JP6485956B2 - Nonaqueous electrolyte and nonaqueous secondary battery - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte and a non-aqueous secondary battery using the same.

  Secondary batteries such as lithium ion secondary batteries can achieve a large energy density in charge and discharge compared to lead batteries and nickel cadmium batteries. Utilizing this characteristic, application to portable electronic devices such as mobile phones and notebook personal computers is widespread. Recently, development of a secondary battery that is particularly lightweight and capable of obtaining a high energy density has been underway. Further, there is a demand for miniaturization and long life. In addition to portable electronic devices, use as large storage batteries such as hybrid vehicles (HEV), plug-in hybrid vehicles (PHEV), electric vehicles (EV), airplanes and smart grids has begun.

Examples of the electrolyte solution for the lithium ion non-aqueous secondary battery include ethylene carbonate, propylene carbonate having high dielectric constant, diethyl carbonate having high viscosity, and carbonate-based solvents combining these, lithium hexafluorophosphate (LiPF ₆ ), etc. A combination with an electrolyte salt is used. These substances have high conductivity and are stable in potential.
In addition, attempts have been made to improve the battery performance by adding a functional additive to the electrolyte of the lithium ion non-aqueous secondary battery.

For example, Patent Document 1 discloses a non-aqueous secondary battery using a non-aqueous secondary battery electrolyte containing a small amount of cyclopentadienyl complex, and Patent Document 2 includes a specific aromatic compound. A non-aqueous secondary battery using an electrolyte for a non-aqueous secondary battery is described.
Patent Document 3 proposes an electrolytic solution for an electrochemical device using an ionic metal complex having an electron-withdrawing ligand as an electrolyte and a fluorine-containing organic solvent.

In addition, it is known that a film called SEI (Solid Electrolyte Interface) is formed on the electrode by an oxidation-reduction reaction at the interface between the electrode and the electrolyte in the lithium ion non-aqueous secondary battery. There is a technique for suppressing the deterioration of the electrolyte. In this technique, in order to suppress reductive decomposition of the electrolytic solution on the negative electrode and oxidative decomposition of the electrolytic solution on the positive electrode, respectively, a compound for forming an SEI film on the electrolytic solution (hereinafter referred to as SEI agent). Add.
Vinylene carbonate and the like are known as SEI agents for negative electrodes. However, the development of the positive electrode SEI agent has not progressed so much, and the patent documents 1 to 3 do not describe the positive electrode SEI agent.

JP 2014-029827 A JP 2009-192153 A JP 2001-256983 A

  With the development of HEV and the like in recent years, there is an increasing number of scenes where it is required to drive a non-aqueous secondary battery at a high potential. In order to drive the non-aqueous secondary battery at a high potential, it is important that the electrolyte does not undergo oxidative decomposition even at a high potential.

As a result of intensive studies by the present inventors, the complex such as the ionic metal complex described in Patent Document 3 is not dissolved in the non-aqueous electrolyte, and the specific non-ionic fluorine-containing metal compound is sufficient for the non-aqueous electrolyte. It has been found that even in a battery driven at a high potential, it functions as a positive electrode SEI agent.
The present invention has been made based on this finding. That is, the present invention uses a nonaqueous electrolytic solution containing a specific fluorine-containing metal compound and the nonaqueous electrolytic solution, so that an increase in resistance is suppressed even in a battery driven at high potential, and storage stability is also achieved. It is an object of the present invention to provide a non-aqueous secondary battery with improved resistance.

The above problem has been solved by the following means.
(1) a fluorine-containing metal compound represented by the following formula (I), a non-aqueous electrolyte solution containing a nonaqueous solvent containing a fluorine-containing compound,
A non-aqueous electrolyte in which the fluorine-containing compound is selected from carbonates, ethers and ester compounds containing fluorine atoms, and the content of the fluorine-containing compound with respect to the non-aqueous electrolyte is more than 10% by mass .

式（ＣＰ）において、Ｒ ^１１ は炭素数１〜８のアルキル基、炭素数１〜１０のアルキルシリル基、炭素数２〜２０のアルケニル基、炭素数２〜１０のアルキニル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルスルファニル基、炭素数０〜１０のアミノ基、シアノ基、カルボキシル基、−ＣＯＯＲ、−ＯＣＯＲ、−ＣＯＲ、−ＣＯＮＲ _２ または炭素数１〜１０のスルホニル基含有基、ホスフィニル基、またはハロゲノ基を表す。Ｒは水素原子、炭素数１〜８のアルキル基または炭素数３〜１２のシクロアルキル基を表す。複数のＲ ^１１ が結合して、脂肪族性または芳香族性の環を形成してもよい。ａ２は０〜５の整数を表す。＊はＭとの連結部位を表す。
In the formula (I), R ¹ is an alkoxy group, —COOR, —OCOR, —CONR ₂ or a group represented by the following formula (CP), R is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 carbon atoms. A cycloalkyl group of ˜12 , R ^f is a group represented by any one selected from the group consisting of the following formulas (II) -1 to (II) -4 and (II) -6 , M is Ti, Zr or Represents Fe .
n is to table the valence of M. p is 1-4 integer, q is 0, 1 or 2, I p + q = n der, n represents an integer of 2 to 4.
If R ¹ and ^{R f} there are a plurality, each of the plurality of ^{R 1} and ^{R f} may be the same or different, ^{R 1} together, ^{R f} together, bonded each ^{R 1} and ^{R f} form a ring It may be .

In the formula (CP), R ¹¹ represents an alkyl group having 1 to 8 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or 1 to 1 carbon atoms. 8 alkoxy groups, C 1-8 alkylsulfanyl groups, C 0-10 amino groups, cyano groups, carboxyl groups, —COOR, —OCOR, —COR, —CONR ₂ or C 1-10 sulfonyl It represents a group-containing group, a phosphinyl group, or a halogeno group. R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. A plurality of R ¹¹ may combine to form an aliphatic or aromatic ring. a2 represents an integer of 0 to 5. * Represents a linking site with M.

In the formulas (II) -1 to (II-4) and (II) -6, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or carbon having at least one fluorine atom. R ² represents a heteroaryl group having an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom in the ring , R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴ Represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 20 carbon atoms having at least one fluorine atom, and R ⁵ represents a fluorine atom or at least one fluorine atom having 1 to 8 carbon atoms. Alkyl group, C1-C10 alkylsilyl group, C2-C20 alkenyl group, C2-C10 alkynyl group, C1-C8 alkoxy group, C1-C8 alkyl Rufaniru group, an amino group having 1 to 10 carbon atoms, -COOR, -OCOR, -COR, -CONR ₂ or represents a sulfonyl group-containing group having 1 to 10 carbon atoms, ^{R 6} is an alkyl group having 1 to 8 carbon atoms, C1-C10 alkylsilyl group, C2-C20 alkenyl group, C2-C10 alkynyl group, C1-C8 alkoxy group, C1-C8 alkylsulfanyl group, C0 10 amino group, a cyano group, a carboxyl group, -COOR, -OCOR, -COR, -CONR _2, a sulfonyl group-containing group or a phosphinyl group having 1 to 10 carbon atoms. R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms.
If R ² ~ R ⁶ there are a plurality forming a plurality of ^R 2 ~ ^{R 6} may be the same or ^{different, R 1, R 2, R} 3, R 5 and ^{R 6} are respectively connected ring You may do it.
a1 represents an integer of 1 to 5, b1 represents an integer of 0 to 4, and a1 + b1 = 1 to 5.
* Represents a linking site of the M.
(2 ) A nonaqueous secondary battery comprising the nonaqueous electrolyte solution according to (1) , a positive electrode, and a negative electrode.
( 3 ) The nonaqueous secondary battery according to ( 2 ), wherein the driving potential is 4.6 V or more.
( 4 ) The non-aqueous solution according to ( 2 ) or ( 3 ), wherein the positive electrode contains any one of a spinel-type lithium nickel manganate, an olivine-type cobalt phosphate compound, and a solid solution represented by the following formula (MA-8) Secondary battery.
LiM ¹ O ₂ —Li ₂ MnO ₃ solid solution formula (MA-8)
In the formula (MA-8), M ¹ represents one or more elements selected from Co, Ni, Fe, Mn, Cu and V.

  In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The non-aqueous electrolyte solution of the present invention containing a specific fluorine-containing metal compound can be used even in a battery in which the specific fluorine-containing metal compound exhibits sufficient solubility in the non-aqueous electrolyte and is driven at a high potential. By using the nonaqueous electrolytic solution of the invention, it has become possible to provide a nonaqueous secondary battery in which an increase in resistance is suppressed and storage stability is improved.

It is a longitudinal cross-sectional view which shows typically the mechanism of the lithium non-aqueous secondary battery which concerns on preferable embodiment of this invention. It is a longitudinal cross-sectional view which shows the specific structure of the lithium non-aqueous secondary battery which concerns on preferable embodiment of this invention. It is a longitudinal cross-sectional view which shows the structure of a 2032 type coin battery typically.

Hereinafter, the present invention will be described in detail.
In addition, description of the component requirement described below may be made | formed based on typical embodiment and a specific example. However, the present invention is not limited to such an embodiment.

[Fluorine-containing metal compound represented by formula (I)]
The nonaqueous electrolytic solution of the present invention contains a fluorine-containing metal compound represented by the following formula (I).

In the formula (I), R ¹ represents a monovalent organic group, R ^f represents a monovalent organic group having a fluorine atom, and M represents a transition metal element.
n represents the valence of M, p represents an integer of 1 or more, q represents 0 or an integer of 1 or more, and p + q = n.
If R ¹ and ^{R f} there are a plurality, each of the plurality of ^{R 1} and ^{R f} may be the same or different, ^{R 1} together, ^{R f} together, bonded each ^{R 1} and ^{R f} form a ring It may be.

The monovalent organic group in R ¹ is alkyl group, alkenyl group, alkoxy group, alkylamino group, silylamino group, sulfonic acid group, isocyanate group (NCO), isothiocyanate group (NCS), sulfanyl group, phosphinyl group, carbonyl. Any of a group-containing group, an aryl group, a heteroaryl group and a group represented by the following formula (CP) is preferable.

In the formula (CP), R ¹¹ is an alkyl group, alkylsilyl group, alkenyl group, alkynyl group, alkoxy group, alkylsulfanyl group, amino group, amide group, cyano group, carboxyl group, carbonyl group-containing group, sulfonyl group-containing group. Represents a phosphinyl group or a halogeno group. A plurality of R ¹¹ may combine to form an aliphatic or aromatic ring. a2 represents an integer of 0 to 5. * Represents a linking site with M.

R ¹ is more preferably any one of an alkoxy group, an alkylamino group, a silylamino group, a sulfonic acid group, a carbonyl group-containing group and a group represented by the formula (CP). And any one of the groups represented by formula (CP) is more preferable.

The alkyl group for R ¹ preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples of the alkyl group for R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl.
The alkenyl group for R ¹ preferably has 2 to 20 carbon atoms and may have a substituent such as an acyl group.
The alkoxy group for R ¹ preferably has 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, butoxy and isopropoxy.
The alkylamino group in R ¹ preferably has 1 to 8 carbon atoms, and examples thereof include N, N-dimethylamino and N, N-diethylamino.
The silylamino group in R ¹ preferably has 0 to 20 carbon atoms and is substituted with 1 to 3 groups selected from the group consisting of an alkylamino group, an arylamino group, an arylalkylamino group, and a monovalent heterocyclic amino group. Silylamino group formed. Examples include trimethylsilylamino, triethylsilylamino, tert-butyldimethylsilylamino, triphenylsilylamino and diphenylmethylsilylamino.
The carbonyl group-containing group in R ¹ is preferably represented by —COOR, —OCOR, —COR or —CONR ₂ (R is a hydrogen atom, an alkyl group or a cycloalkyl group), and —COOR, —OCOR or —CONR ₂ is particularly preferable. The alkyl group in R preferably has 1 to 8 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms.
Examples of the aryl group for R ¹ include aryl groups having 6 to 10 carbon atoms, which may have a substituent such as an alkoxy group. Specific examples include phenyl, tolyl and naphthyl, and phenyl or naphthyl is preferred.
The heteroaryl group in R ¹ is preferably a heteroaryl group having 2 to 20 carbon atoms, and the heteroatom in the ring is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. Specific heteroaryl rings include indole, carbazole, oxazole and thiophenine.

Here, the monovalent organic group in R ¹ is preferably not a fluoro group. Further, as described later, the monovalent organic group in R ¹ may have a substituent. However, it preferably has no halogen atom as a substituent.

The alkyl group in R ^11, an alkenyl group, an alkoxy group and carbonyl group-containing group has the same meaning as in R ^1.
The alkylsilyl group in R ¹¹ preferably has 1 to 10 carbon atoms, and examples thereof include trimethylsilyl.
The alkynyl group in R ¹¹ preferably has 2 to 10 carbon atoms, and examples thereof include ethynyl.
The alkylsulfanyl group in R ¹¹ preferably has 1 to 8 carbon atoms, for example,
And methanesulfanyl.
The amino group for R ¹¹ preferably has 0 to 10 carbon atoms, and examples thereof include dimethylamino.
The sulfonyl group-containing group in R ¹¹ preferably has 1 to 10 carbon atoms, and examples thereof include methanesulfonyl.
The halogeno group for R ¹¹ includes fluoro, chloro, bromo and iodo, but is preferably not a fluoro group.

The monovalent organic group having a fluorine atom in R ^f is preferably represented by any one selected from the group consisting of the following formulas (II) -1 to (II) -6.

In formulas (II) -1 to (II) -6, R ² represents an alkyl group, aryl group or heteroaryl group having at least one fluorine atom, R ³ represents a hydrogen atom or a monovalent organic group, R ⁴ represents an alkyl group or alkenyl group having at least one fluorine atom, R ⁵ represents a fluorine atom or an organic group having at least one fluorine atom, and R ⁶ represents a monovalent organic group.
Ar represents an aryl group or heteroaryl group having at least one fluorine atom.
If R ² to R ⁶ and Ar there are a plurality, each of the plurality of ^R 2 to R ⁶ and Ar may be the same or ^{different, R 1, R 2, R} 3, R 5 and ^{R 6} are linked respectively May form a ring. R ⁵ and R ⁶ may form a condensed ring with the cyclopentadienyl ring.
a1 represents an integer of 1 to 5, b1 represents an integer of 0 to 4, and a1 + b1 = 1 to 5.
* Represents a linking site with M.

The monovalent organic group in R ³ is preferably an alkyl group or a silyl group.
The monovalent organic group in R ⁵ is an alkyl group, alkylsilyl group, alkenyl group, alkynyl group, alkoxy group, alkylsulfanyl group, amino group, amide group, carboxyl group, carbonyl group-containing group or sulfonyl group-containing group. It is preferable.
The monovalent organic group in R ⁶ is alkyl group, alkylsilyl group, alkenyl group, alkynyl group, alkoxy group, alkylsulfanyl group, amino group, amide group, cyano group, carboxyl group, carbonyl group-containing group, sulfonyl group-containing It is preferably a group or a phosphinyl group.
The alkyl group, alkenyl group, alkoxy group, carbonyl group-containing group, aryl group and heteroaryl group in R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and Ar have the same meaning as R ¹ .
In addition, the alkylsilyl group, alkynyl group, alkylsulfanyl group, amino group, and sulfonyl group-containing group in R ⁵ and R ^{6 have} the same meanings as R ¹¹ .

  The transition metal element as M is preferably Ti, Zr, Fe, Hf and Y, and particularly preferably Ti, Zr and Fe.

p is preferably 1 to 2, q is preferably 1 to 2, and n is preferably 2 to 4.
a1 is preferably from 1 to 2, and b1 is preferably from 0 to 2.
a2 is preferably 0-2.

  Specific examples of the fluorine-containing metal compound represented by the formula (I) are shown below, but the present invention is not construed as being limited thereto.

The fluorine-containing metal compound represented by the formula (I) can be synthesized by a conventional method such as reacting M ⁿ Cl _n with R ^f Na and R ¹ Na. ^{Here, M, R} f, R ¹ and n are defined as ^{M, R f,} R ¹ and n in formula (I).

  The addition amount of the fluorine-containing metal compound represented by the formula (I) is preferably 0.05% by mass to 2% by mass with respect to the nonaqueous electrolytic solution, and 0.1% by mass to 1.5% by mass. More preferably.

  The fluorine-containing metal compounds represented by the formula (I) may be used alone or in combination of two or more. Moreover, you may use together with the other functional additive mentioned later.

  The fluorine-containing metal compound represented by the formula (I) has sufficient solubility in a non-aqueous electrolyte solution as described later. Moreover, by using the non-aqueous electrolyte containing the fluorine-containing metal compound represented by the formula (I), it is possible to achieve an effect of suppressing the increase in resistance and improving the storage stability of the non-aqueous secondary battery.

(Electrolytes)
The electrolyte used for the non-aqueous electrolyte of the present invention is preferably a salt of a metal ion belonging to Group 1 or Group 2 of the periodic table. The salt of the metal ion to be used is appropriately selected depending on the purpose of use of the nonaqueous electrolytic solution. For example, lithium salt, potassium salt, sodium salt, calcium salt, magnesium salt and the like can be mentioned. When used in a non-aqueous secondary battery or the like, lithium salt is preferable from the viewpoint of output. When the nonaqueous electrolytic solution of the present invention is used as a nonaqueous electrolytic solution for a lithium ion secondary battery, a lithium salt may be selected as a metal ion salt. As a lithium salt, the lithium salt normally used for the electrolyte of the non-aqueous electrolyte for lithium ion secondary batteries is preferable, for example, what is described below is preferable.

(L-1) Inorganic lithium salts: inorganic fluoride salts such as LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ ; perhalogenates such as LiClO ₄ , LiBrO ₄ , LiIO ₄ ; inorganic chloride salts such as LiAlCl ₄ etc

(L-2) Fluorine-containing organic lithium salt: Perfluoroalkane sulfonate such as LiCF ₃ SO ₃ ; LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ CF ₂ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , Perfluoroalkanesulfonylimide salts such as LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ); perfluoroalkanesulfonylmethide salts such as LiC (CF ₃ SO ₂ ) ₃ ; Li [PF ₅ (CF ₂ CF ₂ CF ₃ )], Li [PF ₄ (CF ₂ CF ₂ CF ₃ ) ₂ ], Li [PF ₃ (CF ₂ CF ₂ CF ₃ ) ₃ ], Li [PF ₅ (CF ₂ CF ₂ CF ₂ CF _{3 )], Li [PF 4 (} CF 2 CF 2 CF 2 CF 3) 2], Li [PF 3 (CF 2 CF 2 CF 2 CF 3) 3] perfluoroalkyl fluoride such as Phosphoric acid salts, and the like

(L-3) Oxalatoborate salt: lithium bis (oxalato) borate, lithium difluorooxalatoborate, etc.

Among these, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ , LiClO ₄ , Li (Rf ¹ SO ₃ ), LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ) are preferred, and lithium imides such as LiPF ₆ , LiBF ₄ , LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ) More preferred are salts. Here, Rf ¹ and Rf ² each represent a perfluoroalkyl group.
In addition, the electrolyte used for a non-aqueous electrolyte may be used individually by 1 type, or may combine 2 or more types arbitrarily.

  The salt concentration of the electrolyte (preferably a metal ion belonging to Group 1 or Group 2 of the periodic table or a metal salt thereof) in the non-aqueous electrolyte is appropriately selected depending on the intended use of the non-aqueous electrolyte. Is 10% by mass to 50% by mass, more preferably 15% by mass to 30% by mass, based on the total mass of the non-aqueous electrolyte. The molar concentration is preferably 0.5M to 1.5M. In addition, when evaluating as a density | concentration of ion, what is necessary is just to calculate by salt conversion with the metal applied suitably.

(Non-aqueous solvent)
The nonaqueous electrolytic solution of the present invention contains a nonaqueous solvent.
As the non-aqueous solvent used in the present invention, an aprotic organic solvent is preferable, and an aprotic organic solvent having 2 to 10 carbon atoms is particularly preferable.
Such non-aqueous solvents include linear or cyclic carbonate compounds, lactone compounds, linear or cyclic ether compounds, ester compounds, nitrile compounds, amide compounds, oxazolidinone compounds, nitro compounds, linear or cyclic sulfones or Examples thereof include sulfoxide compounds and phosphate esters.
In addition, as a preferable bond, a compound having an ether bond, a carbonyl bond, an ester bond or a carbonate bond is preferable. These compounds may have a substituent, for example, the below-mentioned substituent T is mentioned.

Examples of the non-aqueous solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2 -Methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, butyric acid Methyl, methyl isobutyrate, methyl trimethylacetate, ethyl trimethylacetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, Examples thereof include N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N′-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide and dimethyl sulfoxide. These may be used alone or in combination of two or more. Among these, at least one member selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and γ-butyrolactone is preferable. Particularly, high viscosity (high dielectric constant) such as ethylene carbonate or propylene carbonate. A combination of a solvent (for example, relative dielectric constant ε ≧ 30) and a low viscosity solvent (for example, viscosity ≦ 1 mPa · s) such as dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate is more preferable. By using a mixed solvent of such a combination, the dissociation property of the electrolyte salt and the mobility of ions are improved.
The nonaqueous solvent used in the present invention is not limited to these.

(Fluorine-containing compounds)
The nonaqueous electrolytic solution used in the present invention preferably contains a fluorine-containing compound from the viewpoint of solubility of the fluorine-containing metal compound represented by the formula (I) used in the present invention.
The fluorine-containing compound is not particularly limited as long as it contains a fluorine atom and has a melting point of 40 ° C. or less. However, a carbonate, ether or ester compound containing a fluorine atom is preferred, and a carbonate or ether compound containing a fluorine atom is more preferred. preferable. In this specification, the carbonate compound containing a fluorine atom means a compound containing a fluorine atom and having a carbonate bond, and the ether and ester compounds containing a fluorine atom are also used in the same meaning.
From the viewpoint of preventing oxidation of the solvent, it is preferable that part or all of the chain carbonate compound is replaced with a fluorine-containing compound, and from the viewpoint of solution viscosity, a chain carbonate compound or an ether compound containing a fluorine atom is used. Is preferred. Preferred specific examples of the fluorine-containing compound are shown below.

  The content of the fluorine-containing compound with respect to the nonaqueous electrolytic solution is preferably an amount exceeding 10% by mass, more preferably 20% by mass or more, and further preferably 30% by mass or more.

A non-aqueous solvent containing a fluorine-containing compound (hereinafter referred to as a fluorine-containing non-aqueous solvent) has excellent oxidation resistance because the fluorine-containing compound has an electron-attracting fluorine atom, and is a battery driven at a high potential. It can be used for non-aqueous electrolytes that can cope with the above. However, the complex used as a functional additive has poor solubility in a fluorine-containing non-aqueous solvent, and it was not possible to introduce an addition amount necessary for forming a SEI film.
On the other hand, the solubility to a fluorine-containing non-aqueous solvent can be improved by using the fluorine-containing metal compound represented by the formula (I) used in the present invention. Accordingly, it is considered that an effective SEI film can be formed even in a battery driven at a high potential, and as a result, resistance increase can be suppressed and storage stability can be improved.

(Functional additives)
The nonaqueous electrolytic solution of the present invention preferably contains various functional additives in order to improve flame retardancy, improve cycle characteristics, improve capacity characteristics, and the like.
Examples of functional additives that are preferably applied to the nonaqueous electrolytic solution of the present invention are shown below.

<Compound having a sulfur atom>
The compound having a sulfur atom is preferably a compound having a —SO ₂ —, —SO ₃ —, —OS (═O) O— bond, and a cyclic sulfur-containing compound such as propane sultone, propene sultone, ethylene sulfite, Sulfonate esters are preferred.

  Examples of the cyclic sulfur-containing compound include the following Eex1 to Eex12.

  Examples of other functional additives include aromatic compounds, halogen-containing compounds, polymerizable compounds, silicon-containing compounds, nitrile compounds, metal complex compounds and imide compounds described in JP-A-2015-046389, and boron. Containing compounds.

  The nonaqueous electrolytic solution of the present invention may contain at least one selected from the above-described materials, negative electrode SEI agents, flame retardants, overcharge inhibitors and the like. The content ratio of these functional additives in the nonaqueous electrolytic solution is not particularly limited, and is preferably 0.001% by mass to 10% by mass with respect to the entire nonaqueous electrolytic solution (including the electrolyte). By adding these compounds, it is possible to suppress the rupture of the battery at the time of abnormality due to overcharge, or to improve the capacity maintenance characteristic and cycle characteristic after high temperature storage.

In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Preferred substituents include the following substituent T. Unless otherwise specified, the substituent T is also referred to when simply referred to as a substituent, and each group such as an alkyl group is also referred to the corresponding group of the substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butynediynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl 2-chlorophenyl, 3-methylphenyl and the like), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered ring having at least one oxygen atom, sulfur atom, nitrogen atom) A heterocyclic group is preferable, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc., an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as , Methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.) An alkoxycarbonyl group (preferably an alkoxy group having 2 to 20 carbon atoms) Bonyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl and the like, amino groups (preferably including amino groups having 0 to 20 carbon atoms, alkylamino groups, arylamino groups, such as amino, N, N-dimethyl, etc. Amino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfamoyl groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.) ), An acyl group (preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, benzoyl, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyl) Oxy, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms) A carbamoyl group such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc., an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms such as acetylamino, benzoylamino, etc.), an alkylthio group (preferably carbon An alkylthio group having 1 to 20 atoms such as methylthio, ethylthio, isopropylthio, benzylthio, etc., an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms such as phenylthio, 1-naphthylthio, 3-methylphenylthio) 4-methoxyphenylthio etc.), an alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl etc.), a hydroxy group, Anomoto, halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and the like.
Each group may be further substituted with the above-described substituent T. For example, an aralkyl group in which an aryl group is substituted for an alkyl group.

[Method for preparing non-aqueous electrolyte]
The nonaqueous electrolytic solution of the present invention is prepared by a conventional method by dissolving the above components in the above nonaqueous solvent, including an example using a lithium salt as a metal ion salt.

In the present invention, “non-water” means that water is not substantially contained, and a trace amount of water may be contained as long as the effect of the invention is not hindered. Here, substantially not containing means that the concentration of water is 200 ppm (mass basis) or less, preferably 100 ppm or less, more preferably 20 ppm or less.
Actually, it is difficult to make it completely anhydrous, and 1 ppm or more is included.

<Viscosity of non-aqueous electrolyte>
The viscosity of the nonaqueous electrolytic solution of the present invention is not particularly limited. In addition, 10-0.1 mPa * s is preferable in 25 degreeC, and 5-0.5 mPa * s is more preferable.

  The viscosity of the non-aqueous electrolyte was measured by putting 1 mL of a sample in a rheometer (for example, trade name “CLS 500” manufactured by TA Instruments) and using Steel Cone (for example, manufactured by TA Instruments) having a diameter of 4 cm / 2 °. taking measurement. The sample is kept warm in advance until the temperature becomes constant at the measurement start temperature, and the measurement starts thereafter. The measurement temperature is 25 ° C.

<Applications of non-aqueous electrolyte>
Nonaqueous electrolytic solutions containing a fluorine-containing metal compound represented by the formula (I) of the present invention are, for example, electrolytic capacitors, electrochemical capacitors (electric double layer capacitors), and batteries that are charged / discharged by charge transfer of ions. It can be preferably used for solid display elements such as electroluminescence, sensors such as current sensors and gas sensors.
Among these, it is preferable to use for non-aqueous secondary batteries.

[Non-aqueous secondary battery]
The nonaqueous secondary battery of the present invention has the nonaqueous electrolyte solution of the present invention, a positive electrode, and a negative electrode.
Hereinafter, the non-aqueous secondary battery will be described as a typical lithium ion non-aqueous secondary battery (hereinafter also referred to as a lithium secondary battery), but is not limited to the lithium secondary battery.
As a preferred embodiment of the non-aqueous secondary battery, a lithium secondary battery will be described with reference to FIG. 1 schematically showing the mechanism.
The lithium secondary battery 10 of the present embodiment includes the non-aqueous electrolyte 5 of the present invention, a positive electrode C capable of inserting and releasing lithium ions (the positive electrode current collector 1 and the positive electrode active material layer 2), and a lithium ion battery. A negative electrode A (negative electrode current collector 3, negative electrode active material layer 4) capable of insertion / release or dissolution / precipitation. In addition to these members, the separator 9 disposed between the positive electrode and the negative electrode, a current collecting terminal (not shown), an outer case, etc. ). If necessary, a protective element may be attached to at least one of the inside of the battery and the outside of the battery. By adopting such a structure, lithium ions a and b are generated in the non-aqueous electrolyte 5, charging α and discharging β can be performed, and the operation is performed via the operation mechanism 6 via the circuit wiring 7. Alternatively, power storage can be performed. Hereinafter, the configuration of the lithium secondary battery which is a preferred embodiment of the present invention will be described in more detail.

(Battery shape)
The battery shape to which the lithium secondary battery of the present embodiment is applied is not particularly limited, and examples thereof include a bottomed cylindrical shape, a bottomed square shape, a thin shape, a sheet shape, and a paper shape. Any of these may be used. Further, it may be of a different shape such as a horseshoe shape or a comb shape considering the shape of the system or device to be incorporated. Among them, from the viewpoint of efficiently releasing the heat inside the battery to the outside, a square shape such as a bottomed square shape or a thin shape having at least one surface that is relatively flat and has a large area is preferable.

  In a battery having a bottomed cylindrical shape, an external surface area with respect to a power generating element to be filled becomes small. Therefore, it is preferable to design so that Joule heat generated by an internal resistance during charging or discharging can be efficiently released to the outside. Moreover, it is preferable to design so that the filling ratio of the substance having high thermal conductivity is increased and the temperature distribution inside is reduced. FIG. 2 is an example of a bottomed cylindrical lithium secondary battery 100. This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18.

In the bottomed square shape, the ratio of the area S of the largest surface (the product of the width and height of the outer dimensions excluding the terminal portion, unit cm ² ) to the thickness T (unit cm) of the battery outer shape The 2S / T value is preferably 100 or more, and more preferably 200 or more. By increasing the maximum surface, it is possible to improve characteristics such as cycle performance and high-temperature storage, even for high-power and large-capacity batteries, and increase the heat dissipation efficiency during heat generation, so-called `` valve operation '' It can be suppressed.

(Members constituting the battery)
The lithium secondary battery according to the present embodiment includes a non-aqueous electrolyte 5, positive electrode and negative electrode electrode mixtures C and A, and a separator basic member 9 as described with reference to FIG. 1. Hereinafter, each of these members will be described.

(Electrode mixture)
The electrode mixture is obtained by applying a dispersion of an active material and a conductive agent, a binder, a filler, etc. on a current collector (electrode substrate). In a lithium secondary battery, the active material is a positive electrode active material. It is preferable to use a negative electrode mixture in which the positive electrode mixture and the active material are negative electrode active materials.
Next, each component in the dispersion (electrode composition) constituting the electrode mixture will be described.

-Positive electrode active material It is preferable to use a transition metal oxide for the positive electrode active material, and in particular, it has a transition element M ^a (one or more elements selected from Co, Ni, Fe, Mn, Cu, V). Is preferred. Further, mixed element M ^b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed. As such transition metal oxides, for example, specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V ₂ O ₅ , MnO ₂ Etc. As the positive electrode active material, a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the above-described specific transition metal oxide is preferably used.

The transition metal oxides, oxides containing the above transition element M ^a is preferably exemplified. At this time, a mixed element M ^b (preferably Al) or the like may be mixed. The mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. Moreover, those the molar ratio of Li / ^{M a} is synthesized by mixing so that 0.3 to 2.2 is more preferable.

[Transition metal oxide represented by formula (MA) (layered rock salt structure)]
Among the lithium-containing transition metal oxides, those represented by the following general formula are preferable.

Li _aa M ¹ O _bb ··· general formula (MA)

In formula (MA), ^{M 1} are as defined above ^{M a,} and the preferred range is also the same. aa represents 0 to 1.2, preferably 0.1 to 1.15, and more preferably 0.6 to 1.1. bb represents 1-3 and 2 is preferable. A part of M ¹ may be substituted with the mixed element M ^b . The transition metal oxide represented by the general formula (MA) typically has a layered rock salt structure.

  The transition metal oxide is more preferably represented by the following formulas.

The general formula _{(MA-1) Li g CoO} k
The general formula _{(MA-2) Li g NiO} k
The general formula _{(MA-3) Li g MnO} k
Formula _{(MA-4) Li g Co} j Ni 1-j O k
Formula _{(MA-5) Li g Ni} j Mn 1-j O k
Formula _{(MA-6) Li g Co} j Ni i Al 1-j-i O k
Formula _{(MA-7) Li g Co} j Ni i Mn 1-j-i O k

In general formulas (MA-1) to (MA-7), g has the same meaning as the above aa, and the preferred range is also the same. j represents 0.1 to 0.9. i represents 0 to 1; However, 1-j-i is 0 or more. k has the same meaning as the above bb, and the preferred range is also the same.
Specific examples of the transition metal oxides represented by the general formulas (MA-1) to (MA-7) include LiCoO ₂ (lithium cobaltate [LCO]), LiNi ₂ O ₂ (lithium nickelate), LiNi _{0 .85} Co _0.10 Al _0.05 O ₂ (nickel cobalt lithium aluminum oxide [NCA]), LiNi _0.33 Co _0.33 Mn _0.33 O ₂ (nickel manganese lithium cobalt oxide [NMC]), LiNi _{0 .5} Mn _0.5 O ₂ (lithium manganese nickel oxide) and the like.

  The transition metal oxide represented by the general formula (MA) partially overlaps, but when represented by changing the notation, the following are also preferable examples.

_{(I) Li g Ni x Mn} y Co z O 2 (x> 0.2, y> 0.2, z ≧ 0, x + y + z = 1)

Representative:
_{Li g Ni 1/3 Mn 1/3 Co 1/3} O 2
Li _g Ni _1/2 Mn _1/2 O ₂

_{(Ii) Li g Ni x Co} y Al z O 2 (x> 0.7, y>0.1,0.1> z ≧ 0.05, x + y + z = 1)

Representative:
_{Li g Ni 0.8 Co 0.15 Al 0.05} O 2

  In recent years, a solid solution represented by the following formula (MA-8) is also preferred as an active material that can be used at a high potential.

LiM ¹ O ₂ —Li ₂ MnO ₃ solid solution formula (MA-8)

In the formula (MA-8), ^{M 1} has the same meaning as ^{M 1} in the general formula (MA).

[Transition metal oxide represented by general formula (MB) (spinel structure)]
As the lithium-containing transition metal oxide, those represented by the following general formula (MB) are particularly preferable.

Li _c M ² ₂ O _d General formula (MB)

In formula (MB), ^{M 2} are as defined above ^{M a,} and the preferred range is also the same. c represents 0-2, 0.1-1.5 are preferable and 0.6-1.15 are more preferable. d represents 3-5, and 4 is preferable.

  The transition metal oxides represented by the general formula (MB) are more preferably those represented by the following general formulas.

Formula _{(MB-1) Li mm Mn} 2 O nn
Formula _{(MB-2) Li mm Mn} p Al 2-p O nn
Formula _{(MB-3) Li mm Mn} p Ni 2-p O nn

In general formulas (MB-1) to (MB-3), mm is synonymous with c, and the preferred range is also the same. nn has the same meaning as d, and the preferred range is also the same. p represents 0-2. Specific examples of the transition metal oxide include LiMn ₂ O ₄ and LiMn _1.5 Ni _0.5 O ₄ .

  As transition metal oxides represented by the general formula (MB), those represented by the following are also preferred examples.

General formula (αa) LiCoMnO ₄
General formula (αb) Li ₂ FeMn ₃ O ₈
General formula (αc) Li ₂ CuMn ₃ O ₈
General formula (αd) Li ₂ CrMn ₃ O ₈
General formula (αe) Li ₂ NiMn ₃ O ₈

  Of the above, an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.

[Transition metal oxide represented by the general formula (MC)]
As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphate, and among them, those represented by the following general formula (MC) are also preferable.

Li _e M ³ (PO ₄ ) _f: General formula (MC)

  In general formula (MC), e represents 0-2, 0.1-1.5 are preferable and 0.5-1.15 are more preferable. f represents 1-5, and 0.5-2 are preferable.

M ³ represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu. M ³ represents, in addition to the mixing element ^{M b} above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb. Specific examples include, for example, olivine-type iron phosphates such as LiFePO ₄ and Li ₃ Fe ₂ (PO ₄ ) ₃ , iron pyrophosphates such as LiFeP ₂ O ₇ , cobalt phosphate compounds such as LiCoPO ₄ , and Li _3. Monoclinic Nasicon type vanadium phosphate salts such as V ₂ (PO ₄ ) ₃ (lithium vanadium phosphate) can be mentioned.
In addition, said aa, c, g, mm, and e value showing the composition of Li are the values which change by charging / discharging, and are typically evaluated by the value of the stable state when Li is contained. In the general formulas (αa) to (αe), the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.

  Especially as a positive electrode active material, the solid solution represented by the spinel type lithium nickel manganate, olivine type cobalt phosphate, or the said formula (MA-8) is especially preferable, and what is described below is mentioned as a specific example.

LiNi _0.5 Mn _1.5 O ₄
LiCoPO ₄
Li ₂ MnO ₃ —LiNi _0.5 Mn _0.5 O ₂ solid solution

  Since these can be used at a high potential, the battery capacity can be increased, and even when used at a high potential, the capacity retention rate is high, which is particularly preferable.

In the present invention, it is preferable to use a positive electrode active material having a charge region capable of oxidizing an organometallic compound. Specifically, it is preferable to use a material that can maintain normal use at a positive electrode potential (Li / Li ⁺ reference) of 3.5 V or higher. The positive electrode potential is more preferably 3.8 V or more, further preferably 3.9 V or more, and particularly preferably 4 V or more. In particular, the positive potential is preferably 4.1 V or higher, and most preferably 4.2 V or higher. The upper limit is not particularly limited. However, 5.2V or less is practical. By setting it as such a range, cycling characteristics and high-rate discharge characteristics can be improved.
Here, being able to maintain normal use means that the electrode material does not deteriorate and become unusable even when charged at that voltage, and this potential is also referred to as a normal usable potential.
The positive electrode potential (Li / Li ⁺ reference) at the time of charging / discharging is represented by the following formula.

    (Positive electrode potential) = (negative electrode potential) + (battery voltage)

  When lithium titanate is used as the negative electrode, the negative electrode potential is 1.55V. When graphite is used as the negative electrode, the negative electrode potential is 0.1V. The battery voltage is observed during charging and the positive electrode potential is calculated.

The nonaqueous electrolytic solution of the present invention is particularly preferably used in combination with a high potential positive electrode. When a positive electrode with a high potential is used, the electrical properties such as the resistance value in the non-aqueous secondary battery tend to be greatly reduced. However, according to a preferred embodiment of the present invention, the non-aqueous electrolyte solution reduces this decrease. The suppressed good performance can be maintained.
Therefore, the non-aqueous secondary battery of the present invention can be preferably used for use in high potential driving. For example, a non-aqueous secondary battery having a driving potential of 4.6 V or more can be preferably mentioned. The upper limit is not particularly limited, but the practical upper limit of the driving potential is 5.2V or less.
Here, the drive potential means the upper limit of the set potential during charging.

In the non-aqueous secondary battery of the present invention, preferably a lithium ion non-aqueous secondary battery, the average particle size of the positive electrode active material used is not particularly limited, but is preferably 0.1 μm to 50 μm. No particular limitation is imposed on the specific surface area, preferably from 0.01m ² / g~50m ² / g by the BET method. Further, the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.

  To make the positive electrode active material have a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a vibration ball mill, a vibration mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill, a sieve, or the like is used. You may use the positive electrode active material obtained by the baking method, after wash | cleaning with water, acidic aqueous solution, alkaline aqueous solution, and an organic solvent.

  Although the compounding quantity of a positive electrode active material is not specifically limited, 60-98 mass% is preferable in a solid component 100 mass% in the dispersion (mixture) for comprising an active material layer, and 70-95 mass% is more. preferable.

-Negative electrode active material As a negative electrode active material, what can insert and discharge | release lithium ion reversibly is preferable. There is no particular limitation as long as these conditions are satisfied. Examples thereof include carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium alloys such as lithium alone and lithium aluminum alloys, and metals capable of forming an alloy with lithium such as Sn or Si.

These may be used alone or in any combination of two or more, and the ratio in this case may be any ratio. Among these, a carbonaceous material or a lithium composite oxide is preferable from the viewpoint of reliability.
The metal composite oxide is preferably one that can occlude and release lithium, and preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.

  The carbonaceous material used as the negative electrode active material is a material substantially made of carbon. Examples thereof include carbonaceous materials obtained by firing artificial graphite such as petroleum pitch, natural graphite, and vapor-grown graphite, and various synthetic resins such as PAN-based resins and furfuryl alcohol resins. Furthermore, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro Examples thereof include spheres, graphite whiskers, and flat graphite.

  These carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization. Further, the carbonaceous material may have an interplanar spacing, density, and crystallite size as described in JP-A-62-222066, JP-A-2-6856, and 3-45473. preferable. The carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, and the like. It can also be used.

  It is preferable that the metal oxide and metal composite oxide which are negative electrode active materials used in the non-aqueous secondary battery of the present invention, preferably the lithium ion non-aqueous secondary battery, contain at least one of them. Among these metal oxides and metal composite oxides, amorphous oxides are preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. The term “amorphous” as used herein means an X-ray diffraction method using CuKα rays, which has a broad scattering band having an apex in the region of 20 ° to 40 ° in terms of 2θ values, and is a crystalline diffraction line. You may have. The strongest intensity of the crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. Is preferably 5 times or less, and particularly preferably has no crystalline diffraction line.

Among the group of compounds consisting of the above amorphous oxide and chalcogenide, the amorphous oxide and chalcogenide of the semimetal element are more preferable, and the elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Al , Ga, Si, Sn, Ge, Pb, Sb, Bi alone or in combination of two or more thereof, and chalcogenide are particularly preferable. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga ₂ O ₃ , SiO, GeO, SnO, SnO ₂ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , Pb ₃ O ₄ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , Bi ₂ O ₃ , Bi ₂ O ₄ , SnSiO ₃ , GeS, SnS, SnS ₂ , PbS, PbS ₂ , Sb ₂ S ₃ , Sb ₂ S ₅ , such as SnSiS ₃ may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li ₂ SnO ₂ .

  The average particle size of the negative electrode active material is preferably 0.1 μm to 60 μm. To obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used. When pulverizing, wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary. In order to obtain a desired particle size, classification is preferably performed. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.

  The chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and from a mass difference between powders before and after firing as a simple method.

  The negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge includes carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloy, lithium, and the like. An alloyable metal is preferable.

The nonaqueous electrolytic solution of the present invention is preferably combined with a high potential negative electrode (preferably lithium / titanium oxide, potential 1.55 V vs. Li metal) and a low potential negative electrode (preferably containing a carbon material and silicon). Excellent properties are exhibited in any combination of materials and potentials of about 0.1 V versus Li metal. Further, metal or metal oxide negative electrodes (preferably Si, Si oxide, Si / Si oxide, Sn, Sn oxide, SnB _x P _y O _z , Cu, which can be alloyed with lithium, which are being developed for higher capacity) / Sn and a plurality of these composites), and a battery using a composite of these metals or metal oxides and a carbon material as a negative electrode.
In the present invention, it is particularly preferable to use a negative electrode active material containing at least one selected from carbon, silicon (Si), titanium, and tin.

  The nonaqueous electrolytic solution of the present invention is particularly preferably used in combination with a high potential negative electrode. The high potential negative electrode is often used in combination with the above high potential positive electrode, and can suitably cope with large capacity charge / discharge.

-Conductive material The conductive material is preferably an electron conductive material that does not cause a chemical change in a configured non-aqueous secondary battery, preferably a lithium ion non-aqueous secondary battery, and any known conductive material can be used. . Usually, natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber and metal powder (copper, nickel, aluminum, silver (Japanese Patent Laid-Open No. Sho 63- , Etc.), etc.), metal fibers or polyphenylene derivatives (described in JP-A-59-20,971) can be contained as one kind or a mixture thereof. Among these, the combined use of graphite and acetylene black is particularly preferable. 11-50 mass% is preferable and, as for the addition amount of the said electrically conductive agent, 2-30 mass% is more preferable. In the case of carbon or graphite, 2 to 15% by mass is particularly preferable.

-Binders Examples of the binder include polysaccharides, thermoplastic resins, and rubber-elastic polymers. Among them, for example, starch, carboxymethylcellulose, cellulose, diacetylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose. , Sodium alginate, polyacrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer, etc. Polymer, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinyl Nylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate, etc. ) (Meth) acrylic ester copolymer containing acrylic ester, (meth) acrylic ester-acrylonitrile copolymer, polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene-butadiene copolymer , Acrylonitrile-butadiene copolymer, polybutadiene, neoprene rubber, fluororubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, polycarbonate Polyurethane resins, polyester resins, phenolic resins, emulsion (latex) or a suspension such as an epoxy resin is preferable, a latex of polyacrylate, carboxymethyl cellulose, polytetrafluoroethylene, polyvinylidene fluoride is more preferable.

  A binder can be used individually by 1 type or in mixture of 2 or more types. When the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the capacity per electrode unit volume or unit mass decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.

-Filler The electrode compound material may contain the filler. The material forming the filler is preferably a fibrous material that does not cause a chemical change in the non-aqueous secondary battery of the present invention. Usually, fibrous fillers made of materials such as olefin polymers such as polypropylene and polyethylene, glass, and carbon are used. Although the addition amount of a filler is not specifically limited, 0-30 mass% is preferable in a dispersion.

-Current collector As the current collector for the positive electrode and the negative electrode, it is preferable to use an electron conductor that does not cause a chemical change. As the current collector of the positive electrode, in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.

  As the negative electrode current collector, aluminum, copper, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and a copper alloy are more preferable.

As the shape of the current collector, a film sheet is usually used, but a net, a punched one, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used. The thickness of the current collector is not particularly limited. In addition, 1 micrometer-500 micrometers are preferable. Moreover, it is also preferable that the current collector surface is roughened by surface treatment.
An electrode mixture of a non-aqueous secondary battery (preferably a lithium ion non-aqueous secondary battery) is formed by a member appropriately selected from these materials.

(Separator)
The separator used in the non-aqueous secondary battery (preferably a lithium ion non-aqueous secondary battery) of the present invention has a mechanical strength that electrically insulates the positive electrode and the negative electrode, ion permeability, and a contact surface between the positive electrode and the negative electrode. It is preferably made of a material having oxidation / reduction resistance. As such a material, a porous polymer material, an inorganic material, an organic-inorganic hybrid material, glass fiber, or the like is used. These separators preferably have a shut-down function for ensuring reliability, that is, a function of closing a gap at 80 ° C. or higher to increase resistance and interrupting current, and the plugging temperature is preferably 90 ° C. or higher and 180 ° C. or lower. .

  The shape of the holes of the separator is usually circular or elliptical, and the size is preferably 0.05 μm to 30 μm, more preferably 0.1 μm to 20 μm. Furthermore, it may be a rod-like or irregular-shaped hole as in the case of making by a stretching method or a phase separation method. The ratio of these gaps, that is, the porosity, is preferably 20% to 90%, and more preferably 35% to 80%.

  The polymer material may be a single material such as cellulose nonwoven fabric, polyethylene, or polypropylene, or may be a composite material composed of two or more components. What laminated | stacked the 2 or more types of microporous film which changed the hole diameter, the porosity, the obstruction | occlusion temperature of a hole, etc. is preferable.

  Examples of the inorganic material include oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate, and those having a particle shape or fiber shape are used. As the form, a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used. In the thin film shape, those having a pore diameter of 0.01 μm to 1 μm and a thickness of 5 μm to 50 μm are preferably used. In addition to such an independent thin film shape, a separator formed by forming a composite porous layer containing inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used. For example, alumina particles having a 90% particle diameter of less than 1 μm are formed on both surfaces of the positive electrode as a porous layer using a fluororesin binder.

(Production of non-aqueous secondary battery)
As described above, the shape of the non-aqueous secondary battery (preferably a lithium ion non-aqueous secondary battery) of the present invention can be applied to any shape such as a sheet shape, a square shape, and a cylinder shape. A positive electrode active material or a mixture of negative electrode active materials is mainly used after being applied (coated), dried and compressed on a current collector.

Hereinafter, with reference to FIG. 2, a configuration and a manufacturing method thereof will be described using the bottomed cylindrical lithium secondary battery 100 as an example.
In a battery having a bottomed cylindrical shape, an external surface area with respect to a power generating element to be filled becomes small. Therefore, it is preferable to design so that Joule heat generated by an internal resistance during charging or discharging can be efficiently released to the outside. Moreover, it is preferable to design so that the filling ratio of the substance having high thermal conductivity is increased and the temperature distribution inside is reduced. FIG. 2 shows an example of a bottomed cylindrical lithium secondary battery 100. This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18. In addition, in the figure, 20 is an insulating plate, 22 is a sealing plate, 24 is a positive electrode current collector, 26 is a gasket, 28 is a pressure sensitive valve body, and 30 is a current interruption element. In addition, although the illustration in the enlarged circle has changed hatching in consideration of visibility, each member corresponds to the whole drawing by reference numerals.

  First, a negative electrode active material is mixed with a binder or filler used as desired in an organic solvent to prepare a slurry-like or paste-like negative electrode mixture. The obtained negative electrode mixture is uniformly applied over the entire surface of both surfaces of the metal core as a current collector, and then the organic solvent is removed to form a negative electrode mixture layer. Further, the laminate of the current collector and the negative electrode composite material layer is rolled with a roll press or the like to prepare a predetermined thickness to obtain a negative electrode sheet (electrode sheet). At this time, the coating method of each agent, the drying of the coated material, and the method of forming the positive and negative electrodes may be in accordance with conventional methods.

  In the present embodiment, a cylindrical battery is taken as an example, but the present invention is not limited to this. For example, the positive and negative electrode sheets produced by the above method are overlapped with a separator and then processed into a sheet battery as it is, or after being folded and inserted into a rectangular can, the can and the sheet After the electrical connection, the electrolyte may be injected, and the opening may be sealed using a sealing plate to produce a square battery.

  In any embodiment, the safety valve can be used as a sealing plate for sealing the opening. In addition to the safety valve, the sealing member may be provided with various conventionally known safety elements. For example, a fuse, bimetal, PTC element, or the like is preferably used as the overcurrent prevention element.

  In addition to the safety valve, as a countermeasure against the increase in internal pressure of the battery can, a method of cutting the battery can, a method of cracking the gasket, a method of cracking the sealing plate, or a method of cutting the lead plate can be used. Further, the charger may be provided with a protection circuit incorporating measures against overcharge and overdischarge, or may be connected independently.

  For the can and lead plate, a metal or alloy having electrical conductivity can be used. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum, or alloys thereof are preferably used.

  As a method for welding the cap, can, sheet, and lead plate, a known method (for example, direct current or alternating current electric welding, laser welding, or ultrasonic welding) can be used. As the sealing agent for sealing, a conventionally known compound or mixture such as asphalt can be used.

[Applications of non-aqueous secondary batteries]

  Non-aqueous secondary batteries, called lithium-ion batteries, are non-aqueous secondary batteries (lithium ion non-aqueous secondary batteries) that use lithium storage and release for charge and discharge reactions, and non-aqueous batteries that use lithium precipitation and dissolution. It is roughly divided into secondary batteries (lithium metal non-aqueous secondary batteries). In the present invention, application as a lithium ion non-aqueous secondary battery is preferable.

  The non-aqueous secondary battery of the present invention is excellent in suppression of resistance increase due to charge / discharge and storage stability, and thus can be applied to various applications. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military purposes and space. Moreover, it can also combine with a solar cell.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited thereto. Unless otherwise specified, parts and% are based on mass.

Example 1
A nonaqueous electrolytic solution (hereinafter also simply referred to as an electrolytic solution) was prepared as follows.

(1) Preparation of non-aqueous solution in which lithium salt is dissolved Non-aqueous solution (hereinafter simply referred to as a solution) in which each solvent is mixed at a mass ratio shown in Table 1 below and a lithium salt having a concentration shown in Table 1 below is dissolved. ) No. 1-4 were prepared.

<Notes on Table 1>
LiTFSI: Lithium bis (trifluoromethanesulfonyl) imide EC: Ethylene carbonate EMC: Ethyl methyl carbonate B-1, B-2, B-6 and B-8: Fluorine-containing compounds exemplified above

(2) Preparation of electrolytic solution To each of the solutions prepared above, the fluorine-containing metal compound represented by the formula (I) and / or other compounds used in the present invention are added in the addition amounts shown in Table 2 below. Test No. 101 to 120 of the electrolytic solution of the present invention and test no. 121, 122, c01 to c05 of comparative examples were prepared.

Here, the additive described by A- (circle) (for example, A-1) in following Table 2 shows the fluorine-containing metal compound represented by the said illustrated formula (I).
Moreover, the compound as described below was used as another compound.

Here, the above-mentioned other compounds, and the lithium salts and fluorine-containing compounds listed in Table 1 were appropriately purchased from Wako Pure Chemical Industries and Tokyo Kasei.
Moreover, the fluorine-containing metal compound represented by the formula (I) was synthesized by a conventional method such as reacting M ⁿ Cl _n with R ^f Na and R ¹ Na.

Example 2
A 2032 type coin battery was fabricated using each of the electrolyte solutions prepared above.

<Positive electrode>
Active material: From a composition of lithium nickel manganate (LiNi _0.5 Mn _1.5 O ₄ ) 85% by mass, conductive auxiliary agent: 7% by mass of carbon black, binder: PVDF (polyvinylidene fluoride) 8% by mass A positive electrode was produced. In Table 2 below, this is indicated as “LNMO”.
A positive electrode was produced from a composition of active material: lithium cobalt phosphate (LiCoPO ₄ ) 85% by mass, conductive auxiliary agent: carbon black 7% by mass, binder: PVDF (polyvinylidene fluoride) 8% by mass. In Table 2 below, this is indicated as “LCP”.
<Negative electrode>
A negative electrode was prepared from a composition of 92% by mass of active material: Gr (natural graphite) and 8% by mass of binder: PVDF. In Table 2 below, it is indicated as “graphite”.
An anode was prepared from 92% by mass of active material: lithium titanate (Li ₄ Ti ₅ O ₁₂ ) and 8% by mass of PVDF. In Table 2 below, it is indicated as “LTO”.
<Separator>
A separator made of polypropylene having a thickness of 25 μm was prepared.

-Production of 2032 type coin battery Using each of the electrolytic solutions 101 to 122 and c01 to c05, the separator and the positive and negative electrodes described above were used as shown in Table 2 below. 2032 type coin battery and testing of the present invention of 101 to 120 No. 121, 122, 2032 type coin batteries of comparative examples of c01 to c05 were produced.

  The following evaluation was performed for each electrolytic solution and each battery obtained as described above.

<Rate of increase in resistance>
Using the 2032 type battery produced by the above method, 1C constant current charging was performed in a thermostatic bath at 30 ° C. until the battery voltage reached 4.8 V at 4.0 mA. This 4.8 V constant voltage charging was continued until the current value reached 0.12 mA. However, the upper limit of the charging time was 2 hours. Next, 1C constant current discharge was performed at 4.0 mA until the battery voltage reached 3 V, and this charge / discharge was defined as one cycle. The resistance value after repeating charging / discharging up to 10 cycles (hereinafter referred to as “R ₁₀ ”) and the resistance value after repeating charging / discharging until reaching 300 cycles (hereinafter referred to as “R ₃₀₀ ”). ) Were measured by the methods shown below.
(Resistance measurement method)
Discharging was performed at 0.4 mA and 1.0 mA, respectively, and voltage change amounts from 10 seconds to 20 seconds, ΔV _0.4 and ΔV _1.0 were calculated, respectively. As shown in the following equation, a value obtained by dividing the difference in voltage change amount by the current difference during discharge was defined as a resistance value R [Ω].

Resistance value [Ω] = (ΔV _1.0 −ΔV _0.4 ) [mV] / (1.0−0.4) [mA]

Based on R ₁₀ and R ₃₀₀ obtained by the above formula, the resistance increase rate [%] was calculated based on the following formula.

Resistance increase rate [%] = (R ₃₀₀ / R ₁₀ ) × 100

<Preservability>
Using the 2032 type coin battery produced by the above method, 0.2C constant current charging was performed in a thermostat at 30 ° C. until the battery voltage became 4.8 V at 0.8 mA. Thereafter, charging at a constant voltage of 4.8 V was continued until the current value reached 0.03 mA. However, the upper limit of the charging time was 14 hours. Next, 1 C constant current discharge was performed until the battery voltage became 3 V at 4.0 mA. This operation was repeated three times. The electric capacity of the third of this time is Q _1.
Next, 0.2 C constant current charging was performed until the battery voltage became 5.0 V at 0.8 mA in a constant temperature bath at 30 ° C. Thereafter, charging at a constant voltage of 5.0 V was continued until the current value reached 0.03 mA, and the charging process was completed. However, the upper limit of the charging time was 14 hours.
After storing the 2032-type coin battery, which has been charged, in a constant temperature bath at 60 ° C. for 1 week, in a constant temperature bath at 30 ° C., charge at 0.2 C constant current until the battery voltage reaches 4.8 V at 0.8 mA. went. Thereafter, charging at a constant voltage of 4.8 V was continued until the current value reached 0.03 mA. However, the upper limit of the charging time was 14 hours. Next, 1 C constant current discharge was performed until the battery voltage became 3 V at 4.0 mA. This operation was repeated twice. A second electrical capacity at this time, and Q _2.
Based on the electric capacity Q ₁ and Q ₂ obtained above, based on the following equation, to evaluate the storage stability [%].

Preservability [%] = Q ₂ / Q ₁ × 100

<Compound solubility>
0.02 g of each additive listed in Table 2 below was weighed and the solution No. prepared above was weighed. The solubility in 1 at 25 ° C. was examined visually for each mass of the solution. A solution completely dissolved in 1 g of solution is “A”, a solution completely dissolved in 2 g of solution is “B”, a solution completely dissolved in 4 g of solution is “C”, and a solution which is not completely dissolved even when 4 g of solution is added is “D”. ". In the present invention, “C” or higher is an acceptable level.

  The results obtained are summarized in Table 2 below.

<Notes on Table 2>
When an additive is used in combination, “/” is used together, and the addition amount and compound solubility of each corresponding additive alone are described in the order of description.
In any electrolytic solution, the additive is completely dissolved.

As a result, the non-aqueous secondary battery No. 1 using the non-aqueous electrolyte of the present invention was used. 101-120 is a non-aqueous secondary battery using the nonaqueous electrolytic solution containing a fluorine-containing non-aqueous solvent in addition to the fluorine-containing metal compound represented by the formula (I), the rate of increase in resistance suppression and It was further excellent in preservability.
On the other hand, a non-aqueous secondary battery No. 1 using a non-aqueous electrolyte solution of a comparative example not containing an additive. For c01 and c02, the resistance increase rate is not sufficiently suppressed. As for c01, the storage stability was not sufficient. Moreover, the nonaqueous electrolyte No. of the comparative example containing a metal compound as an additive. c04 and c05 are both poorly soluble in the metal compound, and the nonaqueous secondary battery using the nonaqueous electrolytic solution in which the metal compound is dissolved in a very small amount is insufficient in suppressing the rate of increase in resistance. The effect of was low. In addition, the nonaqueous secondary battery No. using the nonaqueous electrolyte solution of the comparative example containing a compound having sufficient solubility in the nonaqueous electrolyte solution as an additive. For c03, a satisfactory resistance increase suppressing effect was not obtained with respect to the nonaqueous secondary battery of the present invention using the fluorine-containing metal compound represented by the formula (I).

  From the results of Example 2, it can be seen that the non-aqueous secondary battery using the non-aqueous electrolyte containing the fluorine-containing metal compound represented by the formula (I) of the present invention exhibits excellent electrical characteristics.

C positive electrode (positive electrode composite)
1 Positive electrode conductive material (current collector)
2 Positive electrode active material layer A Negative electrode (negative electrode composite)
3 Negative electrode conductive material (current collector)
4 Negative electrode active material layer 5 Non-aqueous electrolyte 6 Operating mechanism 7 Circuit wiring 9 Separator 10 Lithium ion non-aqueous secondary battery 12 Separator 14 Positive electrode sheet 16 Negative electrode sheet 18 Exterior can 20 also serving as negative electrode Insulating plate 22 Sealing plate 24 Positive electrode current collector 26 Gasket 28 Pressure sensitive valve body 30 Current interrupting element 100 Bottomed cylindrical shape lithium non-aqueous secondary battery 61 Negative electrode terminal (upper cover)
62 Negative electrode 63 Separator (including electrolyte)
64 Gasket (sealing material)
65 Positive electrode 66 Positive electrode tube (bottom cover)

Claims (4)

A fluorine-containing metal compound represented by the following formula (I), a non-aqueous electrolyte solution containing a nonaqueous solvent containing a fluorine-containing compound,
A non-aqueous electrolyte solution, wherein the fluorine-containing compound is selected from carbonates, ethers and ester compounds containing fluorine atoms, and the content of the fluorine-containing compound with respect to the non-aqueous electrolyte solution is more than 10% by mass .

In the formula (I), R ¹ is an alkoxy group, —COOR, —OCOR, —CONR ₂ or a group represented by the following formula (CP), R is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 carbon atoms. A cycloalkyl group of ˜12 , R ^f is a group represented by any one selected from the group consisting of the following formulas (II) -1 to (II) -4 and (II) -6 , M is Ti, Zr or Represents Fe .
n is to table the valence of M. p is 1-4 integer, q is 0, 1 or 2, I p + q = n der, n represents an integer of 2 to 4.
If R ¹ and ^{R f} there are a plurality, each of the plurality of ^{R 1} and ^{R f} may be the same or different, ^{R 1} together, ^{R f} together, bonded each ^{R 1} and ^{R f} form a ring It may be.

In the formula (CP), R ¹¹ represents an alkyl group having 1 to 8 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or 1 to 1 carbon atoms. 8 alkoxy groups, C 1-8 alkylsulfanyl groups, C 0-10 amino groups, cyano groups, carboxyl groups, —COOR, —OCOR, —COR, —CONR ₂ or C 1-10 sulfonyl It represents a group-containing group, a phosphinyl group, or a halogeno group. R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. A plurality of R ¹¹ may combine to form an aliphatic or aromatic ring. a2 represents an integer of 0 to 5. * Represents a linking site with M.

In the formulas (II) -1 to (II-4) and (II) -6, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or carbon having at least one fluorine atom. R ² represents a heteroaryl group having an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom in the ring, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴ Represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 20 carbon atoms having at least one fluorine atom, and R ⁵ represents a fluorine atom or at least one fluorine atom having 1 to 8 carbon atoms. An alkyl group, an alkylsilyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. A sulfanyl group, an amino group having 1 to 10 carbon atoms, -COOR, -OCOR, -COR, -CONR ₂ or a sulfonyl group-containing group having 1 to 10 carbon atoms, R ⁶ is an alkyl group having 1 to 8 carbon atoms, C1-C10 alkylsilyl group, C2-C20 alkenyl group, C2-C10 alkynyl group, C1-C8 alkoxy group, C1-C8 alkylsulfanyl group, C0 10 amino group, a cyano group, a carboxyl group, -COOR, -OCOR, -COR, -CONR _2, a sulfonyl group-containing group or a phosphinyl group having 1 to 10 carbon atoms. R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms.
If R ² to R ⁶ there are a plurality, forming a plurality of ^R 2 to R ⁶ may be the same or ^{different, R 1, R 2, R} 3, R 5 and ^{R 6} are respectively connected ring You may do it.
a1 represents an integer of 1 to 5, b1 represents an integer of 0 to 4, and a1 + b1 = 1 to 5.
* Represents a linking site with M. A nonaqueous secondary battery comprising the nonaqueous electrolyte solution according to claim 1 , a positive electrode, and a negative electrode. The nonaqueous secondary battery according to claim 2 , wherein the driving potential is 4.6 V or more. The positive electrode, a nonaqueous secondary battery according to claim 2 or 3 containing either a solid solution represented by the spinel-type lithium nickel manganese oxide, olivine-type phosphate cobalt compound and formula (MA-8).
LiM ¹ O ₂ —Li ₂ MnO ₃ solid solution formula (MA-8)
In the formula (MA-8), M ¹ represents one or more elements selected from Co, Ni, Fe, Mn, Cu and V.

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