.

In addition, examples of the positive electrode material capable of inserting and extracting lithium include oxides, disulfides, chalcogenides, and conductive polymers. Examples of the oxide include vanadium oxide (V ₂ O ₅ ), titanium dioxide (TiO ₂ ), and manganese dioxide (MnO ₂ ). Examples of the disulfide include iron disulfide (FeS ₂ ), titanium disulfide (TiS ₂ ), and molybdenum disulfide (MoS ₂ ). The chalcogenide is particularly preferably a layered compound or a spinel compound, such as niobium selenide (NbSe ₂ ). Examples of the conductive polymer include sulfur, polyaniline, polythiophene, polyacetylene, and polypyrrole. Of course, the positive electrode material may be other than the above. Further, two or more kinds of the series of positive electrode materials described above may be mixed in any combination.

  As the conductive agent, for example, a carbon material such as carbon black or graphite is used. Examples of the binder include resin materials such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN), styrene butadiene rubber (SBR), and carboxymethyl cellulose (CMC), and these resin materials. At least one selected from a copolymer or the like mainly composed of is used.

[Negative electrode]
The negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces of a negative electrode current collector 22A having a pair of opposed surfaces. Although not shown, the negative electrode active material layer 22B may be provided only on one surface of the negative electrode current collector 22A.

  The negative electrode current collector 22A is made of, for example, a metal foil such as a copper (Cu) foil, a nickel (Ni) foil, or stainless steel (SUS). The surface of the negative electrode current collector 22A is preferably roughened. This is because the so-called anchor effect improves the adhesion between the negative electrode current collector 22A and the negative electrode active material layer 22B. In this case, the surface of the negative electrode current collector 22A only needs to be roughened at least in a region facing the negative electrode active material layer 22B. Examples of the roughening method include a method of forming fine particles by electrolytic treatment. This electrolytic treatment is a method of providing irregularities by forming fine particles on the surface of the anode current collector 22A by an electrolytic method in an electrolytic bath. The copper foil produced by the electrolytic method is generally called “electrolytic copper foil”. The surface roughness of the negative electrode current collector 22A can be arbitrarily set.

  The negative electrode active material layer 22B includes one or more negative electrode materials capable of inserting and extracting lithium as the negative electrode active material, and the positive electrode active material layer 21B as necessary. It is comprised including the same electrically conductive agent and binder.

  In this non-aqueous electrolyte battery, the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is larger than the electrochemical equivalent of the positive electrode 21, and theoretically, the negative electrode 22 is in the middle of charging. Lithium metal is not deposited.

  In addition, this nonaqueous electrolyte battery is designed such that an open circuit voltage (that is, a battery voltage) in a fully charged state is in a range of, for example, 4.20V or more and 6.00V or less. For example, it is preferable that the open circuit voltage in the fully charged state is 4.25 V or more and 6.00 V or less. When the open circuit voltage in the fully charged state is 4.25 V or higher, the amount of lithium released per unit mass is increased even with the same positive electrode active material as compared to the 4.20 V battery. Accordingly, the amounts of the positive electrode active material and the negative electrode active material are adjusted. Thereby, a high energy density can be obtained.

  Examples of the negative electrode material capable of inserting and extracting lithium include non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbons, cokes, glassy carbons, and fired organic polymer compounds And carbon materials such as carbon fiber and activated carbon. Of these, examples of coke include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body is a carbonized material obtained by firing a polymer material such as a phenol resin or a furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon. Some are classified as: These carbon materials are preferable because the change in crystal structure that occurs during charge and discharge is very small, a high charge and discharge capacity can be obtained, and good cycle characteristics can be obtained. In particular, graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density. Further, non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained. Furthermore, those having a low charge / discharge potential, specifically, those having a charge / discharge potential close to that of lithium metal are preferable because a high energy density of the battery can be easily realized.

  Examples of the negative electrode material capable of inserting and extracting lithium include materials capable of inserting and extracting lithium and containing at least one of a metal element and a metalloid element as a constituent element. . This is because a high energy density can be obtained by using such a material. In particular, the use with a carbon material is more preferable because a high energy density can be obtained and excellent cycle characteristics can be obtained. The negative electrode material may be a single element, alloy or compound of a metal element or metalloid element, or may have at least a part of one or more of these phases. In the present technology, the alloy includes an alloy including one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements. Moreover, the nonmetallic element may be included. Some of the structures include a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or two or more of them.

  Examples of metal elements or metalloid elements constituting the negative electrode material include magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), and germanium (Ge). ), Tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) ) Or platinum (Pt). These may be crystalline or amorphous.

  Among these, as the negative electrode material, a material containing a 4B group metal element or a semimetal element in the short-period type periodic table as a constituent element is preferable, and at least one of silicon (Si) and tin (Sn) is particularly preferable. It is included as an element. This is because silicon (Si) and tin (Sn) have a large ability to occlude and release lithium, and a high energy density can be obtained.

  As an alloy of tin (Sn), for example, as a second constituent element other than tin (Sn), silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr) The thing containing at least 1 sort is mentioned. As an alloy of silicon (Si), for example, as a second constituent element other than silicon (Si), tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr) The thing containing at least 1 sort is mentioned.

  Examples of the tin (Sn) compound or silicon (Si) compound include those containing oxygen (O) or carbon (C). In addition to tin (Sn) or silicon (Si), the above-described compounds are used. Two constituent elements may be included.

  Among these, as this negative electrode material, tin (Sn), cobalt (Co), and carbon (C) are included as constituent elements, and the carbon content is 9.9 mass% or more and 29.7 mass% or less. And the SnCoC containing material whose ratio of cobalt (Co) with respect to the sum total of tin (Sn) and cobalt (Co) is 30 mass% or more and 70 mass% or less is preferable. This is because a high energy density can be obtained in such a composition range, and excellent cycle characteristics can be obtained.

  This SnCoC-containing material may further contain other constituent elements as necessary. Examples of other constituent elements include silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), and molybdenum. (Mo), aluminum (Al), phosphorus (P), gallium (Ga) or bismuth (Bi) are preferable and may contain two or more. This is because the capacity or cycle characteristics can be further improved.

  This SnCoC-containing material has a phase containing tin, cobalt, and carbon, and this phase preferably has a low crystallinity or an amorphous structure. In this SnCoC-containing material, it is preferable that at least a part of carbon (C) as a constituent element is bonded to a metal element or a metalloid element as another constituent element. The decrease in cycle characteristics is considered to be due to aggregation or crystallization of tin (Sn) or the like. However, the combination of carbon (C) with other elements suppresses such aggregation or crystallization. Because it can.

  As a measuring method for examining the bonding state of elements, for example, X-ray photoelectron spectroscopy (XPS) can be cited. In XPS, the peak of the carbon 1s orbital (C1s) appears at 284.5 eV in an energy calibrated apparatus so that the peak of the gold atom 4f orbital (Au4f) is obtained at 84.0 eV if it is graphite. . Moreover, if it is surface contamination carbon, it will appear at 284.8 eV. On the other hand, when the charge density of the carbon element increases, for example, when carbon is bonded to a metal element or a metalloid element, the C1s peak appears in a region lower than 284.5 eV. That is, when the peak of the synthetic wave of C1s obtained for the SnCoC-containing material appears in a region lower than 284.5 eV, at least a part of the carbon contained in the SnCoC-containing material is a metal element or a half of other constituent elements. Combined with metal elements.

  In XPS measurement, for example, the C1s peak is used to correct the energy axis of the spectrum. Usually, since surface-contaminated carbon exists on the surface, the C1s peak of the surface-contaminated carbon is set to 284.8 eV, which is used as an energy standard. In the XPS measurement, the waveform of the C1s peak is obtained as a shape including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. Therefore, by analyzing using, for example, commercially available software, the surface contamination The carbon peak and the carbon peak in the SnCoC-containing material are separated. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).

[Separator]
The separator 23 separates the positive electrode 21 and the negative electrode 22 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. The separator 23 is made of, for example, a porous film made of synthetic resin made of polytetrafluoroethylene, polypropylene, polyethylene, or the like, or a porous film made of ceramic, and these two or more kinds of porous films are laminated. It may be made the structure.

  The separator 23 is impregnated with a non-aqueous electrolyte that is a liquid non-aqueous electrolyte. This nonaqueous electrolytic solution includes a nonaqueous solvent and an electrolyte salt dissolved in the nonaqueous solvent.

The separator 23 may include any of polypropylene (PP), polyvinylidene fluoride (PVdF), and polytetrafluoroethylene (PTFE) in addition to polyethylene. Moreover, it is comprised with the porous film made from a ceramic, and it is good also as a porous film by mixing several types out of polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE). Further, ceramics such as polyvinylidene fluoride (PVdF), alumina (Al ₂ O ₃ ), and silica (SiO ₂ ) are formed on the surface of a porous film of polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE). May be applied. Further, a structure in which two or more porous films of polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE) are laminated may be employed. A porous membrane made of polyolefin is preferable because it is excellent in short-circuit prevention effect and can improve battery safety by a shutdown effect.

[Nonaqueous electrolyte or gel electrolyte]
As the non-aqueous electrolyte, the non-aqueous electrolyte of the first embodiment can be used. Moreover, you may use the gel electrolyte which hold | maintained the non-aqueous electrolyte in the matrix polymer.

(2-2) Manufacturing method of nonaqueous electrolyte battery [Manufacturing method of positive electrode]
A positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and the positive electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like positive electrode mixture slurry Is made. Next, the positive electrode mixture slurry is applied to the positive electrode current collector 21A, the solvent is dried, and the positive electrode active material layer 21B is formed by compression molding with a roll press machine or the like, and the positive electrode 21 is manufactured.

[Production method of negative electrode]
A negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to prepare a paste-like negative electrode mixture slurry. Next, the negative electrode mixture slurry is applied to the negative electrode current collector 22A, the solvent is dried, and the negative electrode active material layer 22B is formed by compression molding with a roll press or the like, thereby producing the negative electrode 22.

[Preparation of non-aqueous electrolyte]
The nonaqueous electrolytic solution is prepared by dissolving an electrolyte salt in a nonaqueous solvent.

[Assembly of non-aqueous electrolyte battery]
The positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like. Thereafter, the positive electrode 21 and the negative electrode 22 are wound through a separator 23 to form a wound electrode body 20. The tip of the positive electrode lead 25 is welded to the safety valve mechanism 15, and the tip of the negative electrode lead 26 is welded to the battery can 11. Thereafter, the wound surface of the wound electrode body 20 is sandwiched between the pair of insulating plates 12 and 13 and stored in the battery can 11. After the wound electrode body 20 is accommodated in the battery can 11, a non-aqueous electrolyte is injected into the battery can 11 and impregnated in the separator 23. After that, the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are fixed to the opening end of the battery can 11 by caulking through the gasket 17. Thereby, the nonaqueous electrolyte battery shown in FIG. 1 is formed.

  In this non-aqueous electrolyte battery, when charged, for example, lithium ions are released from the positive electrode active material layer 21B and inserted into the negative electrode active material layer 22B through the non-aqueous electrolyte. Further, when discharging is performed, for example, lithium ions are released from the negative electrode active material layer 22B and inserted into the positive electrode active material layer 21B through the nonaqueous electrolytic solution.

〔effect〕
The nonaqueous electrolyte battery according to the second embodiment can obtain a high effect in terms of both the end-of-charge voltage suppression caused by the electrochemical reaction during the charging of the nonaqueous electrolyte battery and the uniform discharge capacity. .

3. Third Embodiment In the third embodiment, a laminated film type nonaqueous electrolyte battery using the nonaqueous electrolyte in the first embodiment will be described. In the third embodiment, an example using a gel electrolyte will be described.

(3-1) Configuration of Nonaqueous Electrolyte Battery FIG. 3 shows the configuration of the nonaqueous electrolyte battery according to the third embodiment. This non-aqueous electrolyte battery is a so-called laminate film type, in which a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached is housed in a film-shaped exterior member 40.

  The positive electrode lead 31 and the negative electrode lead 32 are led out from the inside of the exterior member 40 to the outside, for example, in the same direction. The positive electrode lead 31 and the negative electrode lead 32 are each made of a metal material such as aluminum, copper, nickel, or stainless steel, and each have a thin plate shape or a mesh shape.

  The exterior member 40 is made of, for example, a laminate film in which resin layers are formed on both surfaces of a metal layer. In the laminate film, an outer resin layer is formed on a surface of the metal layer that is exposed to the outside of the battery, and an inner resin layer is formed on the inner surface of the battery facing the power generation element such as the wound electrode body 30.

  The metal layer plays the most important role in protecting the contents by preventing the ingress of moisture, oxygen and light, and aluminum (Al) is most often used because of its lightness, extensibility, price and ease of processing. The outer resin layer has a beautiful appearance, toughness, flexibility, and the like, and a resin material such as nylon or polyethylene terephthalate (PET) is used. Since the inner resin layer is a portion that melts and fuses with heat or ultrasonic waves, polyolefin is suitable, and unstretched polypropylene (CPP) is often used. An adhesive layer may be provided between the metal layer, the outer resin layer, and the inner resin layer as necessary.

  The exterior member 40 is provided with a recess that accommodates the wound electrode body 30 that is formed, for example, by deep drawing from the inner resin layer side toward the outer resin layer side, and the inner resin layer is the wound electrode body 30. It is arrange | positioned so that it may oppose. The inner resin layers facing each other of the exterior member 40 are in close contact with each other by fusion or the like at the outer edge of the recess. Between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32, there is an adhesive film 41 for improving the adhesion between the inner resin layer of the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 made of a metal material. Has been placed. The adhesion film 41 is made of a resin material having high adhesion to a metal material, and is made of, for example, polyethylene, polypropylene, or a polyolefin resin such as modified polyethylene or modified polypropylene obtained by modifying these materials.

  The exterior member 40 may be made of a laminate film having another structure, a polymer film such as polypropylene, or a metal film, instead of the aluminum laminate film whose metal layer is made of aluminum (Al).

  FIG. 4 shows a cross-sectional structure taken along line II of the spirally wound electrode body 30 shown in FIG. The wound electrode body 30 is obtained by laminating a positive electrode 33 and a negative electrode 34 via a separator 35 and an electrolyte layer 36 made of a gel electrolyte, and winding the outermost peripheral portion with a protective tape 37 as necessary. Has been.

[Positive electrode]
The positive electrode 33 has a structure in which a positive electrode active material layer 33B is provided on one or both surfaces of a positive electrode current collector 33A. The configurations of the positive electrode current collector 33A and the positive electrode active material layer 33B are the same as those of the positive electrode current collector 21A and the positive electrode active material layer 21B in the second embodiment.

[Negative electrode]
The negative electrode 34 has a structure in which a negative electrode active material layer 34B is provided on one surface or both surfaces of a negative electrode current collector 34A, and the negative electrode active material layer 34B and the positive electrode active material layer 33B are arranged to face each other. Yes. The configurations of the negative electrode current collector 34A and the negative electrode active material layer 34B are the same as those of the negative electrode current collector 22A and the negative electrode active material layer 22B in the second embodiment.

[Separator]
The separator 35 is the same as the separator 23 in the second embodiment.

[Nonaqueous electrolyte]
The electrolyte layer 36 is the gel electrolyte described in the first embodiment. The gel electrolyte is preferable because it can obtain high ionic conductivity and prevent battery leakage. Further, as described in the second embodiment, a nonaqueous electrolytic solution may be used.

(3-2) Manufacturing Method of Nonaqueous Electrolyte Battery This nonaqueous electrolyte battery can be manufactured as follows, for example.

[Method for producing positive electrode and negative electrode]
The positive electrode 33 and the negative electrode 34 can be manufactured by the same method as in the second embodiment.

[Assembly of non-aqueous electrolyte battery]
A precursor solution containing a nonaqueous electrolytic solution, a polymer compound, and a mixed solvent is applied to each of the positive electrode 33 and the negative electrode 34, and the mixed solvent is volatilized to form the electrolyte layer 36. After that, the positive electrode lead 31 is attached to the end of the positive electrode current collector 33A by welding, and the negative electrode lead 32 is attached to the end of the negative electrode current collector 34A by welding.

  Next, the positive electrode 33 and the negative electrode 34 on which the electrolyte layer 36 is formed are laminated via a separator 35 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and a protective tape 37 is attached to the outermost peripheral portion. The wound electrode body 30 is formed by bonding. Finally, for example, the wound electrode body 30 is sandwiched between the exterior members 40, and the outer edges of the exterior members 40 are sealed and sealed by thermal fusion or the like. At that time, the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40. Thereby, the nonaqueous electrolyte battery shown in FIGS. 3 and 4 is completed.

  This nonaqueous electrolyte battery may be manufactured by the following method. Prepare an electrolyte composition containing a non-aqueous electrolyte, a monomer that is a raw material for the polymer compound, a polymerization initiator, and, if necessary, other materials such as a polymerization inhibitor. After the injection, the opening of the exterior member 40 is heat-sealed and sealed in a vacuum atmosphere. Next, the gelled electrolyte layer 36 is formed by applying heat to polymerize the monomer to obtain a polymer compound.

  Moreover, you may produce by the following methods. After the polymer compound is held on the surface of the separator 35 and a non-aqueous electrolyte is injected into the exterior member 40, the opening of the exterior member 40 is heat-sealed in a vacuum atmosphere and sealed. Next, heat is applied to hold the non-aqueous electrolyte in the polymer compound, thereby forming the gel electrolyte layer 36.

〔effect〕
The third embodiment can obtain the same effects as those of the second embodiment.

4). Fourth Embodiment In a fourth embodiment, a battery pack provided with a nonaqueous electrolyte battery using the nonaqueous electrolyte battery in the second embodiment and the third embodiment will be described.

  FIG. 5 is a block diagram showing a circuit configuration example when the nonaqueous electrolyte battery of the present technology is applied to a battery pack. The battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.

  In addition, the battery pack includes a positive electrode terminal 321 and a negative electrode terminal 322. During charging, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.

  The assembled battery 301 is formed by connecting a plurality of nonaqueous electrolyte batteries 301a in series and / or in parallel. This nonaqueous electrolyte battery 301a is a nonaqueous electrolyte battery of the present technology. In addition, in FIG. 5, although the case where the six nonaqueous electrolyte batteries 301a are connected to 2 parallel 3 series (2P3S) is shown as an example, in addition, n parallel m series (n and m are integers). As such, any connection method may be used.

  The switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310. The diode 302b has a reverse polarity with respect to the charging current flowing from the positive terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative terminal 322 in the direction of the assembled battery 301. The diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current. In the example, the switch portion is provided on the + side, but may be provided on the − side.

  The charge control switch 302 a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charge control switch is turned off, only discharging is possible through the diode 302b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 310 so that the charging current flowing in the current path of the assembled battery 301 is cut off.

  The discharge control switch 303a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 310 so that the discharge current does not flow through the current path of the assembled battery 301. After the discharge control switch 303a is turned off, only charging is possible via the diode 303b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 310 so as to cut off the discharging current flowing in the current path of the assembled battery 301.

  The temperature detection element 308 is, for example, a thermistor, is provided in the vicinity of the assembled battery 301, measures the temperature of the assembled battery 301, and supplies the measured temperature to the control unit 310. The voltage detection unit 311 measures the voltage of the assembled battery 301 and each non-aqueous electrolyte battery 301 a that constitutes the same, performs A / D conversion on the measured voltage, and supplies the voltage to the control unit 310. The current measurement unit 313 measures the current using the current detection resistor 307 and supplies this measurement current to the control unit 310.

  The switch control unit 314 controls the charge control switch 302a and the discharge control switch 303a of the switch unit 304 based on the voltage and current input from the voltage detection unit 311 and the current measurement unit 313. The switch control unit 314 sends a control signal to the switch unit 304 when any voltage of the nonaqueous electrolyte battery 301a becomes equal to or lower than the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. To prevent overcharge, overdischarge and overcurrent charge / discharge.

  Here, for example, when the nonaqueous electrolyte battery is a lithium ion secondary battery, the overcharge detection voltage is determined to be, for example, 4.20V ± 0.05V, and the overdischarge detection voltage is determined to be, for example, 2.4V ± 0.1V. It is done.

  As the charge / discharge switch, for example, a semiconductor switch such as a MOSFET can be used. In this case, the parasitic diode of the MOSFET functions as the diodes 302b and 303b. When a P-channel FET is used as the charge / discharge switch, the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively. When the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.

  For example, during overcharge or overdischarge, the control signals CO and DO are set to a high level, and the charge control switch 302a and the discharge control switch 303a are turned off.

  The memory 317 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory. In the memory 317, the numerical value calculated by the control unit 310, the internal resistance value of the battery in the initial state of each nonaqueous electrolyte battery 301a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. is there. (In addition, by storing the full charge capacity of the nonaqueous electrolyte battery 301a, for example, the remaining capacity can be calculated together with the control unit 310.

  The temperature detection unit 318 measures the temperature using the temperature detection element 308, performs charge / discharge control during abnormal heat generation, and performs correction in the calculation of the remaining capacity.

5. Fifth Embodiment In the fifth embodiment, an electronic device, an electric vehicle, and a power storage equipped with the nonaqueous electrolyte battery according to the second and third embodiments and the battery pack according to the fourth embodiment. A device such as an apparatus will be described. The nonaqueous electrolyte batteries and battery packs described in the second to fourth embodiments can be used to supply power to devices such as electronic devices, electric vehicles, and power storage devices.

  Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory cards, pacemakers, hearing aids, power tools, electric shavers, refrigerators, air conditioners, TVs, stereos, water heaters, microwave ovens, dishwashers, washing machines, dryers, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights Etc.

  Further, examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.

  Examples of the power storage device include a power storage power source for buildings such as houses or power generation facilities.

  Below, the specific example of the electrical storage system using the electrical storage apparatus to which the nonaqueous electrolyte battery of this technique is applied among the application examples mentioned above is demonstrated.

  This power storage system has the following configuration, for example. The first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy. The second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device. The third power storage system is an electronic device that receives power supply from the power storage device. These power storage systems are implemented as a system for efficiently supplying power in cooperation with an external power supply network.

  Furthermore, the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information about the power storage device. It is. The fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit. . The sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device. Hereinafter, the power storage system will be described.

(5-1) Power Storage System in Residential House as Application Example An example in which a power storage device using a nonaqueous electrolyte battery of the present technology is applied to a power storage system for a house will be described with reference to FIG. For example, in the power storage system 100 for the house 101, electric power is stored from the centralized power system 102 such as the thermal power generation 102a, the nuclear power generation 102b, and the hydroelectric power generation 102c through the power network 109, the information network 112, the smart meter 107, the power hub 108, and the like. Supplied to the device 103. At the same time, power is supplied to the power storage device 103 from an independent power source such as the home power generation device 104. The electric power supplied to the power storage device 103 is stored. Electric power used in the house 101 is fed using the power storage device 103. The same power storage system can be used not only for the house 101 but also for buildings.

  The house 101 is provided with a power generation device 104, a power consumption device 105, a power storage device 103, a control device 110 that controls each device, a smart meter 107, and a sensor 111 that acquires various types of information. Each device is connected by a power network 109 and an information network 112. As the power generation device 104, a solar cell, a fuel cell, or the like is used, and the generated power is supplied to the power consumption device 105 and / or the power storage device 103. The power consuming device 105 is a refrigerator 105a, an air conditioner 105b, a television receiver 105c, a bath 105d, and the like. Furthermore, the electric power consumption device 105 includes an electric vehicle 106. The electric vehicle 106 is an electric vehicle 106a, a hybrid car 106b, and an electric motorcycle 106c.

  The nonaqueous electrolyte battery of the present technology is applied to the power storage device 103. The nonaqueous electrolyte battery of the present technology may be constituted by, for example, the above-described lithium ion secondary battery. The smart meter 107 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company. The power network 109 may be one or a combination of DC power supply, AC power supply, and non-contact power supply.

  The various sensors 111 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by various sensors 111 is transmitted to the control device 110. Based on the information from the sensor 111, the weather condition, the human condition, etc. can be grasped, and the power consumption device 105 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 110 can transmit information regarding the house 101 to an external power company or the like via the Internet.

  The power hub 108 performs processing such as branching of power lines and DC / AC conversion. Communication methods of the information network 112 connected to the control device 110 include a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, and Wi-Fi. There is a method of using a sensor network according to the standard. The Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Engineers) 802.15.4. IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.

  The control device 110 is connected to an external server 113. The server 113 may be managed by any one of the house 101, the power company, and the service provider. The information transmitted and received by the server 113 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device in the home (for example, a television receiver), but may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, such as a television receiver, a mobile phone, or a PDA (Personal Digital Assistants).

  The control device 110 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 103 in this example. The control device 110 is connected to the power storage device 103, the power generation device 104, the power consumption device 105, the various sensors 111, the server 113 and the information network 112, and has a function of adjusting, for example, the amount of commercial power used and the amount of power generation. Have. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.

  As described above, the electric power can be stored not only in the centralized power system 102 such as the thermal power 102a, the nuclear power 102b, and the hydropower 102c but also in the power storage device 103 from the power generation device 104 (solar power generation, wind power generation). Therefore, even if the generated power of the power generation device 104 fluctuates, it is possible to perform control such that the amount of power transmitted to the outside is constant or discharge is performed as necessary. For example, the electric power obtained by solar power generation is stored in the power storage device 103, and midnight power with a low charge is stored in the power storage device 103 at night, and the power stored by the power storage device 103 is discharged during a high daytime charge. You can also use it.

  In this example, the example in which the control device 110 is stored in the power storage device 103 has been described. However, the control device 110 may be stored in the smart meter 107 or may be configured independently. Furthermore, the power storage system 100 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.

(5-2) Power Storage System in Vehicle as Application Example An example in which the present technology is applied to a power storage system for a vehicle will be described with reference to FIG. FIG. 7 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. A series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.

  The hybrid vehicle 200 includes an engine 201, a generator 202, a power driving force conversion device 203, driving wheels 204a, driving wheels 204b, wheels 205a, wheels 205b, a battery 208, a vehicle control device 209, various sensors 210, and a charging port 211. Is installed. The nonaqueous electrolyte battery of the present technology described above is applied to the battery 208.

  The hybrid vehicle 200 runs using the power driving force conversion device 203 as a power source. An example of the power driving force conversion device 203 is a motor. The electric power / driving force converter 203 is operated by the electric power of the battery 208, and the rotational force of the electric power / driving force converter 203 is transmitted to the driving wheels 204a and 204b. In addition, by using a direct current-alternating current (DC-AC) or reverse conversion (AC-DC conversion) where necessary, the power driving force conversion device 203 can be applied to either an AC motor or a DC motor. The various sensors 210 control the engine speed via the vehicle control device 209 and control the opening (throttle opening) of a throttle valve (not shown). The various sensors 210 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

  The rotational force of the engine 201 is transmitted to the generator 202, and the electric power generated by the generator 202 by the rotational force can be stored in the battery 208.

  When the hybrid vehicle 200 decelerates by a braking mechanism (not shown), the resistance force at the time of deceleration is applied as a rotational force to the power driving force conversion device 203, and the regenerative electric power generated by the power driving force conversion device 203 by this rotational force is used as the battery 208. Accumulated in.

  The battery 208 can be connected to a power source external to the hybrid vehicle 200 to receive power supply from the external power source using the charging port 211 as an input port and store the received power.

  Although not shown, an information processing apparatus that performs information processing related to vehicle control based on information related to the nonaqueous electrolyte battery may be provided. As such an information processing apparatus, for example, there is an information processing apparatus that displays a battery remaining amount based on information on the remaining amount of the battery.

  In addition, the above demonstrated as an example the series hybrid vehicle which drive | works with a motor using the electric power generated with the generator driven by an engine, or the electric power once stored in the battery. However, the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.

  Hereinafter, the present technology will be described in detail by way of examples. The compounds used in the following examples and comparative examples are as follows.

[Overcharge control agent]

Of the above-mentioned overcharge control agents, the positive electrode potential (vs. Li / Li ⁺ ) at the time of the compound reaction is shown in Table 1 below for the overcharge control agents used in Examples in which the safety valve operating time described later was measured. Show.

<Example 1-1-1>
[Production of positive electrode]
Lithium carbonate (Li ₂ CO ₃ ) and cobalt carbonate (CoCO ₃ ) were mixed at a molar ratio of 0.5: 1, and then calcined in air at 900 ° C. for 5 hours to obtain lithium cobalt composite oxide (LiCoO ₂ ). Obtained. Subsequently, 91 parts by mass of lithium cobalt composite oxide (LiCoO ₂ ) as a positive electrode active material, 6 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed. An agent was used. Subsequently, the positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to prepare a paste-like positive electrode mixture slurry. Finally, the positive electrode mixture slurry was uniformly applied and dried on both surfaces of a positive electrode current collector made of a strip-shaped aluminum foil having a thickness of 12 μm using a coating apparatus, and then compression molded using a roll press machine. A positive electrode on which an active material layer was formed was produced.

[Production of negative electrode]
96 parts by mass of a granular graphite powder having an average particle size of 20 μm as a negative electrode active material, 1.5 parts by mass of an acrylic acid modified product of a styrene-butadiene copolymer as a binder, and 1.5 parts by mass of carboxymethyl cellulose as a thickener Then, an appropriate amount of water was stirred to prepare a negative electrode mixture slurry. Next, a negative electrode mixture slurry was uniformly applied and dried on both surfaces of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 15 μm using a coating apparatus, and then compressed and molded using a roll press machine. A negative electrode on which an active material layer was formed was produced.

[Preparation of non-aqueous electrolyte]
Ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) were mixed at a mass ratio EC: DMC: EMC = 30: 40: 30 to make a non-aqueous solvent, and then an electrolyte salt was added to the non-aqueous solvent. As a solution, lithium hexafluorophosphate (LiPF ₆ ) was dissolved at a concentration of 1.0 mol / kg. Subsequently, in the non-aqueous solvent in which the electrolyte salt is dissolved, the above-described overcharge control agent (1-10) is dissolved as an overcharge control agent, and the compound represented by the formula (1-2) is dissolved as an additive compound, A non-aqueous electrolyte was prepared. In addition, the overcharge control agent (1-10) was mixed so that content in the whole composition of a non-aqueous electrolyte might be 5.0 mass%. Moreover, the additive compound was mixed so that content in the whole composition of a non-aqueous electrolyte solution might be 0.1 mass% (2.0 mass% with respect to an overcharge control agent).

[Assembly of cylindrical nonaqueous electrolyte battery]
An aluminum positive electrode lead was welded to one end of the positive electrode current collector. Further, a negative electrode lead made of nickel was welded to one end of the negative electrode current collector. Then, after laminating | stacking a positive electrode and a negative electrode through a separator, it wound in the longitudinal direction and produced the winding electrode body by fixing a winding end part with an adhesive tape. As the separator, a microporous polypropylene film having a thickness of 25 μm was used. Subsequently, after inserting a center pin into the winding center of the wound electrode body, the wound electrode body was sandwiched between a pair of insulating plates and housed in a nickel-plated iron battery can. At this time, the positive electrode lead was welded to the safety valve mechanism, and the negative electrode lead was welded to the battery can.

  Subsequently, a non-aqueous electrolyte was injected into the battery can by a reduced pressure method to impregnate the separator. Finally, a battery lid, a safety valve mechanism, and a heat sensitive resistance element were caulked to the opening end of the battery can via a gasket, and these were fixed. Thereby, the cylindrical non-aqueous electrolyte battery (test battery) was completed. When producing this test battery, the thickness of the positive electrode active material layer was adjusted so that lithium metal did not deposit on the negative electrode during full charge.

<Example 1-1-2> to <Example 1-1-29>
The overcharge control agent mixed in the non-aqueous electrolyte was changed to the overcharge control agent (1-10), and each overcharge control agent shown in Table 2 was used, as in Example 1-1-1. The test batteries of Example 1-1-2 to Example 1-1-29 were produced.

[Battery evaluation]
(A) Average discharge capacity The test batteries of each example and each comparative example were charged at a constant current up to a battery voltage of 4.2 V with a charging current of 0.2 C in an atmosphere at 23 ° C. Then, constant voltage charging was performed, and the charging was terminated when the total charging time reached 8 hours. Thereafter, constant current discharge was performed to a battery voltage of 3.0 V with a discharge current of 0.2 C. “0.2C” is a current value at which the theoretical capacity can be discharged in 5 hours. After performing this charge / discharge cycle for 2 cycles, after performing constant current charge and constant voltage charge with an upper limit voltage of 4.8 V in the 3rd cycle, discharge capacity when performing constant current discharge to a battery voltage of 3.0 V Was measured. Here, the average discharge capacity was an average value obtained from the discharge capacities of 10 test batteries by preparing 10 test batteries of each example and each comparative example and measuring the discharge capacity.

(B) Standard deviation of discharge capacity For each example and each comparative example, the standard deviation of the battery capacity of each of the ten test batteries measured in (a) was determined.

(C) Safety valve operation time After performing 2 cycles of charge / discharge under the same charge / discharge conditions as in (a), after performing a constant current charge to a battery voltage of 4.8 V with a charge current of 0.5 C in the third cycle A constant voltage charge was performed at 4.8 V, and the charge was terminated when the total charge time reached 5 hours. The test battery in such a charged state was stored in an atmosphere at 80 ° C., and the time until the gas was ejected after the safety valve of the test battery was activated was confirmed. In addition, the confirmation of the safety valve operating time is confirmed in Example 1-1-1, Example 1-1-7, Example 1-1-11, Example 1-1-14, Example 1-1-17, Example. It was carried out only for 1-1-19 to Example 1-1-22, Example 1-1-24 to Example 1-1-26, Example 1-1-28 and Example 1-1-29.

  Table 2 below shows the evaluation results. In Table 2, “mass%” is indicated as “wt%”. The same applies to the following tables.

<Example 1-2-1> to <Example 1-229>
The same procedure as in Example 1-1-1 to Example 1-1-29 was carried out, except that the compound shown in formula (2-1) was used instead of the compound shown in formula (1-2) as the additive compound. Test batteries of Example 1-2-1 to Example 1-229 were produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  Table 3 below shows the evaluation results.

<Example 1-3-1> to <Example 1-3-29>
Example 1 was carried out in the same manner as Example 1-1-1 to Example 1-1-29 except that the compound shown in Formula (3) was used instead of the compound shown in Formula (1-2) as the additive compound. The test batteries of 3-1 to Example 1-329 were produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  Table 4 below shows the evaluation results.

<Example 1-4-1> to <Example 1-4-29>
Example 1 was carried out in the same manner as in Example 1-1-1 to Example 1-1-29 except that the compound shown in Formula (4) was used instead of the compound shown in Formula (1-2) as the additive compound. Test samples of 4-1 to Example 1-429 were produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  Table 5 below shows the evaluation results.

<Example 1-5-1> to <Example 1-5-29>
In addition to the compound represented by the formula (1-2) (content 0.1% by mass) as an additive compound, the content of the compound represented by the formula (4) in the total composition of the nonaqueous electrolytic solution is 0.1 mass. % The test batteries of Example 1-5-1 to Example 1-29 were prepared in the same manner as Example 1-1-1 to Example 1-1-29, except that they were mixed so that did. In addition, the sum total of the additive compound was 4.0 mass% with respect to the overcharge control agent.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  Table 6 below shows the evaluation results.

<Example 1-6-1> to <Example 1-6-29>
Instead of the compound shown in Formula (1-2) as an additive compound, the compound shown in Formula (2-1) and the compound shown in Formula (4) are each contained in the entire composition of the nonaqueous electrolytic solution. Example 1-6-1 to Example 1 to Example 1-1-1 to Example 1-1-29, except that the amount was 0.1% by mass (total 0.2% by mass) Test batteries 1-6 to 29 were produced. In addition, the sum total of the additive compound was 4.0 mass% with respect to the overcharge control agent.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  Table 7 below shows the evaluation results.

<Example 1-7-1> to <Example 1-7-29>
In place of the compound represented by Formula (1-2) as the additive compound, the compound represented by Formula (3) and the compound represented by Formula (4) each contained 0.1% in the total composition of the nonaqueous electrolytic solution. Example 1-7-1 to Example 1-7 in the same manner as Example 1-1-1 to Example 1-129, except that mixing was performed so that the content was 5% by mass (total 0.2% by mass). -29 test batteries were prepared. In addition, the sum total of the additive compound was 4.0 mass% with respect to the overcharge control agent.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  Table 8 below shows the evaluation results.

<Comparative Example 1-1-1> to <Comparative Example 1-1-29>
Test batteries of Comparative Example 1-7-1 to Comparative Example 1-7-29 were prepared in the same manner as Example 1-1-1 to Example 1-1-29 except that the additive compound was not mixed.

<Comparative Example 1-1-30>
A test battery of Comparative Example 1-7-30 was produced in the same manner as Example 1-1-1 except that both the overcharge control agent and the additive compound were not mixed.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  Table 9 below shows the evaluation results.

  As can be seen from Comparative Example 1-1-1 to Comparative Example 1-1-29 and Comparative Example 1-1-30 in Table 9, the standard deviation of the discharge capacity when the overcharge control agent is added and when it is not added. And the variation in discharge capacity was reduced. Moreover, it turned out that the operating time of a safety valve becomes a little long and can suppress the gas generation inside a battery.

  On the other hand, as can be seen from Tables 2 to 5 and Table 9, Examples 1-1-1 to Examples in which an additive compound of the present technology was mixed with a non-aqueous electrolyte together with an overcharge control agent that suppresses an increase in voltage In 1-4-29, only the overcharge control agent was mixed, and variation in discharge capacity was less likely to occur than Comparative Example 1-1-1 to Comparative Example 1-1-29 in which the additive compound was not mixed. .

  This is because the test battery of Example 1-1-1 to Example 1-4-29 contains the additive compound of the present technology together with the overcharge control agent in the non-aqueous electrolyte solution. This is because the mobility of the overcharge control agent between the electrodes is increased as compared with the comparative example not included, and the effect of adding the overcharge control agent can be more sufficiently obtained.

  Moreover, it turned out that the same effect is acquired even if it mixes and uses the additive compound of this technique. That is, in Examples 1-5-2 to 1-29, Examples (2-1) and (4) in which the additive compounds of Formula (1-2) and Formula (4) are mixed and used. Examples 1-6-2 to 1-6-29 using a mixture of additive compounds, Examples 1-7-2 to Examples 1-7-2 using a mixture of additive compounds of formula (3) and formula (4) For Example 1-7-29, the same or more effects as those of Example 1-1-1 to Example 1-429 using the same overcharge control agent were obtained. By combining (1-2) or equation (2-1) with equation (4), the variation in discharge capacity was further reduced.

  Moreover, in each Example using the additive compound of this technique with the overcharge control agent which suppresses a voltage rise, the safety valve operation time became long compared with the corresponding comparative example. For this reason, it turned out that gas generation inside a battery can be controlled.

  In the following examples, the effect was confirmed by changing the addition amount of the overcharge control agent.

<Example 1-8-1>
The overcharge control agent (1) so that the content of the overcharge control agent in the total composition of the non-aqueous electrolyte is 1.0% by mass (the addition amount of the additive compound to the overcharge control agent is 10.0% by mass). A test battery was produced in the same manner as in Example 1-1-1 except that the non-aqueous electrolyte mixed with -10) was used.

<Example 1-8-2>
The overcharge control agent (1) so that the content of the overcharge control agent in the total composition of the nonaqueous electrolyte solution is 10.0% by mass (the addition amount of the additive compound to the overcharge control agent is 1.0% by mass). A test battery was produced in the same manner as in Example 1-1-1 except that the non-aqueous electrolyte mixed with -10) was used.

<Example 1-8-3>
The overcharge control agent (1) so that the content of the overcharge control agent in the total composition of the non-aqueous electrolyte is 25.0% by mass (the addition amount of the additive compound to the overcharge control agent is 0.4% by mass). A test battery was produced in the same manner as in Example 1-1-1 except that the non-aqueous electrolyte mixed with -10) was used.

<Example 1-8-4> to <Example 1-8-6>
Test batteries were produced in the same manner as in Example 1-8-1 to Example 1-8-3, except that the overcharge control agent (1-18) was used as the overcharge control agent.

<Example 1-8-7> to <Example 1-8-9>
Test batteries were prepared in the same manner as in Example 1-8-1 to Example 1-8-3, except that the overcharge control agent (4-71) was used as the overcharge control agent.

<Example 1-8-10> to <Example 1-8-12>
Test batteries were prepared in the same manner as in Example 1-8-1 to Example 1-8-3, except that the overcharge control agent (5-3) was used as the overcharge control agent.

<Example 1-8-13> to <Example 1-8-15>
Test batteries were produced in the same manner as in Example 1-8-1 to Example 1-8-3, except that the overcharge control agent (6-9) was used as the overcharge control agent.

<Example 1-8-16> to <Example 1-8-18>
Test batteries were prepared in the same manner as in Example 1-8-1 to Example 1-8-3, except that the overcharge control agent (8-4) was used as the overcharge control agent.

<Example 1-8-19> to <Example 1-8-21>
Test batteries were produced in the same manner as in Example 1-8-1 to Example 1-8-3, except that the overcharge control agent (12-1) was used as the overcharge control agent.

<Example 1-8-22> to <Example 1-8-24>
Test batteries were produced in the same manner as in Example 1-8-1 to Example 1-8-3 except that the overcharge control agent (12-2) was used as the overcharge control agent.

[Battery evaluation]
About each Example, it carried out similarly to Example 1-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 10 below shows the evaluation results.

  As can be seen from Table 10, even when the addition amount of the overcharge control agent was changed, the standard deviation was remarkably smaller than that of each of the comparative examples, and the discharge capacity variation suppressing effect could be confirmed. Further, from Example 1-8-1 to Example 1-8-3 and Example 1-1-1, the smaller the amount of the additive compound added to the overcharge control agent, the smaller the discharge capacity. It turned out that there is a tendency for the variation to decrease.

  In the following examples, the effect was confirmed by changing the composition of the non-aqueous solvent.

<Example 1-9-1>
The composition of the non-aqueous solvent of the non-aqueous electrolyte was determined using ethylene carbonate (EC), 4-fluoro-1,3-dioxolan-2-one (FEC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC). A test battery was produced in the same manner as in Example 1-1-1, except that the mass ratio EC: FEC: DMC: EMC = 20: 10: 40: 30.

<Example 1-9-2>
The composition of the non-aqueous solvent was changed to a mass ratio EC: FEC using ethylene carbonate (EC), 4-fluoro-1,3-dioxolan-2-one (FEC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC). : DMC: EMC = 20: 10: 40: 30, and the content of the overcharge control agent in the entire composition of the non-aqueous electrolyte is 10.0% by mass (the addition amount of the additive compound to the overcharge control agent is 1. A test battery was produced in the same manner as in Example 1-1-1, except that the non-aqueous electrolyte mixed with the overcharge control agent (1-10) was used so as to be 0% by mass).

<Example 1-9-3> to <Example 1-9-4>
Test batteries were prepared in the same manner as in Example 1-9-1 to Example 1-9-2 except that the overcharge control agent (1-18) was used as the overcharge control agent.

<Example 1-9-5> to <Example 1-9-6>
Test batteries were prepared in the same manner as in Example 1-9-1 to Example 1-9-2, except that the overcharge control agent (4-71) was used as the overcharge control agent.

<Example 1-9-7> to <Example 1-9-8>
Test batteries were produced in the same manner as in Example 1-9-1 to Example 1-9-2 except that the overcharge control agent (5-3) was used as the overcharge control agent.

<Example 1-9-9> to <Example 1-9-10>
Test batteries were prepared in the same manner as in Example 1-9-1 to Example 1-9-2, except that the overcharge control agent (6-9) was used as the overcharge control agent.

<Example 1-9-11> to <Example 1-9-12>
Test batteries were produced in the same manner as in Example 1-9-1 to Example 1-9-2 except that the overcharge control agent (8-4) was used as the overcharge control agent.

<Example 1-9-13> to <Example 1-9-14>
Test batteries were prepared in the same manner as in Example 1-9-1 to Example 1-9-2, except that the overcharge control agent (12-1) was used as the overcharge control agent.

<Example 1-9-15> to <Example 1-9-16>
Test batteries were produced in the same manner as in Example 1-9-1 to Example 1-9-2 except that the overcharge control agent (12-2) was used as the overcharge control agent.

<Example 1-10-1>
The composition of the nonaqueous solvent of the nonaqueous electrolyte was changed to a mass ratio EC: VC: DMC: EMC = 29 using ethylene carbonate (EC), vinylene carbonate (VC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC). A test battery was produced in the same manner as Example 1-1-1 except that the ratio was 1:40:30.

<Example 1-10-2>
The composition of the non-aqueous solvent was changed to a mass ratio of EC: VC: DMC: EMC = 29: 1: 40 using ethylene carbonate (EC), vinylene carbonate (VC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC). 30 and overcharge control so that the content of the overcharge control agent in the entire composition of the non-aqueous electrolyte is 10.0% by mass (the addition amount of the additive compound to the overcharge control agent is 1.0% by mass). A test battery was produced in the same manner as in Example 1-1-1, except that the nonaqueous electrolyte mixed with the agent (1-10) was used.

<Example 1-10-3> to <Example 1-10-4>
Test batteries were prepared in the same manner as in Example 1-10-1 to Example 1-10-2, except that the overcharge control agent (1-18) was used as the overcharge control agent.

<Example 1-10-5> to <Example 1-10-6>
Test batteries were prepared in the same manner as in Example 1-10-1 to Example 1-10-2 except that the overcharge control agent (4-71) was used as the overcharge control agent.

<Example 1-10-7> to <Example 1-10-8>
Test batteries were produced in the same manner as in Example 1-10-1 to Example 1-10-2 except that the overcharge control agent (5-3) was used as the overcharge control agent.

<Example 1-10-9> to <Example 1-10-10>
Test batteries were prepared in the same manner as in Example 1-10-1 to Example 1-10-2, except that the overcharge control agent (6-9) was used as the overcharge control agent.

<Example 1-10-11> to <Example 1-10-12>
Test batteries were prepared in the same manner as in Example 1-10-1 to Example 1-10-2, except that the overcharge control agent (8-4) was used as the overcharge control agent.

<Example 1-10-13> to <Example 1-10-14>
Test batteries were prepared in the same manner as in Example 1-10-1 to Example 1-10-2 except that the overcharge control agent (12-1) was used as the overcharge control agent.

<Example 1-10-15> to <Example 1-10-16>
Test batteries were prepared in the same manner as in Example 1-10-1 to Example 1-10-2 except that the overcharge control agent (12-2) was used as the overcharge control agent.

[Battery evaluation]
About each Example, it carried out similarly to Example 1-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Tables 11 and 12 below show the evaluation results.

  As can be seen from Tables 11 and 12, Example 1-9-1 and Example 1-9-2 containing FEC which is a halogenated cyclic carbonate as a non-aqueous solvent have the same addition conditions for the overcharge control agent. It was found that the standard deviation is lower than those of Examples 1-1-1 and 1-8-2 which do not include FEC, and the variation in discharge capacity tends to be reduced as a whole. Similarly, when other overcharge control agents are used, the addition conditions of the overcharge control agents are the same, and the standard deviation is the same as or lower than that of the embodiment not including FEC. It was found that the variation in capacity tends to be small.

  The same was true when VC, which is an unsaturated carbon-bonded cyclic ester carbonate, was included as the non-aqueous solvent.

  In the following examples, an additive was further added to the nonaqueous electrolytic solution to confirm the effect.

<Example 1-11-1>
The overcharge control agent (1) so that the content of the overcharge control agent in the total composition of the nonaqueous electrolyte solution is 10.0% by mass (the addition amount of the additive compound to the overcharge control agent is 1.0% by mass). -10) and a non-aqueous electrolyte solution to which trans-4,5-difluoro-1,3-dioxolan-2-one (DFEC), which is a cyclic carbonate, was added at a concentration of 1.0% by mass. A test battery was produced in the same manner as Example 1-1-1 except that it was used.

<Example 1-11-2> to <Example 1-1-11-8>
Instead of overcharge control agent (1-10), overcharge control agent (1-18), overcharge control agent (4-71), overcharge control agent (5-3), overcharge control agent (6- 9) Tested in the same manner as in Example 1-11-1 except that the overcharge control agent (8-4), the overcharge control agent (12-1), and the overcharge control agent (12-2) were used. Each battery was prepared.

<Example 1-1-11-9> to <Example 1-1-11-16>
Test batteries were prepared in the same manner as in Examples 1-11-1 to 1-1-1-8, except that a non-aqueous electrolyte to which succinonitrile, a dinitrile compound was added, was used instead of DFEC. .

<Example 1-1-11-17> to <Example 1-1-11-24>
Test batteries were prepared in the same manner as in Examples 1-11-1 to 1-1-1-8, except that a nonaqueous electrolytic solution to which succinic anhydride as an acid anhydride was added was used instead of DFEC. did.

<Example 1-1-1-25> to <Example 1-1-11-32>
A test battery was prepared in the same manner as in Example 1-11-1 to Example 1-11-8, except that a nonaqueous electrolytic solution to which propanedisulfonic anhydride as an acid anhydride was added was used instead of DFEC. Produced.

<Example 1-1-11-33> to <Example 1-1-11-40>
Test batteries were prepared in the same manner as in Example 1-11-1 to Example 1-1-11-8, except that a non-aqueous electrolyte to which propene sultone, which is a cyclic sulfonate ester, was added instead of DFEC. did.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 1-1-1, and (c) the safety valve operating time was confirmed.

  The evaluation results are shown in Table 13 and Table 14 below. In the table, trans-4,5-difluoro-1,3-dioxolan-2-one is simply indicated as DFEC.

  Example 1-8-2 in which 10.0% by mass of the overcharge control agent (1-10) is mixed and no further additive such as DFEC is mixed, and 10.0% by mass of the overcharge control When the agent (1-10) and Example 1-11-1 mixed with 1.0% by mass of DFEC were compared, Example 1-11-1 had a large average discharge capacity and a small standard deviation. Therefore, there was little variation in discharge capacity.

  Further, instead of the overcharge control agent (1-10), the overcharge control agent (1-18), the overcharge control agent (4-71), the overcharge control agent (5-3), the overcharge control agent (6 -9), Example 1-11-2 to Example 1-11, using the overcharge control agent (8-4), the overcharge control agent (12-1), and the overcharge control agent (12-2). A higher effect was obtained for 8 as well.

  Similarly, Example 1-11-9 to Example 1-11-16, Example 1-11-17 to Example 1-11 to which succinonitrile, succinic anhydride, propanedisulfonic anhydride and propene sultone were added were added. -24, Examples 1-11-25 to Examples 1-11-32 and Examples 1-11-33 to Examples 1-11-40 each have an average discharge capacity higher than that of Example 1-8-2. Due to the large and small standard deviation, there was little variation in the discharge capacity.

  This is because the chemical stability of the non-aqueous electrolyte is further improved by including the cyclic carbonate, nitrile compound, acid anhydride, and cyclic sulfonate in the non-aqueous electrolyte, and the effect of the additive compound of the present technology is improved. This is thought to be because it became easier to obtain.

  Moreover, in each Example, the safety valve operation time became long. For this reason, it turned out that gas generation inside a battery can be controlled.

In the following examples, other electrolyte salts were added together with lithium hexafluorophosphate (LiPF ₆ ) to the nonaqueous electrolytic solution to confirm the effect.

<Example 1-12-1>
The overcharge control agent (1) so that the content of the overcharge control agent in the total composition of the nonaqueous electrolyte solution is 10.0% by mass (the addition amount of the additive compound to the overcharge control agent is 1.0% by mass). -10) and 0.9 mol / kg of lithium hexafluorophosphate (LiPF ₆ ) and 0.1 mol / kg of lithium tetrafluoroborate (LiBF ₄ ) as an electrolyte salt were further dissolved. A test battery was produced in the same manner as in Example 1-1-1 except that the water electrolyte was used.

<Example 1-12-2> to <Example 1-12-8>
Instead of overcharge control agent (1-10), overcharge control agent (1-18), overcharge control agent (4-71), overcharge control agent (5-3), overcharge control agent (6- 9) Tested in the same manner as in Example 1-12-1 except that the overcharge control agent (8-4), the overcharge control agent (12-1), and the overcharge control agent (12-2) were used. Each battery was prepared.

<Example 1-12-9> to <Example 1-12-16>
Example 1-12-1 to Example 1-12-8 except that a non-aqueous electrolyte to which lithium bistrifluoromethanesulfonylimide (LiTFSI) was added instead of lithium tetrafluoroborate (LiBF ₄ ) Test batteries were prepared in the same manner as described above.

<Example 1-12-17> to <Example 1-12-24>
Example 1-12-1 to Example 1-12-1 except that a nonaqueous electrolytic solution to which lithium bisoxalate borate (LiBOB) represented by the formula (14-6) was added instead of lithium tetrafluoroborate (LiBF ₄ ) was used. Test batteries were prepared in the same manner as in Example 1-12-8.

[Battery evaluation]
About each Example, it carried out similarly to Example 1-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 15 below shows the evaluation results.

  Example 1-8-2 in which 10.0% by mass of overcharge control agent (1-10) was mixed and only lithium hexafluorophosphate was used as an electrolyte salt, and 10.0% by mass of overcharge control In comparison with Example 1-12-1 in which the agent (1-10) was mixed and a part of lithium hexafluorophosphate was replaced with lithium tetrafluoroborate as an electrolyte salt, Example 1-12- No. 1 had a large average discharge capacity and a small standard deviation, so there was little variation in the discharge capacity. Further, instead of the overcharge control agent (1-10), the overcharge control agent (1-18), the overcharge control agent (4-71), the overcharge control agent (5-3), the overcharge control agent (6 -9), Example 1-12-2 to Example 1-12- using the overcharge control agent (8-4), the overcharge control agent (12-1), and the overcharge control agent (12-2) In the case of 8 as well, a higher effect was obtained.

  Similarly, Examples 1-12-9 to 1-12-16 and implementations using lithium bistrifluoromethanesulfonylimide (LiTFSI) or lithium bisoxalate borate (LiBOB) instead of lithium tetrafluoroborate For each of Examples 1-12-17 to Examples 1-12-24, a high effect was obtained by mixing the additive compound of the present technology.

  In the following examples, the effect was confirmed by changing the negative electrode active material to a SnCoC-containing material containing tin (Sn), cobalt (Co), and carbon (C) as constituent elements.

<Example 2-1-1> to <Example 2-1-29>
As the negative electrode active material, an SnCoC-containing material containing tin (Sn), cobalt (Co), and carbon (C) as constituent elements was used instead of the granular graphite powder. When the composition of the SnCoC-containing material was analyzed, the content of tin was 49.5% by mass, the content of cobalt was 29.7% by mass, the content of carbon was 19.8% by mass, and the ratio of tin and cobalt (Co / (Sn + Co)) was 37.5% by mass. At this time, the tin and cobalt contents were measured by inductively coupled plasma (ICP) emission analysis, and the carbon content was measured by a carbon / sulfur analyzer. Further, when the SnCoC-containing material was analyzed by the X-ray diffraction method, a diffraction peak having a half width in the range of 2θ = 20 ° to 50 ° was observed. Further, when the SnCoC-containing material was analyzed by XPS, a peak P1 was obtained as shown in FIG. When this peak P1 is analyzed, a peak P3 of C1s in the SnCoC-containing material is obtained in a region on the lower energy side (region lower than 284.5 eV) together with the peak P2 of the surface contamination carbon appearing at 284.8 eV. It was. From this result, it was confirmed that carbon in the SnCoC-containing material was bonded to other elements.

  Next, 80 parts by mass of the aforementioned SnCoC-containing material powder as a negative electrode active material, 12 parts by mass of graphite as a conductive agent, and 8 parts by mass of polyvinylidene fluoride as a binder are mixed, and N-methyl- which is a solvent is mixed. It was made to disperse | distribute to 2-pyrrolidone and it was set as the negative mix slurry. Finally, the negative electrode mixture slurry was uniformly applied and dried using a coating device on both sides of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 15 μm, and then subjected to compression molding using a roll press. A negative electrode on which an active material layer was formed was produced. Other than this, test batteries were fabricated in the same manner as in Example 1-1-1 to Example 1-1-29.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were obtained in the same manner as in Example 1-1-1, except that the final discharge voltage was 2.5 V, and (c) the safety valve The operating time was confirmed.

  Table 16 below shows the evaluation results.

<Example 2-2-1> to <Example 2-229>
As a negative electrode active material, for the test in the same manner as in Example 1-2-1 to Example 1-229, except that the same SnCoC-containing material as in Example 2-1-1 was used instead of the granular graphite powder. Each battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  Table 17 below shows the evaluation results.

<Example 2-3-1> to <Example 2-3-29>
For the test in the same manner as in Example 1-3-1 to Example 1-329, except that the same SnCoC-containing material as in Example 2-1-1 was used as the negative electrode active material instead of granular graphite powder. A battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  Table 18 below shows the evaluation results.

<Example 2-4-1> to <Example 2-4-29>
For testing in the same manner as in Example 1-4-1 to Example 1-429, except that the same SnCoC-containing material as in Example 2-1-1 was used as the negative electrode active material instead of granular graphite powder. A battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  Table 19 below shows the evaluation results.

<Example 2-5-1> to <Example 2-5-29>
For the test in the same manner as in Example 1-5-1 to Example 1-5-29, except that the same SnCoC-containing material as in Example 2-1-1 was used as the negative electrode active material instead of granular graphite powder. A battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  Table 20 below shows the evaluation results.

<Example 2-6-1> to <Example 2-6-29>
For the test in the same manner as in Example 1-6-1 to Example 1-6-29 except that the same SnCoC-containing material as in Example 2-1-1 was used as the negative electrode active material instead of granular graphite powder. A battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  Table 21 below shows the evaluation results.

<Example 2-7-1> to <Example 2-7-29>
For the test in the same manner as in Example 1-3-1 to Example 1-329, except that the same SnCoC-containing material as in Example 2-1-1 was used as the negative electrode active material instead of granular graphite powder. A battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  The evaluation results are shown in Table 22 below.

<Comparative Example 2-1-1> to <Comparative Example 2-1-30>
For testing in the same manner as Comparative Example 1-1-1 to Comparative Example 1-1-30, except that the same SnCoC-containing material as in Example 2-1-1 was used instead of the granular graphite powder as the negative electrode active material. A battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  Table 23 below shows the evaluation results.

  As can be seen from Table 16 to Table 22 and Table 23, even when the SnCoC-containing material is used as the negative electrode active material, the additive compound of the present technology is added to the non-aqueous electrolyte together with the overcharge control agent that suppresses the voltage increase. By mixing, the effect of suppressing variation in discharge capacity can be obtained as in the case of using a carbon-based material.

  Moreover, in each Example using the additive compound of this technique with the overcharge control agent which suppresses a voltage rise, the safety valve operation time became long compared with the corresponding comparative example. For this reason, it turned out that gas generation inside a battery can be controlled. In particular, when the SnCoC-containing material is used as the negative electrode active material, the amount of gas generated inside the battery increases as compared with the case where graphite is used as the negative electrode active material. For this reason, in a battery using a SnCoC-containing material as a negative electrode active material, it is a very preferable configuration to keep the safety valve operating time long by adding the additive compound of the present technology.

  In the following examples, the effect was confirmed by changing the negative electrode active material to the SnCoC-containing material and changing the addition amount of the overcharge control agent.

<Example 2-8-1> to <Example 2-8-24>
As a negative electrode active material, for testing in the same manner as in Example 1-8-1 to Example 1-8-24, except that the same SnCoC-containing material as in Example 2-1-1 was used instead of granular graphite powder. Each battery was produced.

[Battery evaluation]
About each Example, it carried out similarly to Example 2-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 24 below shows the evaluation results.

  As can be seen from Table 24, even when the SnCoC-containing material was used as the negative electrode active material, the standard deviation was significantly smaller than that of each of the comparative examples within a certain range of the overcharge control agent added, and the discharge capacity was varied. The inhibitory effect was confirmed.

  In the following examples, the negative electrode active material was changed to a SnCoC-containing material, and the effect was confirmed by changing the composition of the nonaqueous solvent.

<Example 2-9-1> to <Example 2-9-16>
As a negative electrode active material, for the test in the same manner as in Example 1-9-1 to Example 1-9-16, except that the same SnCoC-containing material as in Example 2-1-1 was used instead of granular graphite powder. Each battery was produced.

<Example 2-10-1> to <Example 2-10-16>
As a negative electrode active material, for the test in the same manner as in Example 1-10-1 to Example 1-10-16 except that the same SnCoC-containing material as in Example 2-1-1 was used instead of the granular graphite powder. Each battery was produced.

[Battery evaluation]
About each Example, it carried out similarly to Example 2-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 25 and Table 26 below.

  As can be seen from Table 25 and Table 26, even when a SnCoC-containing material is used as the negative electrode active material, 4-fluoro-1,3-halogenated cyclic carbonate is used as the non-aqueous solvent of the non-aqueous electrolyte. Each of the above examples mixed with dioxolan-2-one (FEC) or vinylene carbonate (VC), which is an unsaturated carbon-bonded cyclic ester carbonate, has the same or lower standard deviation than the examples under the same conditions. In particular, it was found that the variation in the discharge capacity tends to be small.

  In the following examples, the negative electrode active material was changed to a SnCoC-containing material, and an additive was further added to the nonaqueous electrolytic solution to confirm the effect.

<Example 2-11-1> to <Example 2-11-40>
As a negative electrode active material, for the test in the same manner as Example 1-11-1 to Example 1-11-1-40, except that the same SnCoC-containing material as in Example 2-1-1 was used instead of the granular graphite powder. Each battery was produced.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were determined in the same manner as in Example 2-1-1, and (c) the safety valve operating time was confirmed.

  The evaluation results are shown in Table 27 and Table 28 below.

  As can be seen from Table 27, even when a SnCoC-containing material is used as the negative electrode active material, trans-4,5-difluoro-1,3-dioxolan-2-one, which is a cyclic carbonate, is used in the non-aqueous electrolyte. By mixing (DFEC), Example 2-8-2, Example 2-8-5, Example 2-8-8, Example 2-8-11, and Example 2-8 not containing these −14, Examples 2-8-17, Examples 2-8-20 and Examples 2-8-23 More than the average discharge capacity, the standard deviation is small, and the variation in the discharge capacity tends to decrease. I understood that.

  Further, from Tables 27 and 28, the average discharge was similarly obtained when succinonitrile as a dinitrile compound, succinic anhydride or propane disulfonic acid as an acid anhydride, and propene sultone as a cyclic sulfonate ester were mixed. It was found that the capacity is large, the standard deviation is small, and the variation in discharge capacity tends to be small.

  Moreover, in each Example using cyclic carbonate with the overcharge control agent which suppresses a voltage rise, and the addition compound of this technique, the safety valve operation time became long compared with the corresponding comparative example.

In the following examples, the negative electrode active material was changed to a metal alloy-based material, and the effect was confirmed by adding other electrolyte salt with lithium hexafluorophosphate (LiPF ₆ ) to the non-aqueous electrolyte.

<Example 2-12-1> to <Example 2-12-24>
As a negative electrode active material, for the test as in Example 1-12-1 to Example 1-12-24, except that the same SnCoC-containing material as in Example 2-1-1 was used instead of granular graphite powder. Each battery was produced.

[Battery evaluation]
About each Example, it carried out similarly to Example 2-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 29 below.

As can be seen from Table 29, even when a SnCoC-containing material is used as the negative electrode active material and lithium hexafluorophosphate (LiPF ₆ ) and another compound are mixed and used as the electrolyte salt, the present technology With the added compound, the average discharge capacity was large and the standard deviation was small, so that the variation in discharge capacity was further reduced.

  In the following examples, the effect was confirmed by changing the negative electrode active material to silicon.

<Example 3-1-1> to <Example 3-1-29>
Silicon was used in place of the granular graphite powder as the negative electrode active material. 95 parts by mass of silicon powder having an average particle diameter of 1 μm as a negative electrode active material and 5 parts by mass of polyimide as a binder were mixed to form a negative electrode mixture, and the negative electrode mixture and N-methyl-2-pyrrolidone were mixed. A negative electrode mixture slurry was prepared. Next, the negative electrode mixture slurry is uniformly applied and dried using a coating apparatus on both sides of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 15 μm, and after compression molding using a roll press machine, a vacuum atmosphere Below, it heated at 400 degreeC for 12 hours, the negative electrode active material layer was formed, and the negative electrode was produced. Other than this, test batteries were fabricated in the same manner as in Example 1-1-1 to Example 1-1-29.

[Battery evaluation]
For each example, (a) the average discharge capacity and (b) the standard deviation of the battery capacity were obtained in the same manner as in Example 1-1-1, except that the final discharge voltage was 2.5 V, and (c) the safety valve The operating time was confirmed.

  The evaluation results are shown in Table 30 below.

<Example 3-2-1> to <Example 3-2-29>
Tested in the same manner as in Example 1-2-1 to Example 1-229 except that a negative electrode using silicon similar to Example 3-1-1 as the negative electrode active material was used instead of the granular graphite powder. Each battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  Table 31 below shows the evaluation results.

<Example 3-3-1> to <Example 3-329>
Tested in the same manner as in Example 1-3-1 to Example 1-329, except that the same negative electrode using silicon as the negative electrode active material instead of granular graphite powder was used. A battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  The evaluation results are shown in Table 32 below.

<Example 3-4-1> to <Example 3-4-29>
Tested in the same manner as in Example 1-4-1 to Example 1-429 except that the negative electrode using silicon similar to Example 3-1-1 as the negative electrode active material was used instead of the granular graphite powder. A battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  Table 33 below shows the evaluation results.

<Example 3-5-1> to <Example 3-5-29>
Tested in the same manner as in Example 1-5-1 to Example 1-5-29 except that the negative electrode using silicon as the negative electrode active material was used in place of the granular graphite powder. A battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  The evaluation results are shown in Table 34 below.

<Example 3-6-1> to <Example 3-6-29>
Tested in the same manner as in Example 1-6-1 to Example 1-6-29 except that a negative electrode using silicon similar to that in Example 3-1-1 as the negative electrode active material was used instead of the granular graphite powder. A battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  Table 35 below shows the evaluation results.

<Example 3-7-1> to <Example 3-7-29>
Tested in the same manner as in Example 1-3-1 to Example 1-329, except that the same negative electrode using silicon as the negative electrode active material instead of granular graphite powder was used. A battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  The evaluation results are shown in Table 36 below.

<Comparative Example 3-1-1> to <Comparative Example 3-1-30>
Tested in the same manner as Comparative Example 1-1-1 to Comparative Example 1-1-30 except that the negative electrode using silicon similar to Example 3-1-1 as the negative electrode active material was used instead of the granular graphite powder. A battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  Table 37 below shows the evaluation results.

  As can be seen from Tables 30 to 36 and Table 37, even if silicon is used as the negative electrode active material, the additive compound of the present technology is mixed with the non-aqueous electrolyte together with the overcharge control agent that suppresses the voltage increase. As a result, the effect of suppressing the variation in discharge capacity can be obtained as in the case of using a carbon-based material.

  Moreover, in each Example using the additive compound of this technique with the overcharge control agent which suppresses a voltage rise, the safety valve operation time became long compared with the corresponding comparative example. For this reason, it turned out that gas generation inside a battery can be controlled.

  In the following examples, the negative electrode active material was changed to silicon, and the effect was confirmed by changing the addition amount of the overcharge control agent.

<Example 3-8-1> to <Example 3-8-24>
Tested in the same manner as in Example 1-8-1 to Example 1-8-24, except that the negative electrode using silicon as the negative electrode active material was used instead of granular graphite powder. Each battery was prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 3-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 38 below.

  As can be seen from Table 38, even when silicon is used as the negative electrode active material, the standard deviation is significantly smaller than that of each comparative example within a certain range of the amount of addition of the overcharge control agent, and the discharge capacity variation suppressing effect Was confirmed.

  In the following examples, the effect was confirmed by changing the composition of the non-aqueous solvent while changing the negative electrode active material to silicon.

<Example 3-9-1> to <Example 3-9-16>
Tested in the same manner as in Examples 1-9-1 to 1-9-16 except that the negative electrode using silicon as the negative electrode active material was used instead of granular graphite powder. Each battery was prepared.

<Example 3-10-1> to <Example 3-10-16>
Tested in the same manner as in Example 1-10-1 to Example 1-10-16 except that the negative electrode using silicon similar to Example 3-1-1 as the negative electrode active material was used instead of the granular graphite powder. Each battery was prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 3-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 39 and Table 40 below.

  As can be seen from Table 39 and Table 40, even when silicon is used as the negative electrode active material, 4-fluoro-1,3-dioxolane-, which is a halogenated cyclic carbonate, is used as the non-aqueous solvent of the non-aqueous electrolyte. Each of the above examples mixed with 2-one (FEC) or vinylene carbonate (VC), which is an unsaturated carbon-bonded cyclic carbonate, has a standard deviation equal to or lower than that of the examples not containing them. It was found that the variation in discharge capacity tends to be small.

  In the following examples, the negative electrode active material was changed to silicon, and an additive was further added to the nonaqueous electrolytic solution to confirm the effect.

<Example 3-11-1> to <Example 3-11-40>
Tested in the same manner as in Example 1-11-1 to Example 1-11-1-40 except that the same negative electrode using silicon as the negative electrode active material was used instead of the granular graphite powder. Each battery was prepared.

[Battery evaluation]
For each example, (a) average discharge capacity and (b) standard deviation of battery capacity were determined in the same manner as in Example 3-1-1, and (c) safety valve operating time was confirmed.

  Table 41 and Table 42 below show the evaluation results.

  As can be seen from Table 41, even when silicon is used as the negative electrode active material, trans-4,5-difluoro-1,3-dioxolan-2-one (DFEC), which is a cyclic carbonate, is used in the non-aqueous electrolyte. ), Succinonitrile, which is a dinitrile compound, succinic anhydride or propane disulfonic acid, which is an acid anhydride, and propene sultone, which is a cyclic sulfonic acid ester, by mixing with an average compared to the examples not containing them The discharge capacity was large and the variation in discharge capacity tended to decrease, and the safety valve operating time was prolonged.

In the following examples, the negative electrode active material was changed to silicon, and other electrolyte salts were added together with lithium hexafluorophosphate (LiPF ₆ ) to the nonaqueous electrolytic solution to confirm the effect.

<Example 3-12-1> to <Example 3-12-24>
Tested in the same manner as in Example 1-12-1 to Example 1-12-24 except that the negative electrode using silicon similar to Example 3-1-1 as the negative electrode active material was used instead of the granular graphite powder. Each battery was prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 3-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 43 below.

As can be seen from Table 43, even when silicon is used as the negative electrode active material and lithium hexafluorophosphate (LiPF ₆ ) and another compound are mixed and used as the electrolyte salt, the additive compound of the present technology As a result, the average discharge capacity was large and the standard deviation was small, so that the variation in discharge capacity was reduced.

  In the following examples, lithium titanate was used as the negative electrode active material, and the effect was confirmed using a laminate type battery covered with a laminate film as a test battery.

<Example 4-1-1>
[Production of positive electrode]
98 parts by mass of lithium cobalt composite oxide (LiCoO ₂ ) obtained in the same manner as in Example 1-1-1, 0.8 parts by mass of ketjen black as a conductive agent, and polyvinylidene fluoride (PVdF as a binder) ) 1.2 parts by mass was mixed to make a positive electrode mixture. Subsequently, the positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to prepare a paste-like positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry was uniformly applied to both surfaces of a positive electrode current collector made of a strip-shaped aluminum foil having a thickness of 12 μm using a coating apparatus and dried. Finally, the dried positive electrode mixture was compression molded using a roll press to produce a positive electrode on which a positive electrode active material layer was formed.

[Production of negative electrode]
A negative electrode mixture prepared by mixing 85 parts by mass of lithium titanate (Li ₄ Ti ₅ O ₁₂ ) as a negative electrode active material, 10 parts by mass of graphite as a conductive agent, and 5 parts by mass of polyvinylidene fluoride (PVdF) as a binder. It was. Subsequently, the negative electrode mixture was dispersed in N-methyl-2-pyrrolidone to prepare a paste-like negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry was uniformly applied to both surfaces of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 μm using a coating apparatus and dried. Finally, the dried negative electrode mixture was compression molded using a roll press to produce a negative electrode on which a negative electrode active material layer was formed.

[Preparation of non-aqueous electrolyte]
The non-aqueous electrolyte was prepared by dissolving the compound represented by the formula (1-2) as an additive compound together with the overcharge control agent (1-10) that suppresses the rise in electric sublimation, as in Example 1-1-1. It was.

[Assembly of laminated nonaqueous electrolyte battery]
An aluminum positive electrode lead was welded to one end of the positive electrode current collector. Further, a negative electrode lead made of nickel was welded to one end of the negative electrode current collector. Then, after laminating | stacking a positive electrode and a negative electrode through a separator, it wound in the flat shape in the longitudinal direction, and the winding electrode body was produced by fixing a winding end part with an adhesive tape. As the separator, a microporous polyethylene film having a thickness of 20 μm was used.

  Subsequently, after sandwiching the wound electrode body between the exterior members, the wound body was accommodated inside the bag-shaped exterior member 40 by heat-sealing the outer edges of the exterior member except for one side. . As the exterior member, an aluminum laminate film having a total thickness of 100 μm and a three-layer structure in which a nylon film having a thickness of 30 μm, an aluminum foil having a thickness of 40 μm, and an unstretched polypropylene film having a thickness of 30 μm were sequentially laminated. . Subsequently, a non-aqueous electrolyte was injected from the opening of the exterior member, and the separator was impregnated with the non-aqueous electrolyte, thereby producing a wound electrode body. Finally, the opening of the exterior member was heat-sealed and sealed in a vacuum atmosphere. As a result, a laminated film type nonaqueous electrolyte battery (test battery) was completed. When producing this test battery, the thickness of the positive electrode active material layer was adjusted so that lithium metal did not deposit on the negative electrode during full charge.

<Example 4-1-2> to <Example 4-1-29>
Example 4-1-2 to Example 4-1-2 was carried out in the same battery configuration as Example 4-1-1 except that the non-aqueous electrolyte was made the same as Example 1-1-2 to Example 1-1-29. The test batteries of Examples 4-1 to 29 were produced.

[Battery evaluation]
(A) Average discharge capacity The test batteries of each example and each comparative example were charged at a constant current up to a battery voltage of 2.8 V with a charging current of 0.2 C in an atmosphere at 23 ° C. Then, constant voltage charging was performed, and the charging was terminated when the total charging time reached 8 hours. Thereafter, constant current discharge was performed to a battery voltage of 1.0 V with a discharge current of 0.2 C. After performing this charge / discharge cycle for two cycles, the discharge capacity when the constant current charge and constant voltage charge were performed with the upper limit voltage set to 3.3 V in the third cycle and then the constant current discharge was performed up to a battery voltage of 1.0 V Was measured. Here, the average discharge capacity was an average value obtained from the discharge capacities of 10 test batteries by preparing 10 test batteries of each example and each comparative example and measuring the discharge capacity.

(B) Standard deviation of discharge capacity For each example and each comparative example, the standard deviation of the battery capacity of each of the ten test batteries measured in (a) was determined.

  Table 44 below shows the evaluation results.

<Example 4-2-1> to <Example 4-229>
Example 4-2-1 to Example 4-2-1 was implemented as a battery configuration similar to Example 4-1-1 except that the non-aqueous electrolyte was configured similarly to Example 1-2-1 to Example 1-229. The test batteries of Example 4-229 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 45 below shows the evaluation results.

<Example 4-3-1> to <Example 4-3-29>
A battery configuration similar to that of Example 4-1-1 except that the nonaqueous electrolytic solution is the same as that of Example 1-3-1 to Example 1-329. Test batteries of Example 4-3-29 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 46 below shows the evaluation results.

<Example 4-4-1> to <Example 4-4-29>
Example 4-4-1 to Example 4-4-1 was implemented as a battery configuration similar to Example 4-1-1 except that the non-aqueous electrolyte was configured similarly to Example 1-4-1 to Example 1-4-29. Test batteries of Example 4-4-29 were produced.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 47 below.

<Example 4-5-1> to <Example 4-5-29>
A battery configuration similar to that of Example 4-1-1 except that the non-aqueous electrolyte is the same as that of Example 1-5-1 to Example 1-5-29. Test batteries of Example 4-5-29 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 48 below.

<Example 4-6-1> to <Example 4-6-29>
Example 4-6-1 to Example 4-6-1 was implemented as a battery configuration similar to Example 4-1-1 except that the non-aqueous electrolyte was configured similarly to Example 1-6-1 to Example 1-6-29. Test batteries of Example 4-6-29 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 49 below.

<Example 4-7-1> to <Example 4-7-29>
Example 4-6-1 to Example 4-6-1 was implemented as a battery configuration similar to Example 4-1-1 except that the non-aqueous electrolyte was configured similarly to Example 1-6-1 to Example 1-6-29. Test batteries of Example 4-6-29 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 50 below.

<Comparative Example 4-1-1> to <Comparative Example 4-1-30>
The non-aqueous electrolyte solution has the same configuration as that of Comparative Example 1-2-1 to Comparative Example 1-2-30, and the battery configuration is the same as that of Example 4-1-1 except that the additive compound is not mixed. Test batteries of Example 4-1 to Comparative example 4-1-30 were produced.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 51 below shows the evaluation results.

  As can be seen from Table 44 to Table 50 and Table 51, in the case of a laminate film type test battery using lithium titanate as the negative electrode active material, the additive compound of the present technology is used together with the overcharge control agent that suppresses the voltage increase. The effect of suppressing variation in discharge capacity can be obtained by mixing the non-aqueous electrolyte.

  In the following examples, the effect was confirmed by changing the addition amount of the overcharge control agent.

<Example 4-8-1> to <Example 4-8-24>
Example 4-8-1 to Example 4-8-1 were carried out in the same battery configuration as Example 4-1-1 except that the non-aqueous electrolyte was configured the same as Example 1-8-1 to Example 1-8-24. Test batteries of Examples 4-8-24 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 52 below.

  As can be seen from Table 52, even in the case of a laminate type non-aqueous electrolyte battery using lithium titanate as the negative electrode active material, the standard deviation is larger than that of each comparative example within a certain range of the addition amount of the overcharge control agent. It was remarkably small, and the effect of suppressing variation in discharge capacity could be confirmed.

  In the following examples, the effect was confirmed by changing the composition of the non-aqueous solvent.

<Example 4-9-1> to <Example 4-9-16>
Example 4-9-1 to Example 4-9-1 were carried out in the same battery configuration as Example 4-1-1 except that the non-aqueous electrolyte was configured the same as Example 1-9-1 to Example 1-9-16. Test batteries of Examples 4-9-16 were produced.

<Example 4-10-1> to <Example 4-10-16>
Example 4-10-1 to Example 4-10-1 were carried out in the same battery configuration as Example 4-1-1 except that the non-aqueous electrolyte was configured in the same manner as Example 1-10-1 to Example 1-10-16. Test batteries of Examples 4-10-16 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 53 and Table 54 below show the evaluation results.

  As can be seen from Table 53 and Table 54, even in the case of a laminate type non-aqueous electrolyte battery using lithium titanate as the negative electrode active material, a halogenated cyclic carbonate is used as the non-aqueous solvent of the non-aqueous electrolyte. Each of the above examples mixed with -fluoro-1,3-dioxolan-2-one (FEC) or vinylene carbonate (VC), which is an unsaturated carbon-bonded cyclic carbonate, is compared to examples that do not contain these. It was found that the standard deviation is equal or lower, and the variation in the discharge capacity tends to be reduced as a whole.

  In the following examples, an additive was further added to the nonaqueous electrolytic solution to confirm the effect.

<Example 4-11-1> to <Example 4-11-40>
Example 4-11-1 to Example 4-11-1 was carried out as a battery configuration similar to Example 4-1-1 except that the non-aqueous electrolyte was configured similarly to Example 1-11-1 to Example 1-11-1-40. Test batteries of Examples 4-11-40 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  The evaluation results are shown in Table 55 and Table 56 below.

  As can be seen from Table 55, even in the case of a laminate-type nonaqueous electrolyte battery using lithium titanate as the negative electrode active material, trans-4,5-difluoro-1, which is a cyclic carbonate, is used in the nonaqueous electrolyte. By mixing 3-dioxolan-2-one (DFEC), the dinitrile compound succinonitrile, the acid anhydride succinic anhydride or propane disulfonic acid, and the cyclic sulfonate ester propene sultone. There was a tendency that the average discharge capacity was large and the variation in the discharge capacity was less than that of the Examples not included.

In the following examples, other electrolyte salts were added together with lithium hexafluorophosphate (LiPF ₆ ) to the nonaqueous electrolytic solution to confirm the effect.

<Example 4-12-1> to <Example 4-12-24>
Example 4-12-1 to Example 4-12-1 were carried out in the same battery configuration as Example 4-1-1 except that the non-aqueous electrolyte was configured the same as Example 1-12-1 to Example 1-12-24. Test batteries of Examples 4-12-24 were prepared.

[Battery evaluation]
About each Example, it carried out similarly to Example 4-1-1, and calculated | required the standard deviation of (a) average discharge capacity and (b) battery capacity.

  Table 57 below shows the evaluation results.

As can be seen from Table 57, lithium hexafluorophosphate (LiPF ₆ ) and other compounds were mixed as the electrolyte salt even in the case of a laminated nonaqueous electrolyte battery using lithium titanate as the negative electrode active material. As a result, the average discharge capacity was large and the standard deviation was small, so that the variation in discharge capacity was further reduced.

  While the present technology has been described with reference to the embodiment and examples, the present technology is not limited to the above-described embodiment and examples, and various modifications can be made. For example, in the embodiments and examples described above, the secondary battery having a winding structure has been described, but the present technology is similarly applied to a secondary battery having a structure in which the positive electrode and the negative electrode are folded or stacked. can do. In addition, it can be applied to a so-called coin-type, button-type or square-type non-aqueous electrolyte battery.

  Moreover, in the said embodiment and Example, although the case where a non-aqueous electrolyte solution was used was demonstrated, this technique is applicable also when using any form of non-aqueous electrolyte. Examples of other forms of non-aqueous electrolytes include so-called gel-like non-aqueous electrolytes in which a non-aqueous solvent and an electrolyte salt are held in a polymer compound.

  Furthermore, in the above embodiments and examples, a so-called lithium ion secondary battery in which the capacity of the negative electrode is represented by a capacity component due to insertion and extraction of lithium has been described. The capacity of the negative electrode used is a so-called lithium metal secondary battery whose capacity is represented by the deposition and dissolution of lithium, or the negative electrode material capable of occluding and releasing lithium is more charged than the positive electrode. The same applies to a secondary battery in which the capacity of the negative electrode includes a capacity component due to insertion and extraction of lithium and a capacity component due to precipitation and dissolution of lithium, and is expressed by the sum thereof, by reducing the capacity. be able to.

  In the above embodiments and examples, a battery using lithium as an electrode reactant has been described. However, another alkali metal such as sodium (Na) or potassium (K), or an alkali such as magnesium or calcium (Ca) is used. The present technology can also be applied to the case of using an earth metal or another light metal such as aluminum.

  DESCRIPTION OF SYMBOLS 11 ... Battery can, 12, 13 ... Insulation board, 14 ... Battery cover, 15 ... Safety valve mechanism, 15A ... Disc board, 16 ... Heat sensitive resistance element, 17 ... Gasket, 20, 30 ... Winding electrode body, 21, 33 ... Positive electrode, 21A, 33A ... Positive electrode current collector, 21B, 33B ... Positive electrode active material layer, 22, 34 ... Negative electrode, 22A, 34A ... Negative electrode current collector, 22B, 34B ... Negative electrode active material layer, 23, 35 ... Separator , 24 ... Center pin, 25, 31 ... Positive electrode lead, 26, 32 ... Negative electrode lead, 36 ... Electrolyte layer, 37 ... Protective tape, 40 ... Exterior member, 41 ... Adhesion film, 100 ... Power storage system, 101 ... Housing, 102a ... thermal power generation, 102b ... nuclear power generation, 102c ... hydroelectric power generation, 102 ... centralized power system, 103 ... power storage device, 104 ... power generation device, 105 ... power consumption device, 105a ... refrigerator, 105 Air conditioner, 105c Television receiver, 105d Bath, 106 Electric vehicle, 106a Electric car, 106b Hybrid car, 106c Electric bike, 107 Smart meter, 108 Power hub, 109 Power grid, 110 Control device, 111 ... sensor, 112 ... information network, 113 ... server, 200 ... hybrid vehicle, 201 ... engine, 202 ... generator, 203 ... power driving force converter, 204a, 204b ... drive wheel, 205a, 205b ... wheel , 208 ... battery, 209 ... vehicle control device, 210 ... various sensors, 211 ... charging port, 301 ... assembled battery, 301a ... secondary battery, 302a ... charge control switch, 302b ... diode, 303a ... discharge control switch, 303b ... Diode, 304 ... Switch part, 307 ... Current detection Resistance, 308 ... temperature detecting element, 310 ... controller, 311 ... voltage detection unit, 313 ... current measuring unit, 314 ... switching control unit, 317 ... memory, 318 ... temperature detecting unit, 321 ... positive terminal, 322 ... negative terminal

Claims (16)

A non-aqueous solvent;
Electrolyte salt,
An overcharge control agent that causes a redox reaction at a predetermined potential;
A non-aqueous electrolyte comprising a non-aqueous electrolyte solution comprising at least one selected from the following additive compound (1) to additive compound (4).

(Wherein R21 and R23 are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group) An alkyl group, an alkenyl group or an alkynyl group, or a group in which they are halogenated R22 is a linear or branched alkylene group, an arylene group, a divalent group containing an arylene group and an alkylene group; Or a group in which they are halogenated.)

(In the formula, R21, R23, and R22 are the same as those in the additive compound (1).)

The non-aqueous electrolyte according to claim 1, wherein the overcharge control agent is at least one selected from the following overcharge control agents (1) to overcharge control agents (12).

(In the formula, Ra is a linear or branched alkyl group, or a group in which they are partially or entirely halogenated. R1 to R5 are independently an alkoxy group, a halogen group, or a nitrile. A group or a linear or branched alkyl group, or a group that is partially or wholly halogenated, or a group in which Ra and R1 to R5 are linked to each other with an adjacent group. (However, Ra and R1 to R5 are linked except when all of R1 to R5 are alkoxy groups.)

(Wherein Rb is a linear or branched alkyl group, or a group in which they are partially or wholly halogenated. R1 to R7 are independently an alkoxy group, a halogen group, or A linear or branched alkyl group, a group in which they are partially or fully halogenated, or a group in which Rb and R1 to R7 are linked to each other, provided that Rb And R1 to R7 are connected except when R1 to R7 are all alkoxy groups.)

(In the formula, Rb and R1 to R7 are the same as the overcharge control agent (2).)

(In the formula, M is a transition metal element, or a group 13 element, group 14 element or group 15 element in the long-period periodic table. Rc is an aryl group or a heterocyclic group, or they are partially or completely. R1 to R4 are independently an alkoxy group, a halogen group, or a linear or branched alkyl group, a group in which they are partially or wholly halogenated, Or, R1 to R4 are groups connected to adjacent groups.)

Wherein R1 to R4 are independently an alkoxy group, a halogen group, or a linear or branched alkyl group, a group in which they are partially or fully halogenated, or R1 to R4 And R5 and R6 are alkoxy groups, halogen groups, or linear or branched alkyl groups, which are partially or all halogenated groups. Or a group in which R5 and R6 are linked to each other, the group to which R5 and R6 are linked to each other is an alkylene group, an alkylene group partially or wholly halogenated, or a group represented by the following general formula (A): A linking group.

In the general formula (A), l ₁ and l ₂ are each independently represent an integer of 0 to 2. A is an alkylene group having 0 to 2 carbon atoms, or an alkylene group in which they are partially or wholly halogenated. )

(In the formula, X represents an N-oxide or N-oxo group. Y represents an oxygen atom or a sulfur atom. R8 to R11 independently represent an alkyl group, an alkenyl group, an alkynyl group, or a partial or All are halogenated groups, or R8 and R9, and R10 and R11 are linked to each other R12 is a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic ring A nitrile group, a heterocyclic group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, an alkenyl group or an alkynyl group, or a group in which they are halogenated, Ether group, amide group, carboxylic ester group, phosphoric ester group, thioester group, cyclic ether or chain ether substituted A kill group.)

(In the formula, X, Y, and R8 to R11 are the same as the overcharge control agent (6). When Y is an oxygen atom, R14 and R15 represent a lone pair, and Y is a sulfur atom. In this case, R14 and R15 independently represent an unshared electron pair or an oxo group, and R13 represents a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or an aromatic carbonized group. An alkyl group, an alkenyl group or an alkynyl group substituted by a hydrogen group or an alicyclic hydrocarbon group, or a group in which they are halogenated, an ether group, an amide group, a carboxylate group, a phosphate group, (It is an alkyl group substituted with a thioester group, a cyclic ether or a chain ether.)

(In the formula, X and R8 to R11 are the same as the overcharge control agent (6). R12 is a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Or an alkyl group, an alkenyl group or an alkynyl group substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group, or a group in which they are halogenated, an ether group, an amide group, a carboxylic acid ester group, (It is an alkyl group substituted with a phosphate ester group, a thioester group, a cyclic ether or a chain ether.)

(Wherein X, R8 to R11 and R12 are the same as the overcharge control agent (8). R16 and R17 independently represent an alkyl group, an alkenyl group, an alkynyl group, or a partial or All are halogenated groups, or R16 and R17 are groups linked together.)

(In formula, X and R8-R11 are the same as that of the said overcharge control agent (8). Z is either of the following general formula (B1)-general formula (B6).

(In General Formula (B1) to General Formula (B6), R12 is the same as the overcharge control agent (8). R18 is independently an alkyl group, an alkenyl group, an alkynyl group, or a part thereof, or All are halogenated groups, or groups in which R18 and R19 are connected to each other, and R19 is a hydrogen group, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, or an ether group. Are independently hydrogen, alkyl, aryl, aralkyl, alkenyl, alkynyl, cycloalkyl or glycidyl.)

(In the formula, X is the same as the above-described overcharge control agent (8). R8 to R11 are independently an alkyl group, an alkenyl group, an alkynyl group, a carboxylic acid ester group, a partial or all of them being halogen. Or a group in which R8 and R9, and R10 and R11 are linked to each other.)

(In the formula, s is 4 or more and 12 or less on average, and D is hydrogen, chlorine or bromine.) The nonaqueous electrolyte according to claim 2, wherein a mixing amount of the overcharge control agent is 0.1% by mass or more and 30% by mass or less with respect to the nonaqueous electrolytic solution. 4. The non-mixing material according to claim 3, wherein an amount of at least one selected from the additive compound (1) to the additive compound (4) is more than 0% by mass and less than 20% by mass with respect to the overcharge control agent. Water electrolyte. The amount of at least one selected from the additive compound (1) and the additive compound (2) is more than 0% by mass and less than 6.0% by mass with respect to the overcharge control agent. Non-aqueous electrolyte. The amount of at least one selected from the additive compound (3) and the additive compound (4) is from 0.00.1% by mass to 30% by mass with respect to the overcharge control agent. The non-aqueous electrolyte described. An electrode group including a positive electrode and a negative electrode;
A non-aqueous electrolyte containing a non-aqueous electrolyte,
The non-aqueous electrolyte is
A non-aqueous solvent;
Electrolyte salt,
An overcharge control agent that causes a redox reaction at a predetermined potential;
A nonaqueous electrolyte battery comprising at least one selected from the following additive compound (1) to additive compound (4).

(Wherein R21 and R23 are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group) An alkyl group, an alkenyl group or an alkynyl group, or a group in which they are halogenated R22 is a linear or branched alkylene group, an arylene group, a divalent group containing an arylene group and an alkylene group; Or a group in which they are halogenated.)

(In the formula, R21, R23, and R22 are the same as those in the additive compound (1).)

The nonaqueous electrolyte battery according to claim 7, wherein the overcharge control agent is at least one selected from the following overcharge control agents (1) to overcharge control agents (12).

(In the formula, Ra is a linear or branched alkyl group, or a group in which they are partially or entirely halogenated. R1 to R5 are independently an alkoxy group, a halogen group, or a nitrile. A group or a linear or branched alkyl group, or a group that is partially or wholly halogenated, or a group in which Ra and R1 to R5 are linked to each other with an adjacent group. (However, Ra and R1 to R5 are linked except when all of R1 to R5 are alkoxy groups.)

(Wherein Rb is a linear or branched alkyl group, or a group in which they are partially or wholly halogenated. R1 to R7 are independently an alkoxy group, a halogen group, or A linear or branched alkyl group, a group in which they are partially or fully halogenated, or a group in which Rb and R1 to R7 are linked to each other, provided that Rb And R1 to R7 are connected except when R1 to R7 are all alkoxy groups.)

(In the formula, Rb and R1 to R7 are the same as the overcharge control agent (2).)

(In the formula, M is a transition metal element, or a group 13 element, group 14 element or group 15 element in the long-period periodic table. Rc is an aryl group or a heterocyclic group, or they are partially or completely. R1 to R4 are independently an alkoxy group, a halogen group, or a linear or branched alkyl group, a group in which they are partially or wholly halogenated, Or, R1 to R4 are groups connected to adjacent groups.)

Wherein R1 to R4 are independently an alkoxy group, a halogen group, or a linear or branched alkyl group, a group in which they are partially or fully halogenated, or R1 to R4 And R5 and R6 are alkoxy groups, halogen groups, or linear or branched alkyl groups, which are partially or all halogenated groups. Or a group in which R5 and R6 are linked to each other, the group to which R5 and R6 are linked to each other is an alkylene group, an alkylene group partially or wholly halogenated, or a group represented by the following general formula (A): A linking group.

In the general formula (A), l ₁ and l ₂ are each independently represent an integer of 0 to 2. A is an alkylene group having 0 to 2 carbon atoms, or an alkylene group in which they are partially or wholly halogenated. )

(In the formula, X represents an N-oxide or N-oxo group. Y represents an oxygen atom or a sulfur atom. R8 to R11 independently represent an alkyl group, an alkenyl group, an alkynyl group, or a partial or All are halogenated groups, or R8 and R9, and R10 and R11 are linked to each other R12 is a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic ring A nitrile group, a heterocyclic group, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, an alkenyl group or an alkynyl group, or a group in which they are halogenated, Ether group, amide group, carboxylic ester group, phosphoric ester group, thioester group, cyclic ether or chain ether substituted A kill group.)

(In the formula, X, Y, and R8 to R11 are the same as the overcharge control agent (6). When Y is an oxygen atom, R14 and R15 represent a lone pair, and Y is a sulfur atom. In this case, R14 and R15 independently represent an unshared electron pair or an oxo group, and R13 represents a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or an aromatic carbonized group. An alkyl group, an alkenyl group or an alkynyl group substituted by a hydrogen group or an alicyclic hydrocarbon group, or a group in which they are halogenated, an ether group, an amide group, a carboxylate group, a phosphate group, (It is an alkyl group substituted with a thioester group, a cyclic ether or a chain ether.)

(In the formula, X and R8 to R11 are the same as the overcharge control agent (6). R12 is a hydrogen group, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Or an alkyl group, an alkenyl group or an alkynyl group substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group, or a group in which they are halogenated, an ether group, an amide group, a carboxylic acid ester group, (It is an alkyl group substituted with a phosphate ester group, a thioester group, a cyclic ether or a chain ether.)

(Wherein X, R8 to R11 and R12 are the same as the overcharge control agent (8). R16 and R17 independently represent an alkyl group, an alkenyl group, an alkynyl group, or a partial or All are halogenated groups, or R16 and R17 are groups linked together.)

(In formula, X and R8-R11 are the same as that of the said overcharge control agent (8). Z is either of the following general formula (B1)-general formula (B6).

(In General Formula (B1) to General Formula (B6), R12 is the same as the overcharge control agent (8). R18 is independently an alkyl group, an alkenyl group, an alkynyl group, or a part thereof, or All are halogenated groups, or groups in which R18 and R19 are connected to each other, and R19 is a hydrogen group, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, or an ether group. Are independently hydrogen, alkyl, aryl, aralkyl, alkenyl, alkynyl, cycloalkyl or glycidyl.)

(In the formula, X is the same as the above-described overcharge control agent (8). R8 to R11 are independently an alkyl group, an alkenyl group, an alkynyl group, a carboxylic acid ester group, a partial or all of them being halogen. Or a group in which R8 and R9, and R10 and R11 are linked to each other.)

(In the formula, s is 4 or more and 12 or less on average, and D is hydrogen, chlorine or bromine.) The non-aqueous electrolyte battery according to claim 8, wherein a mixing amount of the overcharge control agent is 0.1% by mass or more and 30% by mass or less. The non-aqueous solution according to claim 9, wherein the amount of at least one selected from the additive compound (1) to the additive compound (4) is more than 0% by mass and less than 20% by mass with respect to the overcharge control agent. Electrolyte battery. The nonaqueous electrolyte battery according to claim 7,
A control unit for controlling the non-aqueous electrolyte battery;
A battery pack having an exterior enclosing the non-aqueous electrolyte battery. The nonaqueous electrolyte battery according to claim 7,
An electronic device that receives power from the nonaqueous electrolyte battery. The nonaqueous electrolyte battery according to claim 7,
A conversion device that receives supply of electric power from the nonaqueous electrolyte battery and converts it into driving force of a vehicle;
An electric vehicle comprising: a control device that performs information processing relating to vehicle control based on information relating to the nonaqueous electrolyte battery. The nonaqueous electrolyte battery according to claim 7,
A power storage device that supplies electric power to an electronic device connected to the non-aqueous electrolyte battery. The power storage device according to claim 14, further comprising: a power information control device that transmits and receives signals to and from other devices via a network, and performing charge / discharge control of the nonaqueous electrolyte battery based on information received by the power information control device. The electric power system which receives supply of electric power from the nonaqueous electrolyte battery of Claim 7, or supplies electric power to the said nonaqueous electrolyte battery from an electric power generating apparatus or an electric power network.

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