WO2022202866A1 - 全固体二次電池 - Google Patents

全固体二次電池 Download PDF

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Publication number
WO2022202866A1
WO2022202866A1 PCT/JP2022/013369 JP2022013369W WO2022202866A1 WO 2022202866 A1 WO2022202866 A1 WO 2022202866A1 JP 2022013369 W JP2022013369 W JP 2022013369W WO 2022202866 A1 WO2022202866 A1 WO 2022202866A1
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Prior art keywords
solid electrolyte
layer
electrolyte layer
layers
positive electrode
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PCT/JP2022/013369
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English (en)
French (fr)
Japanese (ja)
Inventor
啓子 竹内
一正 田中
佳太郎 大槻
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TDK Corp
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TDK Corp
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Priority to DE112022001730.9T priority Critical patent/DE112022001730T5/de
Priority to US18/277,663 priority patent/US20240128516A1/en
Priority to CN202280023430.8A priority patent/CN117099239A/zh
Priority to JP2023509230A priority patent/JPWO2022202866A1/ja
Publication of WO2022202866A1 publication Critical patent/WO2022202866A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid secondary battery. This application claims priority based on Japanese Patent Application No. 2021-051470 filed in Japan on March 25, 2021, the content of which is incorporated herein.
  • Lithium ion secondary batteries which are currently in general use, conventionally use an electrolyte (electrolyte solution) such as an organic solvent as a medium for transferring ions.
  • electrolyte electrolyte solution
  • organic solvent organic solvent
  • the solid electrolyte that constitutes an all-solid-state battery is dense. I had a problem.
  • the D50% particle size of the crystal grains of the phosphate-based solid electrolyte is 0.5 ⁇ m or less, and the D90% particle size of the crystal grains is 3 ⁇ m or less. This improves the surface roughness of the green sheet and suppresses the occurrence of short circuits.
  • Patent Document 1 cannot sufficiently obtain the effect of suppressing crack generation due to volumetric expansion and contraction.
  • An object of the present invention is to provide an all-solid secondary battery with good short-circuit resistance.
  • the present invention provides the following means.
  • An all-solid secondary battery includes a plurality of positive electrode layers including a positive electrode active material layer, a plurality of negative electrode layers including a negative electrode active material layer, and a plurality of solid electrolytes including a solid electrolyte.
  • the positive electrode layer and the negative electrode layer have a laminated body alternately laminated with the solid electrolyte layer interposed therebetween, wherein the plurality of solid electrolyte layers include the A first outer solid electrolyte layer and a second outer solid electrolyte layer respectively disposed on both end side sides in the stacking direction of the laminate, and an inner solid electrolyte layer disposed between the first outer solid electrolyte layer and the second outer solid electrolyte layer and an electrolyte layer (having a thickness of t a ), wherein at least one of the first outer solid electrolyte layer and the second outer solid electrolyte layer has the thickness of the inner solid electrolyte layer thick outer solid electrolyte layer (thickness t bn (1 ⁇ n)>t a ).
  • the thick-film outer solid electrolyte layer is composed of a plurality of solid electrolyte layers, and the thickness of the plurality of solid electrolyte layers increases toward the end.
  • the thick-film outer solid electrolyte layer is composed of a plurality of solid electrolyte layers, and in the plurality of solid electrolyte layers, a thick-film outer solid electrolyte layer disposed at the end portion
  • the solid electrolyte may have a crystal structure of any one of a Nasicon type, a garnet type, or a perovskite type.
  • FIG. 1 is an external view of an all-solid secondary battery according to one embodiment of the present invention
  • FIG. It is an outline view of a layered product concerning one embodiment of the present invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram of an example of the all-solid secondary battery which concerns on 1st Embodiment of this invention.
  • FIG. 4 is a schematic cross-sectional view of another example of the all-solid secondary battery according to the second embodiment of the present invention;
  • All-solid secondary batteries include all-solid lithium-ion secondary batteries, all-solid sodium-ion secondary batteries, all-solid magnesium-ion secondary batteries, and the like.
  • An all-solid lithium ion secondary battery will be described below as an example, but the present invention is applicable to all solid-state secondary batteries in general.
  • An all-solid secondary battery includes a laminate having a first electrode layer, a second electrode layer, and a solid electrolyte layer.
  • One of the first electrode layer and the second electrode layer functions as a positive electrode, and the other functions as a negative electrode.
  • the first electrode layer is assumed to be a positive electrode layer
  • the second electrode layer is assumed to be a negative electrode layer.
  • the all-solid secondary battery 100 of the first embodiment has a laminate 10 , a positive electrode external electrode 60 and a negative electrode external electrode 70 .
  • the laminate 10 is a hexahedron having four side surfaces 21, 22, 23, 24, an upper surface 25, and a lower surface 26.
  • a positive electrode external electrode 60 and a negative electrode external electrode 70 are formed on either side of a pair of opposing electrodes.
  • the positive electrode external electrode 60 and the negative electrode external electrode 70 are formed on the side surface 21 and the side surface 22 of the laminate 10 of FIG.
  • the all-solid secondary battery 100 includes a plurality of positive electrode layers 1 each having a positive electrode current collector layer 1A, a positive electrode active material layer 1B, and a side margin layer 3, a negative electrode current collector layer 2A, a negative electrode active material layer 2B, and side margins. It has a laminate 10 in which a plurality of negative electrode layers 2 having layers 3 are alternately laminated with solid electrolyte layers 5 interposed therebetween.
  • the plurality of solid electrolyte layers 5 includes first outer solid electrolyte layers 5BA and second outer solid electrolyte layers 5BA and 5BA disposed on both ends 10a and 10b (upper surface 25 side and lower surface 26 side) in the stacking direction (z direction) of the laminate 10. and an inner solid electrolyte layer 5A (having a thickness of t a ) disposed between the first outer solid electrolyte layer 5BA and the second outer solid electrolyte layer 5BA, and the first outer solid electrolyte layer
  • Both 5BA and second outer solid electrolyte layer 5BB are thick outer solid electrolyte layers 5B (thickness t bn (1 ⁇ n)>t a ) thicker than inner solid electrolyte layer 5A.
  • the thickness tbn of at least one of the outer solid electrolyte layers is preferably larger than the thickness t a of the inner solid electrolyte layer, and preferably 1.2 times or more the thickness t a .
  • the thickness tbn of the outer solid electrolyte layer it is practically assumed to be twice or less the thickness of the inner solid electrolyte layer.
  • the "solid electrolyte layer” in the “plurality of solid electrolyte layers” refers to those interposed between the positive electrode layer and the negative electrode layer. Therefore, the later-described "outer layer (reference numeral 4 in FIG.
  • the first outer solid electrolyte layer 5BA and the second outer solid electrolyte layer 5BA are the outermost on the +z side and the outermost on the ⁇ z side in the stacking direction (z direction) of the laminate 10. refers to one or more solid electrolyte layers placed in the The all-solid secondary battery 100 shown in FIG. In the all-solid secondary battery 100 shown in FIG. 3, the outer layers 4 on both outer sides of the laminate 10 have the same thickness, but may have different thicknesses.
  • the active material layer expands and contracts due to charging and discharging reactions.
  • the entire laminate including the solid electrolyte layer expands and contracts.
  • the degree of expansion and contraction differs between adjacent or adjacent layers, stress is generated and cracks are likely to occur.
  • the electrode layers and the solid electrolyte layers are arranged regularly, and each layer is in an almost equivalent environment, but in the vicinity of the end of the laminate, expansion and contraction do not occur. Due to the difference in expansion and contraction with the surrounding environment (circuit board, etc.), stress concentrates and cracks are likely to occur.
  • the outer layer 4 does not have an active material layer and does not expand or contract. Concentrate and crack more easily. Therefore, in the all-solid secondary battery of the present invention, the solid electrolyte layer disposed at the end of the laminate is thicker than the solid electrolyte layer disposed at the inner portion, so that the solid electrolyte layer expands and contracts. The purpose is to reduce the amount of stress and alleviate stress concentration.
  • the "thick-film outer solid electrolyte layer” may be one layer or multiple layers, but all the solid electrolyte layers constituting the "thick-film outer solid electrolyte layer” must be thicker than the "inner solid electrolyte layer”. requires. All of the “inner solid electrolyte layers” have the same thickness ta .
  • the solid electrolyte layers 5BA1, 5BA2, 5BA3, 5BB1, 5BB2, and 5BB3 are made up of 5BB2 and 5BB3, and the layers located closer to the ends 10a and 10b are thicker. That is, the thicknesses t b1 , t b2 and t b3 of the solid electrolyte layers 5BA1, 5BA2 and 5BA3 are in the relationship of t b1 >t b2 >t b3 .
  • the thicknesses t b1′ , t b2′ and t b3′ have a relationship of t b1′ >t b2′ >t b3′ .
  • the plurality of solid electrolyte layers constituting thick-film outer solid electrolyte layer 5B are more effective in alleviating stress concentration when the thickness gradually increases toward the ends 10a and 10b.
  • each of the first outer solid electrolyte layer 5BA and the second outer solid electrolyte layer 5BB which are the thick-film outer solid electrolyte layer 5B, is composed of three layers. or the number of layers other than three. Also, the number of layers of the first outer solid electrolyte layer 5BA and the number of layers of the second outer solid electrolyte layer 5BB may be different.
  • the thicknesses of the outer solid electrolyte layers are t bn and t bn ' respectively, tb (n+1) ⁇ tbn ⁇ tb (n+1) ⁇ 2 t b(n+1) ' ⁇ t bn ' ⁇ t b(n+1) ' ⁇ 2
  • It is preferable to have a relationship of The inequality sign on the left indicates that the inner solid electrolyte layer disposed on the end side is thicker or equal in thickness to the inner solid electrolyte layer disposed on the inner side.
  • the inequality sign on the right side indicates that the thickness of the inner solid electrolyte layer disposed on the end side is smaller than twice the thickness of the inner solid electrolyte layer disposed on the inner side.
  • the thick-film outer solid electrolyte layer arranged at the end portion 10a in the stacking direction is assumed to be the first thick-film outer solid electrolyte layer from the end portion 10a side, and its thickness is tb1 .
  • the thick-film outer solid electrolyte layer arranged at the end 10b in the stacking direction is the first thick-film outer solid electrolyte layer from the end 10b side, and its thickness is t b1 '. If the difference in thickness between adjacent solid electrolyte layers of the plurality of solid electrolyte layers constituting thick-film outer solid electrolyte layer 5B becomes too large, the effect of alleviating stress concentration is weakened. , the mitigation effect increases.
  • both the first outer solid electrolyte layer 5BA and the second outer solid electrolyte layer 5BB are thicker than the thickness of the inner solid electrolyte layer 5A.
  • the thick-film outer solid electrolyte layer 5B is the thick-film outer solid electrolyte layer 5B
  • an example all-solid secondary battery 101 according to the second embodiment shown in FIG. This is an example of a configuration in which only one first outer solid electrolyte layer 5BA of 5BB is a thick outer solid electrolyte layer 5B thicker than the inner solid electrolyte layer 5A. In this case, only the solid electrolyte layer closest to the end portion 10b is the second outer solid electrolyte layer 5BB, and the solid electrolyte layer inside thereof is the inner solid electrolyte layer 5A.
  • 3 ⁇ q is preferably When the number of thick-film outer solid electrolyte layers is three or more, the effect of alleviating stress concentration is high.
  • the thick-film outer solid electrolyte layer and the inner solid electrolyte layer preferably have solid electrolytes with the same crystal structure.
  • the solid electrolytes constituting the thick-film outer solid electrolyte layer and the inner solid electrolyte layer preferably have a crystal structure of any one of Nasicon type, garnet type, or perovskite type, which exhibits high ionic conductivity.
  • the thick-film outer solid electrolyte layer and the inner solid electrolyte layer have solid electrolytes with the same crystal structure, so charging and discharging reactions occur uniformly in both. Therefore, since the stress load due to the volume expansion is uniformly generated on both sides, cracks inside the laminate are suppressed, and the short-circuit resistance of the battery is improved.
  • each layer constituting the all-solid secondary battery according to the present embodiment will be described in detail below.
  • the active material either one or both of the positive electrode active material and the negative electrode active material
  • the collector either one or both of the positive electrode current collector layer and the negative electrode current collector layer
  • the collector One or both of the positive electrode active material layer and the negative electrode active material layer are collectively called the active material layer
  • one or both of the positive electrode and the negative electrode are collectively called the electrode.
  • Either one or both of the electrode and the negative external electrode may be generically called an external electrode.
  • the solid electrolyte layers are not particularly limited, and consist of, for example, nasicon-type, garnet-type, perovskite-type, and lysicone-type crystal structures.
  • a solid electrolyte having any one crystal structure selected from the group may be included.
  • general solid electrolyte materials such as oxide-based lithium ion conductors having nasicon-type, garnet-type, perovskite-type, and lysicone-type crystal structures can be used.
  • Li (lithium) and M is at least one of Ti (titanium), Zr (zirconium), Ge (germanium), Hf (hafnium) and Sn (tin)), P (phosphorus) and O (oxygen) ) and an ionic conductor having a Nasicon-type crystal structure (for example, Li 1+x Al x Ti 2-x (PO 4 ) 3 ; LATP), and Li (lithium), Zr (zirconium) and La ( an ion conductor having a garnet-type crystal structure containing at least lanthanum) and O (oxygen) (for example, Li 7 La 3 Zr 2 O 12 ; LLZ), or an ion conductor having a garnet-like structure; and an ion conductor having a perovskite structure containing at least Li (lithium), Ti (titanium), La (lanthanum), and O (oxygen) (for example, Li 3x La 2/3-x TiO 3 ; LLTO); ,
  • a plurality of positive electrode layers 1 and negative electrode layers 2 are provided in the laminate 10 and face each other with the solid electrolyte layers interposed therebetween.
  • the positive electrode layer 1 has a positive electrode current collector layer 1A, a positive electrode active material layer 1B, and side margin layers 3.
  • the negative electrode layer 2 has a negative electrode collector layer 2A and a negative electrode active material layer 2B.
  • the positive electrode active material layer 1B and the negative electrode active material layer 2B contain known materials capable of intercalating and deintercalating at least lithium ions as the positive electrode active material and the negative electrode active material.
  • a conductive aid and a conductive ion aid may be included.
  • the positive electrode active material and the negative electrode active material are preferably capable of efficiently intercalating and deintercalating lithium ions.
  • the thicknesses of the positive electrode active material layer 1B and the negative electrode active material layer 2B are not particularly limited, they can be in the range of 0.5 ⁇ m or more and 5.0 ⁇ m or less as an example.
  • positive electrode active materials and negative electrode active materials include transition metal oxides and transition metal composite oxides.
  • the positive electrode active material and the negative electrode active material of the present embodiment preferably contain a phosphoric acid compound as a main component.
  • a phosphoric acid compound as a main component.
  • one or more elements selected from Ti, Al, and Zr lithium vanadium phosphate (LiVOPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 4 (VO) (PO 4 ) 2 ), lithium vanadium pyrophosphate ( Li 2 VOP 2 O 7 , Li 2 VP 2 O 7 ) and Li 9 V 3 (P 2 O 7 ) 3 (PO 4 ) 2 are preferably one or more.
  • Examples of the negative electrode active material include Li metal, Li—Al alloy, Li—In alloy, carbon, silicon (Si), silicon oxide (SiO x ), lithium titanate (Li 4 Ti 5 O 12 ), oxide Titanium ( TiO2 ) can be used.
  • the active materials that constitute the positive electrode active material layer 1B or the negative electrode active material layer 2B there is no clear distinction between the active materials that constitute the positive electrode active material layer 1B or the negative electrode active material layer 2B.
  • a compound exhibiting a nobler potential can be used as the positive electrode active material
  • a compound exhibiting a more base potential can be used as the negative electrode active material.
  • the same material may be used for the positive electrode active material layer 1B and the negative electrode active material layer 2B as long as it is a compound that simultaneously releases lithium ions and absorbs lithium ions.
  • Examples of conductive aids include carbon materials such as carbon black, acetylene black, ketjen black, carbon nanotubes, graphite, graphene, and activated carbon, and metal materials such as gold, silver, palladium, platinum, copper, and tin.
  • an ion-conducting aid is a solid electrolyte.
  • a material similar to the material used for the solid electrolyte layers 5A and 5B can be used.
  • a solid electrolyte is used as the ion-conducting auxiliary, it is preferable to use the same material for the ion-conducting auxiliary, the first outer solid electrolyte layer, the second outer solid electrolyte layer, and the inner solid electrolyte layer.
  • Positive electrode current collector and negative electrode current collector It is preferable to use a material having high electrical conductivity as the material constituting the positive electrode current collector layer 1A and the negative electrode current collector layer 2A.
  • a material having high electrical conductivity For example, silver, palladium, gold, platinum, aluminum, copper, nickel, etc. are preferably used. preferable.
  • copper is more preferable because it hardly reacts with the oxide-based lithium ion conductor and has the effect of reducing the internal resistance of the all-solid secondary battery.
  • Materials constituting the positive electrode current collector layer 1A and the negative electrode current collector layer 2A may be the same material or different materials.
  • the thicknesses of the positive electrode current collector 1A and the negative electrode current collector 2A are not particularly limited, they can be in the range of 0.5 ⁇ m or more and 30 ⁇ m or less as an example.
  • the positive electrode current collector layer 1A and the negative electrode current collector layer 2A preferably contain a positive electrode active material and a negative electrode active material, respectively.
  • the positive electrode current collector layer 1A and the negative electrode current collector layer 2A contain the positive electrode active material and the negative electrode active material respectively, the positive electrode current collector layer 1A and the positive electrode active material layer 1B and the negative electrode current collector layer 2A and the negative electrode active material This is desirable because it improves the adhesion with the substance layer 2B.
  • the ratio of the positive electrode active material and the negative electrode active material in the positive electrode current collector layer 1A and the negative electrode current collector layer 2A of the present embodiment is not particularly limited as long as they function as current collectors. , or the volume ratio of the negative electrode current collector and the negative electrode active material is preferably in the range of 90/10 to 70/30.
  • the side margin layer 3 is preferably provided to eliminate a step between the solid electrolyte layer and the positive electrode layer 1 and a step between the solid electrolyte layer and the negative electrode layer 2 . Therefore, the side margin layers 3 indicate regions other than the positive electrode layer 1 . The presence of such side margin layers 3 eliminates the step between the solid electrolyte layer and the positive electrode layer 1 and the negative electrode layer 2, so that the denseness of the electrodes is increased, and delamination due to firing of the all-solid secondary battery is achieved. (delamination) and warping are less likely to occur.
  • the material forming the side margin layer 3 preferably contains, for example, the same material as the solid electrolyte layer. Therefore, it is preferable to include an oxide-based lithium ion conductor having a nasicon-type, garnet-type, or perovskite-type crystal structure.
  • Li and M is at least one of Ti (titanium), Zr (zirconium), Ge (germanium), Hf (hafnium), Sn (tin)) as a lithium ion conductor having a Nasicon type crystal structure ), P and O, and a garnet-type crystal structure containing at least Li, Zr, La, and O, or an ion conductor having a garnet-like structure.
  • the all-solid secondary battery according to the present embodiment it is possible to suppress the occurrence of cracks and improve short-circuit resistance.
  • the outer layer 4 is provided in either one or both regions (both in FIG. 3) outside the positive electrode layer 1 (positive electrode current collector layer 1A) and the negative electrode layer 2 (negative electrode current collector layer 2A) in the stacking direction. placed.
  • the outer layer 4 the same material as the solid electrolyte layer may be used.
  • the stacking direction corresponds to the z direction in FIG.
  • the thickness of the outer layer 4 is not particularly limited, it is, for example, 20 ⁇ m or more and 100 ⁇ m or less.
  • the thickness is 20 ⁇ m or more, the positive electrode layer 1 or the negative electrode layer 2 closest to the surface in the stacking direction of the laminate 10 is less likely to be oxidized due to the influence of the atmosphere in the firing process, so that the capacity is high and the environment is high temperature and high humidity. Also, sufficient moisture resistance is ensured, resulting in a highly reliable all-solid secondary battery.
  • the thickness is 100 ⁇ m or less, the all-solid secondary battery has a high volumetric energy density.
  • the all-solid secondary battery of the present invention can be manufactured by the following procedure.
  • a simultaneous firing method may be used, or a sequential firing method may be used.
  • the co-firing method is a method of stacking materials for forming each layer and producing a laminate by batch firing.
  • the sequential firing method is a method in which each layer is produced in order, and a firing step is entered every time each layer is produced.
  • the use of the co-firing method can reduce the number of working steps for the all-solid secondary battery.
  • the use of the co-firing method makes the resulting laminate more dense. A case of using the simultaneous firing method will be described below as an example.
  • the co-firing method includes a process of creating a paste of each material constituting the laminate, a process of applying and drying the paste to fabricate a green sheet, and a process of stacking the green sheets and firing the fabricated laminate at the same time.
  • a paste can be obtained by mixing the powder of each material with a vehicle.
  • the vehicle is a general term for a medium in a liquid phase, and includes solvents, binders, and the like.
  • the binder contained in the paste for molding the green sheet or printed layer is not particularly limited, but polyvinyl acetal resin, cellulose resin, acrylic resin, urethane resin, vinyl acetate resin, polyvinyl alcohol resin, etc. can be used.
  • the slurry can include at least one of the resins.
  • the paste may contain a plasticizer.
  • the type of plasticizer is not particularly limited, but phthalates such as dioctyl phthalate and diisononyl phthalate may be used.
  • a positive electrode current collector layer paste, a positive electrode active material layer paste, a solid electrolyte layer paste, a negative electrode active material layer paste, a negative electrode current collector layer paste, and a side margin layer paste are produced.
  • a green sheet is produced.
  • a green sheet is obtained by coating the prepared paste on a base material such as PET (polyethylene terephthalate) in a desired order, drying it if necessary, and peeling off the base material.
  • the method of applying the paste is not particularly limited. For example, known methods such as screen printing, coating, transfer, and doctor blade can be employed.
  • the prepared solid electrolyte layer paste is applied to a desired thickness on a base material such as polyethylene terephthalate (PET) and dried as necessary to prepare a solid electrolyte green sheet (inner solid electrolyte layer).
  • the solid electrolyte green sheet (first outer solid electrolyte layer) and the solid electrolyte green sheet (second outer solid electrolyte layer) are prepared by the same procedure. to make. At least one of the first outer solid electrolyte layer and the second outer solid electrolyte layer is a thick outer solid electrolyte layer thicker than the inner solid electrolyte layer.
  • the method for producing the green sheet for solid electrolyte is not particularly limited, and known methods such as doctor blade method, die coater, comma coater, gravure coater, etc. can be adopted.
  • the positive electrode active material layer 1B, the positive electrode current collector layer 1A, and the positive electrode active material layer 1B are printed and laminated in order on the solid electrolyte green sheet by screen printing to form the positive electrode layer 1. Furthermore, in order to fill the step between the solid electrolyte green sheet and the positive electrode layer 1, a side margin layer 3 is formed in a region other than the positive electrode layer 1 by screen printing, and a positive electrode unit (solid electrolyte layer, positive electrode layer 1 and side margins) is formed. layer 3) is produced. A positive electrode unit is prepared for each of the thick film outer solid electrolyte layer and the inner solid electrolyte layer.
  • the negative electrode unit can also be produced in the same manner as the positive electrode unit.
  • the positive electrode unit and the negative electrode unit are alternately offset so that one end of the positive electrode and one end of the negative electrode are not aligned, and are stacked up to a predetermined number of layers, thereby forming an element of an all-solid secondary battery.
  • a laminated substrate is produced.
  • the laminated substrate can be provided with outer layers on both main surfaces of the laminated body, if necessary.
  • the same material as the solid electrolyte layer can be used, for example, a green sheet for solid electrolyte can be used.
  • the first outer solid electrolyte layer and the second outer solid electrolyte layer may be provided in one layer or in multiple layers (at multiple locations).
  • a parallel-type all-solid secondary battery is manufactured. It is sufficient to stack the layers without allowing them to overlap.
  • the produced laminated substrate can be collectively pressurized by a mold press, hot water isostatic press (WIP), cold water isostatic press (CIP), isostatic press, etc., to improve adhesion.
  • Pressurization is preferably performed while heating, and can be performed at, for example, 40 to 95°C.
  • the produced laminated substrate can be cut into unfired all-solid-state secondary battery laminates using a dicing machine.
  • the laminate is sintered by removing the binder and firing the laminate of the all-solid secondary battery. Debiking and firing can be performed at a temperature of 600° C. to 1000° C. in a nitrogen atmosphere.
  • the retention time for debaying and firing is, for example, 0.1 to 6 hours.
  • Barrel polishing is performed to prevent chipping and to expose the current collector layer on the end face by chamfering the corners of the laminate. It may be carried out on the laminate 10 of the unfired all-solid secondary battery, or may be carried out on the laminate 10 after firing. Barrel polishing methods include dry barrel polishing that does not use water and wet barrel polishing that uses water. When wet barrel polishing is performed, an aqueous solution such as water is separately introduced into the barrel polishing machine.
  • the barrel treatment conditions are not particularly limited, and can be adjusted as appropriate as long as defects such as cracks and chips do not occur in the laminate.
  • external electrodes can be provided in order to efficiently draw current from the laminate 10 of the all-solid secondary battery.
  • a positive electrode external electrode 60 and a negative electrode external electrode 70 are formed on a pair of opposing side surfaces 21 and 22 of the laminate 10 .
  • Methods for forming the external electrodes include a sputtering method, a screen printing method, a dip coating method, and the like.
  • a screen printing method and the dip coating method an external electrode paste containing metal powder, resin, and solvent is prepared and formed as external electrodes.
  • a baking process is performed to remove the solvent, and a plating process is performed to form terminal electrodes on the surfaces of the external electrodes.
  • the sputtering method external electrodes and terminal electrodes can be formed directly, so the baking process and the plating process are not required.
  • the laminate 10 of the all-solid secondary battery may be sealed in a coin cell, for example, in order to improve moisture resistance and impact resistance.
  • the sealing method is not particularly limited, and for example, the fired laminate may be sealed with a resin.
  • an insulating paste such as Al 2 O 3 may be applied or dip-coated around the laminate, and the insulating paste may be heat-treated for sealing.
  • the method for manufacturing an all-solid secondary battery including the step of forming the side margin layer using the side margin layer paste was illustrated, but the method for manufacturing an all-solid secondary battery according to this embodiment is It is not limited to this example.
  • the step of forming the side margin layers using the side margin layer paste may be omitted.
  • the side margin layer may be formed, for example, by deforming the solid electrolyte layer paste during the manufacturing process of the all-solid secondary battery.
  • Example 1 Preparation of positive electrode active material and negative electrode active material
  • a positive electrode active material and a negative electrode active material were produced by the following procedure. Li 2 CO 3 , V 2 O 5 and NH 4 H 2 PO 4 were used as starting materials, wet-mixed in a ball mill for 16 hours, and dehydrated and dried. The obtained powder is calcined in a nitrogen-hydrogen mixed gas at 850° C. for 2 hours, and after calcining, it is wet-pulverized again with a ball mill for 16 hours, and finally dehydrated and dried to obtain powders of the positive electrode active material and the negative electrode active material. got
  • the positive electrode active material paste and the negative electrode active material paste were prepared by adding 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent to 100 parts of the powder of the positive electrode active material and the negative electrode active material obtained together, and mixing and dispersing the mixture.
  • a positive electrode active material paste and a negative electrode active material paste were prepared.
  • Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (aluminum titanium phosphate) having a Nasicon type crystal structure lithium).
  • JCPDS card 35-0754: LiTi 2 (PO 4 ) 3 was referred to.
  • one of the sheets of the first outer solid electrolyte layer and one of the sheets of the second outer solid electrolyte layer, which are arranged inside thereof, have a thickness of 11 ⁇ m when the laminate chip is formed. made.
  • one of the sheets of the first outer solid electrolyte layer and one of the sheets of the second outer solid electrolyte layer, which are arranged further inside than the solid electrolyte layer arranged inside have a thickness when the laminate chip is formed. was made to have a thickness of 8 ⁇ m.
  • 25 sheets of the inner solid electrolyte layer were prepared with a thickness of 5 ⁇ m when the laminate chip was formed.
  • the Cu powder and the positive electrode active material and the negative electrode active material powder prepared were mixed so that the volume ratio was 80/20, and then 100 parts of the mixture and 10 parts of ethyl cellulose as a binder. and 50 parts of dihydroterpineol as a solvent were added and mixed and dispersed to prepare a positive electrode current collector layer paste and a negative electrode current collector layer paste.
  • thermosetting external electrode paste was prepared by mixing and dispersing Cu powder, an epoxy resin, and a solvent in a ball mill.
  • An all-solid secondary battery was produced by the following procedure.
  • a positive electrode active material layer having a thickness of 5 ⁇ m was printed on a portion of the main surface of the first outer solid electrolyte layer sheet using a screen printer, and dried at 80° C. for 10 minutes.
  • a positive electrode current collector layer having a thickness of 5 ⁇ m was printed on the positive electrode active material layer using a screen printer, and dried at 80° C. for 10 minutes.
  • a positive electrode active material layer having a thickness of 5 ⁇ m is formed by printing using a screen printer, and dried at 80° C. for 10 minutes to form a sheet main surface of the first outer solid electrolyte layer.
  • a positive electrode layer in which a positive electrode current collector layer was sandwiched between positive electrode active material layers was formed on a part of .
  • a solid electrolyte layer (side margin layer) having substantially the same height as the positive electrode layer is formed by printing on the sheet main surface of the first outer solid electrolyte layer where the positive electrode layer is not formed by printing, and the temperature is maintained at 80° C. for 10 minutes. Dried.
  • a positive electrode unit was produced in which the positive electrode layer and the solid electrolyte layer were printed and formed on the main surface of the first outer solid electrolyte layer.
  • a positive electrode unit was produced in which the positive electrode layer and the solid electrolyte layer were formed by printing on the main surfaces of the second outer solid electrolyte layer and the inner solid electrolyte layer.
  • a negative electrode unit was produced in the same manner as the positive electrode unit.
  • the positive electrode unit and the negative electrode unit were laminated while shifting one end of the positive electrode layer and the negative electrode layer.
  • the first and second outer solid electrolyte layers having a thickness of 17 ⁇ m are arranged at the first layer as the bottom layer and the 31st layer as the top layer.
  • the first and second outer solid electrolyte layers having a thickness of 11 ⁇ m are arranged on the 3rd layer and the 30th layer, and the first and second outer solid electrolyte layers having a thickness of 8 ⁇ m are arranged on the 3rd layer and the 29th layer.
  • the positive electrode unit and the negative electrode unit were alternately laminated in this order so that the inner solid electrolyte layer having a thickness of 5 ⁇ m was arranged on the 1st to 28th layers.
  • a laminated substrate composed of 3 second outer solid electrolyte layers, 25 inner solid electrolyte layers, and 3 first outer solid electrolyte layers arranged in order in the stacking direction, for a total of 31 solid electrolyte layers, was fabricated. .
  • a plurality of inner solid electrolyte layer sheets were laminated on the upper and lower surfaces of the laminated substrate, and an outer layer made of a solid electrolyte layer was provided.
  • the outer layers provided on the upper and lower surfaces were formed to have the same thickness.
  • the laminated substrate was thermo-compressed by a mold press, and then cut to produce a laminated chip.
  • the laminate chip was placed on a ceramics setter and kept at 600° C. for 2 hours in a nitrogen atmosphere to remove the binder. Then, the laminate chip was baked by holding at 750° C. for 2 hours in a nitrogen atmosphere, and taken out after natural cooling.
  • Example 1 An all-solid secondary battery according to Example 1 is produced. did.
  • Thickness evaluation of solid electrolyte layer Thickness evaluation of solid electrolyte layer
  • thickness tb of the first and second outer solid electrolyte layers tb1, tb2, tb3 , tb1, tb2', t b3′
  • FE-SEM field emission scanning electron microscope
  • a straight line perpendicular to the positive electrode active material layer 1B or the negative electrode active material layer 2B positioned at the end in the stacking direction is drawn in the center of the laminated cross-sectional photograph, and the adjacent positive electrode active material layer 1B and the negative electrode active material are drawn on the straight line.
  • the length between the layers 2B was defined as the thickness of the solid electrolyte layer sandwiched between the adjacent positive electrode active material layer 1B and negative electrode active material layer 2B.
  • the thickness of the solid electrolyte layer refers to the thickness of the solid electrolyte layer at the center of the laminate 10 in the width direction.
  • the width direction of the laminate is the direction in which the laminate 10 is sandwiched between the positive electrode external electrode 60 and the negative electrode external electrode 70, and refers to the x direction in FIG.
  • the thickness of the 1st and 31st layers was 17 ⁇ m
  • the thickness of the 2nd and 30th layers was 11 ⁇ m
  • the thickness of the 3rd and 29th layers was 8 ⁇ m
  • the thickness of the 4th to 28th layers was 5 ⁇ m. there were.
  • the ratio of the thickness of the innermost outer solid electrolyte layer to the thickness of the innermost outer solid electrolyte layer is 1.5 times (17 ⁇ m/11 ⁇ m), and the thickness ratio of the next inner adjacent outer solid electrolyte layers was about 1.4 times (11 ⁇ m/8 ⁇ m), and the thickness ratio between the inner solid electrolyte layer and the outer solid electrolyte layer adjacent to each other was 1.6 times (8 ⁇ m/5 ⁇ m).
  • the all-solid secondary battery according to Comparative Example 1 differs from Example 1 in that all 31 solid electrolyte layers have the same thickness of 5 ⁇ m. That is, the all-solid secondary battery according to Comparative Example 1 does not have a thick-film outer solid electrolyte layer.
  • the all-solid-state secondary battery according to Example 2 has a thickness of 9 ⁇ m for the 1st and 31st layers, a thickness of 7 ⁇ m for the 2nd and 30th layers, and a thickness of 6 ⁇ m for the 3rd and 29th layers. different from 1.
  • the ratio of the thickness of the innermost outer solid electrolyte layer to the thickness of the innermost outer solid electrolyte layer was about 1.3 times (9 ⁇ m/7 ⁇ m).
  • the thickness ratio between the inner adjacent outer solid electrolyte layers is about 1.2 times (7 ⁇ m/6 ⁇ m), and the thickness ratio between the inner adjacent outer solid electrolyte layer and the inner solid electrolyte layer is 1.2 times (6 ⁇ m). /5 ⁇ m).
  • the all-solid secondary battery according to Example 3 has a thickness of 13 ⁇ m for the 1st and 31st layers, a thickness of 12 ⁇ m for the 2nd and 30th layers, and a thickness of 11 ⁇ m for the 3rd and 29th layers. different from 1.
  • the ratio of the thickness of the outer solid electrolyte layer on the inner side to the thickness of the outer solid electrolyte layer on the most end side is about 1.1 times (13 ⁇ m/12 ⁇ m).
  • the thickness ratio between the inner adjacent outer solid electrolyte layers is about 1.1 times (12 ⁇ m/11 ⁇ m), and the thickness ratio between the inner adjacent outer solid electrolyte layer and the inner solid electrolyte layer is 2.2 times (11 ⁇ m). /5 ⁇ m).
  • Example 4 The all-solid secondary battery according to Example 4 differs from Example 1 in that the first to third layers and the 29th to 31st layers all have a thickness of 6 ⁇ m.
  • the ratio of the thickness of the outer solid electrolyte layer on the inner side to the thickness of the outer solid electrolyte layer on the most end side is 1 (6 ⁇ m/6 ⁇ m)
  • the thickness ratio between the outer solid electrolyte layers was 1 (6 ⁇ m/6 ⁇ m)
  • the thickness ratio between the inner solid electrolyte layer and the inner solid electrolyte layer was 1.2 (6 ⁇ m/5 ⁇ m). .
  • Example 5 In the all-solid secondary battery according to Example 5, the first and second outer solid electrolyte layers as thick-film outer solid electrolyte layers each consist of two layers, the first layer and the 31st layer having a thickness of 11 ⁇ m, and the second layer having a thickness of 11 ⁇ m. and the 30th layer differ from Example 1 in that the thickness is 8 ⁇ m.
  • the ratio of the thickness of the outer solid electrolyte layer on the inner side to the thickness of the outer solid electrolyte layer on the outermost side is about 1.4 times (11 ⁇ m/8 ⁇ m).
  • the thickness ratio of the adjacent outer solid electrolyte layer and the inner solid electrolyte layer was 1.6 times (8 ⁇ m/5 ⁇ m).
  • each of the first and second outer solid electrolyte layers as the thick-film outer solid electrolyte layer consists of two layers, the first layer and the 31st layer have a thickness of 12 ⁇ m, and the second layer has a thickness of 12 ⁇ m. and the 30th layer differ from Example 1 in that the thickness is 11 ⁇ m.
  • the ratio of the thickness of the outer solid electrolyte layer on the inner side to the thickness of the outer solid electrolyte layer on the outermost side is about 1.1 times (12 ⁇ m/11 ⁇ m).
  • the thickness ratio of the adjacent outer solid electrolyte layer and the inner solid electrolyte layer was 2.2 times (11 ⁇ m/5 ⁇ m).
  • Example 7 In the all-solid secondary battery according to Example 7, the first and second outer solid electrolyte layers as thick-film outer solid electrolyte layers each consist of one layer, and the first layer and the 31st layer have a thickness of 15 ⁇ m. It differs from Example 1. In the all-solid secondary battery according to Example 7, the ratio of the thickness of the inner solid electrolyte layer to the thickness of the outer solid electrolyte layer closest to the edge was three times (15 ⁇ m/5 ⁇ m).
  • Example 8 The all-solid secondary battery according to Example 8 has only the first outer solid electrolyte layer as the thick-film outer solid electrolyte layer, the first outer solid electrolyte layer consists of three layers, the 31st layer has a thickness of 17 ⁇ m, The difference from Example 1 is that the thickness of the 30th layer is 11 ⁇ m and the thickness of the 29th layer is 8 ⁇ m. Met.
  • the ratio of the thickness of the innermost outer solid electrolyte layer to the thickness of the innermost outer solid electrolyte layer is 1.5 times (17 ⁇ m/11 ⁇ m), and the thickness ratio of the next inner adjacent outer solid electrolyte layers was about 1.4 times (11 ⁇ m/8 ⁇ m), and the thickness ratio between the inner solid electrolyte layer and the outer solid electrolyte layer adjacent to each other was 1.6 times (8 ⁇ m/5 ⁇ m).
  • the all-solid secondary battery according to Example 9 has only the first outer solid electrolyte layer as the thick-film outer solid electrolyte layer, the first outer solid electrolyte layer consists of one layer, and the 31st layer has a thickness of 15 ⁇ m. A certain point is different from the first embodiment.
  • the ratio of the thickness of the inner solid electrolyte layer to the thickness of the outer solid electrolyte layer closest to the edge was three times (15 ⁇ m/5 ⁇ m).
  • CC charging constant current charging
  • CC discharge constant current charging
  • the above charging and discharging were regarded as one cycle, and the short-circuit occurrence rate was obtained from the number of short-circuited all-solid secondary batteries out of 100 all-solid secondary batteries obtained by repeating this cycle up to 1000 cycles.
  • a short circuit was determined when the voltage dropped sharply during CC charging and then stopped rising.
  • Table 1 shows the results of the short-circuit resistance test for the all-solid secondary batteries according to Examples 1 to 9 and Comparative Example 1.
  • the short circuit occurrence rate was 3%, showing the next highest short circuit resistance.
  • the short-circuit occurrence rate was 5%, and the thick-film outer solid electrolyte layers were provided at both ends of the laminate. It is the same as the short-circuit occurrence rate of Example 5 in which two layers are symmetrically provided on each end, but exhibits a higher short-circuit resistance than the short-circuit occurrence rate of Example 6 in which two layers are symmetrically provided on both ends. .
  • Example 7 the short-circuit occurrence rates of Examples 3 and 4 were lower than those of Example 7 in which one thick-film outer solid electrolyte layer was provided symmetrically at both ends of the laminate, and the short-circuit rates of Examples 5 and 6 were lower than those of Example 7. The incidence was lower than in Example 7.
  • the number of layers is generally in descending order (three layers, two layers, 1 layer order) has high short-circuit resistance.
  • Example 8 in which three thick-film outer solid electrolyte layers are provided at one end of the laminate, and Example 7, in which one thick-film outer solid electrolyte layer is symmetrically provided at both ends of the laminate. It showed the same short resistance.
  • Example 10-18 In the all-solid secondary batteries according to Examples 10 to 18, the solid electrolyte material of any one of the first and second outer solid electrolyte layers and the inner solid electrolyte layer or all the solid electrolyte materials is changed to a material other than LATP.
  • An all-solid secondary battery was produced in the same procedure as in Example 1 except that the procedure was the same as in Example 1, and the battery was evaluated in the same procedure as in Example 1.
  • Example 10 In the all-solid secondary battery according to Example 10, all the solid electrolyte materials of the first and second outer solid electrolyte layers and the inner solid electrolyte layer were changed to LZP (LiZr 2 (PO 4 ) 3 ). prepared an all-solid secondary battery in the same procedure as in Example 1, and evaluated the battery in the same procedure as in Example 1. A solid electrolyte of LZP was produced by the following synthesis method.
  • Example 11 In the all-solid secondary battery according to Example 11 , all the solid electrolyte materials of the first and second outer solid electrolyte layers and the inner solid electrolyte layer were changed to LLZ ( Li7La3Zr2O12 ). Except for this, an all-solid secondary battery was produced in the same procedure as in Example 1, and the battery was evaluated in the same procedure as in Example 1.
  • the LLZ solid electrolyte was produced by the following synthesis method.
  • the solid electrolyte obtained from XRD measurement and ICP analysis was confirmed to be Li7La3Zr2O12 .
  • Example 12 In the all-solid secondary battery according to Example 12, all the solid electrolyte materials of the first and second outer solid electrolyte layers and the inner solid electrolyte layer were changed to LLTO (Li 0.3 La 0.55 TiO 3 ). An all-solid secondary battery was produced in the same procedure as in Example 1 except that the procedure was the same as in Example 1, and the battery was evaluated in the same procedure as in Example 1. A solid electrolyte of LLTO was produced by the following synthesis method.
  • Example 13 In the all-solid secondary battery according to Example 13, all the solid electrolyte materials of the first and second outer solid electrolyte layers and the inner solid electrolyte layer were LSPO (Li 3.5 Si 0.5 P 0.5 O 4 ), an all-solid secondary battery was produced in the same procedure as in Example 1, and the battery was evaluated in the same procedure as in Example 1.
  • a solid electrolyte of LSPO was produced by the following synthesis method.
  • LSPO For LSPO, starting materials of Li 2 CO 3 , SiO 2 and commercially available Li 3 PO 4 were weighed so that the molar ratio was 2:1:1, and wet-mixed for 16 hours in a ball mill using water as a dispersion medium. After that, it was dehydrated and dried. The obtained powder was calcined at 950° C. for 2 hours in the air, wet-ground again for 16 hours with a ball mill, and finally dehydrated and dried to obtain a solid electrolyte powder. From the results of XRD measurement and ICP analysis, it was confirmed that the powder was Li 3.5 Si 0.5 P 0.5 O 4 (LSPO).
  • Example 14-18 In the all-solid secondary batteries according to Examples 14 to 18, the solid electrolyte material of the inner solid electrolyte layer was LATP, but the solid electrolyte material of the first and second outer solid electrolyte layers was changed to a material other than LATP. Except for this, an all-solid secondary battery was produced in the same procedure as in Example 1, and the battery was evaluated in the same procedure as in Example 1.
  • Example 14 An all-solid secondary battery according to Example 14 was fabricated in the same procedure as in Example 1, except that the solid electrolyte material of the first and second outer solid electrolyte layers was changed to LTP. , the battery was evaluated in the same procedure as in Example 1.
  • the solid electrolyte obtained from XRD measurement and ICP analysis was confirmed to be LiTi 2 (PO 4 ) 3 .
  • Example 15 An all-solid secondary battery according to Example 15 was produced in the same manner as in Example 1, except that the solid electrolyte material of the first and second outer solid electrolyte layers was changed to LAGP. , the battery was evaluated in the same procedure as in Example 1.
  • the solid electrolyte obtained from XRD measurement and ICP analysis was confirmed to be Li 1.3 Al 0.3 Ge 1.7 (PO 4 ) 3 .
  • Example 16 An all-solid secondary battery according to Example 16 was produced in the same manner as in Example 1, except that the solid electrolyte material of the first and second outer solid electrolyte layers was changed to LYZP. , the battery was evaluated in the same procedure as in Example 1.
  • Example 17 An all-solid secondary battery according to Example 18 was produced in the same procedure as in Example 1, except that the solid electrolyte material of the first and second outer solid electrolyte layers was changed to LLZ. , the battery was evaluated in the same procedure as in Example 1.
  • Example 18 An all-solid secondary battery according to Example 18 was manufactured in the same manner as in Example 1, except that the solid electrolyte materials of the first and second outer solid electrolyte layers were changed to LATP+LGPT. The battery was evaluated in the same procedure as in Example 1.
  • Table 2 shows the results of the short-circuit resistance test for the all-solid secondary batteries according to Examples 10-18. For reference, Table 2 also shows Example 1.
  • Example 1 in which it is LATP has the best short-circuit resistance.
  • other solid electrolyte materials Examples 10 to 13
  • the short circuit resistance was equivalent.
  • the solid electrolyte material of the inner solid electrolyte layer is LATP
  • the solid electrolyte material of the first and second outer solid electrolyte layers is solid
  • the short circuit resistance was better than when the electrolyte material was different from LATP (Examples 14 to 18).

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JP2008123953A (ja) * 2006-11-15 2008-05-29 Toyota Motor Corp 蓄電装置
JP2019140024A (ja) * 2018-02-14 2019-08-22 トヨタ自動車株式会社 被転写物上に固体電解質積層体を積層する方法
WO2019189007A1 (ja) * 2018-03-30 2019-10-03 本田技研工業株式会社 固体電池
JP2021027044A (ja) * 2019-08-05 2021-02-22 Tdk株式会社 全固体電池

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JP7045292B2 (ja) 2018-09-11 2022-03-31 太陽誘電株式会社 全固体電池、全固体電池の製造方法、および固体電解質ペースト
JP7161981B2 (ja) 2019-09-24 2022-10-27 Kddi株式会社 対象追跡手段の切り替えが可能な対象追跡プログラム、装置及び方法

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JP2008123953A (ja) * 2006-11-15 2008-05-29 Toyota Motor Corp 蓄電装置
JP2019140024A (ja) * 2018-02-14 2019-08-22 トヨタ自動車株式会社 被転写物上に固体電解質積層体を積層する方法
WO2019189007A1 (ja) * 2018-03-30 2019-10-03 本田技研工業株式会社 固体電池
JP2021027044A (ja) * 2019-08-05 2021-02-22 Tdk株式会社 全固体電池

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