WO2022209114A1 - 固体電池及び固体電池の製造方法 - Google Patents
固体電池及び固体電池の製造方法 Download PDFInfo
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- WO2022209114A1 WO2022209114A1 PCT/JP2022/000421 JP2022000421W WO2022209114A1 WO 2022209114 A1 WO2022209114 A1 WO 2022209114A1 JP 2022000421 W JP2022000421 W JP 2022000421W WO 2022209114 A1 WO2022209114 A1 WO 2022209114A1
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- electrode layer
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- negative electrode
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Images
Classifications
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- H—ELECTRICITY
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- 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
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/11—Primary casings; Jackets or wrappings characterised by their shape or physical structure having a chip structure, e.g. micro-sized batteries integrated on chips
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/049—Processes for forming or storing electrodes in the battery container
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/058—Construction or manufacture
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- 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
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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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
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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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
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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
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
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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
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
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- 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
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- 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 solid-state batteries and solid-state battery manufacturing methods.
- a solid battery using a solid electrolyte instead of an electrolytic solution is known as an electrolyte.
- a technique is known in which the surface of a battery element, in which a solid electrolyte layer is provided between a positive electrode layer and a negative electrode layer facing each other, is covered with a protective layer containing a polymer compound. Furthermore, compared to a protective layer containing a polymer compound, the surface of the battery element is less likely to crack and fall off due to moisture and gas adsorption, and the bonding strength with the battery element is high, making it difficult to fall off due to vibration, impact, etc. , a technique of covering with a protective layer made of an insulating material other than resin, and a technique of using glass or ceramics as such an insulating material.
- a solid battery in which a solid battery body having an electrolyte layer and a positive electrode layer and a negative electrode layer partially provided on both main surfaces thereof is covered with a protective layer using a solid electrolyte.
- a solid battery using a solid electrolyte as a protective layer may not have sufficient strength depending on the environment in which it is mounted or used. Insufficient strength of the solid-state battery may lead to cracking or chipping of the protective layer, resulting in penetration of moisture or gas into the solid-state battery, and the performance of the solid-state battery may be degraded.
- the present invention aims to realize a solid-state battery with excellent strength.
- a solid state battery comprising:
- FIG. 1 is a diagram (part 1) for explaining a configuration example of a solid-state battery
- FIG. 2 is a diagram (part 2) illustrating a configuration example of a solid-state battery
- It is a figure explaining an example of the coating film of a solid battery.
- FIG. 4 is a diagram (part 1) explaining an example of a process of forming a positive electrode layer part
- FIG. 11 is a diagram (part 2) illustrating an example of a process of forming a positive electrode layer part
- FIG. 4 is a diagram (part 1) illustrating an example of a process of forming a negative electrode layer part
- FIG. 1 is a diagram (part 1) for explaining a configuration example of a solid-state battery
- FIG. 2 is a diagram (part 2) illustrating a configuration example of a solid-state battery
- It is a figure explaining an example of the coating film of a solid battery.
- FIG. 4 is a diagram (part 1) explaining an example of a process of forming a positive electrode layer part
- FIG. 11 is a diagram (part 2) explaining an example of a step of forming a negative electrode layer part; It is a figure explaining an example of the formation process of a structure.
- FIG. 10 is a diagram (part 1) for explaining another example of the structure forming process;
- FIG. 12 is a diagram (part 2) explaining another example of the structure forming process;
- It is a figure explaining an example of the cutting process of a structure.
- It is a figure explaining an example of the heat treatment process of a structure.
- FIG. 10 is a diagram (part 1) explaining another example of the solid-state battery manufacturing method;
- FIG. 10 is a diagram (part 2) explaining another example of the solid-state battery manufacturing method;
- FIG. 11 is a diagram (part 3) explaining another example of the solid-state battery manufacturing method;
- FIG. 1 is a diagram illustrating an example of a solid battery.
- FIG. 1A schematically shows a perspective view of essential parts of an example of a solid-state battery.
- FIG. 1B schematically shows an example of a cross-sectional view along the chain line P1 in FIG. 1A
- FIG. 1C shows an example of a cross-sectional view along the dotted line P2 in FIG. 1A. is schematically shown.
- a solid-state battery 1 shown in FIGS. 1A to 1C is an example of a chip-type battery.
- a solid battery 1 includes a solid battery body 10 and a coating film 20 .
- the solid battery main body 10 includes an electrolyte layer 13, and a positive electrode laminated on one main surface 13a (also referred to as a first main surface) and the other main surface 13b (also referred to as a second main surface) on the opposite side thereof. It has a layer 11 and a negative electrode layer 12 .
- the solid battery main body 10 is an example of a laminate of an electrolyte layer 13 , a positive electrode layer 11 and a negative electrode layer 12 .
- Electrolyte layer 13 contains a solid electrolyte.
- An oxide solid electrolyte can be used for the solid electrolyte of the electrolyte layer 13 .
- the electrolyte layer 13 uses LAGP, which is a kind of NASICON (Na super ionic conductor) type (also referred to as "Nasicon type”) oxide solid electrolyte.
- LAGP is an oxide solid electrolyte represented by the general formula Li 1+x Al x Ge 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 1), and is called aluminum-substituted lithium germanium phosphate.
- the positive electrode layer 11 laminated on one main surface 13a of the electrolyte layer 13 contains a positive electrode active material.
- a positive electrode active material Li 2 CoP 2 O 7 , hereinafter referred to as “LCPO”
- LCPO lithium cobalt pyrophosphate
- the positive electrode layer 11 may contain a solid electrolyte and a conductive aid in addition to the positive electrode active material.
- the solid electrolyte of the positive electrode layer 11 for example, the same material as the oxide solid electrolyte used for the electrolyte layer 13 is used. That is, in this example, LAGP is used as the oxide solid electrolyte of the positive electrode layer 11 .
- Carbon materials such as carbon fiber, carbon black, graphite, graphene, and carbon nanotubes are used as the conductive aid of the positive electrode layer 11, for example.
- Negative electrode layer 12 laminated on the other main surface 13b of electrolyte layer 13 contains a negative electrode active material. Titanium oxide (TiO 2 ), for example, is used as the negative electrode active material of the negative electrode layer 12 .
- the negative electrode layer 12 may contain a solid electrolyte and a conductive aid in addition to the negative electrode active material.
- the solid electrolyte of the negative electrode layer 12 for example, the same material as the oxide solid electrolyte used for the electrolyte layer 13 is used. That is, in this example, LAGP is used as the oxide solid electrolyte of the negative electrode layer 12 .
- Carbon materials such as carbon fiber, carbon black, graphite, graphene, and carbon nanotubes are used as the conductive aid for the negative electrode layer 12, for example.
- the positive electrode layer 11 is provided on a part of the main surface 13a of the electrolyte layer 13, and the negative electrode layer 12 is provided on the electrolyte layer 13.
- the positive electrode layer 11 and the negative electrode layer 12 are provided on a part of the main surface 13b and partially overlap with each other with the electrolyte layer 13 interposed therebetween.
- lithium ions are conducted from the positive electrode layer 11 to the negative electrode layer 12 via the electrolyte layer 13 and incorporated therein. Lithium ions conduct and are taken in. In the solid battery main body 10, charge/discharge operation is realized by such lithium ion conduction.
- the coating film 20 is part of the positive electrode layer 11 and part of the negative electrode layer 12 of the solid battery main body 10, in this example, the part 11a (also referred to as the first part) on the side surface of the positive electrode layer 11 and the side surface of the negative electrode layer 12.
- the solid battery main body 10 is covered so that the portion 12a (also referred to as the second portion) is exposed.
- the portion 11a of the positive electrode layer 11 and the portion 12a of the negative electrode layer 12 are opposed to each other in the direction perpendicular to the stacking direction of the electrolyte layer 13, the positive electrode layer 11 and the negative electrode layer 12.
- a portion 11 a of the positive electrode layer 11 and a portion 12 a of the negative electrode layer 12 exposed from the coating film 20 are used for electrical connection with the outside of the solid battery main body 10 .
- the side surface of the solid battery 1 where the portion 11a of the positive electrode layer 11 is exposed from the coating film 20 is referred to as the positive electrode lead-out surface 1a
- the side surface where the portion 12a of the negative electrode layer 12 is exposed from the coating film 20 is referred to as the negative electrode lead-out surface 1b.
- the coating film 20 is in contact with the surface of the positive electrode layer 11 excluding the other portion of the main surface 13a of the electrolyte layer 13 on which the positive electrode layer 11 is provided and the portion 11a exposed from the positive electrode lead-out surface 1a. Then, the solid battery main body 10 is covered.
- the coating film 20 is in contact with the other part of the main surface 13b of the electrolyte layer 13 where the negative electrode layer 12 is provided on part of the main surface 13b, and the surface of the negative electrode layer 12 excluding the part 12a exposed from the negative electrode lead-out surface 1b. Then, the solid battery main body 10 is covered.
- the coating film 20 covers the solid battery main body 10 so as to be in contact with the side surface of the electrolyte layer 13 (the surface connecting the main surface 13a and the main surface 13b) except for the positive electrode lead-out surface 1a and the negative electrode lead-out surface 1b. .
- An insulating coating film 20 having a higher hardness than the solid electrolyte used is used.
- an insulating coating film 20 having higher hardness than the solid electrolyte used for the electrolyte layer 13 is used.
- an insulating coating film 20 having higher hardness than the solid electrolyte used for the electrolyte layer 13 and the solid electrolyte used for the positive electrode layer 11 and the negative electrode layer 12 is used.
- the insulating properties of the coating film 20 refer to properties that have no or sufficiently low influence on the lithium ion conduction and electronic conduction of the solid battery main body 10 .
- Glass or ceramics, for example, is used for the insulating coating film 20 having higher hardness than the solid electrolyte used in the solid battery main body 10 .
- the coating film 20 has the function of protecting the solid battery main body 10 from external force and the external environment. Therefore, the coating film 20 has hardness and insulating properties as described above, and also has low permeability to moisture or gases such as hydrogen and oxygen, and is capable of achieving good sealing performance. Furthermore, the coating film 20 preferably has a coefficient of thermal expansion similar to that of each layer of the electrolyte layer 13, the positive electrode layer 11, and the negative electrode layer 12 of the solid battery main body 10. Also, the adhesion with each layer is preferable. is preferably used. Glass or ceramics is one type of material that can have these properties, and is suitable as a material for forming the coating film 20 that covers the solid battery main body 10 .
- a structure including a material (referred to as a “coating material”) that covers the solid battery body 10 so that twelve portions 12a are exposed is formed.
- this structure is fired at a predetermined temperature (also referred to as a first temperature).
- the coating material covering the solid battery main body 10 is sintered, and the insulating coating film 20 having higher hardness than the solid electrolyte used for the solid battery main body 10 is formed from the coating material.
- the solid electrolyte used in the solid battery main body 10 may be sintered, and the coating material covering the solid battery main body 10 may be sintered to form the coating film 20 . That is, the solid electrolyte used in the solid battery main body 10 and the coating material covering the solid battery main body 10 are made of materials having the same sintering temperature, or the same or the same degree of sintering temperature. and the coating material may be sintered together.
- the solid battery body 10 is used in such a manner that the portion 11a of the positive electrode layer 11 is exposed on the positive electrode lead-out surface 1a and the portion 12a of the negative electrode layer 12 is exposed on the negative electrode lead-out surface 1b. It is covered with a coating film 20 having a higher hardness than the solid electrolyte used.
- a coating film 20 As a protective layer of the solid battery main body 10, cracking and chipping due to external force can be suppressed, compared with the case where a solid electrolyte is used for the protective layer, for example. Intrusion of moisture or gas from the chipped portion, and deterioration of the performance of the solid-state battery 1, such as short circuit and increase in resistance caused by it, can be effectively suppressed.
- the coating film 20 as described above as the protective layer of the solid battery main body 10 as described above, the solid battery 1 having excellent strength and excellent environmental resistance is realized.
- the coating film 20 has a coefficient of thermal expansion similar to that of each layer of the solid battery main body 10, thereby suppressing delamination due to expansion and contraction of each layer due to the external temperature environment. be done.
- the coating film 20 having good adhesion to each layer of the solid battery main body 10 is used, so that the solid state can be prevented when a force is applied from the outside or when each layer expands and contracts. Peeling of the coating film 20 from the battery body 10 is suppressed.
- the coating film 20 has a relatively low sintering temperature of 900° C. or lower, for example, 650° C. or lower, which is the same as, equivalent to, or about the same as the sintering temperature of the solid electrolyte.
- a relatively low sintering temperature of 900° C. or lower, for example, 650° C. or lower, which is the same as, equivalent to, or about the same as the sintering temperature of the solid electrolyte.
- thermal deterioration of the solid battery body 10 due to the formation of the coating film 20 is suppressed, and an increase in man-hours is suppressed by collectively sintering the coating material and the solid electrolyte.
- the solid-state battery 1 having excellent strength and environmental resistance is realized, and such a solid-state battery 1 can be manufactured efficiently.
- FIG. 2A schematically shows a perspective view of an essential part of an example of a solid-state battery
- FIG. 2B schematically shows an example of a cross-sectional view along chain line P3 in FIG. 2A.
- FIG. 3A schematically shows a perspective view of essential parts of an example of a solid-state battery
- FIG. 3B schematically shows an example of a cross-sectional view along the dotted line P4 in FIG. 3A.
- FIG. 3 are diagrams schematically showing the same solid-state battery, and are diagrams for explaining cross-sectional structures at different positions of the same solid-state battery.
- a solid-state battery 1A shown in FIGS. 2(A) and 2(B) and FIGS. 3(A) and 3(B) is an example of a chip-type battery.
- the solid battery 1A includes a solid battery main body 10A, a coating film 20A, an external electrode 31 (also referred to as a first external electrode) and an external electrode 32 (also referred to as a second external electrode).
- the solid battery main body 10A has a plurality of electrolyte layers 13, a plurality of positive electrode layers 11 and a plurality of negative electrode layers 12, as shown in FIGS. 2(B) and 3(B).
- the plurality of electrolyte layers 13, the plurality of positive electrode layers 11, and the plurality of negative electrode layers 12 of the solid battery main body 10A are arranged so that one electrolyte layer 13 is interposed between a pair of the positive electrode layer 11 and the negative electrode layer 12. Laminated.
- the solid battery body 10A shown in this example has a structure in which the negative electrode layer 12, the electrolyte layer 13, the positive electrode layer 11, the electrolyte layer 13, the negative electrode layer 12, the electrolyte layer 13, and the positive electrode layer 11 are laminated in this order from the bottom. ing.
- each positive electrode layer 11 is provided on a part of the main surface 13a (also referred to as the first main surface) of the electrolyte layer 13 on which it is laminated, and each negative electrode layer 12 is laminated thereon.
- a pair of the positive electrode layer 11 and the negative electrode layer 12 provided on a part of the main surface 13b (also referred to as a second main surface) of the electrolyte layer 13 and facing each other with one electrolyte layer 13 interposed therebetween are separated from each other with the electrolyte layer 13 interposed therebetween. are provided so as to partially overlap each other.
- the solid battery main body 10A is an example of a laminate in which a plurality of electrolyte layers 13, a plurality of positive electrode layers 11 and a plurality of negative electrode layers 12 are laminated in this way.
- each electrolyte layer 13 of the solid battery body 10A for example, one containing LAGP, which is an oxide solid electrolyte, is used.
- LAGP for each positive electrode layer 11 of the solid battery main body 10A, for example, one containing LCPO as a positive electrode active material, LAGP as an oxide solid electrolyte, and a carbon material as a conductive aid is used.
- For each negative electrode layer 12 of the solid battery main body 10A for example, one containing TiO 2 as a negative electrode active material, LAGP as an oxide solid electrolyte, and a carbon material as a conductive aid is used.
- lithium ions are conducted from the positive electrode layer 11 through the electrolyte layer 13 to the negative electrode layer 12 and taken in. Lithium ions conduct and are taken in.
- such lithium ion conduction in the positive electrode layer 11 and the negative electrode layer 12 facing each other and the electrolyte layer 13 interposed therebetween realizes charge/discharge operation.
- the coating film 20A is formed at a portion 11a (also referred to as a first portion) on the side surface of each positive electrode layer 11 and a portion 12a (second portion) on the side surface of each negative electrode layer 12 of the solid battery body 10A. ) is exposed, the solid battery body 10A is covered.
- the side surface of the solid battery 1A where the portion 11a of the positive electrode layer 11 is exposed from the coating film 20A is the positive electrode lead-out surface 1Aa
- the side surface where the portion 12a of the negative electrode layer 12 is exposed from the coating film 20A is the negative electrode lead-out surface 1Ab.
- the coating film 20A is applied to a portion of the main surface 13a of the electrolyte layer 13 where the positive electrode layer 11 is provided and the other portion of the main surface 13a of the electrolyte layer 13 and the positive electrode lead-out surface.
- the solid battery main body 10A is covered so as to be in contact with the surface of the positive electrode layer 11 excluding the portion 11a exposed from 1Aa.
- the coating film 20A is in contact with the other part of the main surface 13b of the electrolyte layer 13 where the negative electrode layer 12 is provided on a part of the main surface 13b and the surface of the negative electrode layer 12 excluding the part 12a exposed from the negative electrode lead-out surface 1Ab.
- the solid battery body 10A is covered. Further, the coating film 20A covers the solid battery main body 10A so as to be in contact with the side surface of the electrolyte layer 13 except for the positive electrode lead-out surface 1Aa and the negative electrode lead-out surface 1Ab.
- the coating film 20A covers the solid battery main body 10A so as to be in contact with the side surface of the electrolyte layer 13 except for the positive electrode lead-out surface 1Aa and the negative electrode lead-out surface 1Ab.
- the coating film 20A includes an insulation layer having a higher hardness than the solid electrolyte used in the solid battery main body 10A, for example, the solid electrolyte of the electrolyte layer 13, or the solid electrolyte used in the electrolyte layer 13, the positive electrode layer 11, and the negative electrode layer 12.
- a flexible coating film 20A is used.
- the coating film 20A a material having high hardness and insulating properties, low moisture and gas permeability, and excellent airtightness is used.
- the coating film 20A preferably has a coefficient of thermal expansion similar to that of each layer constituting the solid battery main body 10A, and preferably has good adhesion to each layer. .
- glass or ceramics is used for the coating film 20A.
- the external electrode 31 is provided on the positive electrode lead-out surface 1Aa of the solid battery 1A, and is exposed from the positive electrode lead-out surface 1Aa of the solid battery main body 10A. part of the side surface of the electrolyte layer 13).
- the external electrode 32 is provided on the negative electrode lead-out surface 1Ab of the solid battery 1A, and the portion 12a of the negative electrode layer 12 of the solid battery body 10A exposed from the negative electrode lead-out surface 1Ab (and part of the side surface of the electrolyte layer 13).
- Various conductor materials can be used for the external electrodes 31 and 32 .
- a conductive paste containing metal particles such as silver (Ag) or conductive particles such as carbon particles is dried and cured, or a sputtering method, a plating method, or the like is used. Those formed by deposition of the various metals used are used.
- the solid battery main body 10A is covered with the coating film 20A having higher hardness than the solid electrolyte used therein, except for the positive electrode lead-out surface 1Aa and the negative electrode lead-out surface 1Ab.
- the coating film 20A having higher hardness than the solid electrolyte used therein, except for the positive electrode lead-out surface 1Aa and the negative electrode lead-out surface 1Ab.
- a portion of the coating film 20A is provided in a portion recessed inward from the side surface of the electrolyte layer 13, thereby exhibiting an anchor effect and effectively peeling the coating film 20A from the solid-state battery main body 10A. suppressed.
- the positive electrode lead-out surface 1Aa a part of the coating film 20A is provided in a recessed portion between the pair of electrolyte layers 13 facing each other with the negative electrode layer 12 interposed therebetween.
- the strength between the electrolyte layers 13 is increased, and the support of the positive electrode layer 11 laminated on each of them is strengthened.
- the strength of the positive electrode layer 11 on the positive electrode lead-out surface 1Aa is increased, and cracking and chipping of the positive electrode layer 11 are suppressed.
- a portion of the coating film 20A is provided between the pair of electrolyte layers 13 facing each other with the positive electrode layer 11 interposed therebetween, and is recessed inward from the side surfaces of the pair of electrolyte layers 13.
- the strength between the electrolyte layers 13 is increased, and the support of the negative electrode layer 12 laminated to each of them is strengthened.
- the strength of the negative electrode layer 12 on the negative electrode lead-out surface 1Ab is increased, and cracking and chipping of the negative electrode layer 12 are suppressed.
- the coating film 20A as described above as the protective layer of the solid battery main body 10A as described above, the solid battery 1A having excellent strength and excellent environmental resistance is realized.
- the coating film 20A has a coefficient of thermal expansion similar to that of each layer of the solid battery main body 10A. be done.
- the solid state can be prevented when a force is applied from the outside or when each layer expands and contracts. Peeling of the coating film 20A from the battery main body 10A is suppressed.
- Such a coating film 20A also realizes a solid-state battery 1A having excellent strength and environmental resistance.
- a solid battery main body 10A having an electrolyte layer 13 and a positive electrode layer 11 and a negative electrode layer 12 laminated on its main surface 13a and main surface 13b, respectively, an external electrode 31 and an external electrode 32 and a coating material covering the solid battery main body 10A so that the portion 11a of the positive electrode layer 11 and the portion 12a of the negative electrode layer 12, which are respectively connected to the electrodes, are exposed.
- a predetermined temperature also referred to as a first temperature
- the coating material covering the solid battery main body 10A is sintered to form the coating film 20A.
- a sintering temperature of 650° C. or lower for example, a sintering temperature of 650° C. or lower is used, thermal deterioration of the solid battery main body 10A due to the formation of the coating film 20A will occur. suppressed. Furthermore, if a coating material having a sintering temperature that is the same as, equal to, or about the same as the sintering temperature of the solid electrolyte used in the solid battery main body 10A is used, the solid electrolyte and the coating material can be sintered under one condition. and can be sintered together. Details of the manufacturing method of the solid battery 1A will be described later.
- the coating film 20A is used for the coating film 20A formed by firing the coating material.
- the coating film 20A may take various forms such as glass, crystallized glass, polycrystal, and single crystal.
- the coating film 20A may be made of one material phase, or may be made of two or more material phases.
- the coating film 20A may include two or more material phases with different physical properties, for example, two or more material phases with different hardness.
- FIG. 4 is a diagram explaining an example of a coating film of a solid-state battery.
- FIG. 4A schematically shows a cross-sectional view of an essential part of an example of a solid-state battery (a cross-sectional view along the dotted line P4 in FIG. 3A), and FIG. An enlarged view of the portion Q1 is schematically shown.
- the coating film 20A covering the solid battery main body 10A of the solid battery 1A as shown in FIG. 4A, for example, as shown in FIG. ) and a material phase 22 (also referred to as a second material phase).
- the coating film 20A includes a glass or ceramic material phase 21 having a predetermined hardness (also referred to as a first hardness) and a material phase 22 having a hardness higher than that of the material phase 21 (also referred to as a second hardness). and are included. Ceramics, for example, is used as the material phase 22 having a higher hardness than the material phase 21 .
- the material phase 22 is included in the material phase 21 in, for example, a particulate form as shown in FIG. 4(B). It should be noted that the particulate material phase 22 does not necessarily need to be uniformly dispersed and contained in the material phase 21 . Although FIG. 4B shows the particulate material phase 22, the material phase 21 may contain a fiber-like or sheet-like material phase having higher hardness. Often, multiple types of material phases may be included.
- the coating film 20A By configuring the coating film 20A such that the material phase 22 having a higher hardness than the material phase 21 of glass or ceramics is included, the hardness of the coating film 20A is increased compared to the case where only the material phase 21 is included. can be further increased. By covering the solid battery main body 10A with such a coating film 20A, the solid battery 1A having even higher strength and excellent environmental resistance is realized.
- electrolyte paste An electrolyte paste containing a solid electrolyte, a binder, a plasticizer, a dispersant and a diluent is prepared.
- an electrolyte paste is prepared using LAGP, which is an oxide solid electrolyte, as the solid electrolyte.
- a positive electrode paste containing a positive electrode active material, a solid electrolyte, a conductive aid, a binder, a plasticizer, a dispersant and a diluent is prepared.
- a positive electrode paste is prepared using LCPO as a positive electrode active material, LAGP, which is an oxide solid electrolyte, as a solid electrolyte, and carbon nanofibers as a conductive aid.
- a negative electrode paste containing a negative electrode active material, a solid electrolyte, a conductive aid, a binder, a plasticizer, a dispersant and a diluent is prepared.
- a negative electrode paste is prepared using TiO 2 as a negative electrode active material, LAGP, which is an oxide solid electrolyte, as a solid electrolyte, and carbon nanofibers as a conductive aid.
- a glass paste containing a glass component is prepared as a coating material paste.
- a glass paste containing a glass component called so-called low-melting-point glass, which is melted and sintered by firing at around 600° C., is prepared.
- a glass sheet as a coating material sheet is formed by applying and drying the prepared glass paste.
- the coating material paste and the coating material sheet are one form of the coating material that is formed as the coating film 20A by firing.
- the coating material paste and the coating material sheet are used such that the hardness after firing is higher than the hardness of the solid electrolyte contained in the electrolyte layer 13, the positive electrode layer 11, and the negative electrode layer 12 after firing.
- the coating material paste and the coating material sheet should have a thermal expansion coefficient after firing that is approximately the same as that of the electrolyte layer 13, the positive electrode layer 11, and the negative electrode layer 12 after firing. is preferred.
- a ceramic material such as particulate Al 2 O 3 may be added to the coating material paste and the coating material sheet. In this case, the glass component contained in the coating material paste and the coating material sheet becomes the first material phase, and the ceramic material such as particulate Al 2 O 3 becomes the second material phase.
- FIG. 5A schematically shows a perspective view of essential parts of an example of the preparation process of the support.
- FIG. 5B schematically shows a perspective view of essential parts of an example of the process of forming the positive electrode layer.
- FIG. 5C schematically shows a perspective view of essential parts of an example of the process of forming the first coating material layer.
- FIG. 5D schematically shows a perspective view of essential parts of an example of the process of forming an electrolyte layer.
- FIG. 5E schematically shows a perspective view of essential parts of an example of the process of forming the second coating material layer.
- FIG. 5A schematically shows a perspective view of essential parts of an example of the preparation process of the support.
- FIG. 5B schematically shows a perspective view of essential parts of an example of the process of forming the positive electrode layer.
- FIG. 5C schematically shows a perspective view of essential parts of an example of the process of forming the first coating material layer.
- FIG. 5D schematically shows a perspective view of essential parts of
- FIG. 6(A) schematically shows a perspective view of a main part corresponding to FIG. 5(E), which is an example of a positive electrode layer part.
- FIG. 6(B) schematically shows an example of a cross-sectional view taken along chain line P3a in FIG. 6(A).
- FIG. 6(C) schematically shows an example of a cross-sectional view taken along the dotted line P4a in FIG. 6(A).
- a polyethylene terephthalate (PET) film for example, is used for the support 50 shown in FIG. 5(A).
- a part of the prepared support 50 as shown in FIG. 5(A) was coated with a positive electrode paste by screen printing as shown in FIG. 5(B).
- the positive electrode paste is dried to form the positive electrode layer 11 .
- a coating material paste is applied around the positive electrode layer 11 formed on a part of the support 50 by screen printing as shown in FIG.
- the applied coating material paste is dried to form the coating material layer 24 .
- Coating material layer 24 is also referred to as a buried layer.
- an electrolyte paste is applied by screen printing as shown in FIG.
- the deposited electrolyte paste is dried to form electrolyte layer 13 .
- a coating material paste is applied and applied by screen printing on a portion of the coating material layer 24 not covered by the electrolyte layer 13, as shown in FIG. 5(E).
- the resulting coating material paste is dried to form a coating material layer 24 (embedding layer).
- the cross-sectional structure shown in FIG. A part having a cross-sectional structure as shown in FIG. 6(C) is formed at the position of dotted line P4a as shown in 6(A).
- Parts such as those shown in FIGS. 6A to 6C (and FIG. 5E) can be used as positive electrode layer parts.
- parts obtained by peeling off the support 50 from parts as shown in FIGS. 6(A) to 6(C) can be used as positive electrode layer parts.
- a part as shown in FIG. 5C or a part obtained by peeling off the support 50 from the part before forming the electrolyte layer 13 can be used as the positive electrode layer part.
- the coating of the positive electrode paste on the support 50 and the coating of the coating material paste around it are performed alternately in order to adjust the thickness of the positive electrode layer 11 and the amount of active material. may be repeated multiple times.
- the drying of the positive electrode paste and the coating material paste may be performed each time after each coating, or may be performed collectively after multiple coatings of the positive electrode paste and the coating material paste.
- the application of the electrolyte paste and the application of the coating material paste on the outside thereof when forming the positive electrode layer part may be alternately repeated multiple times in order to adjust the thickness of the electrolyte layer 13 or the like.
- the electrolyte paste and the coating material paste may be dried after each coating, or may be dried all at once after coating the electrolyte paste and the coating material paste a plurality of times.
- the positive electrode layer 11 and the surrounding coating material layer 24 are formed on the support 50, and then Although an example has been shown in which the electrolyte layer 13 and the outer coating material layer 24 are formed, this order can be reversed. That is, the electrolyte layer 13 and the coating material layer 24 outside thereof are formed on the support 50 according to the above example, and then the positive electrode layer 11 and the coating material layer 24 around it are formed. good.
- FIG. 7A schematically shows a perspective view of essential parts of an example of the preparation process of the support.
- FIG. 7B schematically shows a perspective view of a main part of an example of a step of forming a negative electrode layer.
- FIG. 7C schematically shows a perspective view of essential parts of an example of the process of forming the first coating material layer.
- FIG. 7D schematically shows a perspective view of essential parts of an example of the process of forming an electrolyte layer.
- FIG. 7E schematically shows a perspective view of essential parts of an example of the process of forming the second coating material layer.
- FIG. 7A schematically shows a perspective view of essential parts of an example of the preparation process of the support.
- FIG. 7B schematically shows a perspective view of a main part of an example of a step of forming a negative electrode layer.
- FIG. 7C schematically shows a perspective view of essential parts of an example of the process of forming the first coating material layer.
- FIG. 7D schematically shows
- FIG. 8(A) schematically shows a perspective view of a main part corresponding to FIG. 7(E), which is an example of a negative electrode layer part.
- FIG. 8B schematically shows an example of a cross-sectional view taken along chain line P3b in FIG. 8A.
- FIG. 8(C) schematically shows an example of a cross-sectional view taken along the dotted line P4b in FIG. 8(A).
- a part of the support 50 such as a PET film is coated with a negative electrode paste by screen printing as shown in FIG. 7(B).
- the negative electrode paste is dried to form the negative electrode layer 12 .
- a coating material paste is applied around the negative electrode layer 12 formed on a part of the support 50 by screen printing as shown in FIG.
- the applied coating material paste is dried to form a coating material layer 24 (embedded layer).
- an electrolyte paste is applied onto the negative electrode layer 12 and part of the coating material layer 24 formed therearound by screen printing.
- the deposited electrolyte paste is dried to form electrolyte layer 13 .
- a coating material paste is applied by screen printing on a portion of the coating material layer 24 not covered by the electrolyte layer 13, as shown in FIG.
- the resulting coating material paste is dried to form a coating material layer 24 (embedded layer).
- the cross-sectional structure shown in FIG. A part having a cross-sectional structure as shown in FIG. 8(C) is formed at the position of dotted line P4b as shown in 8(A).
- Parts as shown in FIGS. 8A to 8C (and FIG. 7E) can be used as negative electrode layer parts.
- a part obtained by peeling off the support 50 from the part shown in FIGS. 8A to 8C can also be used as the negative electrode layer part.
- a part such as shown in FIG. 7C before the electrolyte layer 13 is formed or a part obtained by peeling the support 50 from the part can be used as the negative electrode layer part.
- the application of the negative electrode paste onto the support 50 and the application of the coating material paste around it are performed alternately in order to adjust the thickness of the negative electrode layer 12 and the amount of active material. may be repeated multiple times.
- the drying of the negative electrode paste and the coating material paste may be performed each time after each application, or may be performed collectively after the application of the negative electrode paste and the coating material paste a plurality of times.
- the application of the electrolyte paste and the application of the coating material paste on the outside thereof when forming the negative electrode layer part may be alternately repeated a plurality of times in order to adjust the thickness of the electrolyte layer 13 or the like.
- the electrolyte paste and the coating material paste may be dried after each coating, or may be dried all at once after coating the electrolyte paste and the coating material paste a plurality of times.
- the negative electrode layer 12 and the surrounding coating material layer 24 are formed on the support 50, and then Although an example has been shown in which the electrolyte layer 13 and the outer coating material layer 24 are formed, this order can be reversed. That is, the electrolyte layer 13 and the outer coating material layer 24 may be formed on the support 50 according to the above example, and then the negative electrode layer 12 and the surrounding coating material layer 24 may be formed. good.
- FIG. 9 is a diagram illustrating an example of a structure forming process.
- FIG. 9A schematically shows a cross-sectional view of an essential part of an example of the process of laminating a group of parts.
- FIG. 9B schematically shows a cross-sectional view of an essential part of an example of the process of laminating the coating material sheets.
- 9(A) and 9(B) schematically show cross sections of the parts group corresponding to the positions of the dashed line P3a in FIG. 6(A) and the dashed line P3b in FIG. 8(A). ing.
- the positive electrode layer parts and the negative electrode layer parts of the predetermined form obtained as described above are laminated, for example, as shown in FIG. 9(A).
- the support 50 is separated from the positive electrode layer part shown in FIG.
- the support 50 removed from the negative electrode layer part shown in FIG. 8(B) is laminated, and the support 50 removed from the positive electrode layer part shown in FIG. 5(C) is laminated thereon.
- the support 50 is peeled off from the structure shown in FIG. are thermo-compressed under the pressure and temperature conditions of , to form a structure 5 as shown in FIG.
- the positive electrode layer parts and the negative electrode layer parts are laminated so as to overlap with each other.
- the step of forming the positive electrode layer part and the negative electrode layer part when they are laminated, in the cross sections shown in FIGS. Coating is performed so that the layer 11 and the layer 11 partially overlap each other.
- the positive electrode layer 12 and the positive electrode layer 11 facing each other with the electrolyte layer 13 interposed therebetween overlap as a whole.
- Parts and negative electrode layer parts are laminated.
- the negative electrodes facing each other across the electrolyte layer 13 in a cross section orthogonal to the cross sections shown in FIGS. 9A and 9B Coating is performed so that the layer 12 and the positive electrode layer 11 have a positional relationship in which they entirely overlap.
- a laminate (of the solid battery main body 10A) having a positive electrode layer 11, a negative electrode layer 12, and an electrolyte layer 13 interposed therebetween is produced by the steps shown in FIGS. 9A and 9B.
- a structure 5 is formed including a basic structure), and a coating material sheet 23 and a coating material layer 24 provided so as to cover it (basic structure of the coating film 20A).
- FIGS. 10A to 10D and 11A to 11D schematically show principal part cross-sectional views of an example of each step of forming a structure.
- a negative electrode paste is applied onto a portion of the coating material sheet 23 and dried to form the negative electrode layer 12 .
- a coating material paste is applied around the negative electrode layer 12 formed on a portion of the coating material sheet 23, and dried to form a coating material layer 24 ( buried layer) is formed.
- an electrolyte paste is applied onto the negative electrode layer 12 and part of the coating material layer 24 surrounding it, and dried to form the electrolyte layer 13 .
- a coating material paste was applied and applied on a portion of the coating material layer 24 not covered by the electrolyte layer 13 using a screen printing method.
- the coating material paste is dried to form a coating material layer 24 (embedding layer).
- a positive electrode paste is applied on a part of the electrolyte layer 13 and dried to form the positive electrode layer 11 .
- a coating material paste is applied around the positive electrode layer 11 formed on a part of the electrolyte layer 13 and dried to form a coating material layer 24 (embedded). layer) is formed.
- an electrolyte paste is applied onto the positive electrode layer 11 and part of the coating material layer 24 surrounding it, and dried to form the electrolyte layer 13.
- a coating material paste was applied and applied on a portion of the coating material layer 24 not covered by the electrolyte layer 13 using a screen printing method.
- the coating material paste is dried to form a coating material layer 24 (embedded layer).
- a negative electrode paste is applied on a part of the electrolyte layer 13 and dried to form the negative electrode layer 12 .
- a coating material paste is applied around the negative electrode layer 12 formed on a part of the electrolyte layer 13 and dried to form a coating material layer 24 (embedded). layer) is formed.
- the electrolyte layer 13 is formed on the negative electrode layer 12 and part of the coating material layer 24 therearound using the electrolyte paste in the same procedure as above, and the electrolyte layer 13 is formed on the outside thereof.
- a coating material layer 24 (embedded layer, not shown) is formed using a coating material paste, and a cathode layer 11 is formed on a portion of the electrolyte layer 13 using a cathode paste.
- a coating material layer 24 (embedded layer) is formed around the positive electrode layer 11 formed on a portion of the electrolyte layer 13 using a coating material paste.
- the coating material sheet 23 is formed on the positive electrode layer 11 and the surrounding coating material layer 24 using a coating material paste, or a previously prepared coating material sheet 23 is laminated. Thereby, a structure 5 as shown in FIG. 11(D) is formed.
- the negative electrode paste and coating material paste are applied onto the coating material sheet 23 (FIG. 10A), and the negative electrode paste and coating material paste are applied onto the electrolyte layer 13 (FIG. 10A).
- 11(B) and 11(C)) may be alternately repeated a plurality of times in order to adjust the thickness of the negative electrode layer 12 and the amount of the active material.
- the drying of the negative electrode paste and the coating material paste may be performed each time after each application, or may be performed collectively after the application of the negative electrode paste and the coating material paste a plurality of times.
- the coating of the positive electrode paste and the coating of the coating material paste on the electrolyte layer 13 depend on the thickness of the positive electrode layer 11 and the active material. For adjustment of the amount, etc., it may be performed alternately and repeatedly a plurality of times. In this case, the drying of the positive electrode paste and the coating material paste may be performed each time after each coating, or may be performed collectively after multiple coatings of the positive electrode paste and the coating material paste.
- the positive electrode layer 11, the negative electrode layer 12, and the electrolyte layer 13 interposed therebetween are formed by the steps shown in FIGS. 10A to 10D and 11A to 11D. and a laminate (basic structure of the solid battery main body 10A), and a coating material sheet 23 and a coating material layer 24 (basic structure of the coating film 20A) provided to cover it. may be formed.
- FIG. 12 is a diagram explaining an example of the cutting process of the structure. 12(A) and 12(B) schematically show cross-sectional views of a main part of an example of a step of cutting a structure.
- FIG. 12(A) for the structure 5 formed by the method shown in the first example (FIGS. 5 to 9) or the second example (FIGS. 10 and 11).
- Cutting is performed at predetermined positions C1 and C2.
- the structure 5 is cut at a position C1 where the end surface of the positive electrode layer 11 is exposed on one cut surface and at a position C2 where the end surface of the negative electrode layer 12 is exposed on the other cut surface.
- a structure 5a is formed in which the end surfaces of the positive electrode layer 11 and the negative electrode layer 12 are exposed at the cut surfaces, as shown in FIG. 12B.
- the cut surfaces of the structure 5a where the end surfaces of the positive electrode layer 11 and the negative electrode layer 12 are exposed are the positive electrode lead surface 1Aa and the negative electrode lead surface 1Ab, respectively, which will be described later.
- FIG. 13 is a diagram illustrating an example of a heat treatment process for a structure.
- 13A and 13B schematically show cross-sectional views of essential parts of an example of a heat treatment process for a structure.
- the structure 5a obtained by cutting is transported to a heat treatment furnace 40 as shown in FIG.
- the structure 5a transported to the heat treatment furnace 40 is subjected to a heat treatment for degreasing that mainly burns out organic components such as binders, and a heat treatment for firing that mainly sinters the solid electrolyte and the coating material.
- the heat treatment for degreasing can be performed under conditions of holding at 500° C. for 10 hours in an atmosphere containing oxygen.
- the heat treatment for firing can be performed under conditions of holding at 600° C. for 2 hours in an atmosphere containing nitrogen or oxygen.
- the solid electrolyte and the coating material can be separated by firing under one condition. can be sintered at once.
- the heat treatment for firing sinters the solid electrolyte in the electrolyte layer 13 included in the structure 5a. Moreover, the solid electrolytes in the positive electrode layer 11 and the negative electrode layer 12 included in the structure 5a are sintered. As a result, a solid battery main body 10A having a positive electrode layer 11, a negative electrode layer 12, and an electrolyte layer 13 interposed therebetween is formed as shown in FIG. 13(B).
- the heat treatment for firing sinters the coating material in the coating material sheet 23 and the coating material layer 24 included in the structure 5a, and integrates them with each other.
- the coating material sheet 23 and the coating material layer 24 cover the solid battery main body 10A as shown in FIG. A membrane 20A is formed.
- the coating film 20A formed by firing may take various forms such as glass, crystallized glass, polycrystal, and single crystal, and may consist of one material phase, or two or more different physical properties. of the material phase may be included.
- a ceramic material such as particulate Al 2 O 3 is added to the coating material of the coating film 20A
- the coating film 20A having a higher hardness is formed than when a coating material that is not added is used.
- the coating film 20A is bonded to the electrolyte layer 13, the positive electrode layer 11 and the negative electrode layer 12 of the solid battery body 10A by this heat treatment.
- the coating film 20A obtained by firing may have a coefficient of thermal expansion similar to that of each layer of the solid battery main body 10A depending on the properties of the coating material used, and may have good adhesion to each layer. can have
- the cut surface of the structure 5a shown in FIG. 13B where the end surface of the positive electrode layer 11 is exposed that is, the cut surface at the position C1 becomes the positive electrode lead-out surface 1Aa, and the positive electrode layer 11 exposed from the positive electrode lead-out surface 1Aa.
- the end surface of the is a portion 11a to be connected to the external electrode 31.
- the end face of the is a portion 12a to be connected to the external electrode 32. As shown in FIG.
- an external electrode 31 is formed on the positive electrode extraction surface 1Aa of the structure 5a, and an external electrode 32 is formed on the negative electrode extraction surface 1Ab.
- a method of coating, drying, and curing a conductive paste, or a method of depositing metal by a sputtering method, a plating method, or the like is applied to the positive electrode lead-out surface 1Aa and the negative electrode lead-out surface 1Ab of the structure 5a after the heat treatment, respectively.
- An external electrode 31 and an external electrode 32 are formed.
- the solid battery 1A as shown in FIGS. 2A and 2B (and FIGS. 3A and 3B) is obtained.
- the solid battery main body 10A is covered with a coating film 20A having higher hardness than the solid electrolyte used therein, except for the positive electrode lead-out surface 1Aa and the negative electrode lead-out surface 1Ab.
- a part of the coating film 20A is provided as a buried layer in a portion recessed inward from the side surface of the electrolyte layer 13 .
- peeling of the coating film 20A is effectively suppressed by the anchor effect, and support and strength of the positive electrode layer 11 on the positive electrode lead-out surface 1Aa and the negative electrode layer 12 on the negative electrode lead-out surface 1Ab are enhanced.
- the solid-state battery 1A having excellent strength and excellent environmental resistance can be manufactured. It should be noted that a method as shown in FIGS. 14 to 16 below can also be adopted for manufacturing the solid-state battery.
- FIGS. 14 to 16 are diagrams for explaining another example of the solid-state battery manufacturing method.
- FIGS. 14 and 15 are diagrams for explaining an example of the process of forming electrode layer parts.
- FIG. 14A schematically shows a main part perspective view of an example of the preparation process of the support.
- FIG. 14B schematically shows a perspective view of essential parts of an example of the process of forming the electrode layer.
- FIG. 14C schematically shows a perspective view of essential parts of an example of the process of forming the first coating material layer.
- FIG. 14D schematically shows a perspective view of essential parts of an example of the process of forming an electrolyte layer.
- FIG. 14E schematically shows a perspective view of essential parts of an example of the process of forming the second coating material layer.
- FIG. 14A schematically shows a main part perspective view of an example of the preparation process of the support.
- FIG. 14B schematically shows a perspective view of essential parts of an example of the process of forming the electrode layer.
- FIG. 15(A) schematically shows a perspective view of a main part corresponding to FIG. 14(E), which is an example of an electrode layer part.
- FIG. 15(B) schematically shows an example of a cross-sectional view taken along chain line P3c in FIG. 15(A).
- FIG. 15(C) schematically shows an example of a cross-sectional view taken along the dotted line P4c in FIG. 15(A).
- 16A and 16B are diagrams for explaining an example of a process of forming a structure and external electrodes.
- FIG. 16A schematically shows a cross-sectional view of an essential part of an example of the process of laminating a group of parts.
- FIG. 16B schematically shows a fragmentary cross-sectional view of an example of the step of cutting the structure.
- FIG. 16C schematically shows a fragmentary cross-sectional view of an example of a step of forming external electrodes on a structure after heat treatment.
- a positive electrode paste or a negative electrode paste (“electrode paste”) is applied on a part of the support 50 such as a PET film by screen printing, as shown in FIG. 14(B). ) is applied, and the applied positive electrode paste or negative electrode paste is dried to form the positive electrode layer 11 or the negative electrode layer 12 (also referred to as “electrode layer”).
- a coating material is applied around the electrode layer formed on a portion of the support 50 using a screen printing method, as shown in FIG. 14(C). A paste is applied and the applied coating material paste is dried to form a coating material layer 24 (embedding layer).
- Electrolyte layer 13 is formed such that around its entire perimeter, coating material layer 24 is left uncovered by electrolyte layer 13 .
- a coating material paste is applied all around the electrolyte layer 13 by screen printing as shown in FIG. A material layer 24 (buried layer) is formed.
- the cross-sectional structure shown in FIG. A part having a cross-sectional structure as shown in FIG. 15(C) is formed at the position of dotted line P4c as shown in 15(A).
- Parts as shown in FIGS. 15A to 15C (and FIG. 14E) are used as positive electrode layer parts or negative electrode layer parts (also referred to as "electrode layer parts") depending on the type of electrode layer. be able to.
- a part as shown in FIG. 14C or a part obtained by peeling the support 50 from the part before forming the electrolyte layer 13 may be used as the electrode layer part.
- the positive electrode layer is formed so that a part of the positive electrode layer 11 (a part on the side of the positive electrode lead-out surface 1Ba described later) protrudes outside the electrolyte layer 13. 11 and an electrolyte layer 13 are formed.
- the negative electrode layer 12 is arranged so that a part of the negative electrode layer 12 (a part on the side of the negative electrode lead-out surface 1Bb described later) protrudes outside the electrolyte layer 13. and an electrolyte layer 13 are formed.
- the electrode layer of the positive electrode layer 11 or the negative electrode layer 12 and the surrounding coating material layer on the support 50 are shown. 24, followed by the formation of the electrolyte layer 13 and the surrounding coating material layer 24, this order can be reversed. That is, the electrolyte layer 13 and the coating material layer 24 around it are formed on the support 50 according to the above example, and then the electrode layer of the positive electrode layer 11 or the negative electrode layer 12 and the coating material layer 24 around it are formed. Forming may be performed.
- the electrode layer part thus formed is used, and according to the example of the method shown in the first example (FIGS. 5 to 9), as shown in FIG.
- the positive electrode layer part, the negative electrode layer part and the coating material sheet 23 are laminated and thermally compressed to form the structure 7 .
- the positive electrode layer 11 or the negative electrode layer 12 is formed, the coating material layer 24 is formed around it, the electrolyte layer 13 is formed thereon, and the coating material layer 24 is formed around it.
- a structure 7 as shown may be obtained.
- the structure 7 formed as shown in FIG. 16A is cut at positions where the end faces of the positive electrode layer 11 and the negative electrode layer 12 are exposed, resulting in a structure as shown in FIG. 16B.
- a body 7a is formed.
- the structure 7a among the electrolyte layer 13, the positive electrode layer 11, and the negative electrode layer 12, only the positive electrode layer 11 (its portion 11a) is exposed from the positive electrode lead-out surface 1Ba, and the electrolyte layer 13 is also exposed from the positive electrode lead-out surface 1Ba in addition to the negative electrode layer 12. Not exposed from 1Ba.
- the negative electrode layer 12 (its portion 12a) is exposed from the negative electrode lead-out surface 1Bb. It is not exposed from the lead-out surface 1Bb.
- the structure 7a after cutting is subjected to heat treatment for degreasing and firing, whereby the organic components such as the binder are burned away, and the solid electrolyte and the coating material are burned. tied.
- the solid battery main body 10B having the positive electrode layer 11 and the negative electrode layer 12 and the electrolyte layer 13 interposed therebetween, and the solid battery body 10B covering the solid battery main body 10B are formed.
- a coating film 20B having a higher hardness than the electrolyte is formed.
- an external electrode 31 and an external electrode 32 are formed on the positive electrode lead-out surface 1Ba and the negative electrode lead-out surface 1Bb, respectively, to obtain a solid battery 1B as shown in FIG. 16(C).
- the positive electrode layer 11 (its portion 11a) of the solid battery main body 10B is exposed on the positive electrode lead-out surface 1Ba, and the positive electrode layer 11 is supported by a part of the coating film 20B having higher hardness than the electrolyte layer 13. be.
- the negative electrode layer 12 (its portion 12a) of the solid battery main body 10B is exposed on the negative electrode lead-out surface 1Bb, and the negative electrode layer 12 is supported by a part of the coating film 20B having higher hardness than the electrolyte layer 13.
- the support and strength of the positive electrode layer 11 on the positive electrode lead-out surface 1Ba and the negative electrode layer 12 on the negative electrode lead-out surface 1Bb are further enhanced.
- the coating material paste used for forming the coating films 20A and 20B of the solid batteries 1A and 1B was applied, dried and heat-treated under the same conditions as in the production of the solid batteries 1A and 1B.
- prepared the samples as samples, two kinds of coating material pastes containing different glass components were each coated, dried, and heat-treated under predetermined conditions (“Glass 1” and “Glass 2” in Table 1). .
- samples were prepared by adding 10 wt . "Glass 2 + 10 wt.% Al2O3 ").
- samples were prepared by coating, drying, and heat-treating the electrolyte paste used for forming the electrolyte layer 13 of the solid batteries 1A and 1B under the same conditions as in the production of the solid batteries 1A and 1B. (“Electrolyte” in Table 1). Each of these five prepared samples was mirror-finished, and then measured five times or more at each load of 200 g, 500 g, and 1000 g using a Vickers hardness tester. ].
- a coating material paste containing a glass component, or a coating material paste to which Al 2 O 3 particles are further added. can be said to make it possible to cover the solid battery bodies 10A and 10B with the coating films 20A and 20B having higher hardness than the solid electrolyte used therein.
- the solid battery main body 10 including one positive electrode layer 11 and one negative electrode layer 12 is covered with the coating film 20, and the solid battery main bodies 10A and 10B including two positive electrode layers 11 and two negative electrode layers 12 are coated.
- An example of covering with films 20A and 20B is shown.
- the number of layers of each of the positive electrode layer 11 and the negative electrode layer 12 included in the solid battery main body covered with the coating film is not limited to the above example, and the solid battery main body including three or more layers each can be formed as described above. It can also be covered with a coating film.
- the coating material sheet 23 and the coating material layer 24, which is the embedding layer may be formed from coating material pastes having different compositions.
- the coating material sheet 23 and the coating material layer 24 are sintered and integrated by the heat treatment, and if the coating films 20A and 20B having higher hardness than the solid electrolyte used in the solid battery main bodies 10A and 10B are obtained, the coating The material sheet 23 and the coating material layer 24 may be formed from coating material pastes having different compositions. Also, when the coating material layer 24 is formed through multiple coatings of the coating material paste, different coating material pastes may be used in different coatings.
- the LAGP of the electrolyte layer 13 is not limited to the composition of Li1.5Al0.5Ge1.5 ( PO4 ) 3 , but may be Li1.4Al0.4Ge1.6 ( PO4 ) 3 .
- a NASICON-type LAGP of the composition may be used.
- the electrolyte layer 13 contains Li 1.3 Al 0.3 Ti, which is one type of NASICON-type LATP (general formula Li 1+z Al z Ti 2-z (PO 4 ) 3 , 0 ⁇ z ⁇ 1).
- garnet-type lithium lanthanum zirconate Li 7 La 3 Zr 2 O 12 , hereinafter referred to as “LLZ”), perovskite-type lithium lanthanum titanate (Li 0.5 La 0.5 TiO 3 , hereinafter referred to as “LLT”), partially nitrided ⁇ -lithium phosphate ( ⁇ -Li 3 PO 4 , hereinafter referred to as “LiPON”), and other oxide solid electrolytes may be used.
- LLZ lithium lanthanum zirconate
- LLT perovskite-type lithium lanthanum titanate
- LiPON partially nitrided ⁇ -lithium phosphate
- other oxide solid electrolytes may be used.
- the positive electrode layer 11 and the negative electrode layer 12 in addition to LAGP, other oxide solid electrolytes such as LATP, LLZ, LLT, LiPON, etc. may be used as long as a certain performance can be achieved in combination with the active material used. may be used.
- the electrolyte layer 13, the positive electrode layer 11, and the negative electrode layer 12 are preferably NASICON-type oxide solid electrolytes represented by the general formula Li 1+y Al y M 2-y (PO 4 ) 3 .
- the composition ratio y is in the range of 0 ⁇ y ⁇ 1
- M is one or both of germanium (Ge) and titanium (Ti).
- the same kind of oxide solid electrolytes may be used, or different kinds of oxide solid electrolytes may be used.
- One type of oxide solid electrolyte may be used for each of the electrolyte layer 13, the positive electrode layer 11, and the negative electrode layer 12, or two or more types of oxide solid electrolytes may be used.
- LCPO was exemplified as the positive electrode active material contained in the positive electrode layer 11, but the positive electrode active material may be lithium cobalt phosphate ( LiCoPO4 ), lithium vanadium phosphate ( Li3V2 ( PO4) ) 3 , hereinafter referred to as “LVP”), etc. may be used.
- LiCoPO4 lithium cobalt phosphate
- Li3V2 ( PO4) ) 3 lithium vanadium phosphate
- LVP lithium vanadium phosphate
- the positive electrode layer 11 one kind of material may be used as a positive electrode active material, or two or more kinds of materials may be used.
- TiO 2 was exemplified as the negative electrode active material contained in the negative electrode layer 12, but the negative electrode active material may be a metal such as LATP, LVP, niobium oxide (Nb 2 O 5 ), nickel (Ni), or the like. Silicide or the like may also be used.
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Abstract
Description
本発明の目的、特徴及び利点は、本発明の例として好ましい実施の形態を表す添付の図面と関連した以下の説明により明らかになるであろう。
図1は固体電池の一例について説明する図である。図1(A)には固体電池の一例の要部斜視図を模式的に示している。図1(B)には図1(A)の鎖線P1に沿った断面図の一例を模式的に示し、図1(C)には図1(A)の点線P2に沿った断面図の一例を模式的に示している。
固体電池本体10は、電解質層13、並びにその一方の主面13a(第1主面とも言う)及びそれとは反対側の他方の主面13b(第2主面とも言う)にそれぞれ積層された正極層11及び負極層12を有する。固体電池本体10は、電解質層13、正極層11及び負極層12の積層体の一例である。
また、固体電池1では、そのコーティング膜20に、固体電池本体10の各層と同程度の熱膨張係数を有するものを用いることで、外部の温度環境による各層の膨張及び収縮に伴う層間剥離が抑えられる。また、固体電池1では、そのコーティング膜20に、固体電池本体10の各層との密着性が良好なものを用いることで、外部から力が加えられた際や各層が膨張及び収縮する際の固体電池本体10からのコーティング膜20の剥離が抑えられる。また、固体電池1では、そのコーティング膜20に、焼結温度が900℃以下といった比較的低いもの、例えば、650℃以下といった固体電解質の焼結温度と同じか又は同等或いは同程度のものを用いることで、コーティング膜20の形成に伴う固体電池本体10の熱劣化が抑えられ、更に、コーティング材料と固体電解質との一括焼結によって工数の増大が抑えられる。こういったコーティング膜20によっても、強度に優れ、耐環境性に優れた固体電池1が実現され、また、そのような固体電池1が効率的に製造されるようになる。
次に、固体電池の構成例について述べる。
図2及び図3は固体電池の構成例について説明する図である。図2(A)には固体電池の一例の要部斜視図を模式的に示し、図2(B)には図2(A)の鎖線P3に沿った断面図の一例を模式的に示している。図3(A)には固体電池の一例の要部斜視図を模式的に示し、図3(B)には図3(A)の点線P4に沿った断面図の一例を模式的に示している。尚、図2及び図3は、同じ固体電池を模式的に示した図であって、同じ固体電池の異なる位置の断面構造を説明するための図である。
また、固体電池1Aでは、そのコーティング膜20Aに、固体電池本体10Aの各層と同程度の熱膨張係数を有するものを用いることで、外部の温度環境による各層の膨張及び収縮に伴う層間剥離が抑えられる。また、固体電池1Aでは、そのコーティング膜20Aに、固体電池本体10Aの各層との密着性が良好なものを用いることで、外部から力が加えられた際や各層が膨張及び収縮する際の固体電池本体10Aからのコーティング膜20Aの剥離が抑えられる。こういったコーティング膜20Aによっても、強度に優れ、耐環境性に優れた固体電池1Aが実現される。
次に、上記のような構成を有する固体電池の製造方法について述べる。
まず、電解質ペースト、正極ペースト、負極ペースト、並びにコーティング材料ペースト及びコーティング材料シートの形成の一例について、それぞれ説明する。
固体電解質、バインダー、可塑剤、分散剤及び希釈剤を含む電解質ペーストが準備される。一例として、固体電解質に酸化物固体電解質であるLAGPを用いた電解質ペーストが準備される。
正極活物質、固体電解質、導電助剤、バインダー、可塑剤、分散剤及び希釈剤を含む正極ペーストが準備される。一例として、正極活物質にLCPO、固体電解質に酸化物固体電解質であるLAGP、導電助剤にカーボンナノファイバーを用いた正極ペーストが準備される。
負極活物質、固体電解質、導電助剤、バインダー、可塑剤、分散剤及び希釈剤を含む負極ペーストが準備される。一例として、負極活物質にTiO2、固体電解質に酸化物固体電解質であるLAGP、導電助剤にカーボンナノファイバーを用いた負極ペーストが準備される。
コーティング材料ペーストとして、ガラス成分を含むガラスペーストが準備される。例えば、600℃付近での焼成により溶融、焼結される、いわゆる低融点ガラスと称されるガラス成分を含むガラスペーストが準備される。準備されたガラスペーストが塗工及び乾燥されることで、コーティング材料シートとしてのガラスシートが形成される。尚、コーティング材料ペースト及びコーティング材料シートは、焼成によりコーティング膜20Aとして形成される、コーティング材料の一形態である。
(正極層パーツの形成)
図5及び図6は正極層パーツの形成工程の一例について説明する図である。図5(A)には支持体の準備工程の一例の要部斜視図を模式的に示している。図5(B)には正極層の形成工程の一例の要部斜視図を模式的に示している。図5(C)には第1のコーティング材料層の形成工程の一例の要部斜視図を模式的に示している。図5(D)には電解質層の形成工程の一例の要部斜視図を模式的に示している。図5(E)には第2のコーティング材料層の形成工程の一例の要部斜視図を模式的に示している。また、図6(A)には図5(E)に対応する要部斜視図であって正極層パーツの一例の要部斜視図を模式的に示している。図6(B)には図6(A)の鎖線P3aに沿った断面図の一例を模式的に示している。図6(C)には図6(A)の点線P4aに沿った断面図の一例を模式的に示している。
図7及び図8は負極層パーツの形成工程の一例について説明する図である。図7(A)には支持体の準備工程の一例の要部斜視図を模式的に示している。図7(B)には負極層の形成工程の一例の要部斜視図を模式的に示している。図7(C)には第1のコーティング材料層の形成工程の一例の要部斜視図を模式的に示している。図7(D)には電解質層の形成工程の一例の要部斜視図を模式的に示している。図7(E)には第2のコーティング材料層の形成工程の一例の要部斜視図を模式的に示している。また、図8(A)には図7(E)に対応する要部斜視図であって負極層パーツの一例の要部斜視図を模式的に示している。図8(B)には図8(A)の鎖線P3bに沿った断面図の一例を模式的に示している。図8(C)には図8(A)の点線P4bに沿った断面図の一例を模式的に示している。
図9は構造体の形成工程の一例について説明する図である。図9(A)にはパーツ群の積層工程の一例の要部断面図を模式的に示している。図9(B)にはコーティング材料シートの積層工程の一例の要部断面図を模式的に示している。尚、図9(A)及び図9(B)には、パーツ群の、上記図6(A)の鎖線P3a及び図8(A)の鎖線P3bの位置に対応する断面を、模式的に示している。
図10及び図11は構造体の形成工程の別例について説明する図である。図10(A)~図10(D)及び図11(A)~図11(D)にはそれぞれ、構造体形成の各工程の一例の要部断面図を模式的に示している。
図12は構造体の切断工程の一例について説明する図である。図12(A)及び図12(B)には構造体の切断工程の一例の要部断面図を模式的に示している。
図13は構造体の熱処理工程の一例について説明する図である。図13(A)及び図13(B)には構造体の熱処理工程の一例の要部断面図を模式的に示している。
尚、固体電池の製造には、次の図14~図16に示すような方法を採用することもできる。
次に、固体電池に用いるコーティング膜の硬度を評価した結果について説明する。結果を表1に示す。
以上の説明では、正極層11及び負極層12が1層ずつ含まれる固体電池本体10をコーティング膜20で覆い、正極層11及び負極層12が2層ずつ含まれる固体電池本体10A,10Bをコーティング膜20A,20Bで覆う例を示した。コーティング膜で覆う固体電池本体に含まれる正極層11及び負極層12の各々の層数は、上記の例に限定されるものではなく、各々が3層以上含まれる固体電池本体を上記のようなコーティング膜で覆うこともできる。
1a,1Aa,1Ba 正極引出面
1b,1Ab,1Bb 負極引出面
5,5a,7,7a 構造体
10,10A,10B 固体電池本体
11 正極層
11a,12a 部位
12 負極層
13 電解質層
13a,13b 主面
20,20A,20B コーティング膜
21,22 材料相
23 コーティング材料シート
24 コーティング材料層
31,32 外部電極
40 熱処理炉
50 支持体
Claims (7)
- 固体電解質を含む電解質層と、前記電解質層の第1主面の一部に設けられた正極層と、前記電解質層の前記第1主面とは反対側の第2主面の一部に設けられた負極層とを有する積層体と、
前記正極層の第1部位及び前記負極層の第2部位が露出するように前記積層体を覆い、前記固体電解質よりも高い硬度を有する絶縁性のコーティング膜と
を含むことを特徴とする固体電池。 - 前記コーティング膜は、ガラス又はセラミックスを含むことを特徴とする請求項1に記載の固体電池。
- 前記第1主面の一部に前記正極層が設けられる前記電解質層の前記第1主面の他部と、前記積層体から露出する前記第1部位を除く前記正極層の表面とに接するように、前記コーティング膜が設けられ、
前記第2主面の一部に前記負極層が設けられる前記電解質層の前記第2主面の他部と、前記積層体から露出する前記第2部位を除く前記負極層の表面とに接するように、前記コーティング膜が設けられることを特徴とする請求項1に記載の固体電池。 - 前記正極層の前記第1部位と前記コーティング膜とに接する第1外部電極と、
前記負極層の前記第2部位と前記コーティング膜とに接する第2外部電極と
を含むことを特徴とする請求項1に記載の固体電池。 - 前記コーティング膜は、第1硬度を有する第1材料相と、前記第1硬度よりも高い第2硬度を有する第2材料相とを含むことを特徴とする請求項1に記載の固体電池。
- 固体電解質を含む電解質層と、前記電解質層の第1主面の一部に設けられた正極層と、前記電解質層の前記第1主面とは反対側の第2主面の一部に設けられた負極層とを有する積層体と、
前記正極層の第1部位及び前記負極層の第2部位が露出するように前記積層体を覆うコーティング材料と
を含む構造体を形成する工程と、
前記構造体を第1温度で焼成し、前記コーティング材料から、前記固体電解質よりも高い硬度を有する絶縁性のコーティング膜を形成する工程と
を含むことを特徴とする固体電池の製造方法。 - 前記構造体を前記第1温度で焼成する工程では、前記固体電解質を焼結させると共に、前記コーティング膜を形成することを特徴とする請求項6に記載の固体電池の製造方法。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10188922A (ja) * | 1996-12-26 | 1998-07-21 | Nisshin Steel Co Ltd | 電気自動車搭載用電池ケース |
JP2013211560A (ja) * | 2013-04-23 | 2013-10-10 | Seiko Instruments Inc | 電気化学セル |
JP2014241242A (ja) * | 2013-06-12 | 2014-12-25 | 新光電気工業株式会社 | 電池及びその製造方法 |
JP2019145486A (ja) * | 2018-02-20 | 2019-08-29 | Fdk株式会社 | 全固体電池 |
WO2020054549A1 (ja) * | 2018-09-14 | 2020-03-19 | 株式会社村田製作所 | 固体電池および固体電池群 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10188922A (ja) * | 1996-12-26 | 1998-07-21 | Nisshin Steel Co Ltd | 電気自動車搭載用電池ケース |
JP2013211560A (ja) * | 2013-04-23 | 2013-10-10 | Seiko Instruments Inc | 電気化学セル |
JP2014241242A (ja) * | 2013-06-12 | 2014-12-25 | 新光電気工業株式会社 | 電池及びその製造方法 |
JP2019145486A (ja) * | 2018-02-20 | 2019-08-29 | Fdk株式会社 | 全固体電池 |
WO2020054549A1 (ja) * | 2018-09-14 | 2020-03-19 | 株式会社村田製作所 | 固体電池および固体電池群 |
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