WO2021149382A1 - 電池 - Google Patents

電池 Download PDF

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Publication number
WO2021149382A1
WO2021149382A1 PCT/JP2020/045749 JP2020045749W WO2021149382A1 WO 2021149382 A1 WO2021149382 A1 WO 2021149382A1 JP 2020045749 W JP2020045749 W JP 2020045749W WO 2021149382 A1 WO2021149382 A1 WO 2021149382A1
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WIPO (PCT)
Prior art keywords
layer
solid
current collector
active material
positive electrode
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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/JP2020/045749
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English (en)
French (fr)
Japanese (ja)
Inventor
英一 古賀
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.)
Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Priority to JP2021572995A priority Critical patent/JP7611496B2/ja
Priority to CN202080093734.2A priority patent/CN114982032A/zh
Priority to EP20915728.8A priority patent/EP4095972A4/en
Publication of WO2021149382A1 publication Critical patent/WO2021149382A1/ja
Priority to US17/851,053 priority patent/US12362385B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
    • 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
    • H01M10/052—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
    • H01M10/058—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
    • H01M50/291—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
    • H01M50/293—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
    • H01M50/509—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the type of connection, e.g. mixed connections
    • H01M50/51—Connection only in series
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
    • H01M50/521—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the material
    • H01M50/526—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the material having a layered structure
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
    • 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

  • This disclosure relates to batteries.
  • Patent Document 1 discloses an all-solid-state battery in which a bipolar electrode is formed by a composite current collector of a positive electrode and a negative electrode.
  • Patent Document 2 discloses a battery using a bipolar electrode having an adhesive layer made of a metal filler, a carbon filler and an epoxy resin, and a gel polymer electrolyte, which adheres a current collector.
  • the battery according to one embodiment of the present disclosure includes a plurality of solid-state battery cells and a connection layer located between the plurality of solid-state battery cells, and the plurality of solid-state battery cells are respectively a positive electrode current collector.
  • the positive electrode active material layer, the solid electrolyte layer containing the inorganic solid electrolyte, the negative electrode active material layer, and the negative electrode current collector are laminated in this order, and the plurality of solid battery cells have a structure in which the positive electrode active material layer, the solid electrolyte layer containing the inorganic solid electrolyte, and the negative electrode current collector are laminated in this order.
  • connection layer is laminated, and the connection layer contains a conductive material, and the Young's ratio of the connection layer is the positive electrode current collector, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode collection. It is smaller than the young rate of the electric body.
  • FIG. 1 is a diagram showing a schematic configuration of a battery according to an embodiment.
  • FIG. 2 is a diagram showing a schematic configuration of a battery according to a modification 1 of the embodiment.
  • FIG. 3 is a diagram showing a schematic configuration of a battery according to a modification 2 of the embodiment.
  • a battery having a bipolar current collector has a positive electrode active material layer coated on one surface of the front and back surfaces of the bipolar current collector, and a negative electrode active material layer coated on the other surface, and each battery cell. Is formed, and they are pressurized and integrated.
  • the bipolar electrode will be sandwiched between the active material layers. Stress tends to concentrate on the bipolar electrode, and defects such as tearing of the bipolar electrode are likely to occur.
  • the present disclosure provides a highly reliable series-connected battery.
  • the battery according to one aspect of the present disclosure includes a plurality of solid-state battery cells and a connection layer located between the plurality of solid-state battery cells, and the plurality of solid-state battery cells have a positive electrode current collector and a positive electrode current collector, respectively.
  • the positive electrode active material layer, the solid electrolyte layer containing the inorganic solid electrolyte, the negative electrode active material layer, and the negative electrode current collector are laminated in this order, and the plurality of solid battery cells are electrically driven.
  • One of the positive electrode current collectors and the other negative electrode current collector of two adjacent solid-state battery cells among the plurality of solid-state battery cells are laminated via the connection layer.
  • connection layer contains a conductive material, and the Young's ratio of the connection layer is the positive electrode current collector, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector. It is smaller than the young rate of the body.
  • the battery according to this embodiment is a series-connected battery. Further, one positive electrode current collector and the other negative electrode current collector of adjacent solid-state battery cells are laminated via a connection layer that is easily deformed because it is smaller than the Young's modulus of each component of the plurality of solid-state battery cells. NS. Therefore, the stress on the plurality of solid-state battery cells caused by expansion or contraction due to the temperature change of each component of the plurality of solid-state battery cells, repeated charging / discharging, and the like is relaxed by the deformation of the connecting layer. As a result, damage to each component of the plurality of solid-state battery cells is suppressed. In addition, the connection layer also relieves stress caused by external heat, shock, vibration, etc. to the battery. Therefore, according to this aspect, a highly reliable series-connected battery can be realized.
  • connection layer may contain a resin.
  • connection layer may contain a solid electrolyte.
  • connection layer may have voids.
  • the voids in the connecting layer also relieve stress on the plurality of solid-state battery cells. Further, the Young's modulus of the connecting layer can be controlled in a wide range by changing the shape and volume of the voids.
  • the thickness of the connecting layer may be 1 ⁇ m or more and 20 ⁇ m or less.
  • the stress on the solid-state battery can be relaxed while suppressing the decrease in the volumetric energy density, so that the reliability of the battery and the volumetric energy density can be compatible with each other.
  • connection layer may be located inside the outer periphery of the positive electrode current collector and the negative electrode current collector in a plan view.
  • a buffer layer located between the plurality of solid-state battery cells and made of a material different from the connection layer is further provided, and the Young's modulus of the buffer layer is determined by the positive electrode current collector and the positive electrode activity. It may be less than or equal to the Young's modulus of the material layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector.
  • the plurality of solid-state battery cells are laminated via the connection layer and the buffer layer made of different materials, so that the stress on the plurality of solid-state battery cells under a wider range of conditions is relieved.
  • the buffer layer may be provided so as to surround the outer periphery of the connection layer in a plan view and may have a frame shape.
  • the buffer layer surrounds the outer circumference of the connection layer, the buffer layer and the connection layer between the plurality of solid-state battery cells are easily deformed evenly with respect to stress from any direction.
  • the Young's modulus of the buffer layer may be smaller than the Young's modulus of the connecting layer.
  • the buffer layer is more easily deformed than the connecting layer, it can be deformed before the connecting layer to relieve stress, so that the stress relieving effect on a plurality of solid-state battery cells can be enhanced. ..
  • the buffer layer does not have to contain a conductive material.
  • the buffer layer does not contain a conductive material, it becomes soft and the thermal conductivity decreases. As a result, it is easily deformed and the temperature is less likely to change, so that it functions as a buffering material against external shocks and thermal shocks, and can enhance the effect of relieving stress on a plurality of solid-state battery cells.
  • the buffer layer may contain the inorganic solid electrolyte.
  • the battery can be efficiently manufactured in the manufacturing process.
  • the inorganic solid electrolyte may have lithium ion conductivity.
  • each figure is not necessarily exactly illustrated.
  • substantially the same configurations are designated by the same reference numerals, and duplicate description will be omitted or simplified.
  • the x-axis, y-axis, and z-axis indicate the three axes of the three-dimensional Cartesian coordinate system.
  • the z-axis direction is the thickness direction of the battery.
  • the "thickness direction” is a direction perpendicular to the surface on which each layer is laminated.
  • plan view means a case where the battery is viewed along the stacking direction of the battery
  • thickness in the present specification is the length of the battery and each layer in the stacking direction. ..
  • inside and outside in “inside” and “outside” mean the inside and outside when the battery is viewed along the stacking direction of the battery.
  • the terms “upper” and “lower” in the battery configuration do not refer to the upward direction (vertically upward) and the downward direction (vertically downward) in absolute spatial recognition, but in the laminated configuration. It is used as a term defined by the relative positional relationship based on the stacking order. Also, the terms “upper” and “lower” are used not only when the two components are spaced apart from each other and another component exists between the two components, but also when the two components It also applies when the two components are placed in close contact with each other and touch each other.
  • FIG. 1 is a diagram showing a schematic configuration of a battery according to the present embodiment.
  • FIG. 1A is a cross-sectional view of the battery 100 according to the present embodiment
  • FIG. 1B is a plan view of the battery 100 as viewed from above in the z-axis direction. ..
  • FIG. 1 (a) shows a cross section at the position indicated by the line I-I in FIG. 1 (b).
  • the plan-view shape of each component of the battery when the battery 100 is viewed from above is represented by a solid line.
  • the battery 100 has a structure in which two solid-state battery cells 1a and 1b are laminated, and a connection layer 16 located between the solid-state battery cells 1a and 1b and the solid-state battery cells 1a and 1b. And.
  • the battery 100 is a series-connected battery, and the solid-state battery cells 1a and 1b are electrically connected in series.
  • the connection layer 16 electrically connects the solid-state battery cell 1a and the solid-state battery cell 1b in series.
  • the solid battery cells 1a and 1b are in contact with the positive electrode current collector 11, the positive electrode active material layer 12 arranged in contact with the positive electrode current collector 11, the negative electrode current collector 13, and the negative electrode current collector 13, respectively. It has a negative electrode active material layer 14 to be arranged, and a solid electrolyte layer 15 arranged between the positive electrode active material layer 12 and the negative electrode active material layer 14 and containing an inorganic solid electrolyte.
  • the positive electrode active material layer 12 and the negative electrode active material layer 14 are arranged between the positive electrode current collector 11 and the negative electrode current collector 13.
  • the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13 are arranged in this order from the bottom, respectively. It has a laminated structure.
  • the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13 are each rectangular in a plan view.
  • the shapes of the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13 in a plan view are not particularly limited, and may be circular, elliptical, polygonal, or the like. It may have a shape other than a rectangle.
  • the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13 have the same shape, position, and size in a plan view.
  • the positive electrode current collector 11 of one solid-state battery cell 1a of two adjacent solid-state battery cells and the negative electrode current collector 13 of the other solid-state battery cell 1b are laminated via a connection layer 16. That is, the two adjacent solid-state battery cells 1a and the solid-state battery cell 1b are laminated via the connecting layer 16 so that the vertical directions are the same.
  • the solid-state battery cells 1a and 1b and the connecting layer 16 have the same shape, position, and size in a plan view.
  • the solid-state battery cell 1a and the solid-state battery cell 1b are separated from each other with the connection layer 16 interposed therebetween.
  • the positive electrode current collector 11, the negative electrode current collector 13, and the solid electrolyte layer 15 of the solid-state battery cells 1a and 1b have the same shape, position, and size in a plan view.
  • the positive electrode current collector 11 of the solid-state battery cell 1a and the negative electrode current collector 13 of the solid-state battery cell 1b are in contact with the connection layer 16.
  • the positive electrode current collector 11 and the negative electrode current collector 13 may be collectively referred to as a “current collector”.
  • the current collector may be made of a conductive material and is not particularly limited.
  • the current collector may be, for example, a foil-like body, a plate-like body, or a mesh-like body made of stainless steel, nickel, aluminum, iron, titanium, copper, palladium, gold, platinum, or an alloy of two or more of these. It may be used.
  • the material of the current collector may be appropriately selected in consideration of the manufacturing process, the operating temperature, the fact that it does not melt and decompose at the operating pressure, and the battery operating potential and conductivity applied to the current collector.
  • the material of the current collector can also be selected according to the required tensile strength and heat resistance.
  • the current collector may be a high-strength electrolytic copper foil or a clad material in which dissimilar metal foils are laminated.
  • the thickness of the current collector is, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • the surface of the current collector in contact with the connection layer 16 is processed into an uneven rough surface from the viewpoint of improving the adhesion with the connection layer 16 and strengthening the laminated structure of the solid-state battery cells 1a and 1b. You may use the thing. Further, the surface of the current collector in contact with the connection layer 16 may be coated with an adhesive component such as a conductive organic binder. Thereby, the adhesiveness between the current collector and the connection layer 16 can be improved.
  • the positive electrode active material layer 12 is laminated in contact with one surface of the positive electrode current collector 11.
  • the positive electrode active material layer 12 contains at least the positive electrode active material.
  • the positive electrode active material layer 12 is a layer mainly composed of a positive electrode material such as a positive electrode active material.
  • the positive electrode active material is a substance in which metal ions such as lithium (Li) ions or magnesium (Mg) ions are inserted or removed from the crystal structure at a higher potential than that of the negative electrode, and oxidation or reduction is carried out accordingly.
  • the type of the positive electrode active material can be appropriately selected according to the type of the battery, and a known positive electrode active material can be used.
  • Examples of the positive electrode active material include compounds containing lithium and a transition metal element, and specifically, an oxide containing lithium and a transition metal element, a phosphoric acid compound containing lithium and a transition metal element, and the like. Can be mentioned.
  • Examples of oxides containing lithium and transition metal elements include LiNi x M 1-x O 2 (where M is Co, Al, Mn, V, Cr, Mg, Ca, Ti, Zr, Nb, Mo).
  • W which are at least one element, x is a lithium nickel composite oxide such as 0 ⁇ x ⁇ 1), lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate.
  • Layered oxides such as (LiMn 2 O 4 ) and lithium manganate having a spinel structure (for example, LiMn 2 O 4 , Li 2 Mn O 3 and Li MO 2 ) are used.
  • the phosphoric acid compound containing lithium and a transition metal element for example, lithium iron phosphate (LiFePO 4 ) having an olivine structure or the like is used.
  • sulfides such as sulfur (S) and lithium sulfide (Li 2 S) can be used as the positive electrode active material.
  • the positive electrode active material particles are coated with lithium niobate (LiNbO 3 ) or the like.
  • the added material can be used as the positive electrode active material.
  • the positive electrode active material only one of these materials may be used, or two or more of these materials may be used in combination.
  • the positive electrode active material layer 12 may contain at least the positive electrode active material.
  • the positive electrode active material layer 12 may be a mixture layer composed of a mixture of the positive electrode active material and another additive material.
  • additive materials for example, a solid electrolyte such as an oxide-based solid electrolyte or a sulfide-based solid electrolyte, a conductive auxiliary material such as acetylene black, and a binder binder such as polyethylene oxide or polyvinylidene fluoride are used. sell.
  • the positive electrode active material layer 12 improves ionic conductivity such as lithium ion conductivity in the positive electrode active material layer 12 by mixing the positive electrode active material and other additive materials such as a solid electrolyte in a predetermined ratio. At the same time, the electron conductivity can be improved.
  • the thickness of the positive electrode active material layer 12 is, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • the negative electrode active material layer 14 is laminated in contact with one surface of the negative electrode current collector 13.
  • the negative electrode active material layer 14 contains at least the negative electrode active material.
  • the negative electrode active material layer 14 is a layer mainly composed of a negative electrode material such as a negative electrode active material.
  • the negative electrode active material refers to a substance in which metal ions such as lithium (Li) ions or magnesium (Mg) ions are inserted or removed from the crystal structure at a lower potential than that of the positive electrode, and oxidation or reduction is carried out accordingly.
  • the type of positive electrode / negative electrode active material can be appropriately selected according to the type of battery, and a known negative electrode active material can be used.
  • the negative electrode active material for example, a carbon material such as natural graphite, artificial graphite, graphite carbon fiber or resin calcined carbon, an alloy-based material to be mixed with a solid electrolyte, or the like can be used.
  • the alloy-based material include LiAl, LiZn, Li 3 Bi, Li 3 Cd, Li 3 Sb, Li 4 Si, Li 4.4 Pb, Li 4.4 Sn, Li 0.17 C or Li C 6 .
  • Lithium alloys, oxides of lithium such as lithium titanate (Li 4 Ti 5 O 12 ) and transition metal elements, metal oxides such as zinc oxide (ZnO) and silicon oxide (SiO x ), and the like can be used.
  • the negative electrode active material only one of these materials may be used, or two or more of these materials may be used in combination.
  • the negative electrode active material layer 14 may contain at least the negative electrode active material.
  • the negative electrode active material layer 14 may be a mixture layer composed of a mixture of the negative electrode active material and another additive material.
  • additive materials for example, a solid electrolyte such as an oxide-based solid electrolyte or a sulfide-based solid electrolyte, a conductive auxiliary material such as acetylene black, and a binder binder such as polyethylene oxide or polyvinylidene fluoride are used. sell.
  • the negative electrode active material layer 14 improves ionic conductivity such as lithium ion conductivity in the negative electrode active material layer 14 by mixing the positive electrode negative electrode active material and other additive materials such as a solid electrolyte in a predetermined ratio. At the same time, the electron conductivity can be improved.
  • the thickness of the negative electrode active material layer 14 is, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • the positive electrode active material layer 12 and the negative electrode active material layer 14 of the solid-state battery cells 1a and 1b, respectively, have the same shape, position, and size in a plan view.
  • the solid electrolyte layers 15 of the solid-state battery cells 1a and 1b are arranged between the positive electrode active material layer 12 and the negative electrode active material layer 14, and are in contact with the positive electrode active material layer 12 and the negative electrode active material layer 14.
  • the solid electrolyte layer 15 contains at least an inorganic solid electrolyte as a solid electrolyte.
  • the solid electrolyte layer 15 contains, for example, an inorganic solid electrolyte as a main component.
  • the inorganic solid electrolyte may be any known inorganic solid electrolyte for batteries that does not have electron conductivity and has ionic conductivity.
  • As the inorganic solid electrolyte for example, an inorganic solid electrolyte that conducts a metal ion such as lithium ion or magnesium ion can be used.
  • the type of the inorganic solid electrolyte may be appropriately selected according to the conduction ion species.
  • a solid electrolyte such as a sulfide-based solid electrolyte, a halogen-based solid electrolyte, and an oxide-based solid electrolyte can be used.
  • a sulfide-based solid electrolyte having lithium ion conductivity, a halogen-based solid electrolyte, or an oxide-based solid electrolyte may be used.
  • Examples of the sulfide-based solid electrolyte include Li 2 SP 2 S 5 series, Li 2 S-SiS 2 series, Li 2 SB 2 S 3 series, Li 2 S-GeS 2 series, and Li 2 S-.
  • SiS 2 -Li I series, Li 2 S-SiS 2 -Li 3 PO 4 series, Li 2 S-Ge 2 S 2 series, Li 2 S-GeS 2- P 2 S 5 series or Li 2 S-GeS 2- ZnS Lithium-containing sulfides such as systems can be used.
  • oxide-based solid electrolyte examples include lithium-containing metal oxides such as Li 2 O-SiO 2 or Li 2 O-SiO 2- P 2 O 5, and lithium-containing metal oxides such as Li x P yO 1-z N z.
  • Metal nitrides, lithium phosphate (Li 3 PO 4 ), lithium-containing transition metal oxides such as lithium titanium oxide, and the like can be used.
  • the solid electrolyte only one of these materials may be used, or two or more of these materials may be used in combination.
  • the halogen-based solid electrolyte is a solid electrolyte containing a halide.
  • the halide is, for example, a compound consisting of Li, M'and X'.
  • M' is at least one element selected from the group consisting of metal elements other than Li and metalloid elements.
  • X' is at least one element selected from the group consisting of F, Cl, Br, and I.
  • "Metallic elements” are all elements contained in groups 1 to 12 of the periodic table (excluding hydrogen) and all elements contained in groups 13 to 16 of the periodic table (however). , B, Si, Ge, As, Sb, Te, C, N, P, O, S and Se).
  • Metalloid element represents B, Si, Ge, As, Sb and Te.
  • M' may include Y (yttrium).
  • Examples of the halide containing Y include Li 3 YCl 6 and Li 3 YBr 6 .
  • halides for example, Li 2 MgX '4, Li 2 FeX' 4, Li (Al, Ga, In) X '4, Li 3 (Al, Ga, In) X' 6, LiOX ' and LiX 'Is mentioned.
  • examples of the halide include Li 3 InBr 6 , Li 3 InCl 6 , Li 2 FeCl 4 , Li 2 CrCl 4 , Li 3 OCl and Li I.
  • oxide-based solid electrolyte examples include Li 7 La 3 Zr 2 O 12 (LLZ), Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) or (La, Li) TiO 3 (LLTO) and the like are used.
  • the solid electrolyte layer 15 may contain a binder such as polyethylene oxide or polyvinylidene fluoride, in addition to the above-mentioned inorganic solid electrolyte.
  • the thickness of the solid electrolyte layer 15 is, for example, 5 ⁇ m or more and 150 ⁇ m or less.
  • the material of the inorganic solid electrolyte may be composed of agglomerates of particles. Further, the material of the inorganic solid electrolyte may be composed of a sintered structure.
  • the positive electrode current collector 11 and the negative electrode current collector 13 and the connection layer 16 of the solid-state battery cells 1a and 1b, respectively, have the same shape, position, and size in a plan view.
  • the positive electrode current collector 11 of the solid-state battery cell 1a and the negative electrode current collector 13 of the solid-state battery cell 1b are all in contact with the connection layer 16 on the surface on the connection layer 16 side.
  • connection layer 16 is smaller than the Young's modulus of the positive electrode current collector 11 and the negative electrode current collector 13. As a result, the stress on the solid-state battery cells 1a and 1b caused by the expansion or contraction of the current collector due to the temperature change is relaxed by the deformation of the connection layer 16. Further, the connection layer 16 is deformed between the current collectors due to the pressurization of the lamination process in the manufacture of the battery 100, and the bondability between the connection layer 16 and the current collectors above and below the connection layer 16 is improved. In addition, peeling and cracking at the interface between the current collector and the connection layer 16 due to an external impact, a cooling cycle, or the like are suppressed. Therefore, the reliability of the battery 100 is improved.
  • the Young's modulus of the connecting layer 16 is smaller than the Young's modulus of the solid electrolyte layer 15.
  • the Young's modulus of the connecting layer 16 is smaller than the Young's modulus of the positive electrode active material layer 12 and the negative electrode active material layer 14.
  • the stress on the solid-state battery cells 1a and 1b caused by the expansion or contraction of the positive electrode active material layer 12 and the negative electrode active material layer 14 due to temperature changes and repeated charging / discharging is relaxed by the deformation of the connecting layer 16. Therefore, the reliability of the battery 100 is improved.
  • the relative relationship between these Young's moduluses can be measured by comparing the displacement characteristics with respect to the pressure when the probe is pushed into each component along the stacking direction, or the relative relationship such as the size of the dent. ..
  • connection layer 16 contains a conductive material.
  • a material obtained by mixing an insulating material having an insulating property such as a resin material and a solid electrolyte material and a conductive material having an electron conductivity can be used.
  • the material of the connection layer 16 may be used by adjusting the type and composition of the material in consideration of ease of manufacture in the manufacturing process, stress relaxation performance, thermal shock resistance, cold thermal cycle resistance, and the like.
  • the connection layer 16 is provided with, for example, from the viewpoint of bondability at the time of laminated crimping with the current collector and relaxation of stress on the solid-state battery cells 1a and 1b caused by expansion or contraction of the current collector due to a temperature change.
  • a mixture of a conductive metal and a solid electrolyte or various resin materials, which is softer than a current collector or the like, can be used.
  • connection layer 16 examples include silver, copper, nickel, zinc, aluminum, palladium, gold, platinum, and alloys obtained by combining these metals.
  • the conductive material contained in the connection layer 16 may be a semiconductor material.
  • connection layer 16 may contain a solid electrolyte.
  • the solid electrolyte used in the connecting layer 16 include the inorganic solid electrolyte used in the above-mentioned solid electrolyte layer 15.
  • the solid electrolyte used for the connecting layer 16 and the inorganic solid electrolyte used for the solid electrolyte layer 15 may be of the same type or different types.
  • the connection layer 16 may contain the same material as the solid electrolyte layer 15.
  • a soft solid electrolyte typified by a sulfide-based solid electrolyte or the like is deformed by pressure and easily forms a bonding interface between the particles of the solid electrolyte.
  • connection layer 16 By including the solid electrolyte having such characteristics in the connection layer 16, it becomes easier to relieve the stress on the solid-state battery cells 1a and 1b caused by the expansion or contraction of the current collector due to the temperature change. As a result, the heat impact resistance and the cold heat cycle resistance of the battery 100 are improved.
  • connection layer 16 may contain a resin. This makes it easier to form the connection layer 16 which is softer than the current collector and the like and has a small Young's modulus. Further, since the specific gravity of the resin tends to be smaller than that of the inorganic material, the weight energy density of the battery 100 can be increased by including the resin in the connection layer 16.
  • the resin used for the connection layer 16 may be a thermoplastic resin or a thermosetting resin.
  • the thermoplastic resin include polyethylene resin, polypropylene resin, acrylic resin, polystyrene resin, vinyl chloride resin, silicone resin, polyamide resin, polyimide resin, fluorinated hydrocarbon resin, and polyether.
  • thermosetting resin examples include (i) amino resins such as urea resin, melamine resin and guanamine resin, and (ii) epoxy resins such as bisphenol A type, bisphenol F type, phenol novolac type and alicyclic resin, (iii).
  • thermosetting resin used for the connection layer 16 may be a phenol resin from the viewpoint of connection strength.
  • thermosetting resin used for the connection layer 16 may be an epoxy resin.
  • the connecting layer 16 may be made of a material in which particles of a conductive material or particles of a semiconductor material are contained in a solid electrolyte or a resin. Further, the connecting layer 16 may contain a conductive material as a main component. For example, the connecting layer 16 is composed of a solid electrolyte and a conductive material. As a result, the electric resistance component can be reduced while relaxing the stress caused by the expansion or contraction of the current collector or the like due to the temperature change as described above, so that the battery 100 having a small electrical loss can be realized. be able to.
  • connection layer 16 may be composed of a thermosetting conductor paste containing a metal and a resin as main components.
  • the connecting layer 16 may be made of a material in which the conductor paste contains a solid electrolyte or the like from the viewpoint that the coefficient of thermal expansion and the softness (Young's modulus) of the connecting layer 16 can be adjusted.
  • connection layer 16 may have pores containing air or the like or voids such as air bubbles.
  • the voids may be formed by being surrounded by the material of the connecting layer 16, or may be formed by being surrounded by the connecting layer 16 and the current collector.
  • the voids in the connecting layer 16 can relieve stress on the solid-state battery cells 1a and 1b.
  • the softness (Young's modulus) of the connecting layer 16 can be controlled in a wide range by changing the shape and volume of the voids. Therefore, the stress on the solid-state battery cells 1a and 1b caused by the expansion or contraction of the current collector or the like due to the temperature change can be further relaxed.
  • the method of forming the voids is not particularly limited, and the voids are formed by, for example, the connecting layer 16 being composed of agglomerates of powder material. Further, the voids may be formed by forming the connecting layer 16 with a resin containing bubbles.
  • connection layer 16 may contain a nonflammable material such as metal, ceramics or a solid electrolyte.
  • a nonflammable material such as metal, ceramics or a solid electrolyte.
  • the connecting layer 16 contains a nonflammable material, it also has an effect as a layer wall for suppressing burning when the battery overheats.
  • connection layer 16 may not be formed on the entire surface of the contacting current collector, or may be partially formed by forming a pattern on the surface of the contacting current collector.
  • the connecting layer 16 may be composed of a plurality of layers of different materials.
  • the thickness of the connection layer 16 is not particularly limited, but it is advantageous that the connection layer 16 is thin from the viewpoint of the volumetric energy density of the battery.
  • the thickness of the connection layer 16 may be thinner than the thickness of the current collector from the viewpoint of volumetric energy density.
  • the thickness of the connecting layer 16 is, for example, 1 ⁇ m or more and 20 ⁇ m or less, preferably 2 ⁇ m or more and 10 ⁇ m or less. When the thickness of the connecting layer 16 is within the above range, it is easy to relax the stress caused by the expansion or contraction of the current collector or the like due to the temperature change while suppressing the decrease in the volumetric energy density.
  • the specific gravity of the connecting layer 16 is not particularly limited, but it is preferably smaller from the viewpoint of weight energy density.
  • the specific density of the connection layer 16 may be smaller than the specific gravity of the current collector. As a result, the influence on the weight energy density can be reduced, so that a battery having a high energy density can be obtained.
  • the battery 100 includes a plurality of solid-state battery cells 1a and 1b, and a connection layer 16 located between the plurality of solid-state battery cells 1a and 1b.
  • the plurality of solid-state battery cells 1a and 1b include a positive electrode current collector 11, a positive electrode active material layer 12, a solid electrolyte layer 15 containing an inorganic solid electrolyte, a negative electrode active material layer 14, and a negative electrode current collector 13, respectively. And have a structure in which they are laminated in this order.
  • the plurality of solid-state battery cells 1a and 1b are electrically connected in series.
  • the positive electrode current collector 11 of the solid-state battery cell 1a and the negative electrode current collector 13 of the solid-state battery cell 1b are laminated via the connection layer 16.
  • the connection layer 16 contains a conductive material, and the Young's modulus of the connection layer 16 is the Young's modulus of the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13. Smaller than
  • the battery 100 is a series-connected battery. Further, the positive electrode current collector 11 of the solid-state battery cell 1a and the negative electrode current collector of the solid-state battery cell 1b pass through the connection layer 16 which is easily deformed because the Young's modulus is smaller than the components of the solid-state battery cells 1a and 1b. 13 and 13 are laminated. Therefore, the stress on the solid-state battery cells 1a and 1b caused by the expansion or contraction of each component of the solid-state battery cells 1a and 1b due to the temperature change, the repeated charging and discharging, and the like is relaxed by the deformation of the connecting layer 16.
  • connection layer 16 for example, even when the battery is further multi-layered and enlarged, each component of the solid-state battery cell is less likely to be damaged. Therefore, a highly reliable, high-output and large-capacity battery can be realized.
  • Patent Document 1 discloses an all-solid-state battery in which a bipolar electrode is formed by a composite current collector.
  • the composite current collector described in Patent Document 1 is formed by forming two current collectors by metal bonding, and for example, the two current collectors are bonded by plating or a clad material. Therefore, the composite current collector does not have a connecting portion having a stress relaxing action. Therefore, the connecting portion joined with the metal material cannot obtain the stress relaxing action like the connecting layer 16 of the battery 100 according to the present embodiment. Therefore, when the battery is multi-layered, the stress generated in the bipolar electrode due to the laminating process, thermal shock, etc. tends to cause damage, poor adhesion between the current collector and the power generation element, and voids. Therefore, there is a problem in forming a multi-layered bipolar battery.
  • Patent Document 2 discloses a bipolar battery using a bipolar electrode having an adhesive layer for connecting a current collector and a gel polymer electrolyte.
  • simply connecting the current collectors with an adhesive layer made of a metal filler, an epoxy resin, or the like does not provide the effect of improving reliability due to the stress relaxation characteristics of the adhesive layer as in the battery 100 according to the present embodiment. ..
  • the connecting layer 16 it is indispensable that the adhesive layer is softer than the components of the battery such as the current collector and the electrolyte.
  • FIG. 2 is a diagram showing a schematic configuration of a battery according to a modification 1 of the embodiment.
  • FIG. 2A is a cross-sectional view of the battery 110 according to the present embodiment
  • FIG. 2B is a plan view of the battery 110 as viewed from above in the z-axis direction. ..
  • FIG. 2A shows a cross section at the position shown by line II-II in FIG. 2B.
  • the plan-view shape of each component of the battery when the battery 110 is viewed from above is represented by a solid line or a broken line.
  • the battery 110 according to the first modification of the embodiment is located inside the outer periphery of the current collector in a plan view instead of the connection layer 16 as compared with the battery 100 in the embodiment. It differs in that it includes an arranged connection layer 17.
  • the battery 110 has a structure in which two solid-state battery cells 1a and 1b are laminated, and includes a solid-state battery cells 1a and 1b and a connection layer 17 located between the solid-state battery cells 1a and 1b.
  • the positive electrode current collector 11 of one solid-state battery cell 1a of two adjacent solid-state battery cells and the negative electrode current collector 13 of the other solid-state battery cell 1b are laminated via a connection layer 17. That is, the solid-state battery cell 1a and the solid-state battery cell 1b are laminated via the connecting layer 17 so that the vertical directions are the same.
  • connection layer 17 The area of the connection layer 17 is smaller than that of the positive electrode current collector 11 and the negative electrode current collector 13 in a plan view. Further, the connection layer 17 is located inside the outer periphery of the positive electrode current collector 11 and the negative electrode current collector 13 in a plan view.
  • the materials used for the connection layer 17, the characteristics of the connection layer 17, and the like are the same as those of the connection layer 16.
  • connection layer 17 When the connection layer 17 is located inside the outer periphery of the positive electrode current collector 11 and the negative electrode current collector 13 in a plan view, the conductive material such as metal contained in the connection layer 17 is migrated (that is,).
  • the positive electrode active material layer 12 or the negative electrode active material layer 14 When the positive electrode active material layer 12 or the negative electrode active material layer 14 is brought into contact with the side surface due to (growth of a conductive material such as metal contained in the connection layer 17), or the stacked solid battery cells are cut with a Thomson blade or the like. It is possible to prevent the positive electrode active material layer 12 or the negative electrode active material layer 14 from coming into contact with or adhering to the side surface thereof. As a result, a short circuit and deterioration of characteristics of the battery 110 can be suppressed, so that a highly reliable series-connected battery 110 can be realized.
  • FIG. 3 is a diagram showing a schematic configuration of a battery according to a modification 2 of the embodiment.
  • FIG. 3A is a cross-sectional view of the battery 120 according to the present embodiment
  • FIG. 3B is a plan view of the battery 120 as viewed from above in the z-axis direction. ..
  • FIG. 3A shows a cross section at the position shown by line III-III in FIG. 3B.
  • the plan-view shape of each component of the battery when the battery 110 is viewed from above is represented by a solid line or a broken line.
  • the battery 120 according to the second modification of the embodiment further includes a buffer layer 18 provided so as to surround the outer periphery of the connection layer 17 as compared with the battery 110 in the first modification. It differs in that.
  • the battery 120 has a structure in which two solid-state battery cells 1a and 1b are laminated, and includes the solid-state battery cells 1a and 1b, and a connection layer 17 and a buffer layer 18 located between the solid-state battery cells 1a and 1b. ..
  • the positive electrode current collector 11 of the solid-state battery cell 1a and the negative electrode current collector 13 of the solid-state battery cell 1b are laminated via the connection layer 17 and the buffer layer 18. That is, the solid-state battery cell 1a and the solid-state battery cell 1b are laminated via the connecting layer 17 and the buffer layer 18 so that the vertical directions are the same.
  • the buffer layer 18 is in contact with the positive electrode current collector 11 of the solid-state battery cell 1a and the negative electrode current collector 13 of the solid-state battery cell 1b.
  • the outer periphery of the buffer layer 18 overlaps the outer periphery of the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13.
  • the cushioning layer 18 is provided so as to surround the connecting layer 17 in a plan view, and has a frame shape.
  • the buffer layer 18 is in contact with all sides of the connecting layer 17.
  • the buffer layer 18 and the connection layer 17 may be arranged apart from each other. Further, the outer periphery of the buffer layer 18 may be located inside the outer periphery of the positive electrode current collector 11 and the negative electrode current collector 13.
  • the Young's modulus of the buffer layer 18 is equal to or less than the Young's modulus of the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13. Further, the buffer layer 18 is made of a material different from that of the connecting layer 17. As described above, since the solid-state battery cell 1a and the solid-state battery cell 1b are laminated via the connection layer 17 and the buffer layer 18 made of different materials, the solid-state battery cell 1a and the solid-state battery cell 1b under a wider condition are used. The stress on 1b is relaxed.
  • the Young's modulus of the buffer layer 18 may be smaller than the Young's modulus of the connecting layer 17. As a result, since the buffer layer 18 is more easily deformed than the connection layer 17, it can be deformed before the connection layer 17 to relieve the stress, so that the stress on the solid-state battery cells 1a and 1b in the battery 120 can be relaxed. The mitigation effect can be enhanced.
  • the buffer layer 18 may contain an inorganic solid electrolyte used for the solid electrolyte layer 15.
  • the buffer layer 18 is formed, for example, by using the same material as the inorganic solid electrolyte used for the solid electrolyte layer 15.
  • the battery 120 can be efficiently manufactured in the manufacturing process.
  • the buffer layer 18 can be formed, for example, by coating with a die coat or the like in a normal thick film process, and by a printing process with a screen and a metal mask. After forming the connecting layer 17, the buffer layer 18 may be formed, or the buffer layer 18 may be formed in the reverse order. Further, if the conductivity between the solid-state battery cell 1a and the solid-state battery cell 1b is not impaired, a layer of mixed structure is formed by using a paste in which the material of the connecting layer 17 and the material of the buffer layer 18 are mixed. You may.
  • the buffer layer 18 may contain at least one of a solid electrolyte, a positive electrode active material and a negative electrode active material used in the positive electrode active material layer 12 and the negative electrode active material layer 14 of the solid-state battery cells 1a and 1b. ..
  • the softness of the buffer layer 18 between the solid-state battery cell 1a and the solid-state battery cell 1b, the compression characteristics at the time of pressurization, the thermal expansion / contraction characteristics, and the like can be improved by the positive electrode active material layer 12 and the negative electrode active material layer. Since the characteristics of 14 can be approached, the reliability of the multi-layered battery can be improved.
  • connection layer 17 and the buffer layer 18 having electron conductivity between the solid-state battery cell 1a and the solid-state battery cell 1b provides a wide range of stress relaxation performance to the solid-state battery cells 1a and 1b. It will be possible to control with. Such an effect is exhibited even when the buffer layer 18 contains the inorganic solid electrolyte used for the solid electrolyte layer 15.
  • the buffer layer 18 does not have to contain a conductive material.
  • the buffer layer 18 may be made of a material obtained by removing the conductive material from the constituent material of the connecting layer 17. By removing the conductive material such as metal from the material of the buffer layer 18, the material having a large Young's modulus and thermal conductivity is removed. Since the cushioning layer 18 does not contain a conductive material, it tends to be softer than the connecting layer 17, and the thermal conductivity is also lowered. As a result, the buffer layer 18 is easily deformed and is less likely to change in temperature, so that it functions as a buffering material against external shocks and thermal shocks, and can enhance the effect of relaxing stress on the solid-state battery cells 1a and 1b. can. Further, since the buffer layer 18 is easily deformed, the bondability between the buffer layer 18 and the current collector in contact with the buffer layer 18 is improved.
  • each paste used for printing formation of the positive electrode active material layer 12 and the negative electrode active material layer 14 is prepared.
  • the solid electrolyte used in the mixture of the positive electrode active material layer 12 and the negative electrode active material layer 14 for example, Li 2 SP 2 S 5 having an average particle diameter of about 10 ⁇ m and containing a triclinic crystal as a main component.
  • a glass powder of the system sulfide is prepared.
  • the glass powder for example, a glass powder having a high ionic conductivity of about 2 to 3 ⁇ 10 -3 S / cm can be used.
  • the positive electrode active material for example, a powder of a layered Li / Ni / Co / Al composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2) having an average particle size of about 5 ⁇ m is used. Be done. A paste containing the above-mentioned positive electrode active material and the above-mentioned glass powder is dispersed in an organic solvent or the like to prepare a paste for the positive electrode active material layer. Further, as the negative electrode active material, for example, natural graphite powder having an average particle size of about 10 ⁇ m is used. A mixture containing the above-mentioned negative electrode active material and the above-mentioned glass powder is dispersed in an organic solvent or the like to prepare a paste for the negative electrode active material layer in the same manner.
  • a copper foil having a thickness of about 30 ⁇ m is prepared.
  • a paste for a positive electrode active material layer and a paste for a negative electrode active material layer are printed on one surface of each copper foil in a predetermined shape and a thickness of about 50 ⁇ m to 100 ⁇ m, respectively. ..
  • the positive electrode active material layer paste and the negative electrode active material layer paste are dried at 80 ° C. to 130 ° C. to a thickness of 30 ⁇ m to 60 ⁇ m.
  • a positive electrode plate is obtained as the positive electrode current collector 11 on which the positive electrode active material layer 12 is formed
  • a negative electrode plate is obtained as the negative electrode current collector 13 on which the negative electrode active material layer 14 is formed.
  • a paste used for printing formation with the solid electrolyte layer 15 is prepared.
  • the above-mentioned mixture containing the glass powder is dispersed in an organic solvent or the like to prepare a paste for a solid electrolyte layer.
  • the above-mentioned paste for the solid electrolyte layer is printed on the surfaces of the positive electrode active material layer 12 of the positive electrode plate and the negative electrode active material layer 14 of the negative electrode plate, for example, with a thickness of about 100 ⁇ m, using a metal mask.
  • the positive electrode plate and the negative electrode plate on which the solid electrolyte layer paste is printed are dried at 80 ° C. to 130 ° C.
  • the solid electrolyte printed on the positive electrode active material layer 12 of the positive electrode plate and the solid electrolyte printed on the negative electrode active material layer 14 of the negative electrode plate are in contact with each other and face each other so that the positive electrode plate and the negative electrode plate are opposed to each other. And are laminated.
  • the laminated body is pressurized with a pressurizing die.
  • a pressurizing die Specifically, an elastic sheet having a thickness of 70 ⁇ m and an elastic modulus of about 5 ⁇ 10 6 Pa is inserted between the laminated body and the pressure mold plate, that is, on the upper surface of the current collector of the laminated body. With this configuration, pressure is applied to the laminated body through the elastic sheet. Then, the pressurizing die is pressurized for 90 seconds while being heated to 50 ° C. at a pressure of 300 MPa. As a result, the solid-state battery cell 1a is obtained. Further, the solid-state battery cell 1b can be obtained by the same method as described above.
  • thermosetting conductor paste containing silver particles having an average particle diameter of 0.5 ⁇ m was about 30 ⁇ m as a material for the connection layer 17.
  • the pattern is printed by screen printing with the thickness of.
  • the conductor paste is printed inside the outer circumference of the negative electrode current collector 13 in a plan view.
  • the paste for the solid electrolyte layer as the material of the buffer layer 18 is pattern-printed with a metal mask.
  • the paste for the solid electrolyte layer is printed so as to surround the outer circumference of the conductor paste in a plan view.
  • the connection layer 17 and the buffer layer 18 are formed on the negative electrode current collector 13 of the solid-state battery cell 1b.
  • the positive electrode current collector 11 of the solid-state battery cell 1a is arranged at a predetermined position and crimped so as to be in contact with the connection layer 17 and the buffer layer 18 formed on the negative electrode current collector 13 of the solid-state battery cell 1b. ..
  • a pressure of, for example, about 1 kg / cm 2 the solid-state battery cell 1a and the solid-state battery cell 1b are prevented from moving, and a thermosetting treatment is performed in the air at about 100 ° C. to 300 ° C. for 60 minutes. And cool to room temperature.
  • the battery 120 is obtained.
  • the number of solid-state battery cells to be stacked is prepared, and the formation of the connection layer 17 and the buffer layer 18 and the stacking of the solid-state battery cells are repeated.
  • the method and order of battery formation are not limited to the above examples.
  • the present invention is not limited to this.
  • a doctor blade method for example, a calendar method, a spin coating method, a dip coating method, an inkjet method, an offset method, a die coating method, a spray method, or the like may be used.
  • thermosetting conductor paste containing silver metal particles is shown as an example of the conductor paste, but the present invention is not limited to this.
  • the conductor paste is, for example, a conductive resin paste containing metal particles, a resin, and a main component as main components.
  • a thermosetting conductor paste containing highly conductive metal particles having a high melting point, metal particles having a low melting point, and a resin is used as the conductor paste.
  • the melting point of the highly conductive metal particles having a high melting point is, for example, 400 ° C. or higher.
  • Examples of the material of the highly conductive metal particles having a high melting point include silver, copper, nickel, zinc, aluminum, palladium, gold, platinum and alloys obtained by combining these metals.
  • the melting point of the metal particles having a low melting point may be lower than the curing temperature of the conductor paste, for example, 300 ° C. or lower.
  • Examples of materials for metal particles having a melting point of 300 ° C. or lower include tin, tin-zinc alloy, tin-silver alloy, tin-copper alloy, tin-aluminum alloy, tin-lead alloy, indium, and indium-silver.
  • Examples thereof include alloys, indium-zinc alloys, indium-tin alloys, bismuths, bismuth-silver alloys, bismuth-nickel alloys, bismuth-tin alloys, bismuth-zinc alloys or bismuth-lead alloys.
  • a diffusion region alloyed by a solid phase and liquid phase reaction is formed around the contact portion.
  • the alloy to be formed include a silver-copper alloy, which is a highly conductive alloy when silver or a silver alloy is used for the highly conductive metal particles having a high melting point and copper is used for the current collector. Be done.
  • a silver-nickel alloy, a silver-palladium alloy, or the like can be formed by combining a highly conductive metal particle having a high melting point and a current collector. With this configuration, the current collector in contact with the connection layer 17 is more firmly bonded, for example, it is suppressed that the joint portion between the connection layer 17 and the current collector is peeled off due to a cooling cycle or an impact. ..
  • the shape of the highly conductive metal particles having a high melting point and the metal particles having a low melting point may be any shape such as spherical, flaky, and needle-shaped.
  • the particle size of the highly conductive metal particles having a high melting point and the metal particles having a low melting point is not particularly limited. For example, the smaller the particle size, the more the alloy reaction and diffusion proceed at a lower temperature, so the particle size and shape are appropriately selected in consideration of the influence of the thermal history on the process design and battery characteristics.
  • the resin used for the thermosetting conductor paste may be any resin that functions as a binder for binding, and an appropriate resin is selected depending on the manufacturing process to be adopted, such as printability and coatability.
  • the resin used for the thermosetting conductor paste includes, for example, a thermosetting resin.
  • the thermosetting resin include (i) amino resins such as urea resin, melamine resin and guanamine resin, and (ii) epoxy resins such as bisphenol A type, bisphenol F type, phenol novolac type and alicyclic resin, (iii). ) Oxetane resin, (iv) resol type, novolak type and other phenolic resins, and (v) silicone epoxy, silicone polyester and other silicone-modified organic resins and the like can be mentioned. Only one of these materials may be used for the resin, or two or more of these materials may be used in combination.
  • the positive electrode current collector 11, the positive electrode active material layer 12, the solid electrolyte layer 15, the negative electrode active material layer 14, and the negative electrode current collector 13 have a shape, a position, and a plan view. They were the same size, but not limited to this. In a plan view, the areas of the positive electrode current collector 11, the negative electrode current collector 13, and the solid electrolyte layer 15 are larger than the areas of the positive electrode active material layer 12 and the negative electrode active material layer 14, and the solid electrolyte layer 15 is the positive electrode active material layer. 12 and the side surface of the negative electrode active material layer 14, and may be in contact with the positive electrode current collector 11 and the negative electrode current collector 13.
  • the positive electrode current collector 11 is in contact with the positive electrode active material layer 12 and the solid electrolyte layer 15, and the negative electrode current collector 13 is in contact with the negative electrode active material layer 14 and the solid electrolyte layer 15.
  • the positive electrode current collector 11 and the negative electrode current collector 13 form a connecting layer 16.
  • the stress caused by the material of any layer can be relaxed by the connecting layer 16. Therefore, it is possible to prevent the positive electrode current collector 11 and the negative electrode current collector 13 from being damaged by the stress.
  • the area of the negative electrode active material layer 14 may be larger than the area of the positive electrode active material layer 12.
  • the cushioning layer 18 is provided so as to surround the connecting layer 17 in a plan view and has a frame shape, but the present invention is not limited to this.
  • the arrangement of the buffer layer 18 and the connection layer 17 is not particularly limited as long as the conductivity between the solid-state battery cell 1a and the solid-state battery cell 1b is not impaired.
  • the buffer layer 18 is at least 1 of the connection layer 17. It may be provided on the outside of one side surface. Further, the buffer layer 18 may be provided so as to be surrounded by the connection layer 17. Further, the buffer layers 18 and the connecting layers 17 may be arranged alternately in a stripe shape.
  • the battery according to the present disclosure can be used as a secondary battery such as an all-solid-state battery used in various electronic devices or automobiles, for example.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)
PCT/JP2020/045749 2020-01-24 2020-12-09 電池 Ceased WO2021149382A1 (ja)

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CN202080093734.2A CN114982032A (zh) 2020-01-24 2020-12-09 电池
EP20915728.8A EP4095972A4 (en) 2020-01-24 2020-12-09 BATTERY
US17/851,053 US12362385B2 (en) 2020-01-24 2022-06-28 Battery having a plurality of solid-state battery cells

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WO2023079792A1 (ja) * 2021-11-08 2023-05-11 パナソニックＩｐマネジメント株式会社 積層電池

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US12334589B2 (en) 2019-11-14 2025-06-17 Benan Energy Bipolar structures for use with electrochemical devices, and associated systems and methods
CN119944083B (zh) * 2025-01-07 2026-03-13 合肥国轩高科动力能源有限公司 一种固态软包电池及其制备方法

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WO2023079792A1 (ja) * 2021-11-08 2023-05-11 パナソニックＩｐマネジメント株式会社 積層電池
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EP4095972A4 (en) 2024-01-10
JPWO2021149382A1 (https=) 2021-07-29
US20220328872A1 (en) 2022-10-13
EP4095972A1 (en) 2022-11-30
US12362385B2 (en) 2025-07-15
JP7611496B2 (ja) 2025-01-10

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