WO2021149460A1 - リチウムイオン二次電池 - Google Patents

リチウムイオン二次電池 Download PDF

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Publication number
WO2021149460A1
WO2021149460A1 PCT/JP2020/048845 JP2020048845W WO2021149460A1 WO 2021149460 A1 WO2021149460 A1 WO 2021149460A1 JP 2020048845 W JP2020048845 W JP 2020048845W WO 2021149460 A1 WO2021149460 A1 WO 2021149460A1
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Prior art keywords
layer
solid electrolyte
positive electrode
negative electrode
active material
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Ceased
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PCT/JP2020/048845
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English (en)
French (fr)
Japanese (ja)
Inventor
佳太郎 大槻
田中　一正
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TDK Corp
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TDK Corp
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Priority to DE112020006603.7T priority Critical patent/DE112020006603T5/de
Priority to JP2021573036A priority patent/JP7812662B2/ja
Priority to CN202080094045.3A priority patent/CN115004433B/zh
Priority to US17/794,355 priority patent/US20230096228A1/en
Publication of WO2021149460A1 publication Critical patent/WO2021149460A1/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
    • H01M10/052—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
    • H01M10/056—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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 a lithium ion secondary battery.
  • the present application claims priority based on Japanese Patent Application No. 2020-909573 filed in Japan on January 24, 2020, the contents of which are incorporated herein by reference.
  • Lithium-ion secondary batteries which are generally used as batteries that are currently used as power sources for electronic devices, have conventionally used a liquid electrolyte (electrolyte solution) such as an organic solvent as an electrolyte that is a medium for moving ions. There is.
  • a liquid electrolyte electrolyte solution
  • the function of the battery may deteriorate due to leakage of the electrolyte due to an external impact or the like, and it is required to further improve the reliability of the lithium ion secondary battery.
  • a solid electrolyte is used as the electrolyte instead of the liquid electrolyte, and this is sandwiched between the electrodes and laminated or wound. The development of lithium-ion secondary batteries is underway.
  • solid electrolytes are known to have lower ionic conductivity than liquid electrolytes, and various studies have been conducted to improve the output characteristics of lithium-ion secondary batteries using solid electrolytes.
  • Patent Document 1 discloses that the rate characteristics are improved by mixing a solid electrolyte in the electrode and controlling the ratio of the solid electrolyte to the electrode active material in the thickness direction of the electrode and the void ratio of the electrode.
  • Patent Document 2 a solid electrolyte is mixed in the electrode, and the charge / discharge efficiency is controlled by controlling the difference between the resistivity due to ion transfer and the resistivity due to electron transfer in the electrode to 0 k ⁇ ⁇ cm or more and 100 k ⁇ ⁇ cm or less. Is disclosed to enhance.
  • Patent Document 3 discloses that a solid electrolyte membrane having excellent battery characteristics can be obtained by setting the standard deviation of the thickness of the electrolyte membrane to 5.0 ⁇ m or less.
  • the present invention solves the above problems and provides a lithium ion secondary battery having high output characteristics when a solid electrolyte is used as the electrolyte.
  • the positive electrode layer containing the positive electrode active material and the negative electrode layer containing the negative electrode active material are sequentially loaded via the solid electrolyte layer, and the solid having the thickest thickness in the solid electrolyte layer.
  • the ratio t1 / t2 of the average thickness t1 of the electrolyte layer to the average thickness t2 of the thinnest solid electrolyte layer is 1.02 ⁇ t1 / t2 ⁇ 1.99.
  • the ratio of the average thickness of the solid electrolyte layer is set to the range of the present invention, a charge bias is generated between the positive electrode layer and the negative electrode layer, and the inside of the lithium ion secondary battery is caused by the difference in the average thickness of the solid electrolyte layer. By suppressing the occurrence of a non-uniform reaction, the output characteristics are improved.
  • the standard deviation ⁇ in the average thickness t of each layer of the solid electrolyte layer may be 0.15 ⁇ ⁇ ⁇ 1.66 ( ⁇ m).
  • the positive electrode layer or the negative electrode layer and the solid electrolyte layer has a positive electrode layer or a negative electrode layer and an intermediate layer containing a constituent element of the solid electrolyte. You may.
  • lithium ions are preferably transferred at the interface between the positive electrode layer and the negative electrode layer and the solid electrolyte layer. That is, by reducing the interfacial resistance, the occurrence of charge bias and the subsequent progress of the charge / discharge reaction are further promoted, and high output characteristics can be obtained.
  • the average thickness T of the average thickness t of each solid electrolyte layer may be 4.8 ⁇ T ⁇ 9.8 ( ⁇ m).
  • lithium ions are preferably transferred while sufficiently ensuring the insulation between the positive electrode layer and the negative electrode layer. As a result, high output characteristics can be obtained.
  • the present invention makes it possible to provide a lithium ion secondary battery having high output characteristics.
  • a part of the cross-sectional view of the lithium ion secondary battery of the present embodiment in the stacking direction is shown.
  • a part of the cross-sectional view in the stacking direction in the lithium ion secondary battery of the modified example of this embodiment is shown.
  • the x direction is, for example, a direction in which the positive electrode external electrode 60 and the negative electrode external electrode 70 sandwich the laminate 20.
  • the x-direction and the y-direction are examples of the in-plane direction.
  • the z direction is a direction orthogonal to the x direction and the y direction.
  • the z direction is an example of the stacking direction.
  • the + z direction may be expressed as “up” and the ⁇ z direction may be expressed as “down”.
  • the top and bottom do not always coincide with the direction in which gravity is applied.
  • Lithium-ion secondary battery First, the lithium ion secondary battery according to the present embodiment will be described.
  • the lithium ion secondary battery 1 includes a laminate 20 in which a positive electrode layer 30 and a negative electrode layer 40 are laminated via a solid electrolyte layer 50.
  • the laminated body 20 is sandwiched between the outer layers 55, which will be described later, in the laminating direction, for example.
  • the positive electrode layer 30 has a positive electrode current collector layer 31 and a positive electrode active material layer 32.
  • the negative electrode layer 40 has a negative electrode current collector layer 41 and a negative electrode active material layer 42.
  • a margin layer 80 is formed on the same plane of the positive electrode layer 30 and the negative electrode layer 40.
  • the laminated body 20 is a hexahedron and has two end faces formed as surfaces parallel to the laminating direction, two side surfaces, and an upper surface and a lower surface formed as surfaces orthogonal to the laminating direction.
  • the positive electrode current collector layer 31 is exposed on the first end surface, and the negative electrode current collector layer 42 is exposed on the second end surface.
  • first end face and the second end face face each other, and the first side surface and the second side surface face each other.
  • the positive electrode current collector layer 31 and the negative electrode current collector layer 41 are also exposed on a part of the first side surface and the second side surface.
  • a positive electrode external electrode 60 electrically connected to the positive electrode current collector layer 31 is attached so as to cover the first end surface side of the laminated body 20.
  • the electrical connection is made by connecting the positive electrode external electrode 60 to the positive electrode current collector layer 31 of the positive electrode layer 30 exposed on the first end surface, the first side surface, and the second side surface of the laminated body 20. There is.
  • a negative electrode external electrode 70 electrically connected to the negative electrode current collector layer 41 is attached so as to cover the second end surface side of the laminated body 20.
  • the electrical connection is made by connecting the negative electrode external electrode 70 to the negative electrode current collector layer 41 of the negative electrode layer 40 exposed on the second end surface, the first side surface, and the second side surface of the laminated body 20. There is.
  • either one or both of the positive electrode active material and the negative electrode active material are collectively referred to as an active material, and either or both of the positive electrode active material layer 32 and the negative electrode active material layer 42 are referred to as active materials.
  • an active material layer one or both of the positive electrode current collector layer 31 and the negative electrode current collector layer 41 are collectively referred to as a current collector layer, and either one of the positive electrode layer 30 and the negative electrode layer 40.
  • both are collectively referred to as an electrode layer
  • the first end face and the second end face are collectively referred to as an end face
  • the first side surface and the second side surface are collectively referred to as a side surface
  • the positive electrode external electrode 60 and the negative electrode external electrode 70 are collectively referred to. May be collectively referred to as an external electrode.
  • the margin layer 80 of the lithium ion secondary battery 1 of the present embodiment has a large step in order to eliminate the step between the solid electrolyte layer 50 and the positive electrode layer 30 and the step between the solid electrolyte layer 50 and the negative electrode layer 40. It is preferable to provide it in some cases.
  • the margin layer 80 is preferably provided on the same plane of the positive electrode layer 30 and the negative electrode layer 40. Due to the presence of the margin layer 80, the step between the solid electrolyte layer 50 and the positive electrode layer 30 and the negative electrode layer 40 is eliminated, so that the density between the solid electrolyte layer 50 and the electrode layer is increased, and the lithium ion secondary battery is fired. Delamination and warpage due to the above are less likely to occur.
  • the solid electrolyte layer 50 of the lithium ion secondary battery 1 of the present embodiment is sandwiched between the positive electrode layer 30 and the negative electrode layer 40 in the z direction.
  • FIG. 1 illustrates a case where the solid electrolyte layers 50a, 50b, and 50c are provided.
  • the solid electrolyte layer 50a is the thinnest solid electrolyte layer
  • the solid electrolyte layer 50b is the thickest solid electrolyte layer.
  • the solid electrolyte layer 50c has a thickness of a size between the solid electrolyte layer 50a and the solid electrolyte layer 50b. The thickness of each solid electrolyte layer 50 is determined by the average thickness.
  • the ratio t1 / t2 of the average thickness t1 of the thickest solid electrolyte layer 50b to the average thickness t2 of the thinnest solid electrolyte layer 50a is 1.02 ⁇ t1 / t2 ⁇ 1.99.
  • the average thickness of the solid electrolyte layer 50 is the average thickness in the in-plane direction of only one solid electrolyte layer 50, for example, the average thickness in the x direction.
  • the thickness of the two solid electrolyte layers 50 sandwiching the positive electrode layer 30 is the same in the z direction, and the thickness of the solid electrolyte layer sandwiched between them is thin. However, they may be different from each other, and the solid electrolyte layer to be taught may be thick.
  • the ratio of the average thickness of the thinnest solid electrolyte layer 50a to the average thickness of the thickest solid electrolyte layer 50b within the scope of the present invention, charge bias between the positive electrode layer and the negative electrode layer is generated, and the solid is solid.
  • the output characteristics are improved by suppressing the occurrence of a non-uniform reaction inside the lithium ion secondary battery due to the difference in the average thickness of the electrolyte layer 50.
  • the ratio t1 / t2 of the average thickness t1 of the solid electrolyte layer 50b having the thickest average thickness in the solid electrolyte layer 50 of the present embodiment and the average thickness t2 of the solid electrolyte layer 50a having the thinnest average thickness is 1.02. It is preferable that ⁇ t1 / t2 ⁇ 1.99.
  • the difference in charge bias between the positive electrode layer and the negative electrode layer in the lithium ion battery becomes small, so that the charge bias between the positive electrode layer and the negative electrode layer becomes smaller as a whole lithium ion secondary battery.
  • the average thickness of each solid electrolyte layer in the solid electrolyte layer 50 of the present embodiment can be determined by observing the cross section of the lithium ion secondary battery 1 by SEM.
  • the average value of the thicknesses at five points that divide the solid electrolyte layer 50 into approximately 6 equal parts is the average thickness of the solid electrolyte layer 50
  • the thickness of the solid electrolyte layer 50b having the thickest average thickness is t1.
  • the solid electrolyte layer 50 of the present embodiment preferably has a standard deviation ⁇ of the average thickness t of all the solid electrolyte layers of 0.15 ⁇ ⁇ ⁇ 1.66 ( ⁇ m).
  • the standard deviation ⁇ of the average thickness in all the solid electrolyte layers is 0.55 ⁇ ⁇ ⁇ 1.24 ( ⁇ m).
  • the solid electrolyte layer 50 of the present embodiment has an average thickness T of an average thickness t of each solid electrolyte layer of 4.8 ⁇ T ⁇ 9.8 ( ⁇ m). preferable.
  • lithium ions are preferably transferred while sufficiently ensuring the insulation between the positive electrode layer and the negative electrode layer. As a result, high output characteristics can be obtained.
  • the solid electrolyte layer 50 of the present embodiment is composed of the solid electrolyte as a main component.
  • Known materials can be used as the solid electrolyte, for example, titanium aluminum lithium lithium Li 1 + x Al x Ti 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 0.6), lithium germanium lithium phosphate Li.
  • solid electrolyte of the present embodiment a solid electrolyte whose composition has been changed by changing the composition ratio or substituting different elements may be used as long as the characteristics as a solid electrolyte can be obtained.
  • the solid electrolyte layer 50 of the present embodiment contains a phosphoric acid compound such as titanium aluminum lithium phosphate or germanium aluminum lithium phosphate or Li 0.5 La 0.5 TiO 3 , Li 3.6 Si 0.6 as the solid electrolyte. It is preferable to contain an oxide such as P 0.4 O 4.
  • the main component means that the constituent ratio is the largest as the constituent component occupying the solid electrolyte layer 50.
  • Examples of the subcomponents constituting the solid electrolyte layer 50 of the present embodiment include a sintering filling agent used when forming the solid electrolyte layer, a decomposition product thereof, and the like.
  • a plurality of positive electrode layers 30 and a plurality of negative electrode layers 40 are provided in the laminated body 20.
  • the positive electrode layer 30 and the negative electrode layer 40 are alternately laminated via a solid electrolyte layer.
  • the positive electrode layer 30 has a positive electrode current collector layer 31 and a positive electrode active material layer 32 containing a positive electrode active material.
  • the negative electrode layer 40 has a negative electrode current collector layer 41 and a negative electrode active material layer 42 containing a negative electrode active material.
  • the positive electrode current collector layer 31 and the negative electrode current collector layer 41 are excellent in conductivity.
  • the positive electrode current collector layer 31 and the negative electrode current collector layer 41 are, for example, silver, palladium, gold, platinum, aluminum, copper, and nickel. Copper does not easily react with the positive electrode active material, the negative electrode active material and the solid electrolyte. For example, when copper is used for the positive electrode current collector layer 31 and the negative electrode current collector layer 41, the internal resistance of the lithium ion secondary battery 1 can be reduced.
  • the substances constituting the positive electrode current collector layer 31 and the negative electrode current collector layer 41 may be the same or different.
  • the positive electrode active material layer 32 is formed on one side or both sides of the positive electrode current collector layer 31.
  • the positive electrode active material layer 32 may not be provided on the surface of the positive electrode current collector layer 31 on the side where the opposing negative electrode layer 40 does not exist.
  • the negative electrode active material layer 42 is formed on one side or both sides of the negative electrode current collector layer 41.
  • the negative electrode active material layer 42 may not be present on the surface of the negative electrode current collector layer 41 on the side where the opposing positive electrode layer 30 does not exist.
  • the positive electrode layer 30 or the negative electrode layer 40 located at the uppermost layer or the lowermost layer of the laminated body 20 does not have to have the positive electrode active material layer 32 or the negative electrode active material layer 42 on one side.
  • the positive electrode active material layer 32 and the negative electrode active material layer 42 include a positive electrode active material and a negative electrode active material that transfer electrons.
  • a conductive auxiliary agent, an ion guiding auxiliary agent, a binder and the like may be included. It is preferable that the positive electrode active material and the negative electrode active material can efficiently insert and desorb lithium ions.
  • the positive electrode active material and the negative electrode active material are, for example, transition metal oxides and transition metal composite oxides.
  • Li 3 V 2 (PO 4 ) 3 or LiVOPO 4 lithium vanadium phosphate
  • Li excess solid solution positive electrode lithium titanate (Li 4 Ti 5 O 12)
  • olivine type LiMbPO 4 (where Mb is one or more elements selected from Co, Ni, Mn, Fe, Mg, Nb, Ti, Al and Zr) and phosphoric acid. It is preferable to use a phosphoric acid compound typified by vanadium lithium (Li 3 V 2 (PO 4 ) 3 or LiVOPO 4) as a main component.
  • the positive electrode active material and the negative electrode active material of the present embodiment those whose composition is changed by changing the composition ratio or replacing different elements may be used as long as the characteristics as the positive electrode active material and the negative electrode active material can be obtained.
  • the main component means that the constituent components occupying the positive electrode active material and the negative electrode active material have the largest composition ratio.
  • Examples of the conductive auxiliary agent 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.
  • Examples of the derivatizing agent include solid electrolytes.
  • the solid electrolyte for example, a material similar to the material used for the solid electrolyte layer 50 can be used.
  • a solid electrolyte is used as the ion conductor, it is preferable to use the same material for the ion conductor and the solid electrolyte used for the solid electrolyte layer 50.
  • solid electrolyte When a solid electrolyte is used as the ion guiding agent, different solid electrolytes may be used for the positive electrode active material layer 32 and the negative electrode active material layer 42.
  • the active materials constituting the positive electrode active material layer 32 or the negative electrode active material layer 42 there is no clear distinction between the active materials constituting the positive electrode active material layer 32 or the negative electrode active material layer 42, and the potentials of the two types of compounds are compared, and a compound showing a more noble potential is used as the positive electrode active material. A compound showing a low potential can be used as the negative electrode active material.
  • the material constituting the positive electrode current collector layer 31 and the negative electrode current collector layer 41 of the lithium ion secondary battery 1 of the present embodiment it is preferable to use a material having a high conductivity, for example, silver, palladium, gold, platinum. , Aluminum, copper, nickel and the like are preferably used. In particular, copper is more preferable because it does not easily react with the oxide-based lithium ion conductor and has the effect of reducing the internal resistance of the laminated all-solid-state battery.
  • the same material may be used or different materials may be used as the materials constituting the positive electrode current collector layer 31 and the negative electrode current collector layer 41.
  • the positive electrode current collector layer 31 and the negative electrode current collector layer 41 may contain a positive electrode active material and a negative electrode active material, respectively.
  • the content ratio of the active material contained in each current collector is not particularly limited as long as it functions as a current collector.
  • the positive electrode current collector / positive electrode active material or the negative electrode current collector / negative electrode active material is in the range of 90/10 to 70/30 in volume ratio.
  • the positive electrode current collector layer 31 and the negative electrode current collector layer 41 contain the positive electrode active material and the negative electrode active material, respectively, the positive electrode current collector layer 31, the positive electrode active material layer 32, the negative electrode current collector layer 41, and the negative electrode active material layer are included. Adhesion with 42 is improved.
  • FIG. 1 shows an example in which the intermediate layer 90 exists between the surface of the lowermost positive electrode layer 30 and the solid electrolyte layer 50b in the z direction, and the number and position of the intermediate layers 90 formed are shown in this example. Not limited.
  • the intermediate layer 90 of the present embodiment is preferably a layer containing the positive electrode layer 30 or the negative electrode layer 40 and the constituent elements of the solid electrolyte layer 50.
  • the positive electrode layer 30 or the negative electrode layer 40 and the layer containing the constituent elements of the solid electrolyte layer 50, the positive electrode layer 30, the negative electrode layer 40, the solid electrolyte layer 50, and the intermediate layer 90 are compatible with each other.
  • the interfacial resistance is reduced, the generation of charge bias and the subsequent progress of the charge / discharge reaction are further promoted, and high output characteristics can be obtained.
  • the margin layer 80 of the lithium ion secondary battery 1 of the present embodiment is preferably provided in order to eliminate the step between the solid electrolyte layer 50 and the positive electrode layer 30 and the step between the solid electrolyte layer 50 and the negative electrode layer 40. Due to the presence of such a margin layer 80, the step between the solid electrolyte layer 50 and the positive electrode layer 30 and the negative electrode layer 40 is eliminated, so that the density of the laminate 20 and the positive electrode layer 30 and the negative electrode layer 40 becomes high. Delamination and warpage due to firing of the lithium ion secondary battery 1 are less likely to occur.
  • the same material as the solid electrolyte used for the solid electrolyte layer 50 can be used.
  • the solid electrolyte constituting the margin layer 80 preferably has the same configuration as the solid electrolyte constituting the solid electrolyte layer 50.
  • outer layers (cover layers) 55 can be provided on both main surfaces of the laminated body 20 exposed in the z direction, if necessary.
  • the outer layer on the upper side in the stacking direction is the first outer layer (outermost layer on the upper surface) 55A
  • the outer layer on the lower side in the stacking direction is the second outer layer (outermost layer on the lower surface) 55B.
  • the same material as the solid electrolyte layer can be used for the outer layer 55, but it is not included in the solid electrolyte layer of the present embodiment.
  • the lithium ion secondary battery 1 of the present embodiment can be manufactured by the following procedure.
  • Each material of the positive electrode current collector layer 31, the positive electrode active material layer 32, the solid electrolyte layer 50, the negative electrode current collector layer 41, the negative electrode active material layer 42, the margin layer 80, and the intermediate layer 90 is made into a paste.
  • the method of making a paste is not particularly limited, and for example, a paste can be obtained by mixing the powder of each of the above materials with a vehicle.
  • vehicle is a general term for a medium in a liquid phase, and includes a solvent, a binder, and the like.
  • the binder contained in the paste for forming the green sheet or the printing layer is not particularly limited, but polyvinyl acetal resin, cellulose resin, acrylic resin, urethane resin, vinyl acetate resin, polyvinyl alcohol resin and the like can be used.
  • the slurry can contain 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 paste for a positive electrode current collector layer a paste for a positive electrode active material layer, a paste for a solid electrolyte layer, a paste for a negative electrode active material layer, a paste for a negative electrode current collector layer, a paste for a margin layer and a paste for an intermediate layer can be obtained.
  • the paste for the solid electrolyte layer prepared above is applied on a substrate such as polyethylene terephthalate (PET) to a desired thickness and dried if necessary to prepare a green sheet 5 for a solid electrolyte.
  • the method for producing the green sheet 5 for solid electrolyte is not particularly limited, and known methods such as a doctor blade method, a die coater, a comma coater, and a gravure coater can be adopted.
  • the intermediate layer 90, the positive electrode active material layer 32, the positive electrode current collector layer 31, and the positive electrode active material layer 32 are printed and laminated in this order on the green sheet 5 for solid electrolyte by screen printing to form the intermediate layer 90 and the positive electrode layer 30. do.
  • a margin layer 80 is formed by screen printing in a region other than the positive electrode layer to prepare a positive electrode layer unit.
  • the negative electrode layer unit can also be manufactured by the same method as the positive electrode layer unit, and the negative electrode layer 40 and the margin layer 80 are formed by screen printing on the green sheet 5 for solid electrolyte to prepare the negative electrode layer unit.
  • the positive electrode layer unit and the negative electrode layer unit are alternately offset and laminated so that one ends do not match, and if necessary, outer layers (cover layers) are formed on both main surfaces exposed in the z direction of the laminated body.
  • outer layers cover layers
  • the same material as the solid electrolyte can be used for the outer layer.
  • the sheet used to provide the outer layer may be referred to as the outermost layer sheet. In this embodiment, this outer layer is not treated as the solid electrolyte layer 50 of the laminated body 1.
  • the manufacturing method is for manufacturing a parallel type lithium ion secondary battery, but the manufacturing method for a series type lithium ion secondary battery is such that one end of the positive electrode layer and one end of the negative electrode layer coincide with each other. That is, they may be laminated without offsetting.
  • the manufactured laminated substrates can be collectively pressed by a mold press, hot water isotropic pressure press (WIP), cold water isotropic pressure press (CIP), hydrostatic press, etc. to improve adhesion. Pressurization is preferably performed while heating, and can be performed, for example, at 40 to 95 ° C.
  • WIP hot water isotropic pressure press
  • CIP cold water isotropic pressure press
  • hydrostatic press etc. to improve adhesion. Pressurization is preferably performed while heating, and can be performed, for example, at 40 to 95 ° C.
  • a laminated substrate is produced in consideration of the position in the z direction to be cut later, and the laminated substrate is cut at a predetermined position in the z direction. A plurality of desired laminates may be obtained.
  • the produced laminated substrate can be cut into a laminated body of an unfired lithium ion secondary battery using a dicing device.
  • a lithium ion secondary battery is manufactured by removing and firing a laminate of lithium ion secondary batteries. De-bye and firing can be performed at a temperature of 600 ° C. to 1000 ° C. in a nitrogen atmosphere. The holding time for debuying and firing is, for example, 0.1 to 6 hours.
  • an external electrode can be provided.
  • the positive electrode layer 30 and the negative electrode layer 40 are alternately connected in parallel, via two opposing end faces E1 and E2 of the laminated body and a part of two facing side surfaces S1 and S2. Join. Therefore, a pair of external electrodes are formed so as to sandwich the end faces of the laminated body.
  • the method for forming the external electrode 12 include a sputtering method, a screen printing method, and a dip coating method. In the screen printing method and the dip coating method, a paste for an external electrode containing a metal powder, a resin, and a solvent is prepared and formed as the external electrode 12.
  • a baking step for removing the solvent and a plating process for forming the terminal electrode on the surface of the external electrode are performed.
  • the baking step and the plating process are not required.
  • the laminate of the lithium ion secondary battery 1 may be sealed in, for example, a coin cell in order to enhance moisture resistance and impact resistance.
  • the sealing method is not particularly limited, and for example, the laminated body after firing may be sealed with a resin. Further, an insulating paste having an insulating property such as Al2O3 may be applied or dip-coated around the laminate, and the insulating paste may be sealed by heat treatment.
  • a method for manufacturing a laminated all-solid-state battery having a step of forming a margin layer using a paste for a margin layer has been exemplified, but the method for manufacturing a lithium ion secondary battery according to the present embodiment is this example. Not limited to.
  • the step of forming the margin layer by using the paste for the margin layer may be omitted.
  • the margin layer may be formed, for example, by deforming the paste for the solid electrolyte layer in the manufacturing process of the lithium ion secondary battery.
  • FIG. 2 is a schematic cross-sectional view of the lithium ion secondary battery 1A according to the modified example.
  • the same components as those of the lithium ion secondary battery 1 are designated by the same reference numerals, and the description thereof will be omitted.
  • the lithium ion secondary battery 1A shown in FIG. 2 is different from the lithium ion secondary battery 1 shown in FIG. 1 in that it does not have an intermediate layer 90.
  • Example 1 (Preparation of active material powder)
  • the active material powder lithium vanadium phosphate prepared by the following method was used.
  • Li 2 CO 3 , V 2 O 5 , and NH 4 H 2 PO 4 were used as starting materials, dispersed in pure water, and then wet-mixed with a ball mill for 12 hours.
  • the powder obtained after dehydration drying was calcined at 850 ° C. for 2 hours in a nitrogen-hydrogen mixed gas. After calcining, it was dispersed in pure water, and then wet pulverized with a ball mill for 1 hour. After pulverization, it was dehydrated and dried to obtain lithium vanadium phosphate as an active material powder.
  • the active material layer paste was prepared by adding 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent to 100 parts of the obtained active material powder, and mixing and dispersing the paste.
  • the solid electrolyte powder-01 prepared by the following method was used as the solid electrolyte.
  • Li 2 CO 3 , Al 2 O 3 , TIO 2 , and NH 4 H 2 PO 4 were used as starting materials, dispersed in pure water, and then wet-mixed with a ball mill for 12 hours. .. After mixing, it was dehydrated and dried, and then the obtained powder was calcined in the air at 800 ° C. for 2 hours. After calcining, it was dispersed in pure water, and then wet pulverized with a ball mill for 8 hours. After pulverization, it was dehydrated and dried to obtain a solid electrolyte powder-01.
  • paste for current collector layer As a current collector, the obtained active material powder and Cu powder were mixed so as to have a volume ratio of 80/20. After mixing, 100 parts of the obtained mixture, 10 parts of ethyl cellulose as a binder, and 50 parts of dihydroterpineol as a solvent were added and mixed / dispersed to prepare a paste for a current collector layer.
  • paste-01 for margin layer To prepare the paste-01 for the margin layer, add 100 parts of the obtained solid electrolyte powder-01 to 100 parts of ethanol and 100 parts of toluene as a solvent and wet-mix them with a ball mill, and then 16 parts of a polyvinyl butyral binder and phthalic acid. 4.8 parts of benzyl butyl was further added and mixed to prepare a paste-01 for a margin layer.
  • thermosetting paste for an external electrode was prepared by mixing and dispersing silver powder, an epoxy resin, and a solvent.
  • a lithium ion secondary battery was prepared as follows.
  • An active material layer having a thickness of 5 ⁇ m was formed on a solid electrolyte layer sheet-01 having a thickness of 8 ⁇ m by screen printing, and dried at 80 ° C. for 10 minutes.
  • a current collector layer having a thickness of 5 ⁇ m was formed on the current collector layer in the same printing pattern using screen printing, and dried at 80 ° C. for 10 minutes.
  • an active material layer having a thickness of 5 to 10 ⁇ m is formed again in the same printing pattern using screen printing, and dried at 80 ° C. for 10 minutes to form an electrode layer on the solid electrolyte layer sheet-01.
  • a margin layer having a height substantially flush with the electrode layer was formed on the outer periphery of one end of the electrode layer by screen printing, and dried at 80 ° C. for 10 minutes. Then, the PET film was peeled off to obtain a sheet of the electrode layer unit.
  • a current collector layer having a thickness of 5 ⁇ m was formed on the outermost layer sheet-01 by screen printing, and dried at 80 ° C. for 10 minutes. Further, an active material layer having a thickness of 5 to 10 ⁇ m is formed again in the same printing pattern using screen printing, and dried at 80 ° C. for 10 minutes to form an active material layer on the outermost layer sheet-01.
  • An electrode layer was prepared in which was present on only one side. Next, a margin layer having a height substantially flush with the electrode layer was formed on the outer periphery of one end of the electrode layer by screen printing, and dried at 80 ° C. for 10 minutes. Next, the PET film of the outermost layer sheet-01 was peeled off to obtain a sheet of the lower outermost layer unit.
  • An active material layer having a thickness of 5 to 10 ⁇ m was formed on a solid electrolyte layer sheet-01 having a thickness of 8 ⁇ m in the same printing pattern using screen printing, and dried at 80 ° C. for 10 minutes. Further, a current collector layer having a thickness of 5 ⁇ m is formed again by screen printing and dried at 80 ° C. for 10 minutes, so that the active material layer exists on only one side on the solid electrolyte layer sheet-01.
  • An electrode layer to be used was prepared. Next, a margin layer having a height substantially flush with the electrode layer was formed on the outer periphery of one end of the electrode layer by screen printing, and dried at 80 ° C. for 10 minutes. Next, the outermost layer sheet-01 was laminated on the electrode layer, and the PET films of the solid electrolyte layer sheet-01 and the outermost layer sheet-01 were peeled off to obtain a sheet of the upper outermost layer unit.
  • the prepared laminate was heated to a firing temperature of 750 ° C. in nitrogen at a heating rate of 200 ° C./hour, held at that temperature for 2 hours, and naturally cooled to perform debuying and firing treatment.
  • a laminate of lithium ion secondary batteries was obtained.
  • Example electrode forming process An external electrode paste was applied so as to cover the exposed positive electrodes and negative electrodes on both end faces and both side surfaces of the obtained laminate of the lithium ion secondary battery, and thermosetting was performed at 150 ° C. for 30 minutes to perform a pair of external electrodes. An electrode was formed.
  • a pair of external electrodes formed on a laminated body of a lithium ion secondary battery was used as an evaluation cell in Example 1.
  • the thickness of the solid electrolyte layer in the lithium ion secondary battery produced in Example 1 was measured using a scanning electron microscope (SEM). In the cross section of the lithium ion secondary battery, the thickness of each of the 49 solid electrolyte layers excluding the outer solid electrolyte layer in the 50-layer laminate was measured at 5 points, and the average value was taken as the thickness of each solid electrolyte layer. did.
  • the average thickness t1 of the thickest interlayer solid electrolyte layer is 10.70 ⁇ m
  • the average thickness t2 of the thinnest interlayer solid electrolyte is 5.98 ⁇ m
  • t1 / t2 . rice field.
  • T 8.67 ⁇ m
  • Examples 2 to 9, Comparative Examples 1 to 4 An evaluation cell was produced in the same manner as in Example 1 except that the values of t1, t2, and T were changed by changing the electrode layer unit used when producing the laminate.
  • Example 10 (Preparation of Paste-02 for Solid Electrolyte Layer)
  • the solid electrolyte powder-02 prepared by the following method was used.
  • Li 2 CO 3 , Al 2 O 3 , GeO 2 , and NH 4 H 2 PO 4 were used as starting materials, dispersed in pure water, and then wet-mixed with a ball mill for 12 hours. .. After mixing, it was dehydrated and dried, and then the obtained powder was calcined in the air at 800 ° C. for 2 hours. After calcining, it was dispersed in pure water, and then wet pulverized with a ball mill for 8 hours. After pulverization, it was dehydrated and dried to obtain a solid electrolyte powder-02.
  • paste-02 for margin layer To prepare the paste-02 for the margin layer, add 100 parts of the obtained solid electrolyte powder-02 to 100 parts of ethanol and 100 parts of toluene as a solvent and wet-mix them with a ball mill, and then 16 parts of a polyvinyl butyral binder and phthalic acid. 4.8 parts of benzyl butyl was further added and mixed to prepare a paste-02 for a margin layer.
  • Example 10 An evaluation cell of Example 10 was prepared in the same manner as in Example 1 except that the solid electrolyte sheet-02, the outermost layer sheet-02, and the margin layer paste-02 were used.
  • Example 11 to 18, Comparative Examples 5 to 8 Examples 11 to 18 and Comparative Example 5 are the same as in Example 10 except that the values of t1, t2, and T are changed by changing the electrode layer unit and the like used when producing the laminate. Evaluation cells of No. 8 were prepared.
  • the output characteristics of the evaluation cells produced in this example and the comparative example were evaluated by charging and discharging under the charging and discharging conditions shown below.
  • the charge / discharge current will be referred to as the C (sea) rate notation hereafter.
  • the C rate is expressed as nC ( ⁇ A) (n is a numerical value) and means a current capable of charging / discharging a nominal capacitance ( ⁇ Ah) at 1 / n (h).
  • 1C means a charge / discharge current capable of charging the nominal capacity in 1h
  • 2C means a charge / discharge current capable of charging the nominal capacity in 0.5h.
  • the current of 0.2C is 20 ⁇ A
  • the current of 1C is 100 ⁇ A.
  • the output characteristic evaluation conditions were as follows. In a normal temperature environment, constant current charging (CC charging) is performed at a constant current of 0.2C rate until the battery voltage reaches 1.6V, and then constant voltage charging (CV charging) is performed up to a current value of 0.05C rate. went. After charging, after a 5-minute pause, the battery was discharged at a constant current of 0.2 C rate until the battery voltage reached 0 V (CC discharge). The obtained discharge capacity was defined as 0.2C discharge capacity.
  • CC charging constant current charging
  • CV charging constant voltage charging
  • the ratio of the 1.0C discharge capacity to the 0.2C discharge capacity was calculated by the following formula (1) as the output characteristic in this embodiment.
  • Output characteristics (%) (1.0C discharge capacity ⁇ 0.2C discharge capacity) x 100 ... (1)
  • Table 1 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 1 to 18 and Comparative Examples 1 to 8.
  • the ratio t1 / t2 of the average thickness t1 of the thickest solid electrolyte layer to the average thickness t2 of the thinnest solid electrolyte is 1.02 ⁇ t1 / t2 ⁇ . It can be confirmed that excellent output characteristics can be obtained in the range of 1.99.
  • Example 19 to 26 For evaluation of Examples 10 to 17 in the same manner as in Example 1 except that the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the electrode layer unit used when producing the laminate. A cell was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • Example 27 to 34 For evaluation of Examples 27 to 34 in the same manner as in Example 10 except that the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the electrode layer unit used when producing the laminate. A cell was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • Example 35 (Preparation of paste for intermediate layer)
  • the powder of lithium vanadium phosphate prepared in Example 1 and the powder of lithium aluminum aluminum phosphate were wet-mixed with a ball mill for 16 hours, and dehydrated and dried. After drying, the obtained powder was calcined at 850 ° C. for 2 hours in a nitrogen-hydrogen mixed gas. The calcined product was wet-pulverized with a ball mill and then dehydrated and dried to obtain a base powder for an intermediate layer.
  • the electrode layer unit was formed in the same manner as in Example 3 except that the intermediate layer paste was used on the solid electrolyte sheet and the intermediate layer having a thickness of 2 ⁇ m was formed by screen printing. Made.
  • Example 36 In the preparation of the paste for the intermediate layer, the electrode layer unit was prepared in the same manner as in Example 35, except that titanium oxide (TiO 2) was used as the base powder for the intermediate layer.
  • TiO 2 titanium oxide
  • Example 37 An electrode layer unit was prepared in the same manner as in Example 35, except that aluminum oxide (Al 2 O 3 ) was used as the base powder for the intermediate layer in the preparation of the paste for the intermediate layer.
  • aluminum oxide Al 2 O 3
  • Example 38 An electrode layer unit was prepared in the same manner as in Example 35, except that zirconium oxide (ZrO 2 ) was used as the base powder for the intermediate layer in the preparation of the paste for the intermediate layer.
  • zirconium oxide ZrO 2
  • Example 39 An electrode layer unit was prepared in the same manner as in Example 12 except that zirconium oxide (ZrO 2 ) was used as the base powder for the intermediate layer in the preparation of the paste for the intermediate layer.
  • zirconium oxide ZrO 2
  • the cross section of the obtained electrode layer unit was observed using a scanning electron microscope energy dispersive X-ray spectrometer (SEM-EDS), and the constituent elements contained in the intermediate layer were analyzed.
  • SEM-EDS scanning electron microscope energy dispersive X-ray spectrometer
  • Evaluation cells of Examples 35 to 39 were prepared in the same manner as in Example 3 except that the obtained electrode layer unit was used, and evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.
  • the positive electrode active material paste is prepared using lithium iron phosphate (LiFePO 4 ) as the active material powder, and the negative electrode is prepared using lithium titanate (Li 4 Ti 5 O 12) as the active material powder.
  • An active material paste was prepared.
  • a sheet of the electrode layer unit was prepared in the same manner as in Example 1 except that the prepared paste for the positive electrode active material layer and the paste for the negative electrode active material layer were used.
  • the electrode layer unit prepared using the positive electrode active material layer paste was designated as the positive electrode layer unit, and the electrode layer unit prepared using the negative electrode active material layer paste was designated as the negative electrode layer unit.
  • Example 40 In the production of the laminate, the obtained plurality of positive electrode layer units and negative electrode layer units were alternately laminated while being offset so that one end of the positive electrode layer unit and one end of the negative electrode layer unit did not match.
  • the evaluation cell of Example 40 was prepared in the same manner as in Example 1.
  • Example 41 to 48 Comparative Examples 9 to 12
  • the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the positive electrode layer unit and the negative electrode unit used when producing the laminate. Evaluation cells of 41 to 48 and Comparative Examples 9 to 12 were prepared.
  • the output characteristic evaluation conditions were as follows. In a normal temperature environment, constant current charging (CC charging) is performed at a constant current of 0.2C rate until the battery voltage reaches 3.0V, and then constant voltage charging (CV charging) is performed up to a current value of 0.05C rate. went. After charging, after a 5-minute pause, the battery was discharged at a constant current of 0.2 C rate until the battery voltage reached 1.5 V (CC discharge). The obtained discharge capacity was defined as 0.2C discharge capacity.
  • CC charging constant current charging
  • CV charging constant voltage charging
  • Table 4 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 40 to 48 and Comparative Examples 9 to 12.
  • Example 49 (Preparation of paste-03 for solid electrolyte layer)
  • the solid electrolyte powder-03 prepared by the following method was used.
  • a method for producing the precursor first, Li 2 CO 3 and SiO 2 were mixed and calcined at 800 ° C. to synthesize a precursor.
  • the obtained precursor and Li 3 PO 4 were mixed, pressed at a pressure of 34.5 MPa, and calcined at 1000 ° C. Then, a heat treatment was performed at 400 ° C. to remove impurities on the surface. After the heat treatment, the solid electrolyte powder-03 was obtained by performing dry pulverization with a ball mill for 8 hours.
  • the margin layer paste-03 is obtained by adding 100 parts of the obtained solid electrolyte powder-03 to 100 parts of ethanol and 100 parts of toluene as a solvent and wet-mixing them with a ball mill, and then 16 parts of a polyvinyl butyral binder and phthalic acid. 4.8 parts of benzyl butyl was further added and mixed to prepare a paste for the margin layer-03.
  • Example 49 The evaluation cell of Example 49 was used in the same manner as in Example 40, except that the solid electrolyte sheet-03, the outermost layer sheet-03, and the margin layer paste-03 were used when producing the laminate. Made.
  • Example 50 to 57 Comparative Examples 13 to 16
  • the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the positive electrode layer unit and the negative electrode unit used when producing the laminate. Evaluation cells of 50 to 57 and Comparative Examples 13 to 16 were prepared.
  • Table 5 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 49 to 57 and Comparative Examples 13 to 16. The output characteristics were evaluated under the same evaluation conditions as in Example 40.
  • Example 58 (Preparation of Paste-04 for Solid Electrolyte Layer)
  • solid electrolyte powder-04 prepared by the following method was used.
  • LiCO 3 , La (OH) 3 , and ZrO 2 were dispersed in ethanol as starting materials, and then wet-mixed with a ball mill for 12 hours. After mixing, the powder obtained after drying was heat-treated at 900 ° C. for 5 hours. After the heat treatment, dry pulverization was carried out in a ball mill for 12 hours to obtain a solid electrolyte powder-04.
  • the margin layer paste-04 is obtained by adding 100 parts of the obtained solid electrolyte powder-04 to 100 parts of ethanol and 100 parts of toluene as a solvent and wet-mixing them with a ball mill, and then 16 parts of a polyvinyl butyral binder and phthalic acid. 4.8 parts of benzyl butyl was further added and mixed to prepare a paste for a margin layer-04.
  • Example 58 The evaluation cell of Example 58 was used in the same manner as in Example 40, except that the solid electrolyte sheet-04, the margin layer paste-04, and the outermost layer sheet-04 were used when producing the laminate. Made.
  • Example 59 to 66 Comparative Examples 17 to 20
  • the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the positive electrode layer unit and the negative electrode unit used when producing the laminate. Evaluation cells of 59 to 66 and Comparative Examples 17 to 20 were prepared.
  • Table 6 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 58 to 66 and Comparative Examples 17 to 20. The output characteristics were evaluated under the same evaluation conditions as in Example 40.
  • the solid electrolyte powder-05 prepared by the following method was used.
  • a method for producing the same first, LiCO 3 , La 2 O 3 , and TiO 2 were used as starting materials and dry-mixed in an agate mortar. After mixing, the obtained powder was heat-treated at 1100 ° C. for 12 hours and then sintered at 1250 ° C. for 5 hours. After sintering, the mixture was rapidly cooled to room temperature, and then subjected to dry pulverization in a ball mill for 12 hours to obtain a solid electrolyte powder-05.
  • paste-05 for margin layer To prepare the paste-05 for the margin layer, add 100 parts of the obtained solid electrolyte powder-05 to 100 parts of ethanol and 100 parts of toluene as a solvent and wet-mix them with a ball mill, and then 16 parts of a polyvinyl butyral binder and phthalic acid. 4.8 parts of benzyl butyl was further added and mixed to prepare a paste-05 for a margin layer.
  • a positive electrode active material paste and a negative electrode active material paste were prepared using lithium manganate (LiMn 2 O 4) as the active material powder.
  • Example 67 was prepared in the same manner as in Example 40.
  • Example 68 to 75 Comparative Examples 21 to 24
  • the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the positive electrode layer unit and the negative electrode unit used when producing the laminate. Evaluation cells of 68 to 75 and Comparative Examples 21 to 24 were prepared.
  • the output characteristic evaluation conditions were as follows. In a normal temperature environment, constant current charging (CC charging) is performed at a constant current of 0.2C rate until the battery voltage reaches 2.0V, and then constant voltage charging (CV charging) is performed up to a current value of 0.05C rate. went. After charging, after a 5-minute pause, the battery was discharged at a constant current of 0.2 C rate until the battery voltage reached 0.5 V (CC discharge). The obtained discharge capacity was defined as 0.2C discharge capacity.
  • CC charging constant current charging
  • CV charging constant voltage charging
  • Table 7 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 67 to 68 and Comparative Examples 21 to 24.
  • the solid electrolyte powder-06 prepared by the following method was used.
  • a method for producing the precursor A first, LiOH ⁇ H 2 O and H 3 BO 3 were mixed, placed in an alumina crucible, and heat-treated at 600 ° C. for 3 hours in an air atmosphere to obtain a precursor A.
  • Li 2 SO 4 ⁇ H 2 O was heat-treated at 300 ° C. for 2 hours in an air atmosphere to obtain precursor B.
  • the obtained precursor A and precursor B were mixed and mechanically milled with a ball mill for 100 hours to obtain a solid electrolyte powder-06.
  • Example 76 The evaluation cell of Example 76 was used in the same manner as in Example 40, except that the solid electrolyte sheet-06, the outermost layer sheet-06, and the margin layer paste-06 were used when producing the laminate. Made.
  • Example 77 to 84 Comparative Examples 25 to 28
  • the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the positive electrode layer unit and the negative electrode unit used when producing the laminate. Evaluation cells of 77 to 84 and Comparative Examples 25 to 28 were prepared.
  • Table 8 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 76 to 84 and Comparative Examples 25 to 28. The output characteristics were evaluated under the same evaluation conditions as in Example 40.
  • Example 85 (Preparation of paste-07 for solid electrolyte layer)
  • the solid electrolyte powder-07 prepared by the following method was used.
  • a method for producing the precursor A first, LiOH ⁇ H 2 O and H 3 BO 3 were mixed, placed in an alumina crucible, and heat-treated at 600 ° C. for 3 hours in an air atmosphere to obtain a precursor A.
  • Li 2 SO 4 ⁇ H 2 O was heat-treated at 300 ° C. for 2 hours in an air atmosphere to obtain precursor B.
  • Li 2 CO 3 was mixed with the obtained precursor A and precursor B, and mechanical milling was performed for 100 hours with a ball mill to obtain a solid electrolyte powder-07.
  • Example 85 The evaluation cell of Example 85 was used in the same manner as in Example 40, except that the solid electrolyte sheet-07, the outermost layer sheet-07, and the margin layer paste-07 were used when producing the laminate. Made.
  • Example 86 to 93 Comparative Examples 29 to 32
  • the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed by changing the positive electrode layer unit and the negative electrode unit used when producing the laminate. Evaluation cells of 86 to 93 and Comparative Examples 29 to 32 were prepared.
  • Table 9 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 85 to 93 and Comparative Examples 29 to 32. The output characteristics were evaluated under the same evaluation conditions as in Example 40.
  • Example 94 (Preparation of Sheet-08 for Solid Electrolyte Layer)
  • a solid electrolyte sheet-08 prepared by the following method was used.
  • PEO polyethylene oxide
  • LiTFS LiCF 3 SO 3
  • Teflon Teflon sheet
  • a sheet was formed using a Teflon sheet as a base material by a doctor blade method, dried at room temperature for 24 hours, and then vacuum dried at 60 ° C. to obtain a solid electrolyte layer sheet-07.
  • a thickness in the range of 5 to 15 ⁇ m a plurality of sheets-08 for the solid electrolyte layer having different thicknesses were produced.
  • the active material layer region on both sides of the aluminum foil After forming the active material layer region on both sides of the aluminum foil, it was rolled using a roll press and then punched to an electrode size of 27 mm ⁇ 30 mm using a mold to prepare a positive electrode sheet. At this time, punching was performed so as to include a region in which the active material layer did not exist.
  • Example 95 to 102 Comparative Examples 33 to 36
  • Example 95 to 95 In the same manner as in Example 94, Examples 95 to 95, except that the thickness of the solid electrolyte sheet-08 used when producing the laminate was adjusted and the standard deviation ⁇ in the average thickness of the solid electrolyte layer was changed. Evaluation cells of 102 and Comparative Examples 33 to 36 were prepared.
  • Table 10 shows the evaluation results of the standard deviation ⁇ and the output characteristics of t1, t2, T and the calculated solid electrolyte layer in Examples 94 to 102 and Comparative Examples 33 to 36. The output characteristics were evaluated under the same evaluation conditions as in Example 40.

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