WO2024237330A1 - 固体電解質シートおよび全固体電池 - Google Patents

固体電解質シートおよび全固体電池 Download PDF

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Publication number
WO2024237330A1
WO2024237330A1 PCT/JP2024/018276 JP2024018276W WO2024237330A1 WO 2024237330 A1 WO2024237330 A1 WO 2024237330A1 JP 2024018276 W JP2024018276 W JP 2024018276W WO 2024237330 A1 WO2024237330 A1 WO 2024237330A1
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Prior art keywords
solid electrolyte
sheet
solid
negative electrode
lithium
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PCT/JP2024/018276
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English (en)
French (fr)
Japanese (ja)
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春樹 上剃
健太郎 冨田
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Maxell Ltd
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Maxell Ltd
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Priority to JP2025520645A priority Critical patent/JPWO2024237330A1/ja
Priority to CN202480032318.XA priority patent/CN121285885A/zh
Priority to KR1020257038222A priority patent/KR20250172682A/ko
Priority to EP24807280.3A priority patent/EP4715929A1/en
Publication of WO2024237330A1 publication Critical patent/WO2024237330A1/ja
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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
    • H01M10/052—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
    • H01M10/056—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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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

Definitions

  • the present invention relates to a highly reliable all-solid-state battery and a solid electrolyte sheet that can be used to form the all-solid-state battery.
  • lithium batteries particularly lithium ion batteries, that can meet this demand use lithium-containing composite oxides such as lithium cobalt oxide ( LiCoO2 ) and lithium nickel oxide ( LiNiO2 ) as the positive electrode active material, graphite or the like as the negative electrode active material, and an organic electrolyte solution containing an organic solvent and a lithium salt as the non-aqueous electrolyte.
  • lithium-containing composite oxides such as lithium cobalt oxide ( LiCoO2 ) and lithium nickel oxide ( LiNiO2 ) as the positive electrode active material, graphite or the like as the negative electrode active material, and an organic electrolyte solution containing an organic solvent and a lithium salt as the non-aqueous electrolyte.
  • lithium-ion batteries As devices that use lithium-ion batteries continue to develop, there is a demand for longer life, higher capacity, and higher energy density lithium-ion batteries, as well as a high demand for the reliability of these longer life, higher capacity, and higher energy density lithium-ion batteries.
  • the organic electrolyte used in lithium-ion batteries contains organic solvents, which are flammable substances, and so there is a possibility that the organic electrolyte may generate abnormal heat if an abnormality such as a short circuit occurs in the battery. Furthermore, with the recent trend toward higher energy density in lithium-ion batteries and an increasing amount of organic solvent in the organic electrolyte, there is a demand for even greater reliability in lithium-ion batteries.
  • all-solid-state lithium batteries (all-solid-state batteries) that do not use organic solvents are also being considered.
  • All-solid-state lithium batteries use a molded solid electrolyte that does not use organic solvents instead of the conventional organic solvent-based electrolyte, and are highly reliable with no risk of abnormal heat generation from the solid electrolyte. For this reason, there are high expectations for them, especially in product areas that require high-capacity secondary batteries.
  • Solid-state batteries are also highly reliable and environmentally resistant, and have a long lifespan, making them promising maintenance-free batteries that can contribute to social development while also continuing to contribute to safety and security.
  • Providing solid-state batteries to society can contribute to the achievement of Goal 3 (Ensure healthy lives and promote well-being for all at all ages), Goal 7 (Ensure access to affordable, reliable, sustainable and modern energy for all), Goal 11 (Make cities and human settlements inclusive, safe, resilient and sustainable), and Goal 12 (Ensure sustainable consumption and production patterns) out of the 17 Sustainable Development Goals (SDGs) established by the United Nations.
  • SDGs Sustainable Development Goals
  • Patent Documents 1 to 4 propose filling the voids in a porous substrate such as a nonwoven fabric with a solid electrolyte to create a solid electrolyte sheet that combines lithium ion conductivity and strength, and using this solid electrolyte sheet to construct an all-solid-state secondary battery.
  • Patent Document 4 shows that by making the thickness of the porous substrate 70% or more of the overall thickness of the solid electrolyte sheet, the mechanical strength of the solid electrolyte sheet can be improved, and damage to the solid electrolyte and its falling off from the porous substrate can be prevented even if the area of the solid electrolyte sheet is increased.
  • Patent Document 4 makes it possible to increase the size of an all-solid-state battery, thereby increasing its capacity.
  • the problem of short circuits caused by lithium dendrites that precipitate during charging becomes more likely to occur. Therefore, in all-solid-state batteries, there is a demand for improving reliability so that the occurrence of such problems can be better suppressed even when an attempt is made to increase the capacity.
  • the present invention was made in consideration of the above circumstances, and its purpose is to provide a highly reliable all-solid-state battery and a solid electrolyte sheet that can be used to form the all-solid-state battery.
  • the solid electrolyte sheet of the present invention comprises a porous substrate and a solid electrolyte held in the porous substrate, and has a solid electrolyte layer A containing a solid electrolyte a that reacts with metallic lithium to oxidize lithium, and a solid electrolyte layer B containing a solid electrolyte b that is less reactive with metallic lithium than the solid electrolyte a, and the solid electrolyte layer B is disposed on at least one surface of the solid electrolyte sheet.
  • the all-solid-state battery of the present invention is characterized in that it comprises a positive electrode, a negative electrode, and a solid electrolyte layer, has the solid electrolyte sheet of the present invention as the solid electrolyte layer, and the solid electrolyte layer B of the solid electrolyte sheet faces the negative electrode.
  • the present invention provides a highly reliable all-solid-state battery and a solid electrolyte sheet that can be used to form the all-solid-state battery.
  • FIG. 1 is a cross-sectional view illustrating a schematic example of a solid electrolyte sheet of the present invention.
  • FIG. 2 is a cross-sectional view illustrating a schematic diagram of another example of the solid electrolyte sheet of the present invention.
  • FIG. 1 is a cross-sectional view illustrating a schematic diagram of an example of an all-solid-state battery of the present invention.
  • FIG. 13 is a graph showing the voltage change during the charge-discharge cycle of a cell using the solid electrolyte sheet of Comparative Example 1.
  • the solid electrolyte sheet of the present invention comprises a porous substrate and a solid electrolyte held on the porous substrate, and has a solid electrolyte layer A containing a solid electrolyte a that reacts with metallic lithium to oxidize lithium, and a solid electrolyte layer B containing a solid electrolyte b that is less reactive with metallic lithium than the solid electrolyte a, and the solid electrolyte layer B is disposed on at least one surface of the solid electrolyte sheet.
  • an all-solid-state battery having the solid electrolyte sheet of the present invention as a solid electrolyte layer even if lithium dendrites precipitate on the surface of the negative electrode during charging, the growth of lithium dendrites is inhibited within the solid electrolyte layer (solid electrolyte sheet) by solid electrolyte a, which reacts with metallic lithium contained in solid electrolyte layer A to oxidize lithium, and prevents the lithium dendrites from reaching the positive electrode. Therefore, by using the solid electrolyte sheet of the present invention, it is possible to form an all-solid-state battery that can prevent the occurrence of short circuits due to the precipitation of lithium dendrites.
  • the solid electrolyte sheet of the present invention also has a solid electrolyte layer B containing a solid electrolyte b that is less reactive with metallic lithium than the solid electrolyte a, in addition to the solid electrolyte layer A.
  • the solid electrolyte layer B can contain the solid electrolyte b, such as a sulfide-based solid electrolyte having an argyrodite structure. Therefore, in the solid electrolyte sheet of the present invention, the solid electrolyte layer A can efficiently suppress the growth of lithium ion dendrites, while the solid electrolyte layer B can ensure good lithium ion conductivity.
  • an all-solid-state battery having the solid electrolyte sheet of the present invention (the all-solid-state battery of the present invention)
  • the occurrence of a short circuit due to lithium dendrites can be suppressed while ensuring good battery characteristics, thereby improving the reliability.
  • the solid electrolyte sheet 10 in FIG. 1 is a two-layered sheet having a solid electrolyte layer A20 containing a solid electrolyte a that reacts with metallic lithium to oxidize lithium, and a solid electrolyte layer B30 containing a solid electrolyte b that is less reactive with metallic lithium than the solid electrolyte a.
  • the solid electrolyte sheet 10 has a porous substrate, and the solid electrolyte layer A20 and the solid electrolyte layer B30 share the porous substrate.
  • At least a portion of the solid electrolyte layer A20 is formed by holding the solid electrolyte a in the pores of the porous substrate.
  • At least a portion of the solid electrolyte layer B30 is formed by holding the solid electrolyte b in the pores of the porous substrate.
  • the solid electrolyte sheet 11 in FIG. 2 is a three-layered sheet having solid electrolyte layers B30, 30 above and below the solid electrolyte layer A20.
  • the solid electrolyte sheet 11 also has a porous substrate, and the solid electrolyte layer A20 and the two solid electrolyte layers B30, 30 share the porous substrate.
  • the solid electrolyte layer A20 is formed in its entirety with solid electrolyte a held within the pores of the porous substrate.
  • the two solid electrolyte layers B30 are formed in at least a portion with solid electrolyte b held within the pores of the porous substrate.
  • solid electrolyte layer B is disposed on at least one surface of the solid electrolyte sheet.
  • solid electrolyte layer B is disposed on at least one surface of the solid electrolyte sheet.
  • the ends of the porous substrate may be exposed on the surface of the solid electrolyte sheet together with the solid electrolyte, but it is preferable that the surface of the solid electrolyte sheet and its vicinity are composed only of the solid electrolyte (and a binder, etc., which will be described later) without the porous substrate.
  • the porous substrate may be present over the entire thickness direction of the solid electrolyte sheet, but in order to prevent the porous substrate from impeding ion conduction at the interface between the positive and negative electrodes and the solid electrolyte sheet, it is preferable that the porous substrate is present only in a portion (the inner side of the solid electrolyte sheet) of the solid electrolyte layer A and solid electrolyte layer B arranged on the surface of the solid electrolyte sheet, and the surface of the solid electrolyte sheet and its vicinity are formed only of the solid electrolyte (and a binder, etc.). In other words, it is preferable that the surface of the porous substrate in the solid electrolyte sheet is covered with the solid electrolyte (and a binder, etc.).
  • one of the solid electrolyte layers A and B may be configured to have a porous substrate in part or in its entirety, and the other may be configured to have no porous substrate [formed only of a solid electrolyte (and binder, etc.)].
  • one of the two solid electrolyte layers B may be configured to have a porous substrate in part or in its entirety, and the other may be configured to have no porous substrate [formed only of a solid electrolyte (and binder, etc.)].
  • the solid electrolyte layer A of the solid electrolyte sheet contains a solid electrolyte a that reacts with metallic lithium to oxidize lithium, and the solid electrolyte may include at least one element selected from Ti, Ge, Sn , Al, and Si.
  • Specific examples of such solid electrolytes include La0.05Li0.35TiO3 (LLTO), Li1.5Al0.5Ge1.5 ( PO4 ) 3 ( LAGP ), Li10SnP2S12 ( LSPS ), Li1.4Al0.5Ti1.6 ( PO4 ) 3 ( LATP), Li10GeP2S12 ( LGPS ), Li2O - Al2O3 - SiO2 - P2O5 - TiO2 , and the like .
  • a solid electrolyte b having a lower reactivity with metallic lithium than the solid electrolyte a may be contained (for example, a mixture of the solid electrolyte a and the solid electrolyte b may be contained in the solid electrolyte layer A).
  • the solid electrolyte b include various solid electrolytes exemplified below.
  • solid electrolytes it is preferable to use a sulfide-based solid electrolyte, and it is more preferable to use a solid electrolyte having an argyrodite structure, since this can further improve the lithium ion conductivity of the solid electrolyte layer A and further enhance the characteristics of the all-solid-state battery formed using the solid electrolyte sheet.
  • the content of solid electrolyte a in the total solid electrolyte contained in solid electrolyte layer A is preferably 10 mass % or more, more preferably 20 mass % or more, and particularly preferably 40 mass % or more.
  • the upper limit of the content of solid electrolyte a in the entire solid electrolyte contained in the solid electrolyte layer A is 100 mass%.
  • the content of solid electrolyte a in the entire solid electrolyte contained in the solid electrolyte layer A is preferably 90 mass% or less, and more preferably 80 mass% or less.
  • the solid electrolyte b contained in the solid electrolyte layer B is less reactive with metallic lithium than the solid electrolyte a, and preferably has little or no effect of reacting with metallic lithium to oxidize lithium, and is not particularly limited as long as it has lithium ion conductivity; for example, a sulfide-based solid electrolyte, a hydride-based solid electrolyte, or a halide-based solid electrolyte can be used.
  • the solid electrolyte of the solid electrolyte layer B may be composed only of the solid electrolyte b, but may also contain the solid electrolyte a to the extent that it does not inhibit the battery reaction.
  • Examples of sulfide-based solid electrolytes include particles of Li 2 S-P 2 S 5 , Li 2 S-SiS 2 , Li 2 S-P 2 S 5 -GeS 2 , and Li 2 S-B 2 S 3 -based glass.
  • Examples of hydride-based solid electrolytes include LiBH 4 , solid solutions of LiBH 4 and the following alkali metal compounds (for example, those in which the molar ratio of LiBH 4 to the alkali metal compound is 1:1 to 20:1), etc.
  • Examples of the alkali metal compounds in the solid solutions include at least one selected from the group consisting of lithium halides (LiI, LiBr, LiF, LiCl, etc.), rubidium halides (RbI, RbBr, RbF, RbCl, etc.), cesium halides (CsI, CsBr, CsF, CsCl, etc.), lithium amide, rubidium amide, and cesium amide.
  • lithium halides LiI, LiBr, LiF, LiCl, etc.
  • rubidium halides RbI, RbBr, RbF, RbCl, etc.
  • cesium halides CsI, CsBr, CsF, Cs
  • Other known solid electrolytes that can be used include those described in, for example, WO 2020/070958 and WO 2020/070955.
  • solid electrolyte b of the solid electrolyte layer B only one of the above-mentioned examples may be used, or two or more of them may be used in combination.
  • sulfide-based solid electrolytes are preferred because of their high lithium ion conductivity, sulfide-based solid electrolytes containing Li and P are more preferred, and sulfide-based solid electrolytes having an argyrodite structure, which have particularly high lithium ion conductivity and high chemical stability, are even more preferred.
  • the solid electrolyte contained in the solid electrolyte layer A and the solid electrolyte contained in the solid electrolyte layer B are preferably particles, and the size of the particles is preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less, from the viewpoint of improving the filling property into the pores of the porous substrate and ensuring good lithium ion conductivity and lithium dendrite growth suppression function.
  • the solid electrolyte particles are preferably bound using a binder in order to be well retained in the pores of the porous substrate and to be well adhered to the surface of the porous substrate, but in that case, a larger amount of binder is required, and there is a risk of the resistance value increasing. Therefore, the average particle size of the solid electrolyte particles is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the average particle diameter of the solid electrolyte particles and other particles means the 50% diameter value (D50) in the volume-based integrated fraction when the integrated volume is determined from particles with small particle sizes using a particle size distribution measurement device (such as the Microtrack particle size distribution measurement device " HRA9320 " manufactured by Nikkiso Co., Ltd.).
  • the porous substrate of the solid electrolyte sheet may be made of a fibrous material, such as woven fabric, nonwoven fabric, or mesh, with nonwoven fabric being the most preferred.
  • the fiber diameter of the fibrous material that constitutes the porous substrate is preferably 5 ⁇ m or less, and preferably 0.5 ⁇ m or more.
  • the material of the fibrous material is not particularly limited as long as it does not react with metallic lithium and has insulating properties.
  • resins such as polyolefins such as polypropylene and polyethylene; polystyrene; aramid; polyamide-imide; polyimide; nylon; polyesters such as polyethylene terephthalate (PET); polyarylate; cellulose and modified cellulose; etc.
  • Inorganic materials such as glass, alumina, silica, and zirconia may also be used.
  • a preferred material is polyarylate.
  • the fibrous material may be made of one or more of the materials listed above.
  • the porous substrate may be made of only fibrous materials of the same material, or may be made of a combination of two or more fibrous materials of different materials.
  • the basis weight of the porous substrate is preferably 10 g/m2 or less, and more preferably 8 g/ m2 or less , so as to hold a sufficient amount of solid electrolyte to ensure good lithium ion conductivity and good lithium dendrite growth inhibition function, and from the viewpoint of ensuring sufficient strength, is preferably 3 g/m2 or more, and more preferably 4 g/ m2 or more .
  • a binder to bind the solid electrolyte so that the solid electrolyte is well retained within the pores of the porous substrate and the solid electrolyte covering the surface of the porous substrate is more closely adhered to the porous substrate, thereby improving the shape retention of the solid electrolyte sheet.
  • the binder for the solid electrolyte sheet is preferably one that does not react with the solid electrolyte, and at least one resin selected from the group consisting of butyl rubber, chloroprene rubber, acrylic resin, and fluororesin is preferably used.
  • the thickness of the solid electrolyte sheet is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of optimizing the distance between the positive and negative electrodes of the battery using the solid electrolyte sheet and suppressing the occurrence of short circuits and increases in resistance, and is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the thickness of the porous substrate is preferably 85% or less, and more preferably 80% or less, of the thickness of the solid electrolyte sheet, from the viewpoint of ensuring smooth movement of lithium ions on the positive electrode side and smooth movement of lithium ions on the negative electrode side, as well as better suppressing the precipitation of lithium dendrites that cause charging abnormalities, with the solid electrolyte covering the surface of the porous substrate having the above-mentioned thickness.
  • the porous substrate serves as a component for improving the shape retention of the solid electrolyte sheet, but if the ratio of the thickness of the porous substrate to the solid electrolyte sheet is too small, the shape retention of the solid electrolyte sheet may decrease. Furthermore, when the ratio of the thickness of the porous substrate to the solid electrolyte sheet is relatively large, the effect of smoothing the movement of lithium ions on the positive electrode side and the negative electrode side, as well as suppressing metal precipitation that causes charging abnormalities, becomes more pronounced. For these reasons, the thickness of the porous substrate is preferably 30% or more of the thickness of the solid electrolyte sheet, and more preferably 50% or more.
  • Specific thickness of the porous substrate is, for example, preferably 3 ⁇ m or more, more preferably 8 ⁇ m or more, and preferably 45 ⁇ m or less, more preferably 25 ⁇ m or less.
  • the thickness of the solid electrolyte layer A (if the solid electrolyte sheet has a plurality of solid electrolyte layers A, the total thickness of the layers) is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more, from the viewpoint of better ensuring the effect of suppressing the growth of lithium dendrites.
  • the upper limit of the thickness of the solid electrolyte layer A is set within a range that satisfies the suitable thickness of the solid electrolyte sheet described above and the suitable thickness of the solid electrolyte layer B described below.
  • the thickness of the solid electrolyte layer B (if the solid electrolyte sheet has a plurality of solid electrolyte layers B, the total thickness of the layers) is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more, from the viewpoint of ensuring good lithium ion conductivity.
  • the upper limit of the thickness of the solid electrolyte layer B is set within a range that satisfies the above-mentioned suitable thickness of the solid electrolyte sheet and the suitable thickness of the solid electrolyte layer A.
  • the proportion of the porous substrate in the solid electrolyte sheet is preferably 30% by volume or less, and more preferably 25% by volume or less, from the viewpoint of ensuring good lithium ion conductivity.
  • the proportion of the porous substrate in the solid electrolyte sheet is preferably 5% by volume or more, and more preferably 10% by volume or more.
  • the content of the binder in the solid electrolyte sheet is preferably 0.5 mass% or more, and more preferably 1 mass% or more, of the total amount of the solid electrolyte and binder, from the viewpoint of further improving the shape retention of the solid electrolyte sheet, and from the viewpoint of limiting the amount of the binder to some extent and suppressing the decrease in lithium ion conductivity, it is preferably 5 mass% or less, and more preferably 3 mass% or less.
  • the method for producing the solid electrolyte sheet there are no particular limitations on the method for producing the solid electrolyte sheet, but it is preferable to produce the sheet by a method including a step of dispersing the solid electrolyte and a binder, which is used as necessary, in a solvent to prepare a slurry for forming solid electrolyte layer A and a slurry for forming solid electrolyte layer B, and then successively filling these slurries into the voids of the porous substrate in a wet manner (filling step).
  • the voids of the porous substrate are filled with the slurries while forming coatings of these slurries on the surface of the porous substrate. This method improves the strength of the solid electrolyte sheet and makes it easier to produce a large-area solid electrolyte sheet.
  • Screen printing, doctor blade, immersion, and other coating methods can be used to fill the voids in the porous substrate with a slurry containing a solid electrolyte, and to form a coating film of the slurry on the surface of the porous substrate.
  • the slurry is prepared by adding the solid electrolyte and, if necessary, a binder to a solvent and mixing them. It is preferable to select a solvent for the slurry that does not easily deteriorate the solid electrolyte.
  • a solvent for the slurry that does not easily deteriorate the solid electrolyte.
  • non-polar aprotic solvents such as hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, decalin, toluene, and xylene.
  • an ultra-dehydrated solvent with a water content of 0.001 mass% (10 ppm) or less.
  • fluorine-based solvents such as “Vertrel (registered trademark)” manufactured by Mitsui DuPont Fluorochemicals, “Zeorolla (registered trademark)” manufactured by Nippon Zeon Co., Ltd., and “Novec (registered trademark)” manufactured by Sumitomo 3M Co., Ltd., as well as non-aqueous organic solvents such as dichloromethane and diethyl ether can also be used.
  • the solvent in the slurry is removed by drying, and a solid electrolyte sheet can be obtained by performing pressure molding as necessary.
  • the method for manufacturing the solid electrolyte sheet is not limited to the wet method.
  • the solid electrolyte or a mixture of the solid electrolyte and the binder may be filled in a dry manner, and then pressure molding may be performed.
  • a sheet obtained by molding the mixture of the solid electrolyte and the binder may be attached to the surface of a sheet in which the voids in the porous substrate are filled with the solid electrolyte.
  • the all-solid-state battery of the present invention includes a positive electrode, a negative electrode, and a solid electrolyte layer, and has the solid electrolyte sheet of the present invention as the solid electrolyte layer, and the solid electrolyte layer B of the solid electrolyte sheet faces the negative electrode.
  • the all-solid-state battery of the present invention includes a primary battery and a secondary battery.
  • FIG. 3 A cross-sectional view showing a schematic example of an all-solid-state battery of the present invention is shown in FIG. 3.
  • the battery 100 shown in FIG. 3 has a positive electrode 200, a negative electrode 300, and a solid electrolyte sheet 400 interposed between the positive electrode 200 and the negative electrode 300 enclosed in an exterior body formed of an exterior can 500, a sealing can 600, and a resin gasket 700 interposed between them.
  • the sealing can 600 fits into the opening of the exterior can 500 via a gasket 700, and the open end of the exterior can 500 is tightened inward, so that the gasket 700 comes into contact with the sealing can 600, sealing the opening of the exterior can 500 and creating an airtight structure inside the battery.
  • the outer can and the sealing can can be made of stainless steel or the like.
  • the gasket can be made of polypropylene, nylon, or other materials.
  • fluororesins such as tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), or heat-resistant resins with melting points exceeding 240°C, such as polyphenylene ether (PEE), polysulfone (PSF), polyarylate (PAR), polyethersulfone (PES), polyphenylene sulfide (PPS), and polyetheretherketone (PEEK), can also be used.
  • PEE polyphenylene ether
  • PES polysulfone
  • PPS polyphenylene sulfide
  • PEEK polyetheretherketone
  • Examples of the positive electrode of the all-solid-state battery include a structure in which a layer (positive electrode mixture layer) made of a molded body of a positive electrode mixture containing a positive electrode active material and a solid electrolyte is formed on a current collector, a structure made of only a molded body of a positive electrode mixture (pellets, etc.), and a structure in which a positive electrode mixture containing a positive electrode active material and a solid electrolyte is filled into the pores of a conductive porous substrate.
  • the positive electrode active material can be the same as the positive electrode active material used in conventionally known non-aqueous electrolyte primary batteries.
  • manganese dioxide, lithium-containing manganese oxide e.g., LiMn 3 O 6 , or a composite oxide having the same crystal structure as manganese dioxide ( ⁇ -type, ⁇ -type, or a structure in which ⁇ -type and ⁇ -type are mixed, etc.
  • lithium-containing composite oxide such as Li a Ti 5/3 O 4 (4/3 ⁇ a ⁇ 7/3); vanadium oxide; niobium oxide; titanium oxide; sulfides such as iron disulfide; graphite fluoride; silver sulfides such as Ag 2 S; nickel oxides such as NiO 2 ; and the like.
  • the positive electrode active material may be the same as the positive electrode active material used in conventionally known non-aqueous electrolyte secondary batteries, etc.
  • a spinel-type lithium manganese composite oxide represented by LiMrMn2-rO4 (wherein M is at least one element selected from the group consisting of Li, Na, K, B, Mg, Ca, Sr, Ba, Ti, V, Cr, Zr, Fe, Co, Ni, Cu, Zn, Al, Sn, Sb, In, Nb, Ta, Mo, W, Y, Ru , and Rh, and 0 ⁇ r ⁇ 1)
  • LirMn (1-s-r) NisMtO (2-u) Fv a layered compound represented by LiCo 1-r M r O 2 (wherein M is at least one element selected from the group consisting of Co, Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Zr, Mo, Sn,
  • the average particle size of the positive electrode active material is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less.
  • the positive electrode active material may be either primary particles or secondary particles formed by agglomeration of primary particles.
  • the positive electrode active material has a reaction suppression layer on its surface to suppress reaction with the solid electrolyte contained in the positive electrode.
  • the solid electrolyte may oxidize and form a resistive layer, which may reduce the ionic conductivity in the positive electrode.
  • the reaction suppression layer may be made of a material that has ion conductivity and can suppress the reaction between the particles of the electrode active material (positive electrode active material) and the solid electrolyte.
  • materials that can form the reaction suppression layer include oxides containing Li and at least one element selected from the group consisting of Nb, P, B, Si, Ge, Ti, Zr, Ta and W, more specifically, Nb-containing oxides such as LiNbO 3 , Li 3 PO 4 , Li 3 BO 3 , Li 2 SO 4 , Li 4 SiO 4 , Li 4 GeO 4 , LiTiO 3 , LiZrO 3 , Li 2 WO 4 and the like.
  • the reaction suppression layer may contain only one of these oxides, or may contain two or more of them, and further, a plurality of these oxides may form a composite compound.
  • these oxides it is preferable to use an Nb-containing oxide, and it is more preferable to use LiNbO3 .
  • the reaction suppression layer is preferably present on the surface in an amount of 0.1 to 1.0 parts by mass per 100 parts by mass of the positive electrode active material. This range allows for good suppression of the reaction between the positive electrode active material and the solid electrolyte.
  • Methods for forming a reaction suppression layer on the surface of the positive electrode active material include the sol-gel method, mechanofusion method, CVD method, PVD method, and ALD method.
  • the content of the positive electrode active material in the positive electrode mixture is preferably 60 to 85 mass % in order to increase the energy density of the all-solid-state battery.
  • the positive electrode mixture can contain a conductive assistant.
  • a conductive assistant include carbon materials such as graphite (natural graphite, artificial graphite), graphene, carbon black, carbon nanofibers, and carbon nanotubes.
  • carbon materials such as graphite (natural graphite, artificial graphite), graphene, carbon black, carbon nanofibers, and carbon nanotubes.
  • the conductive assistant when the conductive assistant is contained in the positive electrode mixture, the content is preferably 1.0 parts by mass or more, preferably 7.0 parts by mass or less, and more preferably 6.5 parts by mass or less, when the content of the positive electrode active material is 100 parts by mass.
  • the positive electrode mixture may contain a binder.
  • a binder is a fluororesin such as polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the positive electrode mixture may not contain a binder if good moldability can be ensured in forming the positive electrode without using a binder, such as when a sulfide-based solid electrolyte is contained in the positive electrode mixture (described later).
  • the positive electrode mixture requires a binder, its content is preferably 15% by mass or less, and preferably 0.5% by mass or more. On the other hand, if the positive electrode mixture can obtain moldability without requiring a binder, its content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0% by mass (i.e., no binder is contained).
  • the positive electrode mixture can contain a solid electrolyte.
  • the solid electrolyte contained in the positive electrode mixture is not particularly limited as long as it has lithium ion conductivity, and for example, the same as the solid electrolyte b or solid electrolyte a in the solid electrolyte sheet can be used.
  • sulfide-based solid electrolytes are preferred because they have high lithium ion conductivity and also have the function of increasing the formability of the positive electrode mixture, and sulfide-based solid electrolytes having an argyrodite structure are more preferred.
  • the average particle size of the solid electrolyte is preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more, from the viewpoint of reducing grain boundary resistance, while it is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less, from the viewpoint of forming a sufficient contact interface between the active material and the solid electrolyte.
  • the content of the solid electrolyte in the positive electrode mixture is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, when the content of the positive electrode active material is 100 parts by mass.
  • the content of solid electrolyte in the positive electrode mixture is preferably 65 parts by mass or less, and more preferably 60 parts by mass or less, when the content of the positive electrode active material is 100 parts by mass.
  • the current collector can be a metal foil such as aluminum or stainless steel; a sheet-like conductive porous substrate such as punched metal, net, expanded metal, or foamed metal; or a carbon sheet.
  • a foamed metal porous body As the sheet-like conductive porous substrate, it is preferable to use a foamed metal porous body.
  • a specific example of a foamed metal porous body is "Celmet (registered trademark)" by Sumitomo Electric Industries, Ltd.
  • the positive electrode can be manufactured by applying a positive electrode mixture-containing composition (paste, slurry, etc.) made by dispersing a positive electrode active material and a solid electrolyte, as well as conductive additives and binders, which are added as necessary, in a solvent, to a current collector, drying the composition, and then, if necessary, subjecting the composition to pressure molding, such as calendaring, to form a positive electrode mixture compact (positive electrode mixture layer) on the surface of the current collector.
  • a positive electrode mixture-containing composition paste, slurry, etc.
  • a positive electrode active material and a solid electrolyte as well as conductive additives and binders, which are added as necessary, in a solvent
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode mixture compact may be formed by compressing the positive electrode mixture prepared by mixing the positive electrode active material and solid electrolyte with conductive additives and binders, which are added as necessary, by pressure molding or the like.
  • the positive electrode mixture compact obtained by such a method can be used as a positive electrode as is, as described above, or it can be used as a positive electrode after being bonded to a current collector by pressing or the like.
  • the thickness of the positive electrode mixture compact (positive electrode mixture layer) formed using the solvent-containing positive electrode mixture-containing composition is preferably 10 to 1000 ⁇ m.
  • the thickness of the positive electrode mixture compact obtained by pressure molding is preferably 0.15 to 4 mm.
  • the thickness of the positive electrode current collector is preferably 0.01 to 0.1 mm.
  • the positive electrode can be manufactured, for example, by filling the pores of the conductive porous substrate with the positive electrode mixture-containing composition, drying it, and then, if necessary, subjecting it to pressure molding such as calendaring.
  • a positive electrode mixture that does not contain a solvent and contains a positive electrode active material, a solid electrolyte, a conductive assistant, a binder, etc., may be dry-filled into the pores of a conductive porous substrate, and the positive electrode may be pressure-molded, such as by calendaring, as necessary, to produce a positive electrode.
  • the thickness is preferably 30 to 4000 ⁇ m.
  • the negative electrode of the all-solid-state battery has, for example, a molded body of a negative electrode mixture containing a negative electrode active material, a lithium sheet, or a lithium alloy sheet. Also, a conductive porous substrate having a negative electrode mixture containing a negative electrode active material filled in its pores can be used as the negative electrode.
  • examples include a structure in which a layer of a molded product of the negative electrode mixture (negative electrode mixture layer) is formed on a current collector, and a structure consisting only of a molded product of the negative electrode mixture (such as a pellet).
  • negative electrode active materials include carbon materials such as graphite, lithium titanium oxides (lithium titanate, etc.), simple substances containing elements such as Si and Sn, compounds (oxides, etc.), and alloys thereof. Lithium metal and lithium alloys (lithium-aluminum alloy, lithium-indium alloy, etc.) can also be used as negative electrode active materials.
  • the content of the negative electrode active material in the negative electrode mixture is preferably 40 to 80 mass % in order to increase the energy density of the battery.
  • the negative electrode mixture may contain a conductive additive. Specific examples include the same conductive additives as those exemplified above as those that may be contained in the positive electrode mixture.
  • the content of the conductive additive in the negative electrode mixture is preferably 10 to 30 parts by mass when the content of the negative electrode active material is 100 parts by mass.
  • the negative electrode mixture may contain a binder.
  • a binder Specific examples include the same binders as those exemplified above as those that may be contained in the positive electrode mixture. Note that, for example, in the case where the negative electrode mixture contains a sulfide-based solid electrolyte (described later), if good moldability can be ensured in forming the negative electrode mixture layer without using a binder, the negative electrode mixture may not need to contain a binder.
  • the negative electrode mixture requires a binder, its content is preferably 15% by mass or less, and preferably 0.5% by mass or more. On the other hand, if the negative electrode mixture can obtain moldability without requiring a binder, its content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0% by mass (i.e., no binder is contained).
  • the negative electrode mixture can contain a solid electrolyte.
  • a solid electrolyte is the same as the solid electrolyte b in the solid electrolyte sheet.
  • the average particle size of the solid electrolyte in the negative electrode mixture is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the content of the solid electrolyte in the negative electrode mixture is preferably 30 parts by mass or more, and more preferably 35 parts by mass or more, when the content of the negative electrode active material is 100 parts by mass.
  • the content of solid electrolyte in the negative electrode mixture is preferably 130 parts by mass or less, and more preferably 110 parts by mass or less, when the content of the negative electrode active material is 100 parts by mass.
  • the current collector can be a sheet-like conductive porous substrate such as copper or nickel foil, punched metal, net, expanded metal, or foamed metal; or a carbon sheet; etc.
  • the sheet-like conductive porous substrate it is preferable to use a foamed metal porous body.
  • a specific example of a foamed metal porous body is "Celmet (registered trademark)" by Sumitomo Electric Industries, Ltd.
  • the negative electrode can be manufactured by applying a negative electrode mixture-containing composition (paste, slurry, etc.) made by dispersing the negative electrode active material, and optionally added conductive additives, solid electrolyte, binder, etc., in a solvent onto a current collector, drying the composition, and then, if necessary, subjecting the composition to pressure molding such as calendaring to form a compact of the negative electrode mixture (negative electrode mixture layer) on the surface of the current collector.
  • a negative electrode mixture-containing composition paste, slurry, etc.
  • conductive additives solid electrolyte, binder, etc.
  • Water or an organic solvent such as NMP can be used as the solvent for the negative electrode mixture-containing composition, but when the negative electrode mixture-containing composition also contains a solid electrolyte, it is desirable to select a solvent that is unlikely to deteriorate the solid electrolyte, and it is preferable to use the same solvents as those exemplified above for the solvent of the slurry for forming the solid electrolyte sheet.
  • the negative electrode mixture compact may be formed by compressing the negative electrode mixture prepared by mixing the negative electrode active material, and optionally the conductive additive, solid electrolyte, and binder, by pressure molding or the like.
  • the negative electrode mixture compact obtained by such a method can be used as it is as a negative electrode, or it can be bonded to a current collector by pressing, etc., and used as a negative electrode.
  • the thickness of the negative electrode mixture compact (negative electrode mixture layer) formed using the solvent-containing negative electrode mixture-containing composition is preferably 10 to 1000 ⁇ m.
  • the thickness of the negative electrode mixture compact obtained by pressure molding is preferably 0.15 to 4 mm.
  • the thickness of the negative electrode current collector is preferably 0.01 to 0.1 mm.
  • the negative electrode when a conductive porous substrate such as a punched metal is used for the negative electrode current collector, the negative electrode can be manufactured, for example, by filling the pores of the conductive porous substrate with the above-mentioned negative electrode mixture-containing composition, drying, and then, if necessary, performing pressure molding such as calendaring.
  • a negative electrode manufactured in this manner can ensure high strength, making it possible to hold a solid electrolyte sheet with a larger area.
  • a negative electrode mixture that does not contain a solvent and contains a negative electrode active material, a solid electrolyte, a binder, a conductive assistant, etc., may be dry-filled into the pores of a conductive porous substrate, and the negative electrode may be produced by a method of pressure molding such as calendaring as necessary.
  • the thickness is preferably 30 to 4000 ⁇ m.
  • negative electrodes having lithium or lithium alloy sheets those consisting of these sheets alone or those consisting of these sheets bonded to a current collector are used.
  • Alloying elements for lithium alloys include aluminum, lead, bismuth, indium, and gallium, with aluminum and indium being preferred.
  • the proportion of alloying elements in the lithium alloy is preferably 50 atomic % or less (in this case, the remainder is lithium and unavoidable impurities).
  • a laminate in which a layer containing an alloying element for forming a lithium alloy is laminated on the surface of a lithium layer (layer containing lithium) composed of metallic lithium foil or the like, for example by pressing the layer, and the laminate is brought into contact with a solid electrolyte in a battery to form a lithium alloy on the surface of the lithium layer, thereby forming a negative electrode.
  • a laminate having a layer containing an alloying element on only one side of the lithium layer may be used, or a laminate having layers containing an alloying element on both sides of the lithium layer may be used.
  • the laminate can be formed, for example, by pressing metallic lithium foil and a foil composed of an alloying element.
  • the current collector can also be used when forming a lithium alloy inside the battery to form the negative electrode.
  • a laminate having a lithium layer on one side of the negative electrode current collector and a layer containing an alloying element on the side of the lithium layer opposite the negative electrode current collector may be used, or a laminate having lithium layers on both sides of the negative electrode current collector and each lithium layer having a layer containing an alloying element on the side opposite the negative electrode current collector may be used.
  • the negative electrode current collector and the lithium layer may be laminated by crimping or the like.
  • the layer containing the alloying elements in the laminate to be used as the negative electrode can be, for example, a foil composed of these alloying elements.
  • the thickness of the layer containing the alloying elements is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and is preferably 20 ⁇ m or less, and more preferably 12 ⁇ m or less.
  • the lithium layer of the laminate to be used as the negative electrode can be, for example, metallic lithium foil.
  • the thickness of the lithium layer is preferably 0.1 to 1.5 mm.
  • the thickness of the sheet for the negative electrode having a lithium or lithium alloy sheet is also preferably 0.1 to 1.5 mm.
  • the current collector can be the same as the current collectors exemplified above as those usable for the negative electrode having a molded negative electrode mixture.
  • the positive electrode and the negative electrode can be used in a battery in the form of a laminated electrode body in which the positive electrode and the negative electrode are laminated via the solid electrolyte sheet of the present invention, or in the form of a wound electrode body in which the laminated electrode body is wound.
  • the negative electrode is opposed to the solid electrolyte layer B of the solid electrolyte sheet.
  • the positive electrode can be opposed to the solid electrolyte layer A of the solid electrolyte sheet as in the case of using a solid electrolyte sheet with a two-layer structure as shown in FIG. 1, but it can also be opposed to the solid electrolyte layer B of the solid electrolyte sheet as in the case of using a solid electrolyte sheet with a three-layer structure as shown in FIG. 2.
  • the electrode body When forming the electrode body, it is preferable to pressure mold the positive electrode, negative electrode, and solid electrolyte sheet in a stacked state in order to increase the mechanical strength of the electrode body.
  • the form of the all-solid-state battery is not limited to one having an exterior body composed of an exterior can, a sealing can, and a gasket as shown in FIG. 3 , that is, one generally referred to as a coin-type battery or a button-type battery, and may be, for example, one having an exterior body composed of a resin film or a metal-resin laminate film, one having an exterior body having a metallic, bottomed, tubular (cylindrical or rectangular) exterior can and a sealing structure that seals the opening, or one having a box-shaped exterior body made of ceramics.
  • Example 1 As the insulating porous substrate, a nonwoven fabric made by a melt-blowing method and composed of liquid crystal polyester fibers made of wholly aromatic polyester (Veculus (product name), manufactured by Kurarayflex Co., Ltd., thickness: 16 ⁇ m, basis weight: 4 g/m 2 , tensile strength: 5 N) was used. The tensile strength per basis weight of this substrate was 1.25 N/(g/m 2 ). Xylene (“ultra-dehydrated" grade) was used as a super-dehydrated solvent with a moisture content of 0.001% by mass (10 ppm) or less.
  • Veculus product name
  • Kurarayflex Co., Ltd. thickness: 16 ⁇ m, basis weight: 4 g/m 2 , tensile strength: 5 N
  • the tensile strength per basis weight of this substrate was 1.25 N/(g/m 2 ).
  • Xylene (“ultra-dehydrated” grade) was used as a super-dehydrated solvent with
  • a solid electrolyte a (Li10GeP2S12 ) having an average particle size of 1.0 ⁇ m, an acrylic resin binder, and a dispersant were mixed in a mass ratio of 100:3:1 with a solid content ratio of 40%, and the mixture was stirred for 10 minutes with a Thinky mixer to prepare a uniform slurry (slurry for forming solid electrolyte layer A).
  • the nonwoven fabric was pulled up through the slurry and then vacuum-dried at 120° C. for 1 hour to prepare a sheet A having a thickness of 18 ⁇ m that constitutes the solid electrolyte layer A.
  • a slurry for forming the solid electrolyte layer B was prepared in the same manner as described above, except that the solid electrolyte was a solid electrolyte b (Li 6 PS 5 Cl) having an average particle diameter of 1.0 ⁇ m.
  • the same nonwoven fabric as described above was passed through the slurry and pulled up, and then vacuum dried at 120° C. for 1 hour to produce a sheet B having a thickness of 18 ⁇ m that constitutes the solid electrolyte layer B.
  • the sheet A and the sheet B were laminated and pressed together to produce a solid electrolyte sheet in which the solid electrolyte layer A and the solid electrolyte layer B were laminated.
  • Example 2 Among the solid electrolytes contained in the slurry for forming the solid electrolyte layer A, 50 mass % of the solid electrolyte a was replaced with the same solid electrolyte b as used in Example 1, and the slurry was changed to one containing the solid electrolyte a ( Li10GeP2S12 ) and the solid electrolyte b ( Li6PS5Cl ) in a mass ratio of 50:50.
  • a sheet A having a thickness of 18 ⁇ m constituting the solid electrolyte layer A was produced in the same manner as in Example 1. Furthermore, using this sheet A, a solid electrolyte sheet was produced in the same manner as in Example 1.
  • Example 3 Among the solid electrolytes contained in the slurry for forming the solid electrolyte layer A, 80 mass % of the solid electrolyte a was replaced with the same solid electrolyte b as used in Example 1, and the slurry was changed to one containing the solid electrolyte a ( Li10GeP2S12 ) and the solid electrolyte b ( Li6PS5Cl ) in a mass ratio of 20:80.
  • a sheet A having a thickness of 18 ⁇ m constituting the solid electrolyte layer A was produced in the same manner as in Example 1. Furthermore, a solid electrolyte sheet was produced using this sheet A in the same manner as in Example 1.
  • Example 4 Among the solid electrolytes contained in the slurry for forming the solid electrolyte layer A, 90 mass % of the solid electrolyte a was replaced with the same solid electrolyte b as that used in Example 1, and the slurry was changed to one containing the solid electrolyte a ( Li10GeP2S12 ) and the solid electrolyte b ( Li6PS5Cl ) in a mass ratio of 10:90.
  • a sheet A having a thickness of 18 ⁇ m constituting the solid electrolyte layer A was produced in the same manner as in Example 1. Furthermore, using this sheet A, a solid electrolyte sheet was produced in the same manner as in Example 1.
  • Example 5 A sheet A having a thickness of 18 ⁇ m and constituting the solid electrolyte layer A was produced in the same manner as in Example 3, except that the solid electrolyte a contained in the slurry for forming the solid electrolyte layer A was changed to Li1.5Al0.5Ge1.5 ( PO4 ) 3 . Further, a solid electrolyte sheet was produced in the same manner as in Example 1 using this sheet A.
  • Example 6 A sheet A having a thickness of 18 ⁇ m and constituting the solid electrolyte layer A was produced in the same manner as in Example 3, except that the solid electrolyte a contained in the slurry for forming the solid electrolyte layer A was changed to Li1.4Al0.5Ti1.6 ( PO4 ) 3 . Further, a solid electrolyte sheet was produced in the same manner as in Example 1 using this sheet A.
  • Example 7 A sheet A having a thickness of 18 ⁇ m constituting the solid electrolyte layer A was produced in the same manner as in Example 3, except that the solid electrolyte a contained in the slurry for forming the solid electrolyte layer A was changed to La0.05Li0.35TiO3 . Further, using this sheet A, a solid electrolyte sheet was produced in the same manner as in Example 1.
  • Example 8 A sheet A having a thickness of 18 ⁇ m constituting the solid electrolyte layer A was produced in the same manner as in Example 3, except that the solid electrolyte a contained in the slurry for forming the solid electrolyte layer A was changed to Li 10 SnP 2 S 12. Further, a solid electrolyte sheet was produced in the same manner as in Example 1 using this sheet A.
  • Each solid electrolyte sheet of the examples and comparative examples was sandwiched between two pieces of Li metal foil on both sides, and then both ends were pressed down with two stainless steel plates to create an evaluation cell.
  • Each cell was charged and discharged 10 times at a current density of 0.05 mA/cm 2 (time per cycle: charge: 40 minutes, discharge: 40 minutes), and the current density was changed in sequence to 0.1 mA/cm 2 , 0.2 mA/cm 2 , 0.4 mA/cm 2 , and 0.8 mA/cm 2 , and then the current density was changed in sequence to 1.8 mA/cm 2 at 0.2 mA/cm 2 intervals, and charge/discharge cycles were performed in which charge/discharge was repeated 10 times in the same manner, and the voltage change of the cell was measured during the charge/discharge cycle.
  • the charge time and discharge time per cycle in the charge/discharge cycle are shown in Table 1.
  • the voltage change of the cell using the solid electrolyte sheet of Comparative Example 1 is shown in FIG. 4.
  • solid electrolyte layer A suppresses the growth of lithium dendrites, so that, as shown in Table 2, short circuits are less likely to occur than in the cell using the solid electrolyte sheet of Comparative Example 1, and charging and discharging at a larger current is possible.
  • the all-solid-state battery of the present invention can be used in the same applications as conventionally known primary and secondary batteries, but since it has a solid electrolyte instead of an organic electrolyte solution, it has excellent heat resistance and can be preferably used in applications where it is exposed to high temperatures.
  • the solid electrolyte sheet of the present invention can constitute the all-solid-state battery of the present invention.
  • Solid electrolyte sheet 20 Solid electrolyte layer A 30 Solid electrolyte layer B 100 All-solid-state battery 200 Positive electrode 300 Negative electrode 400 Solid electrolyte sheet 500 Outer can 600 Sealing can 700 Gasket

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JP7803325B2 (ja) 2023-09-05 2026-01-21 トヨタ自動車株式会社 全固体電池

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