WO2021075420A1 - Batterie secondaire au lithium entièrement solide et procédé de production de batterie secondaire au lithium entièrement solide - Google Patents

Batterie secondaire au lithium entièrement solide et procédé de production de batterie secondaire au lithium entièrement solide Download PDF

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WO2021075420A1
WO2021075420A1 PCT/JP2020/038603 JP2020038603W WO2021075420A1 WO 2021075420 A1 WO2021075420 A1 WO 2021075420A1 JP 2020038603 W JP2020038603 W JP 2020038603W WO 2021075420 A1 WO2021075420 A1 WO 2021075420A1
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solid electrolyte
layer
oxide solid
lithium ion
electrode active
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English (en)
Japanese (ja)
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佐藤　一
甲相 朴
博幸 上田
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Ｄａｒｅジャパン株式会社
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Priority to JP2021552390A priority Critical patent/JP7275300B2/ja
Priority to CN202080047305.1A priority patent/CN114026727B/zh
Publication of WO2021075420A1 publication Critical patent/WO2021075420A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an all-solid-state lithium secondary battery and a method for manufacturing an all-solid-state lithium secondary battery.
  • Lithium-ion batteries using non-aqueous electrolytes are widely used.
  • lithium-ion batteries are limited in operating temperature because the electrolytic solution is flammable and there is a risk of ignition, and an organic solvent is used. Therefore, an all-solid-state lithium secondary battery using a polymer electrolyte has been developed.
  • the polymer electrolyte has low ionic conductivity at low temperature, and the operating temperature range is narrower than that of the lithium ion battery using the non-aqueous electrolyte solution. Therefore, an all-solid-state lithium secondary battery using a sulfide-based solid electrolyte has been developed.
  • the operating temperature range is limited because sulfides can react with water to generate hydrogen sulfide. Therefore, it is expected to develop an all-solid-state battery using an oxide-based solid electrolyte that can compensate for such drawbacks of polymer electrolytes and sulfide-based electrolytes.
  • Patent Document 1 a composite solid electrolyte layer having lithium ion conductive oxide particles and a lithium ion conductive amorphous portion inserted between the oxide particles is a positive electrode having a positive electrode active material.
  • An all-solid-state lithium secondary battery sandwiched between a negative electrode having a negative electrode active material and a negative electrode is described.
  • Patent Document 2 describes a solid electrolyte for an all-solid-state lithium-ion secondary battery using an oxide solid electrolyte.
  • an adhesive layer having lithium ion conductivity is provided on the surface of the solid electrolyte main body for the purpose of reducing the resistance at the interface between the solid electrolyte main body and the electrode.
  • An all-solid-state lithium secondary battery using an oxide solid electrolyte as described in Patent Document 1 is easy to handle because it does not easily generate hydrogen sulfide by reacting with water, but the sulfide electrolyte is used. Compared to the all-solid-state lithium secondary battery, the internal resistance is high and the conductivity is low.
  • the adhesive layer of the solid electrolyte described in Patent Document 2 is preferably as thin as possible because the ionic conductivity is an order of magnitude lower than that of the solid electrolyte body.
  • the adhesive layer is made thin, it may not be possible to fill the gap between the electrode and the solid electrolyte body, and there is a concern that the internal resistance will increase.
  • an object of the present invention is to provide a method for manufacturing an all-solid-state lithium secondary battery and an all-solid-state lithium secondary battery that are easy to handle and can achieve a large current.
  • the all-solid lithium secondary battery of the present invention has an oxide solid electrolyte layer containing oxide solid electrolyte particles having lithium ion conductivity and one surface side of the oxide solid electrolyte layer.
  • the positive electrode active material layer comprises a solid electrolyte-dispersed polymer layer in which the oxide solid electrolyte particles are dispersed in a lithium ion conductive polymer material which is arranged between the layers and has lithium ion conductivity.
  • the negative electrode active material layer, the solid electrolyte-dispersed polymer layer, and the oxide solid electrolyte layer are integrated.
  • oxides do not easily generate gases that require careful handling, such as hydrogen sulfide, even when they react with water. Therefore, the all-solid-state lithium secondary battery of the present invention using the oxide solid electrolyte is easy to handle.
  • the state in which the layers are integrated in the present specification means a state in which the layers cannot be peeled off and destruction occurs when the layers are forcibly peeled off. Therefore, in the all-solid-state lithium secondary battery of the present invention, the positive electrode active material layer, the negative electrode active material layer, the solid electrolyte-dispersed polymer layer, and the oxide solid electrolyte layer cannot be separated from each other.
  • the resistors between the positive electrode active material layer, the negative electrode active material layer, the solid electrolyte-dispersed polymer layer, and the oxide solid electrolyte layer integrated in this way are not integrated and are simply arranged adjacent to each other. The resistance between the positive electrode active material layer, the negative electrode active material layer, the solid electrolyte-dispersed polymer layer, and the oxide solid electrolyte layer is reduced.
  • the solid electrolyte-dispersed polymer layer comprises a lithium ion conductive polymer material having lithium ion conductivity and oxide solid electrolyte particles dispersed in the material.
  • the oxide solid electrolyte particles have higher lithium ion conductivity than the lithium ion conductive polymer material. Therefore, the ion conductivity of the solid electrolyte dispersed polymer layer is the lithium ion conductivity as in the adhesive layer of Patent Document 2. Higher than a layer consisting only of a conductive polymer material.
  • the solid electrolyte-dispersed polymer layer of the present invention can be formed thicker than the layer made of only the lithium ion conductive polymer material such as the adhesive layer of Patent Document 2. Therefore, unlike the adhesive layer of Patent Document 2, it is not possible to fill the gap between the electrode and the solid electrolyte main body, so that it is possible to suppress an increase in internal resistance. Therefore, according to the all-solid-state lithium secondary battery of the present invention, the internal resistance can be reduced and a large current can be achieved.
  • a positive electrode active material layer is located on one surface side of an oxide solid electrolyte layer containing oxide solid electrolyte particles and having lithium ion conductivity, and an oxide is formed.
  • the negative electrode active material layer is located on the other surface side of the solid electrolyte layer, and lithium having lithium ion conductivity between at least one of the positive electrode active material layer and the negative electrode active material layer and the oxide solid electrolyte layer.
  • the oxide solid electrolyte layer, the positive electrode active material layer, the negative electrode active material layer, and the negative electrode active material layer so that the solid electrolyte dispersed polymer layer in which the oxide solid electrolyte particles are dispersed is located in the ion conductive polymer material.
  • the step of arranging the solid electrolyte-dispersed polymer layer, the integration of the positive electrode active material layer, the negative electrode active material layer, the solid electrolyte-dispersed polymer layer, and the oxide solid electrolyte layer It is characterized by having a process.
  • an all-solid-state lithium secondary battery capable of achieving a large current with reduced internal resistance by using an oxide solid electrolyte that is easy to handle is manufactured. Can be done.
  • an all-solid-state lithium secondary battery and an all-solid-state lithium secondary battery that are easy to handle and can achieve a large current.
  • FIG. 1 is a cross-sectional view of an all-solid-state lithium secondary battery according to an embodiment of the present invention.
  • the all-solid-state lithium secondary battery 1 of the present embodiment has a battery body 1b arranged in a packaging material 10.
  • the battery element 1b includes an oxide solid electrolyte layer 11, a positive electrode side solid electrolyte dispersion polymer layer 12, a positive electrode active material layer 13, a positive electrode current collector layer 14, and a negative electrode side solid electrolyte dispersion polymer layer 15.
  • the negative electrode active material layer 16 and the negative electrode current collector layer 17 are mainly provided.
  • FIG. 2 is an enlarged view from the positive electrode active material layer 13 to the oxide solid electrolyte layer 11 in FIG.
  • the lithium ion conductive polymer material 11b has entered at least a part between the particles of the oxide solid electrolyte particles 11a, that is, the oxide solid electrolyte particles 11a.
  • the structure is such that the lithium ion conductive polymer material 11b is arranged at least a part between the particles.
  • the oxide solid electrolyte constituting the oxide solid electrolyte particles 11a is not particularly limited as long as it is an oxide solid electrolyte having lithium ion conductivity, and for example, lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide. (LLZO), lithium lanthanum titanium oxide (LLTO), aluminum-substituted germanium lithium phosphate (LAGP), and the like can be mentioned.
  • LATP lithium aluminum titanium phosphate
  • LLZO lithium lanthanum zirconium oxide
  • LAGP aluminum-substituted germanium lithium phosphate
  • silicon (Si) or germanium (Ge) may be added to LATP.
  • the average particle size of the oxide solid electrolyte particles 11a is, for example, 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the particle size refers to, for example, the average particle size measured by a 1090L type laser diffraction type particle size distribution measuring device manufactured by CILAS.
  • the lithium ion conductive polymer material 11b that penetrates between the particles of the oxide solid electrolyte particles 11a has lithium ion conductivity.
  • a lithium ion conductive polymer material 11b include those in which the polymer material has lithium ion conductivity. Examples of such a polymer material include polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF) and the like.
  • PEO polyethylene oxide
  • PEG polyethylene glycol
  • PVDF polyvinylidene fluoride
  • a polymer containing a lithium salt can be mentioned. That is, the polymer does not have lithium ion conductivity, and the polymer contains a lithium salt as a supporting salt, so that the polymer has lithium ion conductivity.
  • lithium salts examples include lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium bis (oxalate) borate (LiBOB), and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). ), Lithium bis (fluorosulfonyl) imide (LiFSI) can be mentioned.
  • a polymer having lithium ion conductivity such as PEO, PEG, and PVDF may be configured to contain a lithium salt. Further, it is preferable that the lithium ion conductive polymer is mixed with the lithium ion conductive oxide solid electrolyte particles.
  • oxide solid electrolyte particles examples include particles similar to the oxide solid electrolyte particles that can be used for the oxide solid electrolyte particles 11a.
  • lithium ion conductive oxides such as LATP and LLZO tend to have high lithium ion conductive polymer ion conductivity, so that the lithium ion conductivity can be further increased by mixing them.
  • the oxide solid electrolyte layer 11 of the present embodiment has a structure in which the lithium ion conductive polymer material 11b is inserted between the oxide solid electrolyte particles 11a, so that the oxide solid electrolyte layer 11 is an oxide solid. It is composed of only the electrolyte particles 11a, and the resistance can be made lower than that in the case where the lithium ion conductive polymer material 11b does not enter between the oxide solid electrolyte particles 11a.
  • the oxide solid electrolyte layer 11 having such a structure may be referred to as a composite solid electrolyte layer.
  • the positive electrode active material layer 13 of the present embodiment has a structure in which the lithium ion conductive polymer material 13b is inserted between the positive electrode active materials 13a and has lithium ion conductivity.
  • the material constituting the positive electrode active material 13a is not particularly limited as long as it contains lithium and can take in and release lithium ions, but for example, lithium manganate (LMO), lithium cobalt oxide (LCO), and the like.
  • the ternary system referred to here refers to containing, for example, nickel, manganese, aluminum, or cobalt.
  • Examples of the lithium ion conductive polymer material 13b that penetrates between the positive electrode active materials 13a include materials similar to those that can be used for the lithium ion conductive polymer material 11b.
  • the lithium ion conductive polymer material 13b that penetrates between the positive electrode active materials 13a and the lithium ion conductive polymer material 11b that penetrates between the particles of the oxide solid electrolyte particles 11a are the same material. However, they may be made of different materials.
  • a conductive auxiliary agent such as acetylene black may be dispersed in the lithium ion conductive polymer material 13b of the positive electrode active material layer 13.
  • the solid electrolyte-dispersed polymer layer is formed by dispersing the oxide solid electrolyte particles 12a in the lithium ion conductive polymer material 12b between the positive electrode active material layer 13 and the oxide solid electrolyte layer 11.
  • the positive electrode side solid electrolyte-dispersed polymer layer 12 is interposed.
  • the lithium ion conductive polymer material 12b constituting the positive electrode side solid electrolyte dispersed polymer layer 12 include materials similar to the materials that can be used for the lithium ion conductive polymer material 11b of the oxide solid electrolyte layer 11. be able to.
  • the oxide solid electrolyte constituting the oxide solid electrolyte particles 12a of the positive electrode side solid electrolyte dispersion polymer layer 12 the oxide solid electrolyte that can be used for the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11
  • the same oxide solid electrolyte as above can be mentioned.
  • the oxide solid electrolyte particles 12a of the positive electrode side solid electrolyte dispersion polymer layer 12 and the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 are made of the same oxide solid electrolyte. preferable.
  • the oxide solid electrolyte particles 12a of the positive electrode side solid electrolyte dispersion polymer layer 12 and the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 may be made of different oxide solid electrolytes.
  • LAGP and LLZO are used as the oxide solid electrolyte constituting the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11, and the oxide solid electrolyte particles of the positive electrode side solid electrolyte dispersed polymer layer 12 are used.
  • LATP is used as the oxide solid electrolyte constituting 12a. With such a combination, the reduction resistance of the oxide solid electrolyte can be improved.
  • the particle size of the oxide solid electrolyte particles 12a of the positive electrode side solid electrolyte dispersion polymer layer 12 may be the same as the particle size of the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11.
  • the average particle size of the oxide solid electrolyte particles 12a is, for example, 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the particle size of the oxide solid electrolyte particles 12a of the positive electrode side solid electrolyte-dispersed polymer layer 12 may be different from the particle size of the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11.
  • the positive electrode side solid electrolyte dispersion height is high. It is preferable because the molecular layer 12 can be made thin and the resistance of the all-solid-state lithium secondary battery 1 can be reduced. Further, when the positive electrode side solid electrolyte-dispersed polymer layer 12 is formed by coating as described later, the oxide solid electrolyte particles 12a are formed between the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 with lithium ion conductivity.
  • the particle size of the oxide solid electrolyte particles 12a of the positive electrode side solid electrolyte dispersion polymer layer 12 may be larger than the particle size of the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11.
  • the average thickness of the positive electrode side solid electrolyte-dispersed polymer layer 12 may be smaller than the particle size of the oxide solid electrolyte particles 12a.
  • the positive electrode side solid electrolyte-dispersed polymer layer 12 becomes thicker at the portion where the oxide solid electrolyte particles 12a are located, and becomes thinner at the portion where the oxide solid electrolyte particles 12a are not located. Therefore, the oxide solid electrolyte particles 12a are likely to come into contact with the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 and the positive electrode active material 13a.
  • the volume ratio of the oxide solid electrolyte particles 12a is larger than the volume ratio of the lithium ion conductive polymer material 12b. By doing so, the resistance of the positive electrode side solid electrolyte-dispersed polymer layer 12 can be further reduced.
  • the oxide solid electrolyte layer 11 and the positive electrode side solid electrolyte dispersed polymer layer 12 are integrated, and the positive electrode active material layer 13 and the positive electrode side solid electrolyte dispersed polymer layer 12 are integrated.
  • the oxide solid electrolyte layer 11 and the positive electrode active material layer 13 are integrated with each other via the positive electrode side solid electrolyte dispersed polymer layer 12. Therefore, when the oxide solid electrolyte layer 11 and the positive electrode active material layer 13 are peeled off, the cell structure is destroyed.
  • the lithium ion conductive polymer material 15b constituting the positive electrode side solid electrolyte dispersed polymer layer 12 and the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a may be the same material.
  • the positive electrode side solid electrolyte dispersion polymer layer 12 and the oxide solid electrolyte layer 11 are preferable from the viewpoint of being able to increase the integrated strength. Further, in this case, it is also preferable from the viewpoint that the positive electrode side solid electrolyte-dispersed polymer layer 12 and the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a can be formed at the same time by coating.
  • the positive electrode side solid electrolyte dispersion polymer layer 12 may be provided on the positive electrode side surface of the oxide solid electrolyte layer 11 in a state where the lithium ion conductive polymer material 11b is inserted between the oxide solid electrolyte particles 11a.
  • the lithium ion conductive polymer material constituting the positive electrode side solid electrolyte dispersed polymer layer 12 and the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a may be different materials from each other. ..
  • PVDF is used as the lithium ion conductive polymer material constituting the positive electrode side solid electrolyte dispersed polymer layer 12, and the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a is used.
  • PEO is preferably used. With such a combination, the cell voltage can be increased by using PVDF, which is less likely to be decomposed than PEO on the high potential side. Therefore, it is possible to contribute to high potential and high energy of the all-solid-state lithium secondary battery 1.
  • the positive electrode side is that the lithium ion conductive polymer material constituting the positive electrode side solid electrolyte-dispersed polymer layer 12 and the lithium ion conductive polymer material 13b that penetrates between the positive electrode active material 13a are the same material as each other. It is preferable from the viewpoint that the integrated strength between the solid electrolyte-dispersed polymer layer 12 and the positive electrode active material layer 13 can be increased. Further, the lithium ion conductive polymer material constituting the positive electrode side solid electrolyte-dispersed polymer layer 12 and the lithium ion conductive polymer material 13b that penetrates between the positive electrode active material 13a may be different materials from each other.
  • PEO is used as the lithium ion conductive polymer material 12b constituting the positive electrode side solid electrolyte-dispersed polymer layer 12
  • PVDF is used as the lithium ion conductive polymer material 13b that penetrates between the positive electrode active materials 13a. Is preferably used.
  • the cell voltage can be increased by using PVDF, which is less likely to be decomposed than PEO on the high potential side. Therefore, it is possible to contribute to high potential and high energy of the all-solid-state lithium secondary battery 1.
  • the positive electrode current collector layer 14 is arranged on the surface side of the positive electrode active material layer 13 opposite to the oxide solid electrolyte layer 11 side, and is integrated with the positive electrode active material layer 13.
  • the positive electrode current collector layer 14 is made of a conductive and non-ionic conductive material. Examples of such a material include a metal and a carbon sheet, and examples of such a metal include copper, aluminum, an iron-nickel alloy, and the like.
  • FIG. 3 is an enlarged view from the negative electrode active material layer 16 to the oxide solid electrolyte layer 11 in FIG.
  • the negative electrode active material layer 16 of the present embodiment has a structure in which the lithium ion conductive polymer material 16b is inserted between the negative electrode active materials 16a and has lithium ion conductivity.
  • the material constituting the negative electrode active material 16a is not particularly limited as long as it can take in and release lithium ions, and is, for example, easily graphitized carbon, non-graphitized carbon, LTO, LMO, Si, Li, and A mixture of these can be mentioned.
  • Examples of the lithium ion conductive polymer material 16b that penetrates between the negative electrode active materials 16a include materials that can be used for the lithium ion conductive polymer material 11b.
  • the lithium ion conductive polymer material 16b that penetrates between the negative electrode active materials 16a and the lithium ion conductive polymer material 11b that penetrates between the particles of the oxide solid electrolyte particles 11a are the same material. However, they may be made of different materials. Further, the lithium ion conductive polymer material 16b that enters between the negative electrode active materials 16a and the lithium ion conductive polymer material 13b that enters between the positive electrode active materials 13a may be the same material or different materials. ..
  • a conductive auxiliary agent such as acetylene black may be dispersed in the lithium ion conductive polymer material 16b of the negative electrode active material layer 16.
  • the solid electrolyte-dispersed polymer layer is formed by dispersing the oxide solid electrolyte particles 15a in the lithium ion conductive polymer material 15b between the negative electrode active material layer 16 and the oxide solid electrolyte layer 11.
  • the negative electrode side solid electrolyte dispersion polymer layer 15 is interposed.
  • Examples of the lithium ion conductive polymer material 15b constituting the negative electrode side solid electrolyte-dispersed polymer layer 15 include materials that can be used for the lithium ion conductive polymer material 11b.
  • the oxide solid electrolyte constituting the oxide solid electrolyte particles 15a of the negative electrode side solid electrolyte dispersion polymer layer 15 the oxide solid electrolyte that can be used for the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11
  • the same oxide solid electrolyte as above can be mentioned.
  • the oxide solid electrolyte particles 15a of the negative electrode side solid electrolyte dispersion polymer layer 15 and the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 are made of the same oxide solid electrolyte. preferable.
  • the oxide solid electrolyte particles 15a of the negative electrode side solid electrolyte dispersion polymer layer 15 and the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 may be made of different oxide solid electrolytes.
  • LATP is used as the oxide solid electrolyte constituting the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11
  • the oxide solid electrolyte particles 15a of the negative electrode side solid electrolyte dispersion polymer layer 15 are used.
  • LAGP and LLZO are used as the constituent oxide solid electrolytes. With such a combination, the reduction resistance at the negative electrode can be improved.
  • the particle size of the oxide solid electrolyte particles 15a of the negative electrode side solid electrolyte dispersion polymer layer 15 may be the same as the particle size of the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11. However, the particle size of the oxide solid electrolyte particles 15a of the negative electrode side solid electrolyte dispersion polymer layer 15 may be different from the particle size of the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11.
  • the negative electrode side solid electrolyte dispersion height is high. It is preferable because the molecular layer 15 can be made thin and the resistance of the all-solid-state lithium secondary battery 1 can be reduced. Further, when the negative electrode side solid electrolyte-dispersed polymer layer 15 is formed by coating as described later, the oxide solid electrolyte particles 15a are formed between the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 with lithium ion conductivity.
  • the particle size of the oxide solid electrolyte particles 15a of the negative electrode side solid electrolyte dispersion polymer layer 15 may be larger than the particle size of the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11.
  • the average thickness of the negative electrode side solid electrolyte-dispersed polymer layer 15 may be smaller than the particle size of the oxide solid electrolyte particles 15a. In this case, the negative electrode side solid electrolyte-dispersed polymer layer 15 becomes thicker at the portion where the oxide solid electrolyte particles 15a are located, and becomes thinner at the portion where the oxide solid electrolyte particles 15a are not located. Therefore, the oxide solid electrolyte particles 15a are likely to come into contact with the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 and the positive electrode active material 13a.
  • the volume ratio of the oxide solid electrolyte particles 15a is larger than the volume ratio of the lithium ion conductive polymer material 15b. By doing so, the resistance of the negative electrode side solid electrolyte-dispersed polymer layer 15 can be further reduced.
  • the oxide solid electrolyte layer 11 and the negative electrode side solid electrolyte dispersed polymer layer 15 are integrated, and the negative electrode active material layer 16 and the negative electrode side solid electrolyte dispersed polymer layer 15 are integrated.
  • the oxide solid electrolyte layer 11 and the negative electrode active material layer 16 are integrated with each other via the negative electrode side solid electrolyte dispersed polymer layer 15. Therefore, when the oxide solid electrolyte layer 11 and the negative electrode active material layer 16 are peeled off, destruction occurs.
  • the lithium ion conductive polymer material 15b constituting the negative electrode side solid electrolyte dispersed polymer layer 15 and the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a may be the same material.
  • the negative electrode side solid electrolyte dispersion polymer layer 15 and the oxide solid electrolyte layer 11 are preferable from the viewpoint of being able to increase the integrated strength. Further, in this case, it is also preferable from the viewpoint that the negative electrode side solid electrolyte-dispersed polymer layer 15 and the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a can be formed at the same time by coating.
  • the negative electrode side solid electrolyte dispersion polymer layer 15 may be provided on the negative electrode side surface of the oxide solid electrolyte layer 11 in a state where the lithium ion conductive polymer material 11b is inserted between the oxide solid electrolyte particles 11a.
  • the lithium ion conductive polymer material constituting the negative electrode side solid electrolyte dispersed polymer layer 15 and the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a may be different materials from each other. ..
  • PVDF, SBR, acrylate and the like can be appropriately used as the lithium ion conductive polymer material constituting the negative electrode side solid electrolyte dispersion polymer layer 15, and the lithium ions entering between the oxide solid electrolyte particles 11a.
  • PEO is used as the conductive polymer material 11b.
  • the negative electrode side is that the lithium ion conductive polymer material constituting the negative electrode side solid electrolyte-dispersed polymer layer 15 and the lithium ion conductive polymer material 16b that penetrates between the negative electrode active material 16a are the same material as each other. It is preferable from the viewpoint that the integrated strength between the solid electrolyte-dispersed polymer layer 15 and the negative electrode active material layer 16 can be increased. Further, the lithium ion conductive polymer material constituting the negative electrode side solid electrolyte-dispersed polymer layer 15 and the lithium ion conductive polymer material 16b that penetrates between the negative electrode active material 16a may be different materials from each other.
  • PVDF is used as the lithium ion conductive polymer material constituting the negative electrode side solid electrolyte-dispersed polymer layer 15
  • PEO and PEO are used as the lithium ion conductive polymer material 13b that penetrates between the negative electrode active materials 16a.
  • a mixture of PVDFs is preferably used. With such a combination, the degree of adhesion between the negative electrode side solid electrolyte dispersion polymer layer 15 and the negative electrode active material layer 16 can be improved.
  • the negative electrode current collector layer 17 is arranged on the surface side of the negative electrode active material layer 16 opposite to the oxide solid electrolyte layer 11 side, and is integrated with the negative electrode active material layer 16. Examples of the material of the negative electrode current collector layer 17 include the same materials as those of the positive electrode current collector layer 14.
  • the packaging material 10 includes a positive electrode current collector layer 14, a positive electrode active material layer 13, a positive electrode side solid electrolyte dispersed polymer layer 12, an oxide solid electrolyte layer 11, a negative electrode side solid electrolyte dispersed polymer layer 15, and a negative electrode active material layer 16. , And a member that accommodates and seals the negative electrode current collector layer 17. A part of the positive electrode current collector layer 14 and the negative electrode current collector layer 17 is led out as electrodes to the outside of the packaging material 10.
  • the structure of the packaging material 10 is not particularly limited as long as external oxygen, moisture and the like are suppressed from entering the region surrounded by the packaging material 10 and do not conduct with the region, but for example, a metal such as aluminum.
  • a foil laminated with a resin layer can be used.
  • the all-solid-state lithium secondary battery 1 of the present embodiment uses an oxide solid electrolyte, and unlike sulfide, it is difficult to generate a gas such as hydrogen sulfide that requires careful handling even if the oxide reacts with water. Therefore, it is easy to handle.
  • the positive electrode active material layer 13, the negative electrode active material layer 16, the positive electrode side solid electrolyte dispersed polymer layer 12, and the negative electrode side solid electrolyte dispersed polymer layer 15 is integrated so as not to be peeled off. The resistance between each of the layers thus integrated is less than the resistance between the layers that are not integrated and are simply arranged adjacent to each other.
  • the positive electrode-side solid electrolyte-dispersed polymer layer 12 interposed between the positive electrode current collector layer 14 and the oxide solid electrolyte layer 11 has high lithium ion conductivity.
  • the oxide solid electrolyte particles 12a are dispersed in the molecular material 12b.
  • the negative electrode side solid electrolyte-dispersed polymer layer 15 interposed between the negative electrode active material layer 16 and the oxide solid electrolyte layer 11 is a lithium ion conductive polymer.
  • the oxide solid electrolyte particles 15a are dispersed in the material 15b.
  • the oxide solid electrolyte particles have higher lithium ion conductivity than the lithium ion conductive polymer material, so that the ion conductivity of the positive electrode side solid electrolyte dispersed polymer layer 12 and the negative electrode side solid electrolyte dispersed polymer layer 15 is lithium. Higher than a layer consisting only of ionic conductive polymer material. Therefore, the positive electrode side solid electrolyte-dispersed polymer layer 12 and the negative electrode side solid electrolyte-dispersed polymer layer 15 of the present embodiment are between the positive electrode active material layer 13 and the oxide solid electrolyte layer 11 and the negative electrode active material layer 16.
  • the internal resistance can be reduced and a large current can be achieved.
  • FIG. 4 is a flowchart of a method for manufacturing the all-solid-state lithium secondary battery 1 according to the embodiment.
  • the method for manufacturing the all-solid-state lithium secondary battery 1 of the present embodiment includes a preparation step P1, an arrangement step P2, an integration step P3, and a sealing step P4.
  • This step is a step of mainly preparing the oxide solid electrolyte layer 11, the positive electrode active material layer 13, the positive electrode current collector layer 14, the negative electrode active material layer 16, and the negative electrode current collector layer 17. ..
  • FIG. 5 is a diagram showing a state of the preparation process.
  • oxide solid electrolyte layer In the preparation of the oxide solid electrolyte layer 11, first, a green sheet in which the oxide solid electrolyte particles 11a are dispersed in the binder is prepared, and then the oxide solid electrolyte particles 11a are integrated with each other by firing. A porous sheet-like member to be the oxide solid electrolyte layer 11 can be obtained. Alternatively, even if the oxide solid electrolyte particles 11a are placed in a mold and molded into a sheet shape, a predetermined pressure is applied and fired to obtain a porous sheet-like member to be the oxide solid electrolyte layer 11. Good.
  • the oxide solid electrolyte particles 11a may be dispersed in the binder and then molded into a sheet to harden the binder.
  • the binder may be made of the lithium ion conductive polymer material 11b.
  • the binder does not have to be made of the lithium ion conductive polymer material 11b, but in the present embodiment, the lithium ion conductive polymer material 11b is inserted between the oxide solid electrolyte particles 11a.
  • the amount of the binder is such that voids are formed between the oxide solid electrolyte particles 11a. In this way, a sheet-like member containing the oxide solid electrolyte particles 11a is obtained.
  • a dispersion liquid in which the oxide solid electrolyte particles are dispersed in the lithium ion conductive polymer material is applied to both surfaces of the sheet-like member containing the oxide solid electrolyte particles 11a and solidified.
  • the lithium ion conductive polymer material coated between the oxide solid electrolyte particles 11a enters, and becomes the lithium ion conductive polymer material 11b arranged between the oxide solid electrolyte particles 11a.
  • the oxide solid electrolyte layer 11 in which the lithium ion conductive polymer material 11b is inserted between the oxide solid electrolyte particles 11a shown in FIG. 5 is obtained.
  • the oxide solid electrolyte particles in the dispersion liquid enter between the oxide solid electrolyte particles 11a from the viewpoint of lowering the resistance.
  • the oxide solid electrolyte particles in the dispersion liquid are the oxide solid electrolyte particles 11a. It is preferable because it easily gets in between.
  • the oxide solid electrolyte particles 11a are dispersed in the binder made of the lithium ion conductive polymer material 11b, and then molded into a sheet to harden the binder, whereby the sheet-like member is described.
  • the lithium ion conductive polymer material 11b since the lithium ion conductive polymer material 11b has entered between the oxide solid electrolyte particles 11a before the coating, the lithium ion conductive polymer material 11b coated between the oxide solid electrolyte particles 11a by the coating. The polymer material does not have to enter.
  • the lithium ion conductive polymer material when the lithium ion conductive polymer material is applied to both sides of the sheet-like member made of the oxide solid electrolyte particles 11a, the lithium ion conductive polymer is applied on both sides of the sheet-like member. Apply a lithium-ion conductive polymer material to the extent that the material becomes a layer. As a result, the lithium ion conductive polymer material on one surface of the oxide solid electrolyte layer 11 solidifies to become the positive electrode side solid electrolyte dispersed polymer layer 12 shown in FIG. 5, and the other of the oxide solid electrolyte layer 11 The lithium ion conductive polymer material on the surface solidifies to form the negative electrode side solid electrolyte-dispersed polymer layer 15 shown in FIG.
  • the positive electrode active material 13a and, if necessary, the conductive auxiliary agent are dispersed in the lithium ion conductive polymer material 13b, and the positive electrode current collector layer 14 is topped. Apply to and dry. In this way, the positive electrode active material layer 13 is provided on the positive electrode current collector layer 14.
  • the negative electrode active material 16a and, if necessary, a conductive auxiliary agent are dispersed in the lithium ion conductive polymer material 16b, and the negative electrode current collector layer 17 is topped. Apply to and dry. In this way, the negative electrode active material layer 16 is provided on the negative electrode current collector layer 17.
  • FIG. 6 is a diagram showing a state of this process.
  • the positive electrode active material layer 13 and the positive electrode current collector layer 14 are laminated on one surface side of the oxide solid electrolyte layer 11, and the positive electrode active material layer 13 is an oxide solid.
  • the electrolyte layer 11 is arranged so as to face the side.
  • the positive electrode side solid electrolyte dispersion polymer layer 12 is located on one surface of the oxide solid electrolyte layer 11 as described above, the positive electrode active material layer 13 is on the positive electrode side solid electrolyte dispersion polymer layer 12. Is placed in.
  • a laminate of the negative electrode active material layer 16 and the negative electrode current collector layer 17 is arranged on the other surface side of the oxide solid electrolyte layer 11 so that the negative electrode active material layer 16 faces the oxide solid electrolyte layer 11 side.
  • the negative electrode side solid electrolyte dispersion polymer layer 15 is located on the other surface of the oxide solid electrolyte layer 11 as described above, the negative electrode active material layer 16 is on the negative electrode side solid electrolyte dispersion polymer layer 15. Is placed in.
  • the oxide solid electrolyte layer 11, the positive electrode side solid electrolyte dispersed polymer layer 12, the positive electrode active material layer 13, the positive electrode current collector layer 14, the negative electrode side solid electrolyte dispersed polymer layer 15, and the negative electrode A battery element 1b in which the active material layer 16 and the negative electrode current collector layer 17 are laminated is obtained.
  • FIG. 7 is a diagram showing this process.
  • integration is performed by a hot press.
  • the battery element 1b is sandwiched between a pair of heated heat press molds 21 and 22.
  • each of the heat press molds 21 and 22 is pressed in a heated state.
  • the temperature of the hot press molds 21 and 22 is higher than the temperature at which the lithium ion conductive polymer material constituting the positive electrode side solid electrolyte-dispersed polymer layer 12 and the negative electrode side solid electrolyte-dispersed polymer layer 15 softens. It is preferable to have.
  • the temperature at which it softens is approximately 100 ° C., so that the temperature of the heat press molds 21 and 22 is preferably higher than this temperature.
  • the temperature of the hot press molds 21 and 22 is more preferably between 110 ° C. and 120 ° C.
  • the pressure for pressing the battery element 1b is, for example, preferably 1 MPa or more and 50 MPa or less from the viewpoint of being able to suppress the outflow of the lithium ion conductive polymer material while firmly integrating the respective layers.
  • a part of the lithium ion conductive polymer material constituting the positive electrode side solid electrolyte dispersed polymer layer 12 may enter the positive electrode active material layer 13, and the negative electrode side solid electrolyte dispersed polymer layer 15 may be formed.
  • a part of the constituent lithium ion conductive polymer material may enter the negative electrode active material layer 16.
  • the positive electrode side solid electrolyte-dispersed polymer layer 12 and the positive electrode active material layer 13 are integrated, and the negative electrode side solid electrolyte-dispersed polymer layer 15 and the negative electrode active material layer 16 are integrated.
  • the battery element 1b in the material 10 is obtained.
  • ⁇ Seal step P4> Next, the integrated battery body 1b is placed in the packaging material 10 and the packaging material 10 is sealed. It is preferable that heat fusion or the like is used for sealing.
  • the positive electrode active material layer 13, the negative electrode active material layer 16, and the oxide solid electrolyte layer 11 are integrated. Therefore, an oxide solid electrolyte that is easy to handle is used, and resistance between the positive electrode active material layer 13 and the oxide solid electrolyte layer 11 and between the negative electrode active material layer 16 and the oxide solid electrolyte layer 11 is increased. It is possible to manufacture the all-solid-state lithium secondary battery 1 which can reduce the current and achieve a large current.
  • the integration step P3 is performed by thermocompression bonding. Therefore, for example, the integration step P3 can be performed more easily than when the integration step P3 is performed by using ultrasonic waves.
  • the oxide solid electrolyte layer 11 is configured such that the lithium ion conductive polymer material 11b is inserted into at least a part between the particles of the oxide solid electrolyte particles 11a.
  • the oxide solid electrolyte layer 11 does not have to have the lithium ion conductive polymer material 11b.
  • the lithium ion conductive polymer material 11b is inserted into at least a part between the particles of the oxide solid electrolyte particles 11a.
  • the lithium ion conductive polymer material 12b constituting the positive electrode side solid electrolyte dispersed polymer layer 12, the lithium ion conductive polymer material 15b constituting the negative electrode side solid electrolyte dispersed polymer layer 15, and the oxide solid electrolyte particles 11a.
  • the material may be different from the lithium ion conductive polymer material 11b that penetrates between the particles of. In this case, in the preparation step P1, when the lithium ion conductive polymer material 11b that penetrates between the particles of the oxide solid electrolyte particles 11a is applied, the lithium ion conductive polymer material 11b is the oxide solid electrolyte particles 11a.
  • the oxide solid electrolyte layer 11 is obtained by applying the coating so as not to form a layer on the sheet member. Then, a lithium ion conductive polymer material to be the positive electrode side solid electrolyte dispersion polymer layer 12 and the negative electrode side solid electrolyte dispersion polymer layer 15 may be coated on the obtained oxide solid electrolyte layer 11.
  • the lithium ion conductive polymer material 13b does not have to enter between the positive electrode active material 13a of the positive electrode active material layer 13, and the lithium ion conductive polymer material between the negative electrode active material 16a of the negative electrode active material layer 16. 16b does not have to enter.
  • the integration step P3 is performed by thermocompression bonding, but the integration step P3 may be performed by a method other than thermocompression bonding such as ultrasonic fusion.
  • the polymer arranged between the particles of the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11 is a polymer having lithium ion conductivity, and lithium in the case where the lithium salt is dispersed in the polymer.
  • the amount of salt was investigated.
  • Example 1 In order to prepare the battery body 1b, a laminate in which solid electrolyte dispersion polymer layers were provided on both sides of the oxide solid electrolyte layer 11 was prepared. In this preparation, first, a porous oxide solid electrolyte particle bonding layer to which the oxide solid electrolyte particles 11a were bonded was prepared.
  • the oxide solid electrolyte particles consist of LLZO.
  • a coating liquid made of a lithium ion conductive polymer material in which oxide solid electrolyte particles and lithium salts were dispersed was applied to both sides of the oxide solid electrolyte particle bonding layer.
  • PEO was used as the lithium ion conductive polymer material
  • LiFSI was used as the lithium salt
  • particles made of LLZO were used as the oxide solid electrolyte particles.
  • the weight ratio of PEO and LiFSI was set to 1: 1.
  • the positive electrode side solid electrolyte-dispersed polymer layer 12 was prepared from a layer made of a coating liquid formed on one surface of the oxide solid electrolyte layer 11 and formed on the other surface of the oxide solid electrolyte layer 11.
  • a negative electrode side solid electrolyte-dispersed polymer layer 15 was prepared from a layer made of a coating liquid.
  • a laminated body in which the positive electrode active material layer 13 is provided on one surface of the positive electrode current collector layer 14 was prepared. Specifically, an aluminum foil is used as the positive electrode current collector layer 14, and lithium nickelate (NCA), carbon black, acrylate, and carboxymethyl cellulose (CMC) are dispersed on one surface of the positive electrode current collector layer 14.
  • the positive electrode active material layer 13 was obtained by applying and drying the solution to obtain the above-mentioned laminate.
  • a laminated body in which the negative electrode active material layer 16 is provided on one surface of the negative electrode current collector layer 17 was prepared. Specifically, a copper foil is used as the negative electrode current collector layer 17, and graphitized carbon, styrene-butadiene block copolymer (SBR), and CMC are dispersed on one surface of the negative electrode current collector layer 17.
  • the negative electrode active material layer 16 was obtained by applying and drying the solution to obtain the above-mentioned laminate.
  • the above three laminated bodies were overlapped and integrated. Specifically, the positive electrode side solid electrolyte dispersion polymer layer 12 provided on one surface of the oxide solid electrolyte layer 11 and the positive electrode active material layer 13 provided on one surface of the positive electrode current collector layer 14. The negative electrode side solid electrolyte dispersion polymer layer 15 provided on the other surface of the oxide solid electrolyte layer 11 and the negative electrode active material layer 16 provided on one surface of the negative electrode current collector layer 17 are laminated. Overlaid. Next, the laminated bodies that were overlapped were integrated by thermocompression bonding.
  • Example 2 A battery element 1b was prepared in the same manner as in Example 1 except that the weight ratio of PEO and LiFSI was 4: 1. When PEO and LiFSI are used in a general all-solid-state lithium secondary battery other than the present invention, the weight ratio thereof is the same as that in this example. Impedance measurement was performed on the battery body 1b in the same manner as in Example 1. The resulting call-call plot is shown in FIG. As a result, the resistance of the battery element of the reference example was approximately 2000 ⁇ .
  • Example 2 Even the resistance of Example 2 is a sufficiently practical low resistance, but the resistance of Example 1 is about 1/40 of the resistance of Example 2. Therefore, the lithium ion height of the lithium ion conductive polymer material 11b that penetrates between the oxide solid electrolyte particles 11a of the oxide solid electrolyte layer 11, the positive electrode side solid electrolyte dispersed polymer layer 12, and the lithium ion conductive polymer material 13b. It was found that when the molecular material is PEO and LiFSI is dispersed in the lithium ion polymer material, the weight of LiFSI with respect to PEO is preferably 1 times or more.
  • the weight of LiFSI with respect to PEO is more than twice, there is a concern about strength, so it is preferable that the weight of LiFSI with respect to PEO is twice or less.
  • an all-solid-state lithium secondary battery and an all-solid-state lithium secondary battery that are easy to handle and can achieve a large current, and are used for automobile batteries and industrial equipment. It is expected to be used in the fields of batteries, batteries for consumer devices, etc.

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Abstract

L'invention concerne une batterie secondaire au lithium entièrement solide (1) comprenant : une couche d'électrolyte solide d'oxyde (11) comprenant des particules d'électrolyte solide d'oxyde (11a) ayant une conductivité des ions lithium ; une couche de matériau actif d'électrode positive (13) disposée sur un côté de surface de la couche d'électrolyte solide d'oxyde (11) ; une couche de matériau actif d'électrode négative (16) disposée sur l'autre côté de surface de la couche d'électrolyte solide d'oxyde (11) ; et une couche de polymère de dispersion d'électrolyte solide disposée entre la couche d'électrolyte solide d'oxyde (11) et au moins soit la couche de matériau actif d'électrode positive (13) soit la couche de matériau actif d'électrode négative (16) et ayant des particules d'électrolyte solide d'oxyde dispersées dans un matériau polymère conducteur d'ions de lithium qui a une conductivité d'ions lithium. La couche de matériau actif d'électrode positive (13), la couche de matériau actif d'électrode négative (16), la couche de polymère de dispersion d'électrolyte solide et la couche d'électrolyte solide d'oxyde (11) sont intégrées.
PCT/JP2020/038603 2019-10-15 2020-10-13 Batterie secondaire au lithium entièrement solide et procédé de production de batterie secondaire au lithium entièrement solide WO2021075420A1 (fr)

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CN202080047305.1A CN114026727B (zh) 2019-10-15 2020-10-13 全固态锂二次电池以及全固态锂二次电池的制造方法

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JP2007066703A (ja) * 2005-08-31 2007-03-15 Ohara Inc リチウムイオン二次電池および固体電解質
JP2009181872A (ja) * 2008-01-31 2009-08-13 Ohara Inc リチウムイオン二次電池およびその製造方法
KR20170141498A (ko) * 2016-06-15 2017-12-26 한국생산기술연구원 전고체 리튬이차전지 및 그의 제조방법

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CN106785009A (zh) * 2016-12-09 2017-05-31 北京科技大学 一种有机无机全固态复合电解质及其制备和应用方法
WO2019054729A1 (fr) * 2017-09-13 2019-03-21 주식회사 엘지화학 Électrode pour batterie tout solide, comprenant un électrolyte solide
CN107732297B (zh) * 2017-10-13 2020-07-14 中国科学院青岛生物能源与过程研究所 一种应用于锂电池的宽电位窗口的多级结构复合固态电解质
CN109768318A (zh) * 2019-03-12 2019-05-17 浙江锋锂新能源科技有限公司 一种混合固液电解质锂蓄电池

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JP2007066703A (ja) * 2005-08-31 2007-03-15 Ohara Inc リチウムイオン二次電池および固体電解質
JP2009181872A (ja) * 2008-01-31 2009-08-13 Ohara Inc リチウムイオン二次電池およびその製造方法
KR20170141498A (ko) * 2016-06-15 2017-12-26 한국생산기술연구원 전고체 리튬이차전지 및 그의 제조방법

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