WO2024005181A1 - 全固体二次電池 - Google Patents

全固体二次電池 Download PDF

Info

Publication number
WO2024005181A1
WO2024005181A1 PCT/JP2023/024343 JP2023024343W WO2024005181A1 WO 2024005181 A1 WO2024005181 A1 WO 2024005181A1 JP 2023024343 W JP2023024343 W JP 2023024343W WO 2024005181 A1 WO2024005181 A1 WO 2024005181A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
negative electrode
layer
electrode layer
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/024343
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
啓子 竹内
久司 小宅
雅之 室井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Corp
Original Assignee
TDK Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TDK Corp filed Critical TDK Corp
Priority to US18/858,526 priority Critical patent/US20250279486A1/en
Priority to JP2024530991A priority patent/JPWO2024005181A1/ja
Priority to EP23831620.2A priority patent/EP4550511A1/en
Priority to CN202380024087.3A priority patent/CN118872118A/zh
Publication of WO2024005181A1 publication Critical patent/WO2024005181A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/02—Details
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid-state secondary battery. This application claims priority based on Japanese Patent Application No. 2022-105471 filed in Japan on June 30, 2022, the contents of which are incorporated herein.
  • Lithium ion secondary batteries that are currently in general use have conventionally used an electrolyte (electrolyte) such as an organic solvent as a medium for moving ions.
  • electrolyte electrolyte
  • organic solvent used in the electrolyte is a flammable substance, there is a need for a battery with higher safety.
  • Patent Documents 1 and 2 a so-called all-solid-state secondary battery that uses a solid electrolyte instead of an electrolytic solution has been proposed (for example, Patent Documents 1 and 2).
  • the all-solid-state secondary batteries of Patent Documents 1 and 2 include a laminate in which a positive electrode layer including a positive electrode active material layer and a negative electrode layer including a negative electrode active material layer alternately overlap with each other with a solid electrolyte layer interposed therebetween; A pair of external electrodes are provided so as to be in contact with each other and to face each other.
  • a positive electrode current collector and a negative electrode current collector are connected to a positive electrode external terminal and a negative electrode external terminal, respectively, and the positive electrode current collector expands and contracts during charging and discharging. If the negative electrode current collector peels off from the positive external terminal, or if the negative electrode current collector peels off from the negative external terminal, there is a concern that the cycle characteristics will deteriorate.
  • the all-solid-state secondary battery of Patent Document 1 aims to improve the adhesion between materials of the same type and achieve high energy density, and also includes means for buffering stress caused by expansion and contraction of the electrode layer. is not provided at all, and as the electrode layer expands and contracts, the current collector may peel off from the external electrode terminal, or cracks may occur in the solid electrolyte layer, resulting in a short circuit.
  • the present invention was made in view of the above circumstances, and suppresses the occurrence of cracks from the end toward an electrode layer having a different polarity from the electrode layer due to the expansion and contraction of the electrode active material during charging and discharging.
  • the purpose is to
  • the all-solid-state secondary battery according to the first aspect of the present invention includes: A laminate in which a positive electrode layer containing a positive electrode active material and a negative electrode layer containing a negative electrode active material are stacked with a solid electrolyte layer interposed therebetween; a positive electrode external terminal that is bonded to the positive electrode layer on a first side of the laminate; and a negative external terminal that is bonded to the negative electrode layer on a second side of the laminate that is different from the first surface.
  • the laminate includes: a region surrounded by the positive electrode layer and the first surface; a region surrounded by the positive electrode layer, the solid electrolyte layer, and the first surface; a region surrounded by the negative electrode layer and the second surface; a region surrounded by the negative electrode layer, the solid electrolyte layer, and the second surface; A void is formed in at least one region of.
  • the ratio of the length of the void to the distance between the negative electrode layer and the first surface is 20% to 100%.
  • the ratio of the length of the void to the distance between the positive electrode layer and the second surface in the in-plane direction of the positive electrode layer may be 20% to 100%.
  • the angle formed through the gap between the two layers that define the gap may be 30° or less.
  • the laminate includes a plurality of positive electrode layers including the outermost positive electrode layer located at the end in the stacking direction, and a plurality of positive electrode layers located at the end in the stacking direction.
  • the laminate includes a plurality of negative electrode layers including an outermost negative electrode layer and a plurality of solid electrolyte layers, and the laminate includes a region surrounded by the outermost positive electrode layer and the first surface, and a region surrounded by the outermost positive electrode layer and the first surface.
  • a void may be formed in at least one region of the enclosed region.
  • the laminate may include a plurality of positive electrode layers and a plurality of negative electrode layers, and the plurality of positive electrode layers and the The ratio of the sum of the number of positive electrode layers in contact with the voids and the number of negative electrode layers in contact with the voids to the total number of the plurality of negative electrode layers may be 10% or more.
  • the positive electrode layer includes a positive electrode current collector and a positive electrode active material layer
  • the negative electrode layer includes a negative electrode current collector and a negative electrode active material layer.
  • the void may be in contact with the positive electrode active material layer or the negative electrode active material layer.
  • At least one of the positive electrode active material and the negative electrode active material may be AgPd.
  • cracks are formed from the end portion through the solid electrolyte layer to an electrode layer having a different polarity from the above electrode layer, or to an external terminal having a different polarity. The occurrence can be suppressed.
  • FIG. 1 is a sectional view of an all-solid-state secondary battery according to an embodiment of the present invention.
  • 2 is a sectional view showing a modification of the all-solid-state secondary battery of FIG. 1.
  • FIG. 2 is a sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • FIG. 2 is a sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • FIG. 2 is a sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • FIG. 2 is a sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • FIG. 1 is a sectional view of an all-solid-state secondary battery according to an embodiment of the present invention.
  • the all-solid-state secondary battery 100A shown in FIG. 1 includes a laminate 1A in which a positive electrode layer 10A and a negative electrode layer 20A are laminated with a solid electrolyte layer 30 interposed therebetween, a positive electrode external terminal 2 connected to the laminate 1A, and a negative electrode external A terminal 3 is provided.
  • the stacking direction of the positive electrode layer 10A and the negative electrode layer 20A in the laminate 1A is the z direction
  • the direction in which the positive electrode layer 10A and the negative electrode layer 20A extend in FIG. 1 is a direction perpendicular to the z direction. Let the direction be the x direction, and let the direction perpendicular to the x and z directions be the y direction.
  • the laminate 1A has a substantially hexahedral shape, and has an upper surface St and a lower surface Sb, which are end surfaces in the lamination direction, and four side surfaces parallel to the lamination direction.
  • the end surface that joins to the positive electrode layer 10A is referred to as a first surface S1
  • the end surface that joins to the negative electrode layer 20A is referred to as a second surface S2.
  • the first surface S1 and the second surface S2 are end surfaces in the x direction.
  • the laminate included in the all-solid-state secondary battery according to the present embodiment includes a region surrounded by the positive electrode layer 10 and the first surface S1, a region surrounded by the positive electrode layer 10, the solid electrolyte layer 30, and the first surface S1, A void is provided in at least one of the region surrounded by the negative electrode layer 20 and the second surface S2, and the region surrounded by the negative electrode layer 20, the solid electrolyte layer 30, and the second surface S2.
  • the laminate 1A shown in FIG. 1 has a void 50a in a region surrounded by the positive electrode layer 10 and the first surface S1, and has a void 50b in a region surrounded by the negative electrode layer 20 and the second surface S2.
  • the positive electrode layer 10A includes a positive electrode active material.
  • the positive electrode layer 10A includes, for example, a positive electrode current collector 11A and a positive electrode active material layer 12A provided on at least one of the main surfaces of the positive electrode current collector 11A.
  • the positive electrode layer 10A is joined to the positive external terminal 2 on the first surface S1.
  • the positive electrode layer 10A spreads in the direction from the first surface S1 to the second surface S2.
  • the positive electrode layer 10A does not extend to the second surface S2.
  • the end on the first surface S1 side that is, the end in the ⁇ x direction
  • the end on the opposite side that is, the end in the +x direction is referred to as one end that does not extend to the side surface.
  • the positive electrode current collector 11A is made of, for example, a material with high conductivity.
  • the positive electrode current collector 11A is made of, for example, at least one of silver (Ag), palladium (Pd), gold (Au), platinum (Pt), aluminum (Al), copper (Cu), and nickel (Ni). It is composed of a metal or alloy containing a metal element, or a non-metal such as carbon (C). An example of such an alloy is AgPd.
  • the positive electrode current collector 11A has, for example, a flat portion 11Ap that extends in a direction intersecting the stacking direction and has a substantially flat shape, and a flat portion 11A that is located closer to the positive electrode external terminal 2 than the flat portion 11Ap and is curved in the stacking direction. It has a curved portion 11Aw.
  • the curved portion 11Aw is joined to the positive external terminal 2.
  • the angle between the curved portion 11Aw of the positive electrode current collector 11A and the positive external terminal 2 is, for example, 45° to 90°, and may be 60° to 90°.
  • the curved portion 11Aw has a shape that is spaced apart from the positive electrode active material layer 12A in the lamination direction as it approaches the positive electrode external terminal 2 in the x direction, and has a linear shape or a shape that is spaced apart from the positive electrode active material layer 12A in the lamination direction as it approaches the positive electrode external terminal 2 in the x direction.
  • the shape may be such that it approaches the positive electrode current collector 11A.
  • the positive electrode layer 10A When the positive electrode layer 10A is composed of a flat part 11Ap and a curved part 11Aw of the current collector, and a flat part 12Ap of the active material layer, the curved part 11Aw of the current collector and the flat part 12Ap of the active material layer are separated from each other. become. That is, the positive electrode layer 10A has an open structure at one extending end.
  • the angle of the curved portion 11Aw with respect to the flat portion 11Ap is, for example, greater than 0° and less than or equal to 45°, and preferably greater than 0° and less than or equal to 30°.
  • the positive electrode active material layer 12A includes, for example, a positive electrode active material layer flat portion 12Ap that extends in a direction intersecting the stacking direction and has a substantially flat shape.
  • the flat portion 12Ap is joined to the positive external terminal 2.
  • the flat portion 12Ap has an angle of 80° to 90° with the positive external terminal 2 at one extending end.
  • the positive electrode active material layer 12A includes a known compound capable of inserting and extracting at least lithium ions as a positive electrode active material.
  • the positive electrode active material is, for example, a compound that exhibits a more noble potential than the negative electrode active material.
  • the positive electrode active material layer 12A may also contain a conductive aid or an ion conductive aid. It is preferable that the positive electrode active material can efficiently insert and extract lithium ions.
  • the positive electrode active material includes transition metal oxides and transition metal composite oxides.
  • each element may be replaced with a different element, or the composition may be changed from a stoichiometric composition.
  • Examples of the conductive aid include carbon materials such as carbon black, acetylene black, Ketjen black, carbon nanotubes, graphite, graphene, and activated carbon, and metal materials such as gold, silver, palladium, platinum, copper, and tin.
  • An example of the ion-conducting aid is a solid electrolyte.
  • the same material as the material used for the solid electrolyte layer 30 can be used for the solid electrolyte.
  • the ion-conducting auxiliary agent and the solid electrolyte used for the solid electrolyte layer 30 use the same material.
  • the negative electrode layer 20A includes a negative electrode active material.
  • the negative electrode layer 20A includes, for example, a negative electrode current collector 21A and a negative electrode active material layer 22A provided on at least one of the main surfaces of the negative electrode current collector 21A.
  • the negative electrode active material layer 22A is located, for example, on the inside in the stacking direction with respect to the negative electrode current collector 21A.
  • the negative electrode layer 20A is joined to the negative external terminal 3 at the second surface S2.
  • the negative electrode layer 20A spreads in the direction from the second surface S2 toward the first surface S1.
  • the negative electrode layer 20A does not extend to the first surface S1.
  • the end on the second surface S2 side that is, the end in the +x direction is referred to as one end extending to the side surface, and is opposite to the one end extending to the side.
  • the side end, that is, the end in the ⁇ x direction is called one end that does not extend to the side.
  • the negative electrode current collector 21A includes, for example, a flat portion 21Ap that extends in a direction intersecting the stacking direction and has a substantially flat shape.
  • the negative electrode active material layer 22A has, for example, a flat portion 22Ap that extends in a direction intersecting the lamination direction and has a substantially flat shape, and a flat portion 22A that is located closer to the negative electrode external terminal 3 than the flat portion 22Ap and is curved in the lamination direction. It has a curved portion 22Aw.
  • the curved portion 22Aw is joined to the negative external terminal 3.
  • the angle between the curved portion 22Aw of the negative electrode active material layer 22A and the negative external terminal 3 is, for example, 45° to 90°, and may be 60° to 90°.
  • the curved portion 22Aw has a shape that is spaced apart from the negative electrode current collector 21A in the stacking direction as it approaches the negative electrode external terminal 3 in the x direction, and has a linear shape or a shape that moves away from the negative electrode current collector 21A as it approaches the negative electrode external terminal 3 in the x direction.
  • the shape may be such that it approaches the negative electrode current collector 21A.
  • the negative electrode layer 20A When the negative electrode layer 20A is composed of the flat part 21Ap, the flat part 22Ap, and the curved part 22Aw in this way, it has a structure in which the flat part 21Ap and the curved part 22Aw are spaced apart. That is, the negative electrode layer 20A has an open structure at one extending end.
  • the angle of the curved portion 22Aw with respect to the flat portion 21Ap is, for example, 45° or less, and preferably 30° or less.
  • the negative electrode current collector 21A is made of, for example, a material with high conductivity.
  • the same material as the positive electrode current collector 11A can be used for the negative electrode current collector 21A.
  • the negative electrode active material layer 22A includes, as a negative electrode active material, a known compound capable of inserting and extracting at least lithium ions.
  • the negative electrode active material is, for example, a compound that exhibits a lower potential than the positive electrode active material.
  • the negative electrode active material layer 22A may also contain a conductive aid or an ion conductive aid. It is preferable that the negative electrode active material can efficiently insert and desorb lithium ions.
  • the solid electrolyte layer 30 includes, for example, an interlayer solid electrolyte layer 31 located between the positive electrode layer 10A and the negative electrode layer 20A, and a margin layer 32 arranged in line with each of the positive electrode layer 10A and the negative electrode layer 20A.
  • the solid electrolyte layer located outside the electrode layer at the end in the stacking direction may also be referred to as an interlayer solid electrolyte layer.
  • the solid electrolyte layer 30 may be made of a perovskite compound such as La 0.5 Li 0.5 TiO 3 , a lysicone compound such as Li 14 Zn(GeO 4 ) 4 , or a garnet compound such as Li 7 La 3 Zr 2 O 12 type compound, LiZr 2 (PO 4 ) 3 , Li 1+x Al x Ti 2-x (PO 4 ) 3 ; LATP(Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ), thiolicone type compounds such as Li 3.25 Ge 0.25 P 0.75 S 4 and Li 3 PS 4 , Li 2 S-P 2 Glass compounds such as S 5 and Li 2 O-V 2 O 5 -SiO 2 , Li 3 PO 4 and Li 3.5 Si 0.5 P 0.5 O 4 (LSPO)
  • a perovskite compound such as La 0.5 Li 0.5 TiO 3
  • a lysicone compound such as Li 14
  • the thickness of the interlayer solid electrolyte layer 31 is preferably in the range of, for example, 0.5 ⁇ m or more and 20.0 ⁇ m or less. By increasing the thickness of the interlayer solid electrolyte layer 31, it is easier to obtain the effect of suppressing a short circuit between the positive electrode layer 10A and the negative electrode layer 20A that sandwich the interlayer solid electrolyte layer 31 therebetween. In addition, by setting the thickness of the interlayer solid electrolyte layer 31 to 20.0 ⁇ m or less, the moving distance of lithium ions can be shortened, so that internal resistance can be easily reduced.
  • the laminate 1A may include a solid electrolyte and may include a margin layer 32 arranged in line with each of the positive electrode layer 10A and the negative electrode layer 20A.
  • the margin layer 32 may be considered a part of the solid electrolyte layer 30.
  • the margin layer 32 is provided, for example, in order to eliminate a step between the positive electrode layer 10A and the interlayer solid electrolyte layer 31 at one end that does not extend, and a step between the negative electrode layer 20A and the interlayer solid electrolyte layer 31 at one end that does not extend. There is. Therefore, for example, on the main surface of the interlayer solid electrolyte layer 31, the margin layer 32 is placed at one end of each electrode layer that does not extend, at approximately the same height as the positive electrode layer 10A or the negative electrode layer 20A (that is, the positive electrode layer 10A and the negative electrode layer 20A). 20A).
  • the margin layer 32 eliminates the level difference between the interlayer solid electrolyte layer 31 and the positive electrode layer 10A, as well as the interlayer solid electrolyte layer 31 and the negative electrode layer 20A, so that the solid electrolyte layer 30 and each electrode layer at one end where each electrode layer does not extend are removed.
  • the density increases, and even if processing is performed to form voids as described below, delamination may occur due to firing of the all-solid-state secondary battery, or unintended damage at one end that does not extend. Warpage is less likely to occur.
  • the distance between the end of the positive electrode layer 10A and the second surface S2 and the distance between the end of the negative electrode layer 20A and the first surface S1 at one end that does not extend are, for example, the same.
  • FIG. 1 shows an all-solid-state secondary battery 100A in which the distance between the end of the positive electrode layer 10A and the second surface S2 and the distance between the end of the negative electrode layer 20A and the first surface S1 at one end that does not extend are the same, The distance is indicated by the symbol L32 .
  • a gap 50a is formed between the positive electrode layer 10A and the first surface S1.
  • the void 50a is defined in the positive electrode layer 10A and the first surface S1. More specifically, the void 50a is defined by the current collector flat portion 11Ap, the curved portion 12Aw, and the first surface S1.
  • the void 50a has a length L50a in the x direction and a length (height) h50a in the z direction.
  • the angle ⁇ 50a of the gap 50a which is the angle formed through the two-layer gap 50a that defines the corner of the gap 50a, is, for example, 45° or less, and preferably 30° or less.
  • the two layers that define the corner of the gap 50a are the positive electrode current collector 11A and the positive electrode active material layer 12A, and more specifically, the positive electrode current collector flat part 11Ap and the curved part 12w. be.
  • the angle of the gap 50a can be calculated based on the length L50a and the height h50a, for example.
  • the shape of the void 50a is assumed to be a right triangle in which the positive electrode active material layer 12A and the first surface S1 are orthogonal to each other, and for example, if (height h50a/length L50a) 2 is 1/3 or less, the positive electrode It is confirmed that the angle ⁇ 50a formed by the curved portion 11Aw of the current collector 11A and the flat portion 12Ap of the positive electrode active material layer with the gap 50a in between is 30° or less.
  • the shape of the void 50b is a right triangle in which the negative electrode current collector 21A and the second surface S2 are orthogonal, for example, if (height h50b/length L50b) 2 is 1/3 or less, the negative electrode It is confirmed that the angle ⁇ 50b formed by the curved portion 22Aw of the active material layer 22A and the gap 50b of the negative electrode current collector 21A is 30° or less.
  • the distance between the negative electrode layer 20A and the first surface S1 and the distance between the positive electrode layer 10A and the second surface S2 are, for example, substantially the same and are indicated by the symbol L32 .
  • the ratios (L 50a /L 32 ) and (L 50b /L 32 ) of the lengths L 50a and L 50b of the voids 50a and 50b to the length L 32 are, for example, 5 to 150 and 20 to 100%. is preferably 50% to 100%.
  • the ratio (L 50a /L 32 ) is 20 or more, stress caused by expansion and contraction of the electrode active material layer during charging and discharging can be further alleviated.
  • the ratios (L 50a /L 32 ) and (L 50b /L 32 ) to 100% or less, the voids become excessively large, making it difficult to inhibit the movement of carriers and electrons.
  • the all-solid-state secondary battery 100A can be manufactured, for example, using the following co-firing method.
  • the co-firing method is a method of producing a laminate by simultaneously firing different materials that are the base materials of the laminate.
  • the co-firing method is used, the number of working steps for the all-solid-state secondary battery 100 can be reduced.
  • the simultaneous firing method is used, the obtained laminate 1A becomes denser.
  • the method for manufacturing an all-solid-state secondary battery includes, for example, a pasting step of creating a paste of each material constituting the laminate, and a step of applying and drying a solid electrolyte paste to form a solid electrolyte layer sheet.
  • the method includes a lamination step of producing a base material of the laminate, and a firing step of simultaneously firing the base material of the produced laminate. Each step will be explained in more detail below.
  • each material of the positive electrode current collector 11A, the positive electrode active material layer 12A, the solid electrolyte layer 30, the negative electrode current collector 21A, and the negative electrode active material layer 22A is made into a paste.
  • the method of pasting is not particularly limited.
  • a paste can be obtained by mixing powders of each material in a vehicle.
  • the vehicle is a general term for a medium in a liquid phase.
  • Vehicles include solvents and binders.
  • the binder contained in the paste is not particularly limited, but polyvinyl acetal resin, cellulose resin, acrylic resin, urethane resin, vinyl acetate resin, polyvinyl alcohol resin, etc. can be used.
  • a paste for a positive electrode current collector 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, and a paste for a negative electrode current collector are produced.
  • a resin paste for forming voids is separately produced using the same method.
  • the resin paste contains only resin as a solid content, and after firing, the resin paste becomes voids.
  • the resin may be any resin, such as ethyl cellulose or acrylic, which melts when heated to a high temperature of 400° C. or higher, further vaporizes, and detaches from the laminate.
  • Solid electrolyte layer formation process Next, a paste for solid electrolyte is applied and dried to form a solid electrolyte layer sheet.
  • a paste for a solid electrolyte layer is formed into a sheet on a PET film by a doctor blade method, and then dried to form a solid electrolyte layer sheet.
  • a positive electrode layer and a negative electrode layer are respectively formed on the solid electrolyte layer sheet to produce a positive electrode unit and a negative electrode unit, respectively.
  • the solid electrolyte layer sheet is, for example, a solid electrolyte layer sheet that becomes the interlayer solid electrolyte layer 31 after lamination and firing.
  • a paste for a positive electrode active material layer is formed on a solid electrolyte layer sheet.
  • the paste for the positive electrode active material layer is printed, for example, by screen printing, and then dried.
  • a resin part is formed by applying a resin paste to one end in the in-plane direction of the base material of the positive electrode active material layer by, for example, screen printing.
  • a paste for a positive electrode current collector is screen printed and dried.
  • the paste for the positive electrode current collector is, for example, screen printed so as to overlap the resin part and the base material for the positive electrode active material layer, and then dried.
  • a paste for the margin layer is screen printed on a region of the solid electrolyte layer sheet other than the positive electrode layer, and is dried to form a base material for the margin layer having approximately the same height as the base material for the positive electrode layer.
  • the same material as the paste for the solid electrolyte layer is used as the paste for the margin layer. Then, the PET film is peeled off. In this way, a positive electrode unit is produced in which the positive electrode current collector is formed on the base material of the solid electrolyte layer, and the resin part and the base material of the positive electrode active material layer are formed thereon.
  • the negative electrode unit is manufactured using the same procedure as the positive electrode unit.
  • the active material layers of the positive electrode unit and the negative electrode unit are stacked alternately with the solid electrolyte layer sheet interposed therebetween, and are offset and stacked so that one end of each does not overlap, thereby producing a base material for a laminate.
  • a solid electrolyte layer sheet is formed on the outside of the positive electrode unit and the negative electrode unit in the stacking direction.
  • the base material for the laminate can be pressurized all at once using a mold press, hot water isostatic press (WIP), cold water isostatic press (CIP), hydrostatic press, etc. to improve adhesion. It is preferable to pressurize while heating, and it can be carried out at, for example, 40 to 95°C.
  • the base material for the laminate is, for example, cut and shaped using a dicing device.
  • the base material of the laminate produced in the above procedure is fired to produce a laminate 1A. Note that it is preferable to perform a binder removal step before firing the laminate (binder removal step).
  • the binder removal step is carried out by placing the prepared base material for the laminate on a ceramic setter for a pedestal, and performing it for 0.1 to 10 hours at a temperature range of 300° C. to 800° C. in a nitrogen atmosphere, for example. be able to.
  • the debinding step may be performed in an argon atmosphere or a nitrogen-hydrogen mixed atmosphere, for example, instead of a nitrogen atmosphere. Further, a reducing atmosphere containing a small amount of oxygen may be used as long as the metal current collector does not oxidize.
  • the laminate 1A can be obtained by heat-treating the base material for the laminate at a temperature range of 600° C. to 1000° C. in a nitrogen atmosphere.
  • the firing time is, for example, 0.1 to 3 hours.
  • the firing may be performed in an argon atmosphere or a nitrogen-hydrogen mixed atmosphere, for example, instead of a nitrogen atmosphere.
  • a part of the electrode layer has a curved part, and a gap is formed between the electrode layer and the side surface of the laminate bonded to the electrode layer.
  • a device having a pedestal, a lid, and a pedestal can be used in the firing process.
  • a pedestal and a lid sandwiched from both sides in the stacking direction of the base material of the laminate, and a pedestal disposed between the pedestal and the lid in the in-plane direction of the base material of the laminate are used.
  • the all-solid-state secondary battery 100A can be manufactured using a ceramic setter or the like as described below.
  • the height of the side surface of the laminate before firing (the above-mentioned pedestal) is The amount of warpage is controlled to a height position h1 , which is the sum of the height increase ⁇ h corresponding to the desired warp angle after firing to the height h0 ) of the side surface of the laminate from the ceramic setter for use.
  • a method can be used in which a ceramic setter for the lid is placed to prevent the laminate from warping any further. In this method, a gap is provided between the lid ceramic setter and the laminate to form a desired warp angle.
  • the height position of the ceramic setter for the lid can be easily adjusted by arranging the height adjustment laminate and the height adjustment ceramic plate at the four corners of the ceramic setter for the base. For example, if you want to make the gap between the unfired laminate and the lid ceramic setter 10 ⁇ m, place 10 ⁇ m thick height adjustment ceramic plates on the unfired laminate at the four corners of the pedestal ceramic setter. What is necessary is to arrange a laminate for height adjustment. Moreover, rapid firing is, for example, firing at a temperature increase rate of 1000° C./hour or more.
  • the ceramic setter used for the pedestal and the lid is preferably a smooth ceramic setter in order to better control warpage. For example, a ceramic setter whose main surface is polished can be used.
  • the ceramic setter may be a dense substrate or a porous substrate having holes.
  • the material is preferably a material whose sintering temperature is higher than that of the laminate, such as zirconia or alumina. In this way, the laminate 1A can be produced.
  • the all-solid-state secondary battery 100A having the voids 50a and 50b can be manufactured by printing a resin part using a 3D printer or the like so that the voids have a desired shape.
  • the resin portion is formed so that its thickness increases as it approaches the electrode terminal.
  • a positive external terminal 2 and a negative external terminal 3 are formed on each of the first surface S1 and the second surface S2 among the side surfaces of the fired laminate 1A.
  • the positive electrode external terminal 2 and the negative electrode external terminal 3 are formed so as to be joined to the positive electrode layer 10A and the negative electrode layer 20A, respectively.
  • the positive electrode external terminal 2 and the negative electrode external terminal 3 can be formed, for example, on the positive electrode layer 10A and the negative electrode layer 20A exposed from the side surface of the laminate 1A by known means such as sputtering, dip coating, screen printing, and spray coating.
  • the positive external terminal 2 and the negative external terminal 3 so as to be bonded only to predetermined portions, they can be formed after, for example, masking with tape or the like.
  • the void 50a is provided in the region surrounded by the positive electrode current collector 11A, the positive electrode active material layer 12A, and the first surface S1, and the negative electrode active material layer 22A, the negative electrode
  • the void 50b in the region surrounded by the current collector 21A and the second surface S2 when the positive electrode active material and the negative electrode active material expand and contract during charging and discharging, the positive electrode active material layer 12A and the negative electrode active material layer, respectively.
  • the stress acting on the solid electrolyte layer 30 can be alleviated by the voids 50a and 50b in contact with the solid electrolyte layer 22A.
  • the all-solid-state secondary battery 100A since the all-solid-state secondary battery 100A has voids 50a and 50b at positions in contact with the electrode active material layer, stress from the electrode active material layer can be more easily relaxed.
  • the first surface S1 and the second surface S2 correspond to, for example, inner surfaces of the positive external terminal 2 and the negative external terminal 3, respectively.
  • the all-solid-state secondary battery according to this embodiment is not limited to the all-solid-state secondary battery 100A shown in FIG. 1, and various changes can be made within the scope of the claims.
  • the all-solid-state secondary battery according to this embodiment may be an all-solid-state secondary battery as shown in FIGS. 2 to 4.
  • the same components as the all-solid-state secondary battery 100A are designated by the same reference numerals, and the description thereof will be omitted.
  • FIG. 2 is a sectional view showing a modification of the all-solid-state secondary battery of FIG. 1.
  • the all-solid-state secondary battery 100B shown in FIG. 2 has a void 50c formed in a region surrounded by the positive electrode layer 10B and the first surface S1, and a void formed in the region surrounded by the negative electrode layer 20B and the second surface S2.
  • the shape of 50d is different from that of the all-solid-state secondary battery 100A shown in FIG.
  • the all-solid-state secondary battery 100B includes a laminate 1B in which a positive electrode layer 10B and a negative electrode layer 20B are stacked with a solid electrolyte layer 30 in between.
  • the positive electrode layer 10B includes, for example, a positive electrode current collector 11B and a positive electrode active material layer 12A provided on the main surface on the inner side in the stacking direction of the positive electrode current collector 11B.
  • the positive electrode current collector 11B has a flat portion 11Bp and an extending portion 12Bx that is located closer to the positive external terminal 2 than the flat portion 11Bp and is joined to the positive external terminal 2.
  • the extending portion 11Bx is, for example, a region that is thinner than the flat portion 11Bp and has a generally rectangular cross-sectional view, and is in contact with the solid electrolyte layer 30.
  • a void 50c is formed in a region surrounded by the extended portion 12Bx, the flat portion 12Bp, the positive electrode active material layer 12A, and the first surface S1.
  • the negative electrode layer 20B includes, for example, a negative electrode current collector 21A and a negative electrode active material layer 22B provided on the inner main surface in the stacking direction of the negative electrode current collector 21A.
  • the negative electrode active material layer 22B has a flat portion 22Bp and an extending portion 22Bx that is located closer to the negative external terminal 3 than the flat portion 22Bp and is joined to the negative external terminal 3.
  • the extending portion 22Bx is, for example, a generally rectangular region in cross section that is thinner than the flat portion 21Bp, and is in contact with the solid electrolyte layer 30.
  • a void 50d is formed in a region surrounded by the extended portion 22Bx, the flat portion 22Bp, the negative electrode current collector 21A, and the second surface S2.
  • the gaps 50c and 50d having a substantially rectangular cross-sectional shape are formed by two layers (a positive electrode current collector 11B and a positive electrode active material layer 12B, a negative electrode current collector 21A and a negative electrode
  • the angle formed through the gaps 50c and 50d of the active material layer 22B) is, for example, 0°.
  • the voids 50c and 50d have a substantially constant height in the stacking direction from the end in the +x direction to the end in the -x direction.
  • the all-solid-state secondary battery 100B can be manufactured by changing the conditions of the firing process from the manufacturing method of the all-solid-state secondary battery 100A, and keeping the other conditions the same.
  • the height of the side surface of the laminate before firing (the height of the side surface of the laminate from the ceramic setter for the pedestal described above)
  • a method can be used in which a ceramic setter for the lid is disposed at h 0 ) to control the amount of warpage to prevent the base material of the laminate from warping. In this method, no gap is provided between the lid ceramic setter and the laminate to form a desired warp angle.
  • it is not necessarily necessary to perform rapid firing, and a gentle temperature increase rate may be used.
  • FIG. 3 is a sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • the all-solid-state secondary battery 100C shown in FIG. There is a gap 50f in a region surrounded by S2.
  • the two adjacent layers that define the corner of the gap 50f are the negative electrode current collector 21C and the solid electrolyte layer 31, and more specifically, the negative electrode current collector curved portion 21Cw and the solid electrolyte layer curved portion 31Cw.
  • the angle of the gap 50f is calculated based on the length L50f and the height h50f, for example.
  • the solid electrolyte layer curved portion 31Cw is a region of the solid electrolyte layer that overlaps the curved portion 21Cw in the stacking direction, and is a region that sandwiches the gap 50f with the curved portion 21Cw.
  • the solid electrolyte layer curved portion 31Cw has peeled off from the negative electrode current collector 21C.
  • the positive electrode layer 10C includes, for example, a positive electrode current collector 11C including a flat portion 11Cp, and a positive electrode active material layer 12A provided inside the positive electrode current collector 11C in the stacking direction and comprising a flat portion 11Ap. In the vicinity of one end where the positive electrode layer 10C extends, the interlayer solid electrolyte layer 31 is, for example, missing and has a curved portion.
  • the negative electrode layer 20C includes, for example, a negative electrode active material layer 22A, and a negative electrode current collector 21C having a flat portion 21Cp and a curved portion 21Cw.
  • the negative electrode current collector 21C has, for example, a flat portion 21Cp that spreads in a direction intersecting the stacking direction and has a substantially flat shape, and a flat portion 21Cp that is located closer to the negative electrode external terminal 3 than the flat portion 21Cp and is curved in the stacking direction. It has a curved portion 21Cw.
  • the all-solid-state secondary battery 100C can be manufactured by changing the conditions of the firing process from the manufacturing method of the all-solid-state secondary battery 100A, and keeping the other conditions the same.
  • the solid electrolyte layer 30, and the first surface S1 for example, when forming the positive electrode unit, after applying the paste for the solid electrolyte layer, in the in-plane direction.
  • a resin paste is applied on one end to form a resin part, and a paste for a positive electrode active material layer and a paste for a positive electrode current collector are sequentially printed and dried so as to overlap with the resin part.
  • the solid electrolyte layer 30, and the second surface S2 for example, after applying the paste for the solid electrolyte layer, apply a resin paste on one end in the in-plane direction. is coated to form a resin part, a negative electrode current collector paste and a negative electrode current collector paste are sequentially printed and dried so as to overlap with the resin part, and then baked.
  • the lid on the one end side from which the positive electrode extends is placed at a height h0 of the side surface of the laminate from the ceramic setter for the pedestal so that the positive electrode layer 10C does not warp.
  • the lid may be placed at a position higher than the height h0 so that the negative electrode layer 20C is warped, and the firing process may be performed.
  • FIG. 4 is a cross-sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • a laminate 1D of an all-solid-state secondary battery 100D shown in FIG. 4 includes a plurality of positive electrode layers 10A, 10D, 10E and a plurality of negative electrode layers 20D, 20E, 20F.
  • the positive electrode layer 10 and the negative electrode layer 20 are alternately stacked with the solid electrolyte layer 30 interposed therebetween.
  • Laminated body 1D has voids 50a and 50g in a region surrounded by positive electrode layer 10A and first surface S1, and in a region surrounded by negative electrode layer 20E, solid electrolyte layer 30, and second surface S2.
  • the positive electrode layer 10A and the negative electrode layer 20F located at the extreme ends in the stacking direction are, for example, current collectors.
  • the active material layer is provided inside the current collector in the stacking direction.
  • the electrode layers excluding the positive electrode layer 10A and the negative electrode layer 20F located at the extreme end in the stacking direction include, for example, a current collector and an active material layer provided on both sides of the main surface of the current collector.
  • the positive electrode layers 10D and 10E include a positive electrode current collector 11 and positive electrode active material layers 12 provided on both sides of the main surface of the positive electrode current collector 11.
  • the negative electrode layer 20D includes a negative electrode current collector 21 and negative electrode active material layers 22 provided on both sides of the main surface of the negative electrode current collector 21.
  • the negative electrode layer 20E includes a negative electrode current collector and negative electrode active material layers 22Ew1 and 22Ew2 provided on both sides of the main surface of the negative electrode current collector.
  • the negative electrode layer 20E has a flat portion 21Ep that spreads in a direction crossing the lamination direction and has a substantially flat shape, and a flat portion 21Ep that is located closer to the negative electrode external terminal 3 than the flat portion 21Bp and is curved in the lamination direction.
  • a negative electrode current collector having a curved part 21Ew, a flat part 22Ep that spreads in a direction crossing the stacking direction and has a substantially flat shape, and a flat part 22Ep located closer to the negative external terminal 3 than the flat part 22Bp
  • the negative electrode active material layers 22Ew1 and 22Ew2 have curved portions 22Ew that are curved in the stacking direction.
  • a region of the solid electrolyte layer that overlaps with the curved portion 22Ew in the stacking direction and that sandwiches the gap 50g with the curved portion 22Ew is referred to as a solid electrolyte layer curved portion 31Ew.
  • the solid electrolyte layer curved portion 31Ew has peeled off from the negative electrode active material layer 22E.
  • the void 50g has, for example, a length L50g in the x direction and a height h50g in the z direction.
  • the angle of the negative electrode active material layer 22Ew2 and the interlayer solid electrolyte layer 31, which are two adjacent layers that define the gap 50g, is calculated based on the length L50g and the height h50g, for example.
  • one of the four outermost positive electrode layers and the outermost negative electrode layer located at the extreme ends in the stacking direction is in contact with the void 50a. Since the outermost positive electrode layer and the outermost negative electrode layer are in contact with the voids, it is easy to obtain the effect of suppressing cracks.
  • the total number of positive electrode layers 10A, 10D, 10E and negative electrode layers 20D, 20E, 20F The ratio of the sum of the number of positive electrode layers in contact with the voids and the number of negative electrode layers in contact with the voids is preferably 10% or more, preferably 15% or more, and more preferably 20% or more. .
  • an all-solid-state secondary battery having a plurality of positive electrode layers and negative electrode layers expands and contracts during charging and discharging
  • the electrode active material which is the starting point of stress, is located at various positions, and there is a risk of cracks occurring at various positions in the laminate. This makes it possible to relieve stress on the solid electrolyte layer 30 due to expansion and contraction of the active material during charging and discharging at various positions in the stacked body 1D, and it is easy to obtain the effect of suppressing cracks.
  • FIG. 5 is a cross-sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • the all-solid-state secondary battery 100E shown in FIG. 4 includes a positive electrode layer consisting of a positive electrode current collector 11F and a positive electrode active material layer 12F, and a negative electrode layer consisting of a negative electrode current collector 21F and a negative electrode active material layer 22F.
  • the positive electrode current collector 11F has a flat portion 11Fp having a substantially flat shape, and a curved portion 11Fw that is located closer to the positive electrode external terminal 2 than the flat portion 11Fp and is curved in the stacking direction.
  • the positive electrode active material layer 12F has a flat portion 12Fp having a substantially flat shape, and a curved portion 12Fw located closer to the positive electrode external terminal 2 than the flat portion 12Fp and curved in the stacking direction.
  • the all-solid-state secondary battery according to this embodiment includes a positive electrode current collector 11F and a positive electrode active material layer 12F that constitute a positive electrode layer 10F, and a negative electrode current collector 21F and a positive electrode active material layer 12F that constitute a negative electrode layer 20F.
  • Each of the negative electrode active material layers 22F has a convex shape in the -z direction.
  • FIG. 6 is a sectional view showing another modification of the all-solid-state secondary battery of FIG. 1.
  • the all-solid-state secondary battery 100F shown in FIG. 6 at least one of the electrode layers included in the positive electrode layer and the negative electrode layer includes a material that functions as both an electrode active material and an electrode current collector.
  • the negative electrode layer 20F includes, for example, a material that functions as both a negative electrode active material and a negative electrode current collector.
  • the electrode layer containing a material having the functions of both an electrode active material and an electrode current collector is sometimes referred to as an integrated layer. In an integrated layer, it can be said that the electrode active material layer and the electrode current collector layer are integrated.
  • Examples of materials that function as both a negative electrode active material and a negative electrode current collector include AgPd, and may also be Si alloys, Sn alloys, etc.
  • the negative electrode layer 20F includes, for example, AgPd, and may be made of an AgPd alloy.
  • the integrated layer has, for example, a flat portion 20Fp and a curved portion 20Fw.
  • the integrated layer has a flat portion 20Fp that spreads in a direction crossing the lamination direction and has a substantially flat shape, and a curved portion that is located closer to the negative electrode external terminal 3 than the flat portion 20Fp and is curved in the lamination direction. It has a section 20Fw.
  • the angle between the curved portion 20Fw and the negative external terminal 3, the shape of the curved portion 20Fw, and the angle between the flat portion 20Fp and the curved portion 20Fw can be the same as in the above embodiment.
  • the void 50f is defined by the negative electrode layer 20F, the solid electrolyte layer 31, and the second surface S2.
  • the angle, length L50f, and height h50f of the gap 50f are the same as in the above embodiment, and are calculated by the same method.
  • FIG. 6 shows an example in which the negative electrode layer is an integral layer
  • the positive electrode layer may be an integral layer.
  • FIG. 6 shows an example in which the negative electrode layer 20F has the flat portion 20Fp and the curved portion 20Fw
  • the negative electrode layer 20F may have a configuration including the flat portion 20Fp.
  • the outermost positive electrode layer and the outermost negative electrode layer refer to the outermost positive electrode layer and negative electrode layer in the stacking direction, respectively, and the all-solid secondary has two or more positive electrode layers and two or more negative electrode layers.
  • the battery includes two outermost positive electrode layers and two outermost negative electrode layers.
  • each electrode layer corresponds to the outermost cathode layer or the outermost anode layer.
  • the voids 50a to 50h formed in the laminate may be formed continuously in the y direction, or may be formed in a portion in the y direction.
  • the all-solid-state secondary batteries 100A, 100B, 100C, 100D, and 100E according to the above embodiments can be implemented by appropriately combining their characteristic configurations.
  • the all-solid-state secondary battery according to the above embodiment may be implemented by replacing the shape of the positive electrode and the shape of the negative electrode.
  • the margin layer 32 may contain a solid electrolyte and may also contain a compound other than the solid electrolyte. Further, the solid electrolyte included in the margin layer 32 may be different from the solid electrolyte included in the interlayer solid electrolyte layer 31.
  • the interlayer solid electrolyte layer 31 includes not only the solid electrolyte layer provided between the positive electrode layer 10 and the negative electrode layer 20 but also a solid electrolyte layer located outside in the stacking direction from the outermost electrode layer in the stacking direction. .
  • Example 1 As Example 1, an all-solid-state secondary battery having a stacked body in which 10 positive electrode layers and 10 negative electrode layers were alternately provided with solid electrolyte layers interposed therebetween was produced, and its characteristics were evaluated.
  • Example 1 an all-solid-state secondary battery including a laminate having a laminate in which four of the 20 electrode layers were in contact with voids was fabricated using the following procedure.
  • the paste for the positive electrode active material layer and the paste for the negative electrode active material layer are prepared by adding 15 parts of ethyl cellulose as a binder and 65 parts of dihydroterpineol as a solvent to 100 parts of Li 3 V 2 (PO 4 ) 3 powder.
  • a positive electrode active material layer paste and a negative electrode active material layer paste were prepared by mixing and dispersing.
  • the paste for the positive electrode current collector and the paste for the negative electrode current collector are prepared by adding 100 parts of Cu as the current collector, 10 parts of ethyl cellulose as the binder, and 50 parts of the solvent dihydroterpineol, and mixing and dispersing them to form the paste for the positive electrode current collector and the paste for the negative electrode current collector.
  • a paste for electric bodies was prepared.
  • a void-forming resin paste was prepared by adding 10 parts of ethyl cellulose as a binder and void-forming resin and 50 parts of dihydroterpineol as a solvent and mixing and dispersing them.
  • a positive electrode unit and a negative electrode unit were produced as follows. An active material layer paste was printed on the interlayer solid electrolyte layer sheet to a thickness of 5 ⁇ m by screen printing. Next, the printed active material layer paste was dried, and a current collector paste was printed on it to a thickness of 5 ⁇ m by screen printing. Next, the printed paste for the current collector was dried, and furthermore, the paste for the active material layer was printed again on it to a thickness of 5 ⁇ m by screen printing. The printed active material layer paste was dried, and then the PET film was peeled off. In this way, an electrode unit sheet was obtained in which the active material layer paste, the current collector paste, and the active material layer paste were printed and dried in this order on the interlayer solid electrolyte layer sheet.
  • Example 1 (Preparation of electrode unit in contact with void)
  • the electrode unit serving as the electrode layer not in contact with the void was produced by the above procedure
  • the electrode unit serving as the electrode layer in contact with the void was produced by the following procedure.
  • ethyl cellulose was used as a resin when producing a positive electrode unit and a negative electrode unit.
  • the region surrounded by the positive electrode layer and the first surface, which is the side surface of the laminate on the side to be bonded to the positive electrode layer, is called the first region
  • the region surrounded by the positive electrode layer, the solid electrolyte layer, and the first surface is called the first region.
  • the region surrounded by the negative electrode layer and the second surface which is the side surface of the laminate on the side that is bonded to the negative electrode layer is the third region
  • the region surrounded by the negative electrode layer, the solid electrolyte layer and the second surface is the fourth region
  • the positive electrode unit which becomes the positive electrode layer having a void in the first region, is made by applying a paste for the positive electrode current collector, and then applying a resin paste to one end in the in-plane direction of the paste for the positive electrode current collector using screen printing. This was applied to form a resin part with a thickness of 2 ⁇ m. Next, a paste for a positive electrode active material layer was screen printed on the surfaces of the resin part and the paste for a positive electrode current collector, and then dried.
  • the positive electrode unit which becomes the positive electrode layer having voids in the second region, is made by applying a paste for the solid electrolyte layer on a PET film and drying it, and then applying screen printing to one end in the in-plane direction of the paste for the solid electrolyte layer.
  • a resin part with a thickness of 2 ⁇ m is formed, and a paste for the positive electrode active material layer is screen printed so as to overlap with the area of the resin part and the paste for the solid electrolyte that does not overlap with the resin part, and then dried. It was formed by sequentially screen printing and drying a current collector paste and a positive electrode active material paste.
  • the negative electrode unit which becomes the negative electrode layer having voids in the third and fourth regions, was formed in the same procedure as the positive electrode unit having voids in the first region and the positive electrode unit having voids in the second region, respectively.
  • the outermost solid electrolyte layer sheets were stacked, and 20 electrode units (10 positive electrode units, 10 negative electrode units) were stacked alternately on top of the outermost solid electrolyte layer sheets with interlayer solid electrolyte layers 31 interposed therebetween.
  • the layer of current collector paste of the odd-numbered electrode units extends only to one end surface
  • the layer of current collector paste of the even-numbered electrode units extends only to the opposite end surface.
  • the units were stacked one on top of the other in a staggered manner.
  • a solid electrolyte layer sheet for the outermost solid electrolyte layer was stacked on top of this stacked unit. Thereafter, this was molded by thermocompression bonding and then cut to produce a laminate.
  • the size of the laminate in the x, y, and z directions was 5 mm, 4 mm, and 1 mm, respectively.
  • the laminate before firing is placed on the ceramic setter for the pedestal, and height adjustment laminates are also placed at the four corners of the ceramic setter for the pedestal, so that the sides of the laminate before firing are
  • a ceramic setter for the lid was placed at the same height as the height h0 , and then co-fired to obtain a laminate.
  • the temperature was raised to a firing temperature of 840°C at a heating rate of 100°C/hour in a nitrogen atmosphere, maintained at that temperature for 2 hours, and allowed to cool naturally after firing.
  • the cross section of the fired laminate of Example 1 was observed with a scanning electron microscope, and the positions and shapes of voids formed in the laminate were evaluated.
  • the cross section was prepared on a plane passing through the center of the laminate in the y direction.
  • the first region, the second region, the third region, and the fourth region are the first positive electrode layer, the tenth positive electrode layer, the first negative electrode layer, and the tenth negative electrode layer from the bottom surface side, respectively. It was confirmed that it was located in the second negative electrode layer.
  • the ratio of the sum of the number of positive electrode layers in contact with voids and the number of negative electrode layers in contact with voids to the total number of positive electrode layers and negative electrode layers was 20%. Further, in the all-solid-state secondary battery of Example 1, all the outermost positive electrode layers and the outermost negative electrode layers located at the ends in the stacking direction were in contact with the voids.
  • the voids formed in Example 1 are all approximately rectangular, and the angle formed by the voids of two adjacent layers in the laminate defining the voids (the angle of the end voids) is 0°. Met.
  • the above length was calculated as the average value of all five locations in the stacking direction of the predetermined electrode layer in the scanning electron microscope image. As a result, the above ratio was 1 in all voids.
  • the above-mentioned charging and discharging was considered to be one cycle, and the short circuit occurrence rate was determined from the number of short-circuited all-solid-state secondary batteries among 100 all-solid-state secondary batteries in which this cycle was repeated up to 1000 cycles.
  • a short circuit was determined when the voltage suddenly dropped during CC charging and then stopped rising.
  • 8 all-solid-state secondary batteries had short circuits after 1000 cycles. That is, the short circuit occurrence rate of the all-solid-state secondary battery of Example 1 after 1000 cycles was 0.8%.
  • Example 2 to 5 Example except that the area forming the resin part was increased and (gap length/distance between the negative electrode layer and the first surface or distance between the positive electrode layer and the second surface) was changed for all voids.
  • An all-solid-state secondary battery was produced under the same conditions as in Example 1.
  • Examples 2, 3, 4, and 5 are each (gap length/distance between the negative electrode layer and the first surface, or distance between the positive electrode layer and the second surface) x 100 (%)
  • the size of the void from the end in the in-plane direction was changed so that the values were 10%, 50%, 80%, and 150%. Note that the lengths of the plurality of gaps provided in one all-solid-state secondary battery were controlled to be approximately the same.
  • Example 6 to Example 9 When performing the firing process, the all-solid secondary was heated under the same conditions as in Example 1, except that a height-adjusting ceramic plate with a height ⁇ h was used and the height h1 of the ceramic setter for the lid was changed. A battery was created.
  • Example 6, Example 7, Example 8, and Example 9 the height ( ⁇ h) of the height adjustment ceramic plate was 0.004 mm, 0.034 mm, 0.100 mm, and 0.142 mm, respectively. did.
  • Example 10 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the position at which the void was formed with respect to the laminate was changed.
  • the first region and the second region were adjusted to be provided in the fourth and fifth positive electrode layers from the bottom end side, respectively, among the ten positive electrode layers, and the third region The fourth region was adjusted to be provided in the fifth and sixth negative electrode layers from the bottom side, respectively, among the ten negative electrode layers.
  • a laminate was produced in which the outermost positive electrode layer and the outermost negative electrode layer did not touch the voids.
  • Example 11 to Example 14 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the number and position of voids were changed.
  • an all-solid-state secondary battery was fabricated, which included a laminate having a void in the first region of the first positive electrode layer from the bottom of 10 positive electrode layers and 10 negative electrode layers.
  • Example 12 a stacked layer having a void in the first region of the first positive electrode layer from the bottom among the ten positive electrode layers and the third region of the first negative electrode layer from the bottom among the ten negative electrode layers.
  • Example 13 among the ten positive electrode layers, the first region of the first, third, fifth, seventh, and tenth positive electrode layers from the bottom side, and the first region of the ten negative electrode layers , an all-solid-state double layer comprising a laminate adjusted so that voids are provided in the third regions of the first, second, fourth, sixth, eighth, and tenth negative electrode layers from the bottom side.
  • the next battery was fabricated.
  • an all-solid-state secondary battery was fabricated such that all electrode layers were in contact with the voids.
  • Examples 1 to 14 compared to Comparative Example 1, the number of cracks from one end of the electrode layer that does not extend to the electrode active material layer having a different polarity from the electrode layer was found to be It was confirmed that there were fewer and shorter lengths. Further, in Examples 2 to 5 and 10 to 14, similarly to Example 1, no curved portions were observed, and all the voids had a substantially flat shape. On the other hand, in Examples 6, 7, 8, and 9, a curved portion was confirmed in at least one of the electrode layer and the solid electrolyte layer, and the angle formed through the gap between the two layers defining the gap was 1°, respectively. , 10°, 30°, and 45°.
  • Example 1 Comparing Example 1 and Example 10, in Example 1 where the outermost electrode layer and the gap are in contact, the occurrence rate of short circuits is lower and the cycle characteristics are improved compared to Example 10 where the outermost electrode layer and the gap are not in contact. It was confirmed that it is effective to provide a gap so as to be in contact with the outermost electrode layer from the viewpoint of this. Comparing Examples 1, 11, 12, 13, and 14, the short circuit occurrence rate decreases in descending order of the proportion of the electrode layer in contact with the void (100%, 50%, 20%). The effectiveness of forming a
  • Example 15 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that the materials of the solid electrolyte, positive electrode layer, and negative electrode layer were changed.
  • the procedure was the same as in Example 1 except that LATP in the solid electrolyte paste was changed to Li 3.5 Si 0.5 P 0.5 O 4 (LSPO) in producing the solid electrolyte layer. did.
  • LVP in the paste for the positive electrode active material layer was changed to LiCoO 2 (LCO), and Cu in the paste for the positive electrode current collector was changed to AgPd. I made it.
  • the negative electrode unit was produced in the same manner as in Example 1, except that LVP in the negative electrode active material layer paste was changed to AgPd, and Cu in the negative electrode current collector paste was changed to AgPd.
  • Example 15 An all-solid-state secondary battery of Example 15 was produced in the same manner as in Example 1, except that the above paste was used. That is, in Example 15, the negative electrode layer was an integral layer in which the negative electrode current collector and the negative electrode active material layer were integrated.
  • Example 16 to Example 19 The all-solid-state secondary batteries of Examples 16 to 19 were produced in the same manner as Examples 2 to 5, except that the materials of the solid electrolyte, positive electrode layer, and negative electrode layer were changed in the same manner as in Example 15. Created. Examples 16 to 19 have the same conditions except for (gap length/distance between the negative electrode layer and the first surface or distance between the positive electrode layer and the second surface).
  • Example 20 to Example 23 The all-solid-state secondary batteries of Examples 20 to 23 were produced in the same manner as Examples 6 to 9, except that the materials of the solid electrolyte, positive electrode layer, and negative electrode layer were changed in the same manner as in Example 15. Created. Examples 20 to 23 have the same conditions except for the angle of the void.
  • Example 24 to Example 28 The all-solid-state secondary batteries of Examples 24 to 28 were produced in the same manner as Examples 10 to 14, except that the materials of the solid electrolyte, positive electrode layer, and negative electrode layer were changed in the same manner as in Example 15. Created. Examples 24 to 28 have the same conditions except for the number and arrangement of voids.
  • Example 29 to Example 32 Example except that the thickness of the active material layer paste printed by screen printing on the interlayer solid electrolyte layer sheet and the thickness of the active material layer paste printed on the dried current collector paste were changed.
  • An all-solid-state secondary battery was produced in the same manner as in Example 15. Examples 29 to 32 have the same conditions except for the thickness of the active material layer paste.
  • Examples 15 to 32 When observing the cross section using a scanning electron microscope, in Examples 15 to 32, compared to Comparative Examples 2 to 5, one end of the electrode layer that does not extend toward the electrode active material layer having a polarity different from that of the electrode layer. It was confirmed that the number of cracks was small and the length was short. Further, in Examples 16 to 29 and 24 to 32, similarly to Example 1, no curved portions were observed, and all the voids had a substantially flat shape. On the other hand, in Examples 20, 21, 23, and 24, a curved portion was confirmed in at least one of the electrode layer and the solid electrolyte layer, and the angle formed through the gap between the two layers defining the gap was 1°, respectively. , 10°, 30°, and 45°.
  • Example 33 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that LATP in the solid electrolyte layer paste was changed to LSPO.
  • Example 34 Except that LATP in the solid electrolyte layer paste was changed to LSPO, Cu in the negative electrode current collector paste was changed to AgPd, and LVP in the negative electrode active material layer paste was changed to AgPd. An all-solid-state secondary battery was produced in the same manner as in Example 1.
  • Example 35 LVP in the paste for the positive electrode active material layer was changed to LCO, Cu in the paste for the positive electrode current collector was changed to AgPd, LVP in the paste for the negative electrode active material layer was changed to AgPd, and the negative electrode collection An all-solid-state secondary battery was produced in the same manner as in Example 1, except that Cu in the electric paste was changed to AgPd.
  • Example 36 An all-solid-state secondary battery was produced in the same manner as in Example 1, except that LVP in the positive electrode active material layer paste was changed to LCO and Cu in the positive electrode current collector paste was changed to AgPd. .
  • 1A, 1B, 1C, 1D, 1E Laminated body
  • 2 Positive electrode external terminal
  • 3 Negative electrode external terminal
  • 10A, 10B, 10C, 10D, 10E, 10F Positive electrode layer
  • 11, 11A, 11B, 11C Positive electrode collection Electric body
  • 11Aw curved part (positive electrode current collector curved part)
  • 11Ap, 11Bp, 11Cp flat part (positive electrode current collector flat part)
  • 11Bx extension part (positive electrode current collector extension part)
  • 12A positive electrode active material layer
  • 12Ap flat part (positive electrode active material layer flat part)
  • 20A, 20B, 20C, 20D, 20E, 20F negative electrode layer
  • 21, 21A, 21C, 21E negative electrode current collector
  • 21Cp, 21Ep flat part (flat part of negative electrode current collector)
  • 21Cw, 21Ew, 21Fw curved part (curved part of negative electrode current collector)
  • 22, 22A, 22B, 22Ew1, 22Ew2 negative electrode active material

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
PCT/JP2023/024343 2022-06-30 2023-06-30 全固体二次電池 Ceased WO2024005181A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US18/858,526 US20250279486A1 (en) 2022-06-30 2023-06-30 All-solid-state secondary battery
JP2024530991A JPWO2024005181A1 (https=) 2022-06-30 2023-06-30
EP23831620.2A EP4550511A1 (en) 2022-06-30 2023-06-30 All-solid-state secondary battery
CN202380024087.3A CN118872118A (zh) 2022-06-30 2023-06-30 全固体二次电池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-105471 2022-06-30
JP2022105471 2022-06-30

Publications (1)

Publication Number Publication Date
WO2024005181A1 true WO2024005181A1 (ja) 2024-01-04

Family

ID=89380779

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/024343 Ceased WO2024005181A1 (ja) 2022-06-30 2023-06-30 全固体二次電池

Country Status (5)

Country Link
US (1) US20250279486A1 (https=)
EP (1) EP4550511A1 (https=)
JP (1) JPWO2024005181A1 (https=)
CN (1) CN118872118A (https=)
WO (1) WO2024005181A1 (https=)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020105662A1 (ja) 2018-11-20 2020-05-28 Tdk株式会社 全固体電池
WO2020137256A1 (ja) * 2018-12-28 2020-07-02 パナソニックＩｐマネジメント株式会社 電池
JP2021027044A (ja) * 2019-08-05 2021-02-22 Tdk株式会社 全固体電池
JP2021108258A (ja) 2019-12-27 2021-07-29 太陽誘電株式会社 全固体電池
JP2022105471A (ja) 2021-01-04 2022-07-14 国立大学法人徳島大学 ライソゾームを標的とした新規ｄｄｓの開発

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020105662A1 (ja) 2018-11-20 2020-05-28 Tdk株式会社 全固体電池
WO2020137256A1 (ja) * 2018-12-28 2020-07-02 パナソニックＩｐマネジメント株式会社 電池
JP2021027044A (ja) * 2019-08-05 2021-02-22 Tdk株式会社 全固体電池
JP2021108258A (ja) 2019-12-27 2021-07-29 太陽誘電株式会社 全固体電池
JP2022105471A (ja) 2021-01-04 2022-07-14 国立大学法人徳島大学 ライソゾームを標的とした新規ｄｄｓの開発

Also Published As

Publication number Publication date
US20250279486A1 (en) 2025-09-04
JPWO2024005181A1 (https=) 2024-01-04
CN118872118A (zh) 2024-10-29
EP4550511A1 (en) 2025-05-07

Similar Documents

Publication Publication Date Title
CN101663788B (zh) 锂离子二次电池以及其制造方法
JP4352016B2 (ja) 無機固体電解質電池及び無機固体電解質電池の製造方法
JP6693226B2 (ja) 全固体型二次電池
CN102246335A (zh) 锂离子二次电池及其制造方法
KR20130083828A (ko) 리튬 이온 이차 전지 및 그 제조 방법
CN109792079B (zh) 全固体锂离子二次电池
JP7414058B2 (ja) 全固体電池
JP7608324B2 (ja) 全固体二次電池
WO2018181379A1 (ja) 全固体二次電池
CN113228375A (zh) 全固体电池
JP2018063850A (ja) 積層体グリーンシート、全固体二次電池及びその製造方法
JPWO2018062085A1 (ja) 全固体リチウムイオン二次電池
CN113169372A (zh) 全固体二次电池
JP2018170189A (ja) 全固体型二次電池
JP7168070B2 (ja) 固体電池
JP7424307B2 (ja) 全固体電池
CN113273015A (zh) 全固体电池
JP7509748B2 (ja) 全固体二次電池
WO2024005181A1 (ja) 全固体二次電池
JP7762070B2 (ja) 積層型全固体電池
WO2023188470A1 (ja) 全固体二次電池
WO2013035526A1 (ja) 全固体電池用積層成形体、全固体電池およびその製造方法
JP2023168868A (ja) 全固体二次電池
WO2024135262A1 (ja) 全固体電池
CN113169375A (zh) 全固体电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23831620

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024530991

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202380024087.3

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2023831620

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023831620

Country of ref document: EP

Effective date: 20250130

WWP Wipo information: published in national office

Ref document number: 2023831620

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 18858526

Country of ref document: US