JP2010033877A - Electrode mixture and all-solid secondary battery using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode mixture capable of enhancing battery performance by maintaining good contact between a solid electrolyte and an active material. <P>SOLUTION: The electrode mixture has a porous active material filled with a lithium ion conductive inorganic solid electrolyte and a conductive assistant. The porous active material is a transition metal oxide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrode mixture and an all solid state secondary battery using the same.

  In recent years, the demand for secondary batteries such as high-performance lithium batteries used in personal digital assistants, portable electronic devices, small household power storage devices, motorcycles powered by motors, electric vehicles, hybrid electric vehicles, etc. has increased. Yes.

  Currently, liquids are used as electrolytes for lithium batteries. However, there are problems in safety such as the reaction between the electrolyte solution and the electrode material due to evaporation and leakage of the electrolyte solution. In order to solve the above problem, many attempts have been made to use a solid as an electrolyte of a secondary battery.

  In a secondary battery using an electrolyte and an active material as a solid (all-solid secondary battery), an electrode is prepared by mixing and molding a powdered solid electrolyte and a powdered active material. In a powder mixture, an ion conduction path is used. In addition, many defects of the electron conduction path occur, and there is a problem that the battery performance is deteriorated. In addition, the entire electrode expands and contracts due to repeated charge / discharge cycles, resulting in poor contact between the particles, resulting in deterioration of charge / discharge characteristics.

Patent Document 1 discloses an electrode for a lithium secondary battery in which a porous electrolyte is filled with an active material. However, only oxide-based solid electrolytes that can be synthesized by the sol-gel method can be applied to this electrode. In general, a sulfide-based solid electrolyte (for example, Li ₂ S—P ₂ S ₅ ) that exhibits higher lithium ion conductivity than an oxide-based solid electrolyte cannot be used for the electrode. Could not get.

  Patent Document 2 discloses an electrode mixture in which a solid electrolyte forms a three-dimensional network. However, as in Patent Document 1, only an oxide-based solid electrolyte can be applied to this electrode mixture.

Patent Documents 3 and 4 disclose a sheet obtained by combining an inorganic solid electrolyte powder and a thermoplastic polymer resin, and a molded body obtained by dry-mixing a sulfide solid electrolyte and a polymer elastic body, respectively. These sheets and molded bodies also could not sufficiently solve the decrease in charge / discharge characteristics.
JP 2006-260887 A JP 2000-311710 A Japanese Patent Laid-Open No. 04-133209 Japanese Patent Laid-Open No. 06-0776828

  An object of this invention is to provide the electrode compound material which can maintain the contact of a solid electrolyte and an active material favorably, and can improve battery performance.

According to the present invention, the following electrode mixture and the like are provided.
1. An electrode mixture formed by filling a porous active material with a lithium ion conductive inorganic solid electrolyte and a conductive additive.
2. 2. The electrode mixture according to 1, wherein the porous active material is a transition metal oxide.
3. 2. The electrode composite material according to 1, wherein the porous active material is Al, Sn, Si, In, or a composite of Li and one or more of these metals.
4). The electrode mixture according to any one of 1 to 3, wherein the lithium ion conductive inorganic solid electrolyte contains one or more elements selected from the group consisting of P, Si and B, Li and S.
5). A positive electrode and a negative electrode;
An all-solid secondary battery comprising a solid electrolyte layer comprising a lithium ion conductive inorganic solid electrolyte sandwiched between the positive electrode and the negative electrode,
An all-solid-state secondary battery in which at least one of the positive electrode and the negative electrode is made of the electrode mixture according to any one of 1 to 4.

  ADVANTAGE OF THE INVENTION According to this invention, the electrode compound material which can maintain the contact of a solid electrolyte and an active material favorably and can improve battery performance can be provided.

The electrode mixture of the present invention comprises a porous active material filled with a lithium ion conductive inorganic solid electrolyte and a conductive additive.
The porous active material of the present invention has continuous voids therein. By filling the inside of the porous active material with a lithium ion conductive inorganic solid electrolyte and a conductive additive, the ionic conductivity and electronic conductivity by the active material network can be improved. Moreover, since the porous active material can ensure the continuity of the filled lithium ion conductive inorganic solid electrolyte, the ion conductivity of the lithium ion conductive inorganic solid electrolyte can be improved.

  In addition, since the continuous voids (three-dimensional network structure) inside the porous active material can absorb expansion / contraction during charging / discharging, the electrode mixture of the present invention improves the charge / discharge cycle characteristics of the battery. be able to.

  The porous active material is preferably a transition metal oxide, or a composite of Al, Sn, Si, In, or one of these metals and Li.

When a transition metal oxide is used as the porous active material, an oxide that can be synthesized by a sol-gel method such as LiCoO ₂ can be used as the transition metal oxide.
As a method of using a transition metal oxide as a porous active material, a generally known method can be used. For example, polymer particles such as polystyrene and polymethyl methacrylate (PMMA) or monodisperse particles are deposited on a substrate, and the oxide precursor sol is filled in the deposit, and the sol is gelled. A porous active material made of a transition metal oxide can be produced by firing and removing the molecular particles.

When using a composite of Li with Al, Sn, Si, In or any one or more of these metals as the porous active material, Li—Al, Li—Sn, Li—Si or the like is used as these metals or composites. be able to. In addition, oxides such as SiO and SnO ₂ or composites thereof can also be used.

As a method of using the metal and the composite as a porous active material, a generally known method such as a colloidal crystal template method can be used.
For example, polystyrene beads (PS beads) are dispersed in ethanol, and the PS beads are fused on the substrate by electrophoresis and deposition heat treatment to form a colloidal crystal. Using this as a template, Sn—Ni alloy plating is carried out to produce a Sn—Ni alloy skeleton, and PS beads are removed by washing with toluene to produce a porous Sn—Ni negative electrode active material (Proceedings of the 48th Battery Conference) 2B13).

  The lithium ion conductive inorganic solid electrolyte is not particularly limited. For example, a material composed of an organic compound, an inorganic compound, or a mixture of an organic compound and an inorganic compound can be used, and preferably contains one or more elements selected from the group consisting of P, Si, and B, Li and S A lithium ion conductive inorganic solid electrolyte is used.

Among lithium ion conductive inorganic solid electrolytes, in particular, sulfide-based inorganic solid electrolytes are known to have higher ionic conductivity than other inorganic compounds, and inorganic solid electrolytes described in JP-A-4-202024 etc. Can be used. Specifically, an inorganic solid electrolyte in which Li ₃ PO ₄ , a halogen, and a halogen compound are appropriately added to an inorganic solid electrolyte composed of a combination of Li ₂ S and SiS ₂ , GeS ₂ , P ₂ S ₅ , B ₂ S _3. Can be used.

  Since lithium ion conductivity is high, lithium ion conduction generated from lithium sulfide and diphosphorus pentasulfide, or lithium sulfide and simple phosphorus and simple sulfur, as well as lithium sulfide, diphosphorus pentasulfide, simple phosphorus and / or simple sulfur It is preferable to use a conductive inorganic solid electrolyte. Hereinafter, a preferable solid electrolyte will be described.

The lithium ion conductive inorganic solid electrolyte can be produced from lithium sulfide and diphosphorus pentasulfide (P ₂ S ₅ ) and / or simple phosphorus and simple sulfur. Specifically, it can be produced by melting these raw materials and then rapidly cooling them. In addition, sulfide glass obtained by treating these raw materials by a mechanical milling method (hereinafter, sometimes referred to as MM method), or a heat-treated product thereof.

As lithium sulfide, those commercially available without limitation can be used, but those having high purity are preferable as described below.
Lithium sulfide has at least a total content of lithium salt of sulfur oxide of 0.15% by mass or less, preferably 0.1% by mass or less, and a content of lithium N-methylaminobutyrate of 0.15% by mass. Hereinafter, it is preferably 0.1% by mass or less. When the total content of the lithium salt of sulfur oxide is 0.15% by mass or less, the solid electrolyte obtained by the melt quenching method or the mechanical milling method described later is a glassy electrolyte (fully amorphous). That is, when the total content of the lithium salt of sulfur oxide exceeds 0.15% by mass, the obtained electrolyte is a crystallized product from the beginning, and the ionic conductivity of this crystallized product is low. Furthermore, even if the crystallized product is subjected to the following heat treatment, the crystallized product is not changed, and a lithium ion conductive inorganic solid electrolyte having a high ion conductivity cannot be obtained.

  Further, when the content of lithium N-methylaminobutyrate is 0.15% by mass or less, a deteriorated product of lithium N-methylaminobutyrate does not deteriorate the cycle performance of the lithium battery.

  Thus, in order to obtain a high ion conductive electrolyte, it is necessary to use lithium sulfide with reduced impurities.

The method for producing lithium sulfide used for producing the high ion conductive electrolyte is not particularly limited as long as it is a method that can reduce at least the impurities.
For example, it can also be obtained by purifying lithium sulfide produced by the following method.
Among the following production methods, the method a or b is particularly preferable.
a. A method in which lithium hydroxide and hydrogen sulfide are reacted at 0 to 150 ° C. in an aprotic organic solvent to produce lithium hydrosulfide, and this reaction solution is then desulfurized at 150 to 200 ° C. -330312).
b. A method of directly producing lithium sulfide by reacting lithium hydroxide and hydrogen sulfide at 150 to 200 ° C. in an aprotic organic solvent (Japanese Patent Laid-Open No. 7-330312).
c. A method of reacting lithium hydroxide and a gaseous sulfur source at a temperature of 130 to 445 ° C. (Japanese Patent Laid-Open No. 9-283156).

  There is no restriction | limiting in particular as a purification method of the lithium sulfide obtained as mentioned above. As a preferable purification method, for example, the method described in International Publication No. WO2005 / 40039 and the like can be mentioned.

  Specifically, the lithium sulfide obtained as described above is washed at a temperature of 100 ° C. or higher using an organic solvent. The organic solvent used for washing is preferably an aprotic polar solvent, and more preferably, the aprotic organic solvent used for lithium sulfide production and the aprotic polar organic solvent used for washing are the same. .

  Examples of the aprotic polar organic solvent preferably used for washing include aprotic polar organic compounds such as amide compounds, lactam compounds, urea compounds, organic sulfur compounds, cyclic organophosphorus compounds, Or it can use suitably as a mixed solvent. In particular, N-methyl-2-pyrrolidone (NMP) is selected as a good solvent.

  The amount of the organic solvent used for washing is not particularly limited, and the number of times of washing is not particularly limited, but is preferably 2 or more. Cleaning is preferably performed under an inert gas such as nitrogen or argon.

  The washed lithium sulfide is dried at a temperature equal to or higher than the boiling point of the organic solvent used for washing for 5 minutes or more, preferably about 2 to 3 hours or more under an inert gas stream such as nitrogen under normal pressure or reduced pressure. Thus, lithium sulfide suitably used in the present invention can be obtained.

P ₂ S ₅ can be used without particular limitation as long as it is industrially manufactured and sold. In place of P ₂ S ₅ , elemental phosphorus (P) and elemental sulfur (S) in a corresponding molar ratio can also be used. Simple phosphorus (P) and simple sulfur (S) can be used without particular limitation as long as they are industrially produced and sold.

  In the present invention, as the solid electrolyte, both a glassy solid electrolyte and a solid electrolyte containing a crystal component can be used. The type should be selected according to the required characteristics. Both may be used.

The mixing molar ratio of the lithium sulfide to diphosphorus pentasulfide or simple phosphorus and simple sulfur is usually 50:50 to 80:20, preferably 60:40 to 75:25.
Particularly preferably, it is about Li ₂ S: P ₂ S ₅ = 68: 32 to 74:26 (molar ratio).

  Examples of the method for producing a sulfide glass that is a glassy electrolyte include a melt quenching method and a mechanical milling method.

In the case of the melt quenching method, a predetermined amount of P ₂ S ₅ and Li ₂ S are mixed in a mortar, and the pellets are placed in a carbon-coated quartz tube and sealed in a vacuum. After reacting at a predetermined reaction temperature, the glass is put into ice and quenched to obtain a sulfide glass.

  The reaction temperature at this time is preferably 400 ° C to 1000 ° C, more preferably 800 ° C to 900 ° C. Moreover, reaction time becomes like this. Preferably it is 0.1 to 12 hours, More preferably, it is 1 to 12 hours. The quenching temperature of the reaction product is usually 10 ° C. or lower, preferably 0 ° C. or lower, and the cooling rate is about 1 to 10,000 K / sec, preferably 1 to 1000 K / sec.

In the case of the MM method, sulfide glass is obtained by mixing a predetermined amount of P ₂ S ₅ and Li ₂ S in a mortar and reacting for a predetermined time by a mechanical milling method.

  The mechanical milling method using the above raw materials can be reacted at room temperature. According to the MM method, since a glassy electrolyte can be produced at room temperature, there is an advantage that a raw material is not thermally decomposed and a glassy electrolyte having a charged composition can be obtained. Further, the MM method has an advantage that the glassy electrolyte can be made into fine powder simultaneously with the production of the glassy electrolyte.

  Although various types of pulverization methods can be used for the MM method, it is particularly preferable to use a planetary ball mill. The planetary ball mill can efficiently generate very high impact energy by rotating the platform while the pot rotates.

  Although the rotation speed and rotation time of the MM method are not particularly limited, the faster the rotation speed, the faster the glassy electrolyte production rate, and the longer the rotation time, the higher the conversion rate of the raw material into the glassy electrolyte.

The electrolyte thus obtained is a glassy electrolyte and usually has an ionic conductivity of about 1.0 × 10 ^{−5 to} 8.0 × 10 ⁻⁴ (S / cm).

  As conditions for the MM method, for example, when a planetary ball mill is used, the rotational speed may be set to several tens to several hundreds of revolutions / minute, and the treatment may be performed for 0.5 hours to 100 hours.

  Although specific examples of the sulfide glass by the melt quenching method and the MM method have been described above, manufacturing conditions such as temperature conditions and processing time can be appropriately adjusted according to the equipment used.

  Thereafter, the obtained sulfide glass is heat-treated at a predetermined temperature to produce a solid electrolyte containing a crystal component.

  The heat treatment temperature for producing such a solid electrolyte is preferably 190 ° C to 340 ° C, more preferably 195 ° C to 335 ° C, and particularly preferably 200 ° C to 330 ° C. When the temperature is lower than 190 ° C., it may be difficult to obtain a crystal with high ion conductivity. When the temperature is higher than 340 ° C., a crystal with low ion conductivity may be generated.

  The heat treatment time is preferably 3 to 240 hours, particularly preferably 4 to 230 hours, when the temperature is 190 ° C or higher and 220 ° C or lower. When the temperature is higher than 220 ° C and not higher than 340 ° C, 0.1 to 240 hours are preferable, 0.2 to 235 hours are particularly preferable, and 0.3 to 230 hours are more preferable. If the heat treatment time is shorter than 0.1 hour, it may be difficult to obtain a crystal with high ion conductivity. If the heat treatment time is longer than 240 hours, a crystal with low ion conductivity may be formed.

The lithium ion conductive inorganic solid electrolyte containing the crystal component thus obtained usually has an ionic conductivity of about 7.0 × 10 ^{−4 to} 5.0 × 10 ⁻³ (S / cm). It is.

This lithium ion conductive inorganic solid electrolyte has 2θ = 17.8 ± 0.3 deg, 18.2 ± 0.3 deg, 19.8 ± 0.3 deg, X-ray diffraction (CuKα: λ = 1.5418４), 21.8 ± 0.3 deg, 23.8 ± 0.3 deg, 25.9 ± 0.3 deg
It is preferable to have diffraction peaks at g, 29.5 ± 0.3 deg, 30.0 ± 0.3 deg. A solid electrolyte having such a crystal structure has extremely high lithium ion conductivity.

  As the conductive assistant, for example, a conductive substance such as acetylene black, carbon black, and carbon nanotube, a conductive polymer such as polyaniline, polyacetylene, and polypyrrole, or a mixture thereof can be used.

The electrode mixture of the present invention is a mixture of a lithium ion conductive inorganic solid electrolyte and a conductive additive dispersed in a solvent, filled inside the porous active material described above by dipping, vacuum impregnation, etc. It can be prepared by removing the solvent.
In addition to the above method, the electrode composite of the present invention can also be obtained by a method in which a mixed powder of a lithium ion conductive inorganic solid electrolyte and a conductive additive is made into a fine powder form to impart fluidity, and the porous active material is filled with the powder as it is. Can be produced.

  The all-solid-state secondary battery of the present invention comprises a positive electrode, a negative electrode, and a solid electrolyte layer composed of a lithium ion conductive inorganic solid electrolyte sandwiched between the positive electrode and the negative electrode, and at least one of the positive electrode and the negative electrode is It consists of an electrode mixture.

FIG. 1 is a schematic cross-sectional view showing an embodiment of an all solid state secondary battery according to the present invention.
In the all-solid-state secondary battery 1, the solid electrolyte layer 20 is sandwiched between a pair of electrodes including a positive electrode 10 and a negative electrode 30, and at least one of the positive electrode 10 and the negative electrode 30 is made of the electrode mixture of the present invention. Current collectors 40 and 42 are provided on the positive electrode 10 and the negative electrode 30, respectively.

As described above, at least one of the positive electrode 10 and the negative electrode 30 is made of the electrode mixture of the present invention, and the other can be formed using a known material.
For example, the positive electrode 10 can be manufactured using a positive electrode mixture composed of a positive electrode active material and a lithium ion conductive inorganic solid electrolyte.

A commercially available positive electrode active material can be used without particular limitation, and a composite oxide of lithium and a transition metal can be suitably used. Specifically, the following materials and similar materials having different composition ratios of the respective elements can be used, and LiCoO ₂ , LiNiCoO ₂ , LiNiO ₂ , LiNiMnCoO ₂ , LiFeMnO ₂ , Li ₂ PtO ₃ , LiMnNiO ₄ , LiMn ₂ Examples include O ₄ , LiNiMnO ₂ , LiNiVO ₄ , LiCrMnO ₄ , LiFePO ₄ , LiFe (SO ₄ ) ₃ , LiCoVO ₄ , LiCoPO ₄ , S, and the like. Although there is no restriction | limiting in particular regarding a particle size, The thing with an average particle diameter of several micrometers-10 micrometers can be used suitably.

  A positive electrode mixture is produced by mixing the positive electrode active material and the lithium ion conductive inorganic solid electrolyte at a predetermined ratio. As a ratio, it can use in the ratio of 20 wt%-95 wt% as solid weight% (wt%) of a positive electrode active material. More preferably, it is 50 wt%-90 wt%, and a more suitable ratio is 60 wt%-80 wt%. As a method of mixing, in addition to a method of mixing the dried powder with an agate mortar or the like, a method of directly adding to an organic solvent and mixing can be used.

  The positive electrode 10 can be produced by forming the positive electrode mixture in a film shape on at least a part of the current collector 40. As a film forming method, in addition to a method of forming a mixed liquid composed of a positive electrode mixture and a solvent, for example, a blast method, an aerosol deposition method, a cold spray method, a sputtering method, a vapor phase growth method, a pressure press A method or a thermal spraying method can also be used. By forming a film by such a method, the porosity of the positive electrode can be further reduced, and electron conduction, electron exchange, and ion conduction can be improved.

  The negative electrode 30 can be produced in the same manner as the positive electrode 10. As a negative electrode material used for preparation of the negative electrode 30, what is used as a negative electrode active material in the battery field | area can be used. For example, carbon materials, specifically artificial graphite, graphite carbon fiber, resin-fired carbon, pyrolytic vapor-grown carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin-fired carbon, polyacene, pitch-based carbon Examples include fibers, vapor grown carbon fibers, natural graphite, and non-graphitizable carbon. Or it may be a mixture thereof. Preferably, it is artificial graphite. Moreover, the metal itself of metal lithium, metal indium, metal aluminum, or metal silicon, or the alloy which combined these metals with another element or compound can be used as a negative electrode material.

The solid electrolyte layer 20 can be manufactured by depositing a particulate lithium ion conductive inorganic solid electrolyte by, for example, a blast method or an aerosol deposition method. Also, a lithium ion conductive inorganic solid electrolyte can be formed by a cold spray method, a sputtering method, a vapor deposition method (chemical vapor deposition: CVD), a thermal spraying method, or the like.
Further, there is a method in which a solution in which a lithium ion conductive inorganic solid electrolyte is mixed with a solvent or a binder (such as a binder or a polymer compound) is applied and applied, and then the solvent is removed to form a film. Also, the solid electrolyte itself, solid electrolyte and binder (binder, polymer compound, etc.) and support (materials and compounds to reinforce the strength of the solid electrolyte layer and prevent short circuit of the solid electrolyte itself) are mixed -It is also possible to form a film by pressing the combined electrolyte under pressure.

Although a solvent will not be specifically limited if it does not have a bad influence on the performance of solid electrolyte, For example, a non-aqueous solvent is mentioned.
Examples of the non-aqueous solvent include solvents used in electrolyte solutions such as dry heptane, toluene, hexane, tetrahydrofuran (THF), N methylpyrrolidone, acetonitrile, dimethoxyethane, and dimethyl carbonate, and preferably have a water content. The solvent is 100 ppm or less, more preferably 50 ppm or less.

As the binder, a thermoplastic resin or a thermosetting resin can be used. For example, polysiloxane, polyalkylene glycol, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer ( FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer ( ETFE resin), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene -Chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer (Na ⁺⁾ ion crosslinked product of polymer or the material, ethylene - (Na ⁺⁾ ion crosslinked product of methacrylic acid copolymer or the materials, ethylene - methyl acrylate copolymer or (Na ⁺⁾ ion crosslinked body, ethylene - can be given (Na ⁺⁾ ion crosslinked product of methyl methacrylate copolymer or the material.

  Among these, polysiloxane, polyalkylene glycol, polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE) are preferable.

As the current collectors 40 and 42, a plate or foil made of copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, indium, lithium, or an alloy thereof, or the like Can be used.
The current collectors 40 and 42 may be the same as or different from each other. For example, a copper foil may be used for the current collector 40 and an aluminum foil may be used for the current collector 42.

The all-solid-state secondary battery can be manufactured by bonding and joining the battery members described above. As a method of joining, there are a method of laminating each member, pressurizing and pressure bonding, a method of pressing through two rolls (roll to roll), and the like.
Moreover, you may join to the joining surface through the active material which has ion conductivity, and the adhesive material which does not inhibit ion conductivity.
In joining, heat fusion may be performed as long as the crystal structure of the solid electrolyte does not change.

The electrode mixture of the present invention can be used for an electrode of an all-solid secondary battery.
The all-solid-state secondary battery of the present invention can be used as a battery for a portable information terminal, a portable electronic device, a small electric power storage device for home use, a motorcycle using a motor as a power source, an electric vehicle, a hybrid electric vehicle, or the like.

It is a schematic sectional drawing which shows one Embodiment of the all-solid-state lithium battery of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 All-solid-state secondary battery 10 Positive electrode 20 Solid electrolyte layer 30 Negative electrode 40,42 Current collector

Claims (5)

  An electrode mixture formed by filling a porous active material with a lithium ion conductive inorganic solid electrolyte and a conductive additive.   The electrode mixture according to claim 1, wherein the porous active material is a transition metal oxide.   The electrode mixture according to claim 1, wherein the porous active material is Al, Sn, Si, In, or a composite of one or more of these metals and Li.   The electrode mixture according to any one of claims 1 to 3, wherein the lithium ion conductive inorganic solid electrolyte contains one or more elements selected from the group consisting of P, Si and B, Li and S. A positive electrode and a negative electrode;
An all-solid secondary battery comprising a solid electrolyte layer comprising a lithium ion conductive inorganic solid electrolyte sandwiched between the positive electrode and the negative electrode,
The all-solid-state secondary battery in which at least one of the said positive electrode and a negative electrode consists of the electrode compound material in any one of Claims 1-4.

Images