CN112072164A - Solid-state lithium battery and preparation method thereof - Google Patents

Solid-state lithium battery and preparation method thereof Download PDF

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Publication number
CN112072164A
CN112072164A CN202010885545.0A CN202010885545A CN112072164A CN 112072164 A CN112072164 A CN 112072164A CN 202010885545 A CN202010885545 A CN 202010885545A CN 112072164 A CN112072164 A CN 112072164A
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active material
binder
solid
positive electrode
negative electrode
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CN112072164B (en
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陈少杰
黄海强
王磊
李瑞杰
周龙捷
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The invention relates to the field of lithium batteries, and discloses a solid-state lithium battery and a preparation method thereof. The solid-state lithium battery comprises a positive electrode, a negative electrode and a solid-state electrolyte layer positioned between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode current collector and a solid-state positive electrode active material layer formed on the positive electrode current collector, and is characterized in that the active material in the solid-state positive electrode active material layer is selected from LiMO2M is selected from one or more of Co, Ni and Mn; the solid electrolyte layer contains a sulfide and a binder; the negative electrode comprises a negative electrode current collector and a negative electrode formed on the negative electrode current collectorAnd an anode active material layer in contact with at least the solid electrolyte layer is a gel-state anode active material layer. The invention can provide a novel solid-state lithium battery which can improve interface contact, rapidly improve the lithium ion conductivity of a system and reduce interface impedance.

Description

Solid-state lithium battery and preparation method thereof
Technical Field
The invention relates to the field of lithium batteries, in particular to a solid-state lithium battery and a preparation method thereof.
Background
The solid-state battery adopts non-flammable solid electrolyte to replace flammable organic liquid electrolyte, so that the safety of a battery system is greatly improved, the high-energy anode and cathode can be better adapted, the weight of the system is reduced, and the synchronous improvement of the energy density is realized. Among various new battery systems, solid-state batteries are the next-generation technology closest to the industry, which has become a consensus of the industry and the scientific community.
At present, the interface of the solid-state lithium battery is improved and prepared by adopting a mode of mutually mixing an inorganic oxide electrolyte or a polymer electrolyte with a liquid electrolyte, but because the ionic conductivity of the inorganic oxide electrolyte and the polymer electrolyte is lower, the internal resistance and the conductivity of the whole battery can be improved only by adding more liquid electrolytes, and the improvement of the overall safety of the solid-state lithium battery is not facilitated by adding more liquid electrolytes. Theoretically, the all-solid-state lithium battery without any electrolyte component has the highest safety, but the all-solid-state system has a relatively large interface problem due to solid-solid contact among particles formed by all inorganic particles, and extra large pressure is required to be applied to directly influence the service condition, the multiplying power and the cycle performance of the battery. Therefore, how to improve the interface while maintaining high safety has been a technical challenge for solid-state lithium battery researchers.
Disclosure of Invention
The invention aims to provide a novel solid-state lithium battery which can improve interface contact, quickly improve the lithium ion conductivity of a system and reduce interface impedance aiming at the defects and defects of the conventional solid-state battery interface fusion technology.
To achieve the above object, one aspect of the present invention providesA solid-state lithium battery comprising a positive electrode including a positive electrode current collector and a solid-state positive active material layer formed on the positive electrode current collector, a negative electrode, and a solid-state electrolyte layer between the positive electrode and the negative electrode, wherein the active material in the solid-state positive active material layer is selected from LiMO2M is selected from one or more of Co, Ni and Mn; the solid electrolyte layer contains a sulfide and a binder; the negative electrode comprises a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector, and the negative electrode active material layer in contact with the solid electrolyte layer is a gel-state negative electrode active material layer.
Preferably, the solid positive active material layer contains 60 to 85 wt% of the positive active material, 2 to 5 wt% of the first conductive agent, 10 to 30 wt% of the sulfide electrolyte, and 1 to 5 wt% of the first binder.
Preferably, the positive electrode current collector is a carbon-coated aluminum foil.
Preferably, the LiMO2Is LiCoO2、LiNi1/3Mn1/3Co1/3O2One or more of NCM523, NCM622, and NCM 811.
Preferably, the first conductive agent is one or more of SP (carbon black), CNT (carbon nanotube), VGCF (carbon fiber), silver powder, and aluminum powder.
Preferably, the sulfide electrolyte is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of (a).
Preferably, the first binder is one or more of polyvinylidene fluoride and a rubber-based binder.
Preferably, the solid electrolyte layer contains a sulfide and a second binder.
Preferably, the sulfide is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of (a).
Preferably, the solid electrolyte layer contains 90 to 99 wt% of the sulfide and 1 to 10 wt% of the second binder.
Preferably, the second binder is one or more of polyvinylidene fluoride and a rubber-based binder.
Preferably, the negative active material layer includes a negative active material, a third binder, a lithium salt, a second conductive agent, and an organic solvent.
Preferably, the negative active material layer contains 40-90% by weight of a negative active material, 1-15% of a second binder, 1-15% of a lithium salt, 1-10% of a second conductive agent, and 10-20% of an organic solvent.
Preferably, the negative active material is one or more of graphite, silicon monoxide, elemental silicon, carbon-coated silicon, and graphene-coated silicon.
Preferably, the negative electrode current collector is a carbon-coated copper foil.
Preferably, the third binder is one or more of polyvinylidene fluoride and a rubber-based binder.
Preferably, the lithium salt is LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4And LiBOB.
Preferably, the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder.
Preferably, the organic solvent is one or more of an alkane solvent, a benzene solvent and a ketone solvent.
Preferably, the organic solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
According to a second aspect of the present invention, there is provided a method of manufacturing a solid-state lithium battery, the method comprising the steps of,
1) coating a first slurry containing a positive electrode active material, a first conductive agent, a sulfide electrolyte, a binder and a first solvent on a positive electrode current collector, and drying to obtain a positive electrode;
2) preparing a second slurry containing sulfide, a second binder and a second solvent into a solid electrolyte layer;
3) coating a third slurry containing a negative electrode active material, a third binder, a lithium salt, a second conductive agent and a third solvent on a negative electrode current collector, and drying to obtain a negative electrode with a solid negative electrode active material layer formed on the negative electrode current collector;
4) contacting the solid negative active material layer on at least one side of the negative electrode with a fourth solvent to obtain a gel negative active material layer;
5) subjecting the positive electrode and the solid electrolyte layer to a first pressing to form a positive electrode/solid electrolyte layer assembly, then laminating the positive electrode/solid electrolyte layer assembly/solid electrolyte layer and a gel state negative electrode active material layer of the negative electrode and performing a second pressing,
wherein the positive electrode active material is selected from LiMO2M is selected from one or more of Co, Ni and Mn.
Preferably, in the first slurry, the content of the positive electrode active material is 60 to 85 wt%, the content of the first conductive agent is 2 to 5 wt%, the content of the sulfide electrolyte is 10 to 30 wt%, and the content of the first binder is 1 to 5 wt%, based on the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte, and the first binder.
Preferably, the first solvent is used in an amount of 100-600 parts by weight, relative to 100 parts by weight of the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte and the first binder.
Preferably, the positive electrode current collector is a carbon-coated aluminum foil.
Preferably, the LiMO2Is LiCoO2、LiNi1/3Mn1/3Co1/3O2、NCM523、One or more of NCM622 and NCM 811.
Preferably, the first conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder.
Preferably, the sulfide electrolyte is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of (a).
Preferably, the first binder is one or more of polyvinylidene fluoride and a rubber-based binder.
Preferably, the first solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
Preferably, in the second slurry, the sulfide is contained in an amount of 90 to 99 wt% and the second binder is contained in an amount of 1 to 10 wt%, based on the total amount of the sulfide and the second binder.
Preferably, the second solvent is used in an amount of 100-600 parts by weight, relative to 100 parts by weight of the total amount of the sulfide and the second binder.
Preferably, the sulfide is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of (a).
Preferably, the second binder is one or more of polyvinylidene fluoride and a rubber-based binder.
Preferably, the second solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
Preferably, in the third slurry, the content of the negative active material is 40 to 90 wt%, the content of the third binder is 1 to 15 wt%, the content of the lithium salt is 1 to 15 wt%, and the content of the second conductive agent is 1 to 15 wt%, based on the total amount of the negative active material, the third binder, the lithium salt, and the second conductive agent.
Preferably, the third solvent is used in an amount of 100-600 parts by weight, relative to 100 parts by weight of the total amount of the anode active material, the third binder, the lithium salt and the second conductive agent.
Preferably, the negative active material is one or more of graphite, silicon monoxide, elemental silicon, carbon-coated silicon, and graphene-coated silicon.
Preferably, the negative electrode current collector is a carbon-coated copper foil.
Preferably, the third binder is one or more of polyvinylidene fluoride and a rubber-based binder.
Preferably, the lithium salt is LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4And LiBOB.
Preferably, the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder.
Preferably, the third solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
Preferably, in step 4), the fourth solvent is used in an amount of 1 to 23 parts by weight with respect to 100 parts by weight of the solid anode active material layer.
Preferably, the fourth solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
Preferably, the conditions of the first pressing include: isostatic pressure of 50-550Mpa, pressure maintaining time of 10-30min, and temperature of 15-100 deg.C.
Preferably, the conditions of the second pressing include: the isostatic pressing pressure is 100-550Mpa, the pressure maintaining time is 10-30min, and the temperature is 15-100 ℃.
Through the technical scheme, the invention can provide the novel solid-state lithium battery which can improve interface contact, can quickly improve the lithium ion conductivity of a system and can reduce interface impedance.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a solid-state lithium battery comprising a positive electrode including a positive electrode current collector and a solid-state positive electrode active material layer formed on the positive electrode current collector, a negative electrode, and a solid-state electrolyte layer between the positive electrode and the negative electrode, wherein an active material in the solid-state positive electrode active material layer is selected from LiMO2M is selected from one or more of Co, Ni and Mn; the solid electrolyte layer contains a sulfide and a binder; the negative electrode comprises a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector, and the negative electrode active material layer in contact with the solid electrolyte layer is a gel-state negative electrode active material layer.
According to the present invention, by using a specific sulfide solid electrolyte layer and by making the negative electrode active material layer in contact with the solid electrolyte layer a gel-state negative electrode active material layer, not only can the battery interface contact be improved, but also the lithium ion conductivity of the system can be rapidly increased and the interface impedance can be reduced.
According to the present invention, in terms of further rapidly increasing the lithium ion conductivity of the system and reducing the interface impedance, it is preferable that the solid positive electrode active material layer contains 60 to 85 wt% of the positive electrode active material, 2 to 5 wt% of the first conductive agent, 10 to 30 wt% of the sulfide electrolyte, and 1 to 5 wt% of the first binder; more preferably, the solid positive electrode active material layer contains 70 to 85 wt% of the positive electrode active material, 3 to 5 wt% of the first conductive agent, 15 to 30 wt% of the sulfide electrolyte, and 2 to 4 wt% of the first binder; further preferably, the solid state positive electrode active material layer contains 75 to 80 wt% of the positive electrode active material, 3 to 4 wt% of the first conductive agent, 15 to 20 wt% of the sulfide electrolyte, and 2 to 3 wt% of the first binder.
In a particularly preferred embodiment of the present invention, the solid positive electrode active material layer contains 79 wt% of the positive electrode active material, 4 wt% of the first conductive agent, 15 wt% of the sulfide electrolyte, and 2 wt% of the first binder.
According to the present invention, the positive electrode current collector is not particularly limited, and various kinds of metal sheets generally used as a positive electrode current collector in the art may be used. Preferably, the positive electrode current collector is a carbon-coated aluminum foil.
According to the invention, preferably, the LiMO2Is LiCoO2、LiNi1/3Mn1/3Co1/3O2One or more of NCM523, NCM622, and NCM 811. By using the positive electrode active material, the positive electrode active material has the advantages of high capacity and high voltage.
According to the present invention, the first conductive agent may be various conductive agents generally used in the art. Preferably, the first conductive agent is one or more of SP (carbon black), CNT (carbon nanotube), AB (acetylene black), VGCF (carbon fiber), silver powder, and aluminum powder.
According to the invention, preferably, the sulfide electrolyte is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of; more preferably, the sulfide is Li10GeP2S12、Li6PS5Cl and Li2S-P2S5One or more of (a).
According to the present invention, preferably, the first binder is one or more of polyvinylidene fluoride and a rubber-based binder; more preferably, the first binder is one or more of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PEO, SBS, SEBS, NBR and SBR. Further, the molecular weight of the first binder is preferably 20 to 500 ten thousand.
According to the present invention, the solid electrolyte layer contains a sulfide and a second binder. Preferably, the sulfide is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of; more preferably, the sulfide is Li10GeP2S12、Li6PS5Cl and Li2S-P2S5One or more of (a).
According to the present invention, preferably, the solid electrolyte layer contains 90 to 99 wt% of sulfide and 1 to 10 wt% of the second binder; more preferably, the solid electrolyte layer contains 95 to 99 wt% of sulfide and 1 to 2 wt% of the second binder.
In a particularly preferred embodiment of the invention, the solid electrolyte layer contains 98% by weight of sulfide and 2% by weight of the second binder.
According to the present invention, preferably, the second binder is one or more of polyvinylidene fluoride and a rubber-based binder; more preferably, the second binder is one or more of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PEO, SBS, SEBS, NBR and SBR. Further, the weight average molecular weight of the second binder is preferably 20 to 500 ten thousand.
According to the present invention, the negative active material layer includes a negative active material, a third binder, a lithium salt, a second conductive agent, and an organic solvent. Preferably, the negative active material layer contains 40 to 90 wt% of a negative active material, 1 to 15 wt% of a third binder, 1 to 15 wt% of a lithium salt, 1 to 15 wt% of a second conductive agent, and 1 to 20 wt% of an organic solvent; more preferably, the negative active material layer contains 40 to 90 wt% of a negative active material, 1 to 15 wt% of a third binder, 1 to 15 wt% of a lithium salt, 1 to 10 wt% of a second conductive agent, and 8 to 20 wt% of an organic solvent; more preferably, the negative active material layer contains 40 to 90 wt% of a negative active material, 1 to 15 wt% of a third binder, 1 to 15 wt% of a lithium salt, 1 to 10 wt% of a second conductive agent, and 10 to 20 wt% of an organic solvent; more preferably, the negative active material layer contains 60 to 90 wt% of a negative active material, 2 to 10 wt% of a third binder, 2 to 10 wt% of a lithium salt, 10 to 15 wt% of a second conductive agent, and 5 to 15 wt% of an organic solvent; further preferably, the negative active material layer contains 65 to 75 wt% of a negative active material, 5 to 10 wt% of a third binder, 5 to 10 wt% of a lithium salt, 5 to 8 wt% of a second conductive agent, and 10 to 12 wt% of an organic solvent.
According to the present invention, preferably, the negative active material is one or more of graphite, silicon monoxide, elemental silicon, carbon-coated silicon, and graphene-coated silicon; more preferably, the anode active material is one or more of graphite, silicon monoxide, and elemental silicon.
According to the present invention, the negative electrode current collector is not particularly limited, and various kinds of metal sheets generally used as a negative electrode current collector in the art may be used. Preferably, the negative electrode current collector is a carbon-coated copper foil.
According to the present invention, preferably, the third binder is one or more of polyvinylidene fluoride and a rubber-based binder; more preferably, the third binder is one or more of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PEO, SBS, SEBS, NBR and SBR. Further, the molecular weight of the third binder is preferably 20 to 500 ten thousand.
According to the present invention, the lithium salt may be one commonly used in the art for lithium batteriesVarious lithium salts. Preferably, the lithium salt is LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4And LiBOB: more preferably, the lithium salt is one or more of LiTFSI, LiFSI, and litdfob.
According to the present invention, preferably, the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder; more preferably, the second conductive agent is one or more of SP, CNT, AB, and VGCF.
According to the present invention, preferably, the organic solvent is one or more of an alkane solvent, a benzene solvent and a ketone solvent; more preferably, the organic solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
According to a second aspect of the present invention, there is provided a method of manufacturing a solid-state lithium battery, wherein the method comprises the steps of,
1) coating a first slurry containing a positive electrode active material, a first conductive agent, a sulfide electrolyte, a first binder and a first solvent on a positive electrode current collector, and drying to obtain a positive electrode;
2) preparing a second slurry containing sulfide, a second binder and a second solvent into a solid electrolyte layer;
3) coating a third slurry containing a negative electrode active material, a third binder, a lithium salt, a second conductive agent and a third solvent on a negative electrode current collector, and drying to obtain a negative electrode with a solid negative electrode active material layer formed on the negative electrode current collector;
4) contacting the solid negative active material layer on at least one side of the negative electrode with a fourth solvent to obtain a gel negative active material layer;
5) subjecting the positive electrode and the solid electrolyte layer to a first pressing to form a positive electrode/solid electrolyte layer assembly, then laminating the positive electrode/solid electrolyte layer assembly/solid electrolyte layer and a gel state negative electrode active material layer of the negative electrode and performing a second pressing,
wherein the positive electrode active material is selected from LiMO2M is selected from one or more of Co, Ni and Mn.
Step 1)
According to the present invention, preferably, in the first slurry, the content of the positive electrode active material is 60 to 85 wt%, the content of the first conductive agent is 2 to 5 wt%, the content of the sulfide electrolyte is 10 to 30 wt%, and the content of the first binder is 1 to 5 wt%, based on the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte, and the first binder; more preferably, the content of the positive electrode active material is 70 to 85 wt%, the content of the first conductive agent is 3 to 5 wt%, the content of the sulfide electrolyte is 15 to 30 wt%, and the content of the first binder is 2 to 4 wt%, based on the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte, and the first binder; further preferably, the content of the positive electrode active material is 75 to 80 wt%, the content of the first conductive agent is 3 to 4 wt%, the content of the sulfide electrolyte is 15 to 20 wt%, and the content of the first binder is 2 to 3 wt%, based on the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte, and the first binder.
In a particularly preferred embodiment of the present invention, in the first slurry, the content of the positive electrode active material is 79% by weight, the content of the first conductive agent is 4% by weight, the content of the sulfide electrolyte is 15% by weight, and the content of the first binder is 2% by weight, based on the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte, and the first binder.
According to the present invention, the amount of the first solvent may be appropriately set according to the amounts of the positive electrode active material, the conductive agent, the sulfide electrolyte, and the first binder used. Preferably, the first solvent is used in an amount of 100-.
According to the present invention, the positive electrode current collector is not particularly limited, and various kinds of metal sheets generally used as a positive electrode current collector in the art may be used. Preferably, the positive electrode current collector is a carbon-coated aluminum foil.
According to the invention, preferably, the LiMO2Is LiCoO2、LiNi1/3Mn1/3Co1/3O2One or more of NCM523, NCM622, and NCM 811. By using the positive electrode active material, the positive electrode active material has the advantages of high capacity and high voltage.
According to the present invention, the first conductive agent may be various conductive agents generally used in the art. Preferably, the first conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder.
According to the invention, preferably, the sulfide electrolyte is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of; more preferably, the sulfide is Li10GeP2S12、Li6PS5Cl and Li2S-P2S5One or more of (a).
According to the present invention, preferably, the first binder is one or more of polyvinylidene fluoride and a rubber-based binder; more preferably, the first binder is one or more of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PEO, SBS, SEBS, NBR and SBR. Further, the molecular weight of the first binder is preferably 20 to 500 ten thousand.
According to the present invention, preferably, the first solvent is one or more of an alkane solvent, a benzene solvent and a ketone solvent; more preferably, the first solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
According to the present invention, as for the method of coating the first slurry on the positive electrode current collector and drying, various methods and conditions generally used in the art may be adopted, and will not be described herein.
Step 2)
According to the present invention, preferably, in the second slurry, the sulfide content is 90 to 99 wt% and the second binder content is 1 to 10 wt%, based on the total amount of the sulfide and the second binder; preferably, the sulfide content is 95 to 99 wt%, and the second binder content is 1 to 5 wt%.
In a particularly preferred embodiment of the invention, the content of sulfide is 98% by weight and the content of the second binder is 2% by weight.
According to the present invention, the amount of the second solvent may be appropriately set according to the amounts of the sulfide and the second binder. Preferably, the amount of the second solvent is 200-600 parts by weight, more preferably 300-500 parts by weight, still more preferably 350-500 parts by weight, and particularly preferably 400-500 parts by weight, relative to 100 parts by weight of the total amount of the sulfide and the second binder.
According to the invention, preferably, the sulphide is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of; more preferably, the sulfide is Li10GeP2S12、Li6PS5Cl and Li2S-P2S5One or more of (a).
According to the present invention, preferably, the second binder is one or more of polyvinylidene fluoride and a rubber-based binder; more preferably, the second binder is one or more of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PEO, SBS, SEBS, NBR and SBR. Further, the weight average molecular weight of the second binder is preferably 20 to 500 ten thousand.
According to the present invention, preferably, the second solvent is one or more of an alkane solvent, a benzene solvent and a ketone solvent; more preferably, the second solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
According to the present invention, the method of preparing the second slurry containing the sulfide, the second binder, and the second solvent into the solid electrolyte layer may employ methods and conditions generally used in the art, and for example, a method of coating the second slurry containing the sulfide, the second binder, and the second solvent on an aluminum foil and drying it may be used.
Step 3)
According to the present invention, preferably, in the third slurry, the content of the negative electrode active material is 40 to 90 wt%, the content of the third binder is 1 to 15 wt%, the content of the lithium salt is 1 to 15 wt%, and the content of the second conductive agent is 1 to 15 wt%, based on the total amount of the negative electrode active material, the third binder, the lithium salt, and the second conductive agent; preferably, the content of the negative active material is 50 to 90 wt%, the content of the third binder is 3 to 13 wt%, the content of the lithium salt is 3 to 13 wt%, and the content of the second conductive agent is 3 to 13 wt%, based on the total amount of the negative active material, the third binder, the lithium salt, and the second conductive agent; further preferably, the content of the negative electrode active material is 75 to 85 wt%, the content of the third binder is 5.5 to 12 wt%, the content of the lithium salt is 5.5 to 12 wt%, and the content of the second conductive agent is 5.5 to 10 wt%, based on the total amount of the negative electrode active material, the third binder, the lithium salt, and the second conductive agent; further preferably, the content of the negative electrode active material is 75 to 85 wt%, the content of the third binder is 5.5 to 12 wt%, the content of the lithium salt is 5.5 to 12 wt%, and the content of the second conductive agent is 5.5 to 8 wt%, based on the total amount of the negative electrode active material, the third binder, the lithium salt, and the second conductive agent.
According to the present invention, the third solvent is preferably used in an amount of 100-.
According to the present invention, preferably, the negative active material is one or more of graphite, silicon monoxide, elemental silicon, carbon-coated silicon, and graphene-coated silicon; more preferably, the anode active material is one or more of graphite, silicon monoxide, and elemental silicon.
According to the present invention, the negative electrode current collector is not particularly limited, and various kinds of metal sheets generally used as a negative electrode current collector in the art may be used. Preferably, the negative electrode current collector is a carbon-coated copper foil.
According to the present invention, preferably, the third binder is one or more of polyvinylidene fluoride and a rubber-based binder; more preferably, the third binder is one or more of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PEO, SBS, SEBS, NBR and SBR. Further, the weight average molecular weight of the third binder is preferably 20 to 500 ten thousand.
According to the present invention, the lithium salt may be various lithium salts generally used in lithium batteries in the art. Preferably, the lithium salt is LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4And LiBOB: more preferably, the lithium salt is one or more of LiTFSI, LiFSI, and litdfob.
According to the present invention, preferably, the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder; more preferably, the second conductive agent is one or more of SP, CNT, AB, and VGCF.
According to the present invention, preferably, the third solvent is one or more of an alkane solvent, a benzene solvent and a ketone solvent; more preferably, the third solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
According to the present invention, the method and conditions for coating the third slurry on the negative electrode current collector and drying may employ methods and conditions generally used in the art, and will not be described herein again.
Step 4)
According to the present invention, in order to obtain a gel-state anode active material layer, the solid-state anode active material layer is brought into contact with a fourth solvent, and the manner of the contact is not particularly limited, and may be, for example, spray coating, dip coating, and drop coating. By contacting the solid negative active material layer with a fourth solvent, the binder in the negative electrode is swollen to form a gel state.
Preferably, in step 4), the fourth solvent is used in an amount of 1 to 23 parts by weight with respect to 100 parts by weight of the solid anode active material layer; more preferably, the fourth solvent is used in an amount of 5 to 20 parts by weight relative to 100 parts by weight of the solid anode active material layer; further preferably, the fourth solvent is used in an amount of 8 to 15 parts by weight relative to 100 parts by weight of the solid anode active material layer; still more preferably, the fourth solvent is used in an amount of 9 to 12 parts by weight with respect to 100 parts by weight of the solid state anode active material layer.
According to the present invention, preferably, the fourth solvent is one or more of an alkane solvent, a benzene solvent and a ketone solvent; more preferably, the fourth solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
Step 5)
According to the invention, the first pressing is preferably an isostatic pressing. Preferably, the conditions of the first pressing include: isostatic pressure of 50-550Mpa, pressure maintaining time of 10-30min, and temperature of 15-100 deg.C.
According to the invention, the second pressing is preferably an isostatic pressing. Preferably, the conditions of the second pressing include: the isostatic pressing pressure is 100-550Mpa, the pressure maintaining time is 10-30min, and the temperature is 15-100 ℃.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
Example 1
1) Coating a first slurry containing a positive electrode active material, a conductive agent, a sulfide electrolyte, a first binder and a first solvent on a positive electrode current collector carbon-coated copper foil, and drying to obtain a positive electrode, wherein the coating weight is 35mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
2) Coating a second slurry containing sulfide, a second binder and a second solvent on an aluminum foil, drying, and removing the aluminum foil to obtain a solid electrolyte layer, wherein the coating amount is 60mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
3) Coating a third slurry containing a negative electrode active material, a third binder, a lithium salt, a conductive agent and a third solvent on the carbon-coated copper foil of the negative electrode current collector, and drying to obtain a negative electrode pole piece, wherein the coating weight is 10mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
4) And contacting the solid negative electrode active material layer on one side of the negative electrode with a fourth solvent to obtain a gel negative electrode active material layer.
5) The positive electrode and the solid electrolyte layer were subjected to isostatic pressing at 25 ℃ for 10min at 500MPa to form a positive electrode/solid electrolyte layer assembly, and then the positive electrode/solid electrolyte layer and the gel-state negative electrode active material layer of the negative electrode were laminated and subjected to isostatic pressing at 100MPa for 5min to obtain a solid-state battery a 1.
The raw materials and the amounts used are shown in table 1, and the composition contents of the positive electrode, the negative electrode, and the solid electrolyte layer are shown in table 2.
Example 2
1) Coating a first slurry containing a positive electrode active material, a conductive agent, a sulfide electrolyte, a first binder and a first solvent on a positive electrode current collector carbon-coated copper foil, and drying to obtain a positive electrode, wherein the coating weight is 30mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
2) Coating the second slurry containing sulfide, the second binder and the second solvent on an aluminum foil, drying, and removing the aluminum foil to obtain a solid electrolyte layer, wherein the coating amount is 58mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
3) Coating a third slurry containing a negative electrode active material, a third binder, a lithium salt, a conductive agent and a third solvent on the carbon-coated copper foil of the negative electrode current collector, and drying to obtain a negative electrode pole piece, wherein the coating weight is 11mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
4) And contacting the solid negative electrode active material layer on one side of the negative electrode with a fourth solvent to obtain a gel negative electrode active material layer.
5) And performing isostatic pressing on the positive electrode and the solid electrolyte layer at 25 ℃ for 500MPa and 10min to form a positive electrode/solid electrolyte layer assembly, and then laminating the gel-state negative electrode active material layer of the positive electrode/solid electrolyte layer assembly/the solid electrolyte layer and the negative electrode and performing isostatic pressing at 100MPa and 5min to obtain the solid battery bare core A2.
The raw materials and the amounts used are shown in table 1, and the composition contents of the positive electrode, the negative electrode, and the solid electrolyte layer are shown in table 2.
Example 3
1) Coating a first slurry containing a positive electrode active material, a conductive agent, a sulfide electrolyte, a first binder and a first solvent on a positive electrode current collector carbon-coated aluminum foil, and drying to obtain a positive electrode, wherein the coating weight is 33mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
2) Coating a second slurry containing sulfide, a second binder and a second solvent on an aluminum foil, drying, and removing the aluminum foil to obtain a solid electrolyte layer, wherein the coating amount is 55mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
3) Will contain a negative electrode active material, a third binderCoating a third slurry of lithium salt, a conductive agent and a third solvent on a negative current collector, and drying to obtain a negative pole piece, wherein the coating weight is 12mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
4) And contacting the solid negative electrode active material layer on one side of the negative electrode with a fourth solvent to obtain a gel negative electrode active material layer.
5) The positive electrode and the solid electrolyte layer were subjected to isostatic pressing at 25 ℃ for 10min at 500MPa to form a positive electrode/solid electrolyte layer assembly, and then the positive electrode/solid electrolyte layer and the gel-state negative electrode active material layer of the negative electrode were laminated and subjected to isostatic pressing at 100MPa for 5min to obtain a solid-state battery a 3.
The raw materials and the amounts used are shown in table 1, and the composition contents of the positive electrode, the negative electrode, and the solid electrolyte layer are shown in table 2.
Example 4
1) Coating a first slurry containing a positive electrode active material, a conductive agent, a sulfide electrolyte, a first binder and a first solvent on a positive electrode current collector carbon-coated aluminum foil, and drying to obtain a positive electrode, wherein the coating weight is 40mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
2) A second slurry containing a sulfide, a second binder, and a second solvent is prepared as a solid electrolyte layer. 4g of sulfide, 0.2g of second binder and 8g of second solvent are stirred into slurry and coated on an aluminum foil, and the drying temperature is 80 ℃ and the drying time is 600 minutes.
3) Coating a third slurry containing a negative electrode active material, a third binder, a lithium salt, a conductive agent and a third solvent on a negative electrode current collector, and drying to obtain a negative electrode plate, wherein the coating weight is 15mg/cm2The drying temperature was 80 ℃ and the drying time was 600 minutes.
4) And contacting the solid negative electrode active material layer on one side of the negative electrode with a fourth solvent to obtain a gel negative electrode active material layer.
5) The positive electrode and the solid electrolyte layer were subjected to isostatic pressing at 25 ℃ for 10min at 500MPa to form a positive electrode/solid electrolyte layer assembly, and then the positive electrode/solid electrolyte layer and the gel-state negative electrode active material layer of the negative electrode were laminated and subjected to isostatic pressing at 100MPa for 5min to obtain a solid-state battery a 4.
The raw materials and the amounts used are shown in table 1, and the composition contents of the positive electrode, the negative electrode, and the solid electrolyte layer are shown in table 2.
Comparative example 1
The procedure of example 1 was followed, except that a third slurry containing a negative active material, a third binder, a lithium salt, a conductive agent and a third solvent was coated on a negative current collector and dried to obtain a negative electrode sheet, wherein the coating amount was 10mg/cm2The temperature of drying was 80 ℃ and the time of drying was 600 minutes, and the step of contacting with the fourth solvent was not performed, to obtain a solid-state battery D1.
The raw materials and the amounts used are shown in table 1, and the composition contents of the positive electrode, the negative electrode, and the solid electrolyte layer are shown in table 2.
TABLE 1
Figure BDA0002655465340000201
Note: "parts" means "parts by weight"
TABLE 2
Figure BDA0002655465340000211
Note: "%" means "% by weight"
Test example
The solid-state batteries obtained in examples 1 to 4 and comparative example 1 were each mounted in a 3Mpa battery holder, subjected to a test at 70 ℃, and subjected to a cycle test at 0.1C, 0.3C rate (1C ═ 380mAh), and having a cut-off voltage of 1V to 4.25V. The results are shown in Table 3.
TABLE 3
Figure BDA0002655465340000212
Table 3 shows that the discharge capacities of the solid-state batteries a1, a2, A3, and a4 at different rates are much higher than that of the solid-state battery of comparative example D1, and in addition, the rate performance of 0.3C/0.1C is greatly improved, so that the technical solution of the present invention can improve the interface contact, rapidly increase the lithium ion conductivity of the system, and reduce the interface impedance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A solid-state lithium battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte layer between the positive electrode and the negative electrode, the positive electrode comprising a positive electrode current collector and a solid-state positive electrode active material layer formed on the positive electrode current collector,
the active material in the solid positive active material layer is selected from LiMO2M is selected from one or more of Co, Ni and Mn;
the solid electrolyte layer contains a sulfide and a binder;
the negative electrode comprises a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector, and the negative electrode active material layer in contact with the solid electrolyte layer is a gel-state negative electrode active material layer.
2. The solid-state lithium battery according to claim 1, wherein the solid-state positive active material layer contains 60 to 85 wt% of the positive active material, 2 to 5 wt% of the first conductive agent, 10 to 30 wt% of the sulfide electrolyte, and 1 to 5 wt% of the first binder;
preferably, the positive current collector is a carbon-coated aluminum foil;
preferably, the LiMO2Is LiCoO2、LiNi1/3Mn1/3Co1/3O2One or more of NCM523, NCM622, and NCM 811;
preferably, the first conductive agent is one or more of SP, CNT, VGCF, silver powder, and aluminum powder;
preferably, the sulfide electrolyte is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of;
preferably, the first binder is one or more of polyvinylidene fluoride and a rubber-based binder.
3. The solid-state lithium battery according to claim 1 or 2, wherein the solid-state electrolyte layer contains a sulfide and a second binder;
preferably, the sulfide is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of;
preferably, the solid electrolyte layer contains 90 to 99 wt% of sulfide and 1 to 10 wt% of the second binder;
preferably, the second binder is one or more of polyvinylidene fluoride and a rubber-based binder.
4. The solid-state lithium battery according to any one of claims 1 to 3, wherein the negative active material layer includes a negative active material, a third binder, a lithium salt, a second conductive agent, and an organic solvent;
preferably, the negative active material layer contains 40-90 wt% of a negative active material, 1-15% of a second binder, 1-15% of a lithium salt, 1-10% of a second conductive agent, and 10-20% of an organic solvent;
preferably, the negative active material is one or more of graphite, silicon monoxide, elemental silicon, carbon-coated silicon and graphene-coated silicon;
preferably, the negative electrode current collector is a carbon-coated copper foil;
preferably, the third binder is one or more of polyvinylidene fluoride and a rubber-based binder;
preferably, the lithium salt is LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4And LiBOB;
preferably, the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder;
preferably, the organic solvent is one or more of alkane solvents, benzene solvents and ketone solvents;
preferably, the organic solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
5. A method for manufacturing a solid-state lithium battery, comprising the steps of,
1) coating a first slurry containing a positive electrode active material, a first conductive agent, a sulfide electrolyte, a binder and a first solvent on a positive electrode current collector, and drying to obtain a positive electrode;
2) preparing a second slurry containing sulfide, a second binder and a second solvent into a solid electrolyte layer;
3) coating a third slurry containing a negative electrode active material, a third binder, a lithium salt, a second conductive agent and a third solvent on a negative electrode current collector, and drying to obtain a negative electrode with a solid negative electrode active material layer formed on the negative electrode current collector;
4) contacting the solid negative active material layer on at least one side of the negative electrode with a fourth solvent to obtain a gel negative active material layer;
5) subjecting the positive electrode and the solid electrolyte layer to a first pressing to form a positive electrode/solid electrolyte layer assembly, then laminating the positive electrode/solid electrolyte layer assembly/solid electrolyte layer and a gel state negative electrode active material layer of the negative electrode and performing a second pressing,
wherein the positive electrode active material is selected from LiMO2M is selected from one or more of Co, Ni and Mn.
6. The method according to claim 5, wherein, in the first slurry, the content of the positive electrode active material is 60 to 85 wt%, the content of the first conductive agent is 2 to 5 wt%, the content of the sulfide electrolyte is 10 to 30 wt%, and the content of the first binder is 1 to 5 wt%, based on the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte, and the first binder;
preferably, the first solvent is used in an amount of 100-600 parts by weight, relative to 100 parts by weight of the total amount of the positive electrode active material, the first conductive agent, the sulfide electrolyte and the first binder;
preferably, the positive current collector is a carbon-coated aluminum foil;
preferably, the LiMO2Is LiCoO2、LiNi1/3Mn1/3Co1/3O2One or more of NCM523, NCM622, and NCM 811;
preferably, the first conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder;
preferably, the sulfide electrolyte is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of;
preferably, the first binder is one or more of polyvinylidene fluoride and rubber-based binder;
preferably, the first solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
7. The method according to claim 5 or 6, wherein in the second slurry, the sulfide content is 90-99 wt% and the second binder content is 1-10 wt%, based on the total amount of sulfide and second binder;
preferably, the second solvent is used in an amount of 100-600 parts by weight, relative to 100 parts by weight of the total amount of sulfide and second binder;
preferably, the sulfide is thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2And Li2S-B2S3One or more of;
preferably, the second binder is one or more of polyvinylidene fluoride and rubber-based binder;
preferably, the second solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
8. The method according to any one of claims 5 to 8, wherein, in the third slurry, the content of the negative active material is 40 to 90 wt%, the content of the third binder is 1 to 15 wt%, the content of the lithium salt is 1 to 15 wt%, and the content of the second conductive agent is 1 to 15 wt%, based on the total amount of the negative active material, the third binder, the lithium salt, and the second conductive agent;
preferably, the third solvent is used in an amount of 100-600 parts by weight, relative to 100 parts by weight of the total amount of the anode active material, the third binder, the lithium salt and the second conductive agent;
preferably, the negative active material is one or more of graphite, silicon monoxide, elemental silicon, carbon-coated silicon and graphene-coated silicon;
preferably, the negative electrode current collector is a carbon-coated copper foil;
preferably, the third binder is one or more of polyvinylidene fluoride and a rubber-based binder;
preferably, the lithium salt is LiTFSI, LiFSI, liddob, LiPF6、LiBF4、LiClO4And LiBOB;
preferably, the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder;
preferably, the third solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
9. The method according to any one of claims 5 to 8, wherein, in step 4), the fourth solvent is used in an amount of 1 to 23 parts by weight relative to 100 parts by weight of the solid anode active material layer;
preferably, the fourth solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane and methylformamide.
10. The method of any one of claims 5-8, wherein the conditions of the first pressing comprise: isostatic pressure of 50-550Mpa, pressure maintaining time of 10-30min, and temperature of 15-100 deg.C;
preferably, the conditions of the second pressing include: the isostatic pressing pressure is 100-550Mpa, the pressure maintaining time is 10-30min, and the temperature is 15-100 ℃.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112599846A (en) * 2020-12-24 2021-04-02 蜂巢能源科技有限公司 Composite electrolyte membrane for all-solid-state lithium metal negative electrode battery, preparation method of composite electrolyte membrane and all-solid-state sulfide lithium ion battery comprising composite electrolyte membrane
CN113659218A (en) * 2021-08-12 2021-11-16 湖南金硅科技有限公司 High-capacity and high-magnification cylindrical lithium ion battery and preparation method thereof
CN113764625A (en) * 2021-08-26 2021-12-07 蜂巢能源科技有限公司 Sulfide silicon-based negative plate, preparation method thereof and all-solid-state lithium ion battery
CN114447406A (en) * 2022-01-28 2022-05-06 蜂巢能源科技(无锡)有限公司 All-solid-state battery cell, preparation method thereof and all-solid-state battery
WO2022205668A1 (en) * 2021-03-29 2022-10-06 万向一二三股份公司 High-nickel ternary composite positive electrode containing solid electrolyte, and lithium ion battery

Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0757731A (en) * 1993-08-19 1995-03-03 Toshiba Battery Co Ltd Alkaline battery
US20020004171A1 (en) * 2000-03-06 2002-01-10 Takaaki Kimijima Nonaqueous electrolyte secondary battery and method of manufacturing the same
JP2004171995A (en) * 2002-11-21 2004-06-17 Mitsubishi Heavy Ind Ltd Lithium secondary battery, and manufacturing method of lithium secondary battery
CN1724585A (en) * 2004-07-23 2006-01-25 上海南都能源科技有限公司 Polyvinildene difluoride copolymer gel state electrolyte film and its preparation technology
CN1838470A (en) * 2006-03-15 2006-09-27 上海南都能源科技有限公司 Gel synergizing type polymer lithium ion battery and preparation method thereof
KR100721215B1 (en) * 2006-12-29 2007-05-23 주식회사 젠트로 Method for repairing and reinforcing damage of reinforced concrete using gel-type sacrificial anode and waterproof material having exellent insulating properties
CN101127392A (en) * 2006-08-17 2008-02-20 李鑫 A secure lithium ion electric core and its making method
CN101312257A (en) * 2007-05-23 2008-11-26 索尼株式会社 Gel electrolyte secondary battery
CN101347726A (en) * 2008-08-22 2009-01-21 中国石化扬子石油化工有限公司 Process for preparing catalyst Pd/TiO2 for hydrogenation of p-carboxybenzaldehyde
CN102195087A (en) * 2010-03-02 2011-09-21 索尼公司 Nonaqueous electrolyte composition and nonaqueous electrolyte battery
CN103367798A (en) * 2012-04-02 2013-10-23 三星精密化学株式会社 Electrolyte for lithium ion secondary battery and lithium ion secondary battery
US20140065489A1 (en) * 2012-08-28 2014-03-06 Honda Motor Co., Ltd. Electrolyte-negative electrode structure, and lithium ion secondary battery comprising the same
US20150037655A1 (en) * 2012-03-28 2015-02-05 Ocean's King Lighting Science & Technology Co., Ltd. Solid electrolyte battery
WO2015151145A1 (en) * 2014-03-31 2015-10-08 株式会社日立製作所 All-solid lithium secondary cell
CN105006592A (en) * 2015-07-22 2015-10-28 成都英诺科技咨询有限公司 Gel electrolyte lithium ion battery with composite electrode and preparation method thereof
US20160268627A1 (en) * 2015-03-09 2016-09-15 Hyundai Motor Company All-solid-state battery containing nano-solid electrolyte and method of manufacturing the same
CN107204483A (en) * 2016-03-16 2017-09-26 株式会社东芝 Nonaqueous electrolyte battery, battery bag and vehicle
CN107665994A (en) * 2016-07-29 2018-02-06 比亚迪股份有限公司 A kind of negative material and preparation method thereof, negative pole and all-solid lithium-ion battery
CN108232318A (en) * 2018-01-30 2018-06-29 陕西煤业化工技术研究院有限责任公司 A kind of production method of all solid state power lithium-ion battery
CN109066020A (en) * 2018-08-02 2018-12-21 云南经济管理学院 A kind of novel semisolid sodium air cell and preparation method thereof
CN109786675A (en) * 2018-12-28 2019-05-21 中国电子科技集团公司第十八研究所 Interface modification method for metal lithium cathode of solid-state lithium battery
CN109841913A (en) * 2017-11-27 2019-06-04 丰田自动车株式会社 The manufacturing method of nonaqueous electrolytic solution secondary battery
CN110311109A (en) * 2019-06-28 2019-10-08 徐州硕祥信息科技有限公司 A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material
CN110518283A (en) * 2019-09-12 2019-11-29 深圳先进技术研究院 Solid state secondary battery and its preparation process, electric car
US10595868B2 (en) * 2003-04-28 2020-03-24 Vascular Graft Colutions Ltd. Graft apparatus
CN111430667A (en) * 2019-12-31 2020-07-17 蜂巢能源科技有限公司 Negative electrode slurry, negative electrode plate, power battery and electric automobile

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0757731A (en) * 1993-08-19 1995-03-03 Toshiba Battery Co Ltd Alkaline battery
US20020004171A1 (en) * 2000-03-06 2002-01-10 Takaaki Kimijima Nonaqueous electrolyte secondary battery and method of manufacturing the same
JP2004171995A (en) * 2002-11-21 2004-06-17 Mitsubishi Heavy Ind Ltd Lithium secondary battery, and manufacturing method of lithium secondary battery
US10595868B2 (en) * 2003-04-28 2020-03-24 Vascular Graft Colutions Ltd. Graft apparatus
CN1724585A (en) * 2004-07-23 2006-01-25 上海南都能源科技有限公司 Polyvinildene difluoride copolymer gel state electrolyte film and its preparation technology
CN1838470A (en) * 2006-03-15 2006-09-27 上海南都能源科技有限公司 Gel synergizing type polymer lithium ion battery and preparation method thereof
CN101127392A (en) * 2006-08-17 2008-02-20 李鑫 A secure lithium ion electric core and its making method
KR100721215B1 (en) * 2006-12-29 2007-05-23 주식회사 젠트로 Method for repairing and reinforcing damage of reinforced concrete using gel-type sacrificial anode and waterproof material having exellent insulating properties
CN101312257A (en) * 2007-05-23 2008-11-26 索尼株式会社 Gel electrolyte secondary battery
US20080292969A1 (en) * 2007-05-23 2008-11-27 Sony Corporation Gel electrolyte secondary battery
CN101347726A (en) * 2008-08-22 2009-01-21 中国石化扬子石油化工有限公司 Process for preparing catalyst Pd/TiO2 for hydrogenation of p-carboxybenzaldehyde
CN102195087A (en) * 2010-03-02 2011-09-21 索尼公司 Nonaqueous electrolyte composition and nonaqueous electrolyte battery
US20150037655A1 (en) * 2012-03-28 2015-02-05 Ocean's King Lighting Science & Technology Co., Ltd. Solid electrolyte battery
CN103367798A (en) * 2012-04-02 2013-10-23 三星精密化学株式会社 Electrolyte for lithium ion secondary battery and lithium ion secondary battery
US20140065489A1 (en) * 2012-08-28 2014-03-06 Honda Motor Co., Ltd. Electrolyte-negative electrode structure, and lithium ion secondary battery comprising the same
WO2015151145A1 (en) * 2014-03-31 2015-10-08 株式会社日立製作所 All-solid lithium secondary cell
US20160268627A1 (en) * 2015-03-09 2016-09-15 Hyundai Motor Company All-solid-state battery containing nano-solid electrolyte and method of manufacturing the same
CN105958116A (en) * 2015-03-09 2016-09-21 现代自动车株式会社 All-solid-state battery containing nano-solid electrolyte and method of manufacturing the same
CN105006592A (en) * 2015-07-22 2015-10-28 成都英诺科技咨询有限公司 Gel electrolyte lithium ion battery with composite electrode and preparation method thereof
CN107204483A (en) * 2016-03-16 2017-09-26 株式会社东芝 Nonaqueous electrolyte battery, battery bag and vehicle
CN107665994A (en) * 2016-07-29 2018-02-06 比亚迪股份有限公司 A kind of negative material and preparation method thereof, negative pole and all-solid lithium-ion battery
CN109841913A (en) * 2017-11-27 2019-06-04 丰田自动车株式会社 The manufacturing method of nonaqueous electrolytic solution secondary battery
CN108232318A (en) * 2018-01-30 2018-06-29 陕西煤业化工技术研究院有限责任公司 A kind of production method of all solid state power lithium-ion battery
CN109066020A (en) * 2018-08-02 2018-12-21 云南经济管理学院 A kind of novel semisolid sodium air cell and preparation method thereof
CN109786675A (en) * 2018-12-28 2019-05-21 中国电子科技集团公司第十八研究所 Interface modification method for metal lithium cathode of solid-state lithium battery
CN110311109A (en) * 2019-06-28 2019-10-08 徐州硕祥信息科技有限公司 A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material
CN110518283A (en) * 2019-09-12 2019-11-29 深圳先进技术研究院 Solid state secondary battery and its preparation process, electric car
CN111430667A (en) * 2019-12-31 2020-07-17 蜂巢能源科技有限公司 Negative electrode slurry, negative electrode plate, power battery and electric automobile

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张德宾 等: "聚偏氟乙烯在锂离子电池中的应用", 《山东化工》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112599846A (en) * 2020-12-24 2021-04-02 蜂巢能源科技有限公司 Composite electrolyte membrane for all-solid-state lithium metal negative electrode battery, preparation method of composite electrolyte membrane and all-solid-state sulfide lithium ion battery comprising composite electrolyte membrane
WO2022205668A1 (en) * 2021-03-29 2022-10-06 万向一二三股份公司 High-nickel ternary composite positive electrode containing solid electrolyte, and lithium ion battery
CN113659218A (en) * 2021-08-12 2021-11-16 湖南金硅科技有限公司 High-capacity and high-magnification cylindrical lithium ion battery and preparation method thereof
CN113764625A (en) * 2021-08-26 2021-12-07 蜂巢能源科技有限公司 Sulfide silicon-based negative plate, preparation method thereof and all-solid-state lithium ion battery
CN114447406A (en) * 2022-01-28 2022-05-06 蜂巢能源科技(无锡)有限公司 All-solid-state battery cell, preparation method thereof and all-solid-state battery
CN114447406B (en) * 2022-01-28 2023-05-05 蜂巢能源科技(无锡)有限公司 All-solid-state battery cell, preparation method thereof and all-solid-state battery

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