JP2008117543A - Lithium secondary battery, and electrode for lithium secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte lithium secondary battery which keeps high capacity even in the condition of storage under high-temperature environment or repeated charging/discharging, and to provide an electrode for such a secondary battery. <P>SOLUTION: The lithium secondary battery uses nonaqueous electrolyte liquid with ion conductivity, and has an electrode in which at least either one of positive electrode or negative electrode includes lithium ion conductive inorganic solid electrolyte powder, which contains the crystal expressed by Li<SB>1+x+y</SB>(Al, Ga)<SB>x</SB>(Ti, Ge)<SB>2-x</SB>Si<SB>y</SB>P<SB>3-y</SB>O<SB>12</SB>(0≤x≤1, 0≤y≤1). The electrode is used for the lithium secondary battery having nonaqueous electrolyte liquid with ion conductivity, and includes lithium ion conductive inorganic solid electrolyte powder, which contains the crystal expressed by Li<SB>1+x+y</SB>(Al, Ga)<SB>x</SB>(Ti, Ge)<SB>2-x</SB>Si<SB>y</SB>P<SB>3-y</SB>O<SB>12</SB>(0≤x≤1, 0≤y≤1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a lithium secondary battery and an electrode for a lithium secondary battery.

Along with the downsizing of electronic devices, there is an increasing demand for the development of secondary batteries that can be recharged and recharged in a compact, lightweight and high energy density battery.
As a secondary battery that satisfies these requirements, a secondary battery using a non-aqueous electrolyte has been put into practical use. This battery has an energy density several times that of a battery using a conventional aqueous electrolyte. Examples include non-aqueous electrolyte secondary batteries that use cobalt acid composite oxide, nickel acid composite oxide, or manganese composite oxide for the positive electrode of a non-aqueous electrolyte secondary battery, and an alloy or carbon material for the negative electrode. It is done.
Japanese Patent Laid-Open No. 10-116632 JP 2002-289176 A JP 2003-173769 A

Thus, as the capacity increases, on the other hand, the safety of the battery has been greatly regarded as a problem. For example, when the battery is in a high temperature state, the non-aqueous electrolyte and the electrode active material may cause a chemical reaction to cause a heat generation phenomenon.
In order not to cause this reaction, the electrolytic solution and the electrode need not be brought into contact with each other, but this does not work as a battery.
In addition, the development of organic solvents and solutes that exhibit stable characteristics even at high temperatures for non-aqueous electrolytes has been actively promoted. However, the performance deteriorates in a high temperature environment of 60 ° C. or higher, and the high temperature characteristics Cannot be said to have improved sufficiently.
For non-aqueous electrolyte secondary batteries, various other methods have been proposed in order to improve the high temperature characteristics, but all of them are less effective and the reliability at high temperatures is insufficient.
Therefore, the present invention has been proposed in view of such circumstances, and a non-aqueous electrolyte lithium secondary battery and a non-aqueous electrolyte that maintain a high capacity even when stored in a high temperature environment or repeated charging and discharging. An object is to provide an electrode for a water electrolyte lithium secondary battery.

  As a result of intensive studies to solve the above problems, the present inventor has found that in a lithium secondary battery, a positive electrode, a negative electrode, or either one of them includes a lithium ion conductive inorganic solid electrolyte having a specific composition, thereby increasing the temperature. It has been found that a highly reliable lithium secondary battery can be obtained even in a high temperature environment by suppressing the chemical reaction between the nonaqueous electrolyte and the electrode active material even in the environment, suppressing the performance degradation of the nonaqueous electrolyte. .

Specifically, a preferred embodiment of the present invention can be expressed by the following configuration.
(Configuration 1)
A lithium secondary battery using a non-aqueous electrolyte having ion conductivity,
At least one of the positive electrode or the negative electrode includes an electrode containing a lithium ion conductive inorganic solid electrolyte powder,
The inorganic solid electrolyte powder contains crystals of Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1). , Lithium secondary battery.
(Configuration 2)
The lithium secondary battery according to Configuration 1, comprising a polymer that absorbs a non-aqueous electrolyte between the positive electrode and the negative electrode.
(Configuration 3)
The lithium secondary battery according to Configuration 1, comprising a separator located between the positive electrode and the negative electrode (Configuration 4)
4. The lithium secondary battery according to any one of configurations 1 to 3, wherein the crystal is a crystal that does not include vacancies or crystal grain boundaries that inhibit ion conduction.
(Configuration 5)
5. The lithium secondary battery according to any one of configurations 1 to 4, wherein the inorganic solid electrolyte powder is a lithium composite oxide glass ceramic.
(Configuration 6)
The lithium secondary battery according to any one of configurations 1 to 5, wherein the inorganic solid electrolyte powder is contained in an amount of 0.1 wt% to 30 wt%.
(Configuration 7)
The lithium secondary battery according to any one of configurations 1 to 7, wherein the inorganic solid electrolyte powder has an average particle size of 20 μm or less.
(Configuration 8)
Containing lithium ion conductive inorganic solid electrolyte powder,
The inorganic solid electrolyte powder contains crystals of Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1). An electrode for a lithium secondary battery using a nonaqueous electrolytic solution having ion conductivity.
(Configuration 9)
9. The electrode according to Configuration 8, wherein the crystal is a crystal that does not include vacancies or crystal grain boundaries that inhibit ion conduction.
(Configuration 10)
The electrode according to Configuration 8 or 9, wherein the inorganic solid electrolyte powder is a lithium composite oxide glass ceramic.
(Configuration 11)
The electrode according to any one of Structures 8 to 10, comprising 0.1 wt% to 30 wt% of the inorganic solid electrolyte powder.
(Configuration 12)
The electrode according to any one of Structures 8 to 11, wherein the inorganic solid electrolyte powder has an average particle size of 20 μm or less.

According to the present invention, by adding a lithium ion conductive inorganic solid electrolyte powder having a specific composition into the electrode, the chemical reaction between the non-aqueous electrolyte and the electrode active material in a high temperature environment is suppressed, In this case, a lithium secondary battery with high reliability and improved charge / discharge characteristics can be obtained.
This is based on the knowledge that the presence of the inorganic solid electrolyte powder around the active material provides an effect of suppressing the chemical reaction between the non-aqueous electrolyte and the electrode active material in a high temperature environment.
In addition, the inorganic solid electrolyte powder covers the active material, so that the inorganic solid electrolyte powder reduces the reaction area between the active material and the non-aqueous electrolyte and suppresses the chemical reaction between the non-aqueous electrolyte and the electrode active material. The effect to do becomes larger.
In addition, by adding a lithium ion conductive inorganic solid electrolyte powder having a specific composition into the electrode, the inorganic solid electrolyte powder in the electrode plays a part in the lithium ion conduction in the electrode. The amount of liquid can be reduced, and the safety of the nonaqueous electrolyte secondary battery can be improved.

In the electrode of the lithium secondary battery of the present invention, at least one of the positive electrode and the negative electrode contains a lithium ion conductive inorganic solid electrolyte powder, and the inorganic solid electrolyte powder is Li _{1 + x + y} (Al, Ga) _x (Ti, Ge). ) _2-x Si _y P _3-y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1).
By including the lithium ion conductive inorganic solid electrolyte powder in the electrode, the chemical reaction between the non-aqueous electrolyte and the electrode active material can be suppressed in a high temperature environment, and the performance degradation of the lithium secondary battery can be suppressed. it can.

However, when the content of the lithium ion conductive inorganic solid electrolyte powder in the electrode is excessively increased, the amount of the active material in the electrode is relatively reduced. In addition, rate characteristics (discharge characteristics) are likely to deteriorate. Therefore, in order to easily obtain a high-capacity battery, the upper limit of the content of the lithium ion conductive inorganic solid electrolyte powder is preferably 30 wt% or less with respect to the electrode mixture containing the inorganic solid electrolyte powder, 20 wt% or less is more preferable, and 10 wt% or less is most preferable.
Specifically, when the rate characteristic is excellent (high), charge / discharge of a large amount of current becomes possible. In other words, it is possible to charge in a short time and to discharge a large amount of current.
In order to easily suppress the chemical reaction between the non-aqueous electrolyte and the electrode active material in a high temperature environment, the lower limit of the content of the lithium ion conductive inorganic solid electrolyte powder includes the inorganic solid electrolyte powder. 0.1 wt% or more is preferable with respect to the electrode mixture, more preferably 1 wt% or more, and most preferably 5 wt% or more.

  According to the structure of this invention, the effect which suppresses the chemical reaction with the electrode active material in a high temperature environment with respect to the non-aqueous electrolyte which has ion conductivity which melt | dissolved lithium salt in the organic solvent is acquired.

As the non-aqueous electrolyte, a known non-aqueous electrolyte can be used. For example, a solution obtained by dissolving a lithium salt in an organic solvent can be used.
As the organic solvent, ester solvents, ether solvents, carbonate solvents, ketone solvents, or the like can be used.
As the lithium salt, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , or LiC (SO ₂ CF ₃ ) ₃ can be used. .

  In this specification, a lithium secondary battery is a lithium ion secondary battery that includes a microporous separator between a positive electrode and a negative electrode and uses a non-aqueous electrolyte having ion conductivity, and a positive electrode and a negative electrode. Lithium polymer secondary batteries containing a polymer that absorbs a non-aqueous electrolyte are generically named, and the effects of the present invention can be obtained in all these batteries.

The lithium ion conductive inorganic solid electrolyte powder is Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1). By including the lithium ion conductive crystal, it is possible to have high ionic conductivity and sufficient conductivity to carry lithium ion movement in the electrode.
Therefore, by including the inorganic solid electrolyte powder containing the lithium ion conductive crystal in the electrode, it is easy to obtain the effect that the solid electrolyte partially takes charge of ion movement in the electrode, and the amount of the electrolyte can be easily reduced. Thus, it becomes easy to improve the safety as a battery. Furthermore, the effect of suppressing the reaction between the active material and the non-aqueous electrolyte can be more easily obtained by containing the inorganic solid electrolyte powder containing the lithium ion conductive crystal in the electrode. For this reason, the lithium ion conductive inorganic solid electrolyte powder preferably contains lithium ion conductive crystals.

In addition, the crystal has an advantage of high lithium ion conductivity, chemical stability and easy handling. Further, this crystal can be precipitated as a crystal in glass ceramics by heat-treating a glass having a specific composition.

The lithium ion conductive crystal is advantageous in terms of ion conduction if it does not include a crystal grain boundary that inhibits ion conduction. In particular, glass ceramics are more preferable because they have few vacancies and crystal grain boundaries that hinder ion conduction, and thus have high ion conductivity and excellent chemical stability.
In addition to glass ceramics, examples of a material that has almost no vacancies or crystal grain boundaries that hinder ion conduction include single crystals of the above crystals, which are difficult to manufacture and expensive. Lithium ion conductive glass ceramics are also advantageous from the viewpoint of ease of production and cost.

Therefore, it is preferable that the lithium ion conductive inorganic solid electrolyte powder is a glass ceramic powder because high ion conductivity is easily obtained and manufacturing is easy. Furthermore, it is more preferable that the lithium ion conductive inorganic solid electrolyte powder is a lithium composite oxide glass ceramic because it has higher chemical stability. In particular, Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) is precipitated as a crystal phase. Glass ceramic powder is most preferred because of its high ionic conductivity and chemical stability.
In the case where the glass ceramic powder is contained in the electrode, the content of the lithium ion conductive inorganic solid electrolyte powder in the electrode is set within the above-described content range, so that the non-high temperature environment can be used. The effect of suppressing the chemical reaction between the water electrolyte and the electrode active material is enhanced.

Crystals of Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) are precipitated as crystal phases. In glass ceramics,
In particular, a crystal of Li _{1 + x + y} (Al, Ga) _x Ti _2-x Si _y P _3-y O ₁₂ (where 0 ≦ x ≦ 0.4, 0 <y ≦ 0.6) is precipitated as a crystal phase. In the case of glass ceramics, a high lithium ion conductivity of about 1 × 10 ⁻³ S / cm can be obtained.

Further, the crystal of Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) is precipitated as a crystal phase. In particular, when y = 0, a crystal of Li _{1 + x} (Al, Ga) _x (Ti, Ge) _2−x P ₃ O ₁₂ (where 0 <x ≦ 0.8) is crystallized. In the case of glass ceramics precipitated as a phase, the lithium ion conductivity is about 1 × 10 ⁻⁴ S / cm. However, since the mother glass before crystal precipitation can be cast into a mold, Can be molded into a relatively large bulk, and as a result, production is easy.

  Here, the glass ceramic is a material obtained by precipitating a crystalline phase in a glass phase by heat-treating the glass, and means a material composed of an amorphous solid and a crystal. In other words, a material that has undergone phase transition to the above, that is, a crystal amount (crystallinity) in the material is 100% by mass. In the case of glass ceramics, even if the material is 100% crystallized, there are almost no voids between crystal grains or in the crystal. On the other hand, ceramics and sintered bodies generally referred to in the manufacturing process cannot avoid the presence of vacancies and grain boundaries in the crystal, and can be distinguished from the glass ceramic of the present invention. it can. In particular, with regard to ionic conduction, in the case of ceramics, due to the presence of vacancies and grain boundaries, the conductivity is considerably lower than the conductivity of the crystal grains themselves. Glass ceramics can suppress a decrease in the conductivity between crystals by controlling the crystallization process, and it becomes easy to obtain a conductivity equivalent to the conductivity inherent to the crystal grains themselves.

Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1) is precipitated as a crystal phase Glass ceramics are expressed in mol%,
Li ₂ O 10~25%, and _{Al 2 O 3 + Ga 2 O} 3 0.5~15%, and TiO ₂ + _{GeO 2} 25~50%, and SiO ₂ 0 to 15%, and P ₂ O ₅ 26 to 40 %
After obtaining glass by melting and quenching the glass containing each of the above components, the glass can be heat treated to precipitate crystals.

  Hereinafter, with regard to preferred embodiments of the composition, the composition ratio and the effect expressed by mol% of each component will be specifically described.

The Li ₂ O component is a useful component for providing Li ⁺ ion carriers and providing lithium ion conductivity. In order to easily obtain good ionic conductivity, the lower limit of the content is preferably 10%, more preferably 13%, and most preferably 14%. Further, if the Li ₂ O component is too much, the thermal stability of the glass tends to be deteriorated and the conductivity of the glass ceramic is also likely to be lowered. Therefore, the upper limit of the content is preferably 25%, and 17%. More preferably, it is 16%.

The Al ₂ O ₃ component can enhance the thermal stability of the mother glass, and at the same time, Al ³⁺ ions are dissolved in the crystal phase, and are effective in improving lithium ion conductivity. In order to obtain this effect more easily, the lower limit of the content is preferably 0.5%, more preferably 5.5%, and most preferably 6%.
However, if the content exceeds 15%, the thermal stability of the glass tends to deteriorate and the conductivity of the glass ceramic tends to decrease, so the upper limit of the content is preferably 15%. In addition, in order to make the said effect easier to obtain, the upper limit of the more preferable content is 9.5%, and the upper limit of the most preferable content is 9%.

The TiO ₂ component contributes to the formation of glass and is a constituent component of the crystal phase, and is a useful component in both the glass and the crystal. In order to vitrify and in order for the crystal phase to precipitate from the glass as a main phase and obtain high ionic conductivity more easily, the lower limit of the content is preferably 25%, and preferably 36% Is more preferred, with 37% being most preferred. Further, if the TiO ₂ component is too much, the thermal stability of the glass tends to be deteriorated and the conductivity of the glass ceramic is also likely to be lowered. Therefore, the upper limit of the content is preferably 50%, and 43%. Is more preferred, with 42% being most preferred.

The SiO ₂ component can improve the meltability and thermal stability of the mother glass, and at the same time, Si ⁴⁺ ions are dissolved in the crystal phase, contributing to an improvement in lithium ion conductivity. In order to obtain this effect more fully, the lower limit of the content is preferably 1%, more preferably 2%, and most preferably 3%. However, if the content exceeds 10%, the conductivity tends to decrease. Therefore, the upper limit of the content is preferably 15%, more preferably 8%, and more preferably 7%. Is most preferred.
Further, when a crystal of Li _{1 + x} (Al, Ga) _x (Ti, Ge) _2−x P ₃ O ₁₂ (where 0 <x ≦ 0.8) is precipitated, the SiO ₂ component is not included (SiO ₂ Ingredients may be 0%).

The P ₂ O ₅ component is a component useful for the formation of glass and is also a component of the crystal phase. If the content is less than 26%, vitrification becomes difficult, so the lower limit of the content is preferably 26%, more preferably 32%, and most preferably 33%. Further, if the content exceeds 40%, the crystal phase hardly precipitates from the glass and it becomes difficult to obtain desired characteristics. Therefore, the upper limit of the content is preferably 40%, more preferably 39%. , 38% is most preferable.

In the case of the above-mentioned composition, glass can be easily obtained by casting molten glass, and glass ceramics having the above crystal phase obtained by heat-treating this glass are 1 × 10 ⁻⁴ S / cm to 1 × 10 6. ^-3 High lithium ion conductivity of S / cm.

In addition to the above composition, Al ₂ O ₃ may be partially or entirely substituted with Ga ₂ O ₃ and TiO ₂ may be substituted with GeO ₂ . Furthermore, in order to lower the melting point or increase the stability of the glass, it is possible to add a small amount of other raw materials within a range that does not greatly deteriorate the ionic conductivity.

In addition, when a crystal of Li _{1 + x + y} (Al, Ga) _x Ti _2-x Si _y P _3-y O ₁₂ (where 0 ≦ x ≦ 0.4, 0 <y ≦ 0.6) is precipitated, GeO _It may not contain _two components (GeO ₂ component is 0%).

The composition of said alkali metal such as Na ₂ O or _{K 2} O other than Li ₂ O is preferably does not contain as much as possible. When these components are present in the glass ceramics, the conductivity of the lithium ions is easily hindered due to the mixing effect of alkali ions, and the conductivity is easily lowered.
Further, when sulfur is added to the composition of the glass ceramic, the lithium ion conductivity is slightly improved, but the chemical durability and stability are deteriorated.
It is desirable that the glass ceramic composition does not contain as much as possible components such as Pb, As, Cd, and Hg that may cause harm to the environment and the human body.

The upper limit of the average particle diameter of the lithium ion conductive inorganic solid electrolyte powder is preferably 20 μm or less in order to facilitate the dispersibility in the electrode in consideration of the active material particle diameter and electrode thickness in the electrode. The following is more preferable, and 5 μm or less is most preferable.
The lower limit of the average particle size of the lithium ion conductive inorganic solid electrolyte powder is preferably 50 nm or more, more preferably 100 nm or more, and more preferably 140 nm or more in order to facilitate the dispersion in the electrode and the binding property between the electrode materials. Most preferred.
The average particle diameter is a value of D50 (cumulative 50% diameter) measured by a laser diffraction method. Specifically, a value measured by a particle size distribution measuring device LS100Q or a submicron particle analyzer N5 manufactured by Beckman Coulter, Inc. Can be used. The average particle diameter is a value expressed on a volume basis.

  As an active material used for the positive electrode material of the lithium secondary battery of the present invention, a transition metal compound capable of occluding and releasing lithium can be used. For example, manganese, cobalt, nickel, vanadium, niobium, molybdenum, titanium Transition metal oxides containing at least one selected from can be used.

The positive electrode of the lithium secondary battery of the present invention contains the above active material, a conductive additive and a binder, and optionally contains the lithium ion conductive inorganic solid electrolyte powder.
As the conductive assistant, carbon-based materials such as acetylene black and other known materials can be used.
As the binder, a fluorine resin such as PVDF (polyvinylidene fluoride) or other known materials can be used.

  In the positive electrode of the present invention, the electrode mixture refers to a mixture of an active material, a conductive additive, a binder, and a lithium ion conductive inorganic solid electrolyte powder.

  The active material used for the negative electrode material includes metal lithium, lithium-aluminum alloy, lithium-indium alloy and other alloys capable of inserting and extracting lithium, transition metal oxides such as titanium and vanadium, and carbon-based materials such as graphite. Is preferably used.

The negative electrode of the lithium secondary battery of the present invention contains the above active material and a binder, and if necessary, a conductive assistant, the lithium ion conductive inorganic solid electrolyte powder, or a nonaqueous ion conductive material. A solid polymer electrolyte that absorbs the electrolyte is included.
As the binder, a fluororesin such as PVDF or other known materials can be used.

  In the negative electrode of the present invention, the electrode mixture refers to a mixture of an active material, a conductive additive, a binder, and a lithium ion conductive inorganic solid electrolyte powder.

The lithium secondary battery of the present invention contains lithium ion conductive inorganic solid electrolyte powder in at least one of the positive electrode and the negative electrode, and a microporous film made of polypropylene or the like is interposed between the positive electrode and the negative electrode as a separator, It can be obtained by placing a current collector on each of the positive electrode and the negative electrode, pouring the nonaqueous electrolyte into the case, and then pouring the nonaqueous electrolyte.
In addition, a polymer solid electrolyte that absorbs a non-aqueous electrolyte such as a lithium ion conductive gel polymer or a polymer solid electrolyte is interposed between the positive electrode and the negative electrode instead of the separator of the microporous membrane, It can also be obtained by arranging the current collector and storing it in the case, and then injecting the non-aqueous electrolyte.

  Hereinafter, the lithium ion lithium secondary battery and the electrode for the lithium secondary battery according to the present invention will be described with specific examples. In addition, this invention is not limited to what was shown to the following Example, In the range which does not change the summary, it can change suitably and can implement.

[Preparation of lithium ion conductive inorganic solid electrolyte powder]
H ₃ PO ₄ , Al (PO ₃ ) ₃ , Li ₂ CO ₃ , SiO ₂ , and TiO ₂ are used as raw materials, and these are mol% in terms of oxide, P ₂ O ₅ is 35.0%, Al ₂ O ₃ is 7.5%, Li ₂ O is 15.0%, TiO ₂ is 38.0% and SiO ₂ is 4.5%. The glass melt was heated and melted at 1500 ° C. for 4 hours in an electric furnace while stirring. Thereafter, the glass melt was dropped into running water to obtain flaky glass, and the glass was crystallized by heat treatment at 950 ° C. for 12 hours to obtain the target glass ceramic. The precipitated crystal phase is Li _{1 + x + y} Al _x Ti _2-x Si _y P _3-y O ₁₂ (0 ≦ x ≦ 0.4, 0 <y ≦ 0.6) as the main crystal phase by powder X-ray diffraction method. It was confirmed that there was. This is called glass ceramics A. Further, the ionic conductivity of the glass ceramic A was about 1 × 10 ⁻³ S / cm.

Next, H ₃ PO ₄ , Al (PO ₃ ) ₃ , Li ₂ CO ₃ , ZrO ₂ , TiO _2, GeO ₂ are used as raw materials, and these are 40. P ₂ O ₅ in mol% in terms of oxide. The composition becomes 0%, Al ₂ O ₃ 8.0%, Li ₂ O 15.0%, ZrO ₂ 1.0%, TiO ₂ 17.0%, GeO ₂ 20.0%. The mixture was uniformly mixed and then placed in a platinum pot, and the glass melt was heated and melted at 1500 ° C. in an electric furnace for 4 hours with stirring. Thereafter, the glass melt was dropped into running water to obtain flaky glass, and the glass was crystallized by heat treatment at 950 ° C. for 12 hours to obtain the target glass ceramic. The precipitated crystal phase is Li _{1 + x} (Al, Ga) _x (Ti, Ge) _2−x P ₃ O ₁₂ (where 0 <x ≦ 0.8) is the main crystal phase by powder X-ray diffraction method. Was confirmed. This is called glass ceramics B. Further, the ionic conductivity of the glass ceramic B was about 1 × 10 ⁻⁴ S / cm.

  The obtained glass ceramics A and B flakes were each pulverized by a lab scale jet mill and classified by a zirconia rotating roller to obtain glass ceramic powder having an average particle size of 20 μm. The obtained powder was further pulverized by a planetary ball mill, an attritor, a bead mill or the like to obtain a glass ceramic powder having an average particle size described in each Example described later.

[Example 1]
1) Preparation of positive electrode 70 wt% of LiCoO ₂ as a positive electrode active material, 5 wt% of acetylene black as a conductive additive, 5 wt% of PVDF as a binder, and 20 wt% of glass ceramics A (average particle diameter 10 μm) are mixed. (N-methylpyrrolidone) was added to prepare a paste. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100micrometer and cut | judged to 50 square mm, and produced the positive electrode. Here, the average particle diameter of LiCoO ₂ was 8 μm.
2) Production of negative electrode Cu foil with a thickness of 18 μm was used as a negative electrode current collector. 92 wt% of graphite as an active material and 8 wt% of PVDF as a binder were mixed, and NMP was added to prepare a paste. This paste was uniformly applied to the negative electrode current collector and dried at 100 ° C. Then, it pressed to thickness 80micrometer, and cut | judged to 52 mm square, and produced the negative electrode. Here, graphite having an average particle diameter of 15 μm was used.
3) Production of Battery The positive electrode and the negative electrode obtained in 1) and 2) above were laminated and wound through a polypropylene microporous film having a thickness of 25 μm cut into 54 mm square, and an electrode body was produced. It was stored in a metal laminated resin film case. Then, the nonaqueous electrolyte (EC (ethylene carbonate): DEC (diethyl carbonate) = 1: 1 volume ratio, LiPF ₆ (lithium hexafluorophosphate): 1 mol / L as the nonaqueous electrolyte concentration) was set to 0. A battery was prepared by injecting 5 cc and sealingly welding.

[Example 2]
75 wt% of LiCoO ₂ as a positive electrode active material, 5 wt% of acetylene black as a conductive agent, 5 wt% of PVDF as a binder, mixed with glass ceramics A (average particle size 3 [mu] m) 15 wt%, a paste by adding NMP Adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100micrometer and cut | judged to 50 square mm, and produced the positive electrode.
A battery was produced in the same manner as in Example 1 using the negative electrode produced in the same manner as in Example 1.

[Example 3]
A mixture of 80 wt% LiCoO ₂ as a positive electrode active material, 5 wt% acetylene black as a conductive additive, 5 wt% PVDF as a binder, and 10 wt% glass ceramics A (average particle diameter 1 μm), and NMP is added to form a paste Adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100micrometer and cut | judged to 50 square mm, and produced the positive electrode.
91.9% by weight of graphite as a negative electrode active material, 8% by weight of PVDF as a binder, and 0.1% by weight of glass ceramics A (average particle size 0.2 μm) were mixed, and NMP was added to prepare a paste. . This paste was uniformly applied to the negative electrode current collector and dried at 100 ° C. Then, it pressed to thickness 80micrometer, and cut | judged to 52 mm square, and produced the negative electrode. Here, graphite having an average particle diameter of 15 μm was used.
A battery was produced in the same manner as in Example 1 using the produced positive electrode and negative electrode.

[Example 4]
78 wt% of LiCoO ₂ as a positive electrode active material, 5 wt% of acetylene black as a conductive agent, 5 wt% of PVDF as a binder, glass ceramics B (average particle size 5 [mu] m) 12 wt% were mixed, paste by adding NMP Adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100micrometer and cut | judged to 50 square mm, and produced the positive electrode.
A battery was produced in the same manner as in Example 1 using the negative electrode produced in the same manner as in Example 1.

[Example 5]
80 wt% of LiCoO ₂ as a cathode active material, conductive additive of acetylene black 5 wt%, 5 wt% of PVDF as a binder, glass ceramics B (average particle diameter 2 [mu] m) 10 wt% were mixed, the paste was added to NMP It was adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100micrometer and cut | judged to 50 square mm, and produced the positive electrode.
A battery was produced in the same manner as in Example 1 using the negative electrode produced in the same manner as in Example 1.

[Example 6]
85% by weight of LiCoO ₂ as a positive electrode active material, 5% by weight of acetylene black as a conductive additive, 5% by weight of PVDF as a binder, and 5% by weight of glass ceramics B (average particle diameter 1 μm) are mixed and pasteed with NMP. Adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100micrometer and cut | judged to 50 square mm, and produced the positive electrode.
91.8 wt% of graphite as a negative electrode active material, 8 wt% of PVDF as a binder, and 0.2 wt% of glass ceramics B (average particle diameter 0.15 μm) were mixed, and NMP was added to prepare a paste. . This paste was uniformly applied to the negative electrode current collector and dried at 100 ° C. to produce a negative electrode. Here, graphite having an average particle diameter of 15 μm was used.
A battery was produced in the same manner as in Example 1 using the produced positive electrode and negative electrode.

[Example 7]
84 wt% of LiCoO ₂ as a positive electrode active material, 5 wt% of acetylene black as a conductive agent, 5 wt% of PVDF as a binder, glass ceramics A (average particle size 1 [mu] m) were mixed 6 wt%, the addition of NMP paste Adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100 micrometers and cut | judged to 50 square mm, and produced the positive electrode The negative electrode was produced similarly to Example 1. FIG. The produced electrode was impregnated with a non-aqueous electrolyte (EC: DEC = 50: 50 vol%, LiPF ₆ : 1 mol / L as the non-aqueous electrolyte concentration). Further, as a polymer electrolyte, a 20 μm-thick PVDF microporous membrane cut into a 54 mm square is impregnated with a nonaqueous electrolyte (EC: DEC = 1: 1 volume ratio, LiPF ₆ : 1 mol / L as the nonaqueous electrolyte concentration). A gel electrolyte was prepared. The obtained positive electrode and negative electrode were laminated via a gel electrolyte to produce an electrode body. This electrode body was housed in a metal laminated resin film case and hermetically sealed to produce a battery.

[Example 8]
82 wt% of LiCoO ₂ as a positive electrode active material, 5 wt% of acetylene black as a conductive agent, 5 wt% of PVDF as a binder, glass ceramics B (average particle size 1 [mu] m) 8 wt% were mixed, paste by adding NMP Adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. Then, it pressed to thickness 100micrometer and cut | judged to 50 square mm, and produced the positive electrode.
The negative electrode was produced in the same manner as in Example 1. The prepared electrode was impregnated with a non-aqueous electrolyte (EC: DEC = 1: 1 volume ratio, LiPF ₆ : 1 mol / L as the non-aqueous electrolyte concentration). Further, as a polymer electrolyte, a 20 μm-thick PVDF microporous membrane cut into a 54 mm square is impregnated with a nonaqueous electrolyte (EC: DEC = 1: 1 volume ratio, LiPF ₆ : 1 mol / L as the nonaqueous electrolyte concentration). A gel electrolyte was prepared. The obtained positive electrode and negative electrode were laminated via a gel electrolyte to produce an electrode body. This electrode body was housed in a metal laminated resin film case and hermetically sealed to produce a battery.

[Comparative Example 1]
70 wt% of LiCoO ₂ as a positive electrode active material, 5 wt% of acetylene black as a conductive agent, 5 wt% of PVDF as a binder, LiBO ₂ (average particle diameter 1.5 [mu] m) were mixed 20 wt%, the addition of NMP The paste was adjusted. This paste was applied to an Al foil current collector and dried at 100 ° C. to produce a positive electrode.
A battery was produced in the same manner as in Example 1 using the negative electrode produced in the same manner as in Example 1.

[Comparative Example 2]
As a positive electrode active material, 84 wt% of LiCoO ₂ , 5 wt% of acetylene black as a conductive additive, 5 wt% of PVDF as a binder, and 20 wt% of Li ₂ SiO ₄ (average particle diameter 2.5 μm) were mixed, and NMP was mixed. In addition, it was adjusted to a paste. This paste was applied to an Al foil current collector and dried at 100 ° C. to produce a positive electrode.
A battery was produced in the same manner as in Example 1 using the negative electrode produced in the same manner as in Example 1.

    The battery produced as described above was fully charged by constant current-constant voltage charging up to 4.2 V at room temperature, and discharged at a current value of 1/6 C to a discharge end voltage of 2.7 V. Next, the same charge / discharge cycle was repeated under a high temperature environment atmosphere of 60 ° C., and the results of determining the capacity maintenance rate at the 100th cycle with respect to the second cycle are shown in Table 1.

Next, the batteries of Examples 1 to 8 and Comparative Examples 1 and 2 were fully charged to 4.2V. And each was short-circuited.
As a result, in the batteries of Comparative Examples 1 and 2, the battery cells generated heat and swollen. However, in Example 1-8 according to the present invention, there was no change in the battery cells. That is, it was found that the safety of the nonaqueous electrolyte battery provided with the electrode containing the lithium composite oxide glass ceramic is improved as compared with the conventional battery.
In addition, the battery was discharged at a current value of 1/6 C to a discharge end voltage of 2.7 V after full charge by constant current-constant voltage charge up to 4.2 V at room temperature. Thereafter, the battery was fully charged by constant current-constant voltage charging to 4.2 V again. In the second cycle discharge, the battery was discharged to 2.7 V at a current value of 1 / 3C. Examples 1 to 8 had 90% or more of the initial discharge capacity, but Comparative Examples 1 to 2 had a low discharge capacity of 60% or less.
From these, it was found that the battery of the present invention maintains the rate characteristics and improves the high safety.

Claims (12)

A lithium secondary battery using a non-aqueous electrolyte having ion conductivity,
At least one of the positive electrode or the negative electrode includes an electrode containing a lithium ion conductive inorganic solid electrolyte powder,
The inorganic solid electrolyte powder contains crystals of Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1). , Lithium secondary battery.   The lithium secondary battery according to claim 1, comprising a polymer that absorbs a non-aqueous electrolyte between the positive electrode and the negative electrode.   The lithium secondary battery according to claim 1, further comprising a separator positioned between the positive electrode and the negative electrode.   The lithium secondary battery according to claim 1, wherein the crystal is a crystal that does not include vacancies or crystal grain boundaries that inhibit ion conduction.   The lithium secondary battery according to claim 1, wherein the inorganic solid electrolyte powder is a lithium composite oxide glass ceramic.   The lithium secondary battery according to any one of claims 1 to 5, comprising 0.1 wt% to 30 wt% of the inorganic solid electrolyte powder.   The lithium secondary battery according to claim 1, wherein the inorganic solid electrolyte powder has an average particle size of 20 μm or less. Containing lithium ion conductive inorganic solid electrolyte powder,
The inorganic solid electrolyte powder contains crystals of Li _{1 + x + y} (Al, Ga) _x (Ti, Ge) _2−x Si _y P _3−y O ₁₂ (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1). An electrode for a lithium secondary battery using a nonaqueous electrolytic solution having ion conductivity.   The electrode according to claim 8, wherein the crystal is a crystal that does not include vacancies or crystal grain boundaries that inhibit ion conduction.   The electrode according to claim 8 or 9, wherein the inorganic solid electrolyte powder is a lithium composite oxide glass ceramic.   The electrode according to any one of claims 8 to 10, comprising 0.1 wt% to 30 wt% of the inorganic solid electrolyte powder. The electrode according to claim 8, wherein the inorganic solid electrolyte powder has an average particle size of 20 μm or less.