CN112072164B - Solid lithium battery and preparation method thereof - Google Patents

Solid lithium battery and preparation method thereof Download PDF

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Publication number
CN112072164B
CN112072164B CN202010885545.0A CN202010885545A CN112072164B CN 112072164 B CN112072164 B CN 112072164B CN 202010885545 A CN202010885545 A CN 202010885545A CN 112072164 B CN112072164 B CN 112072164B
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active material
binder
positive electrode
negative electrode
solid
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CN112072164A (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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    • 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 electrolyte layer between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode current collector and a solid positive electrode active material layer formed on the positive electrode current collector, and is characterized in that the active material in the solid positive electrode active material layer is selected from LiMO 2 M is selected from one or more of Co, ni and Mn; the solid electrolyte layer contains sulfide and a binder; the negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector, and at least the negative electrode active material layer in contact with the solid electrolyte layer is a gel-state negative electrode active material layer. The invention can provide a novel solid-state lithium battery which can improve interface contact, can rapidly improve the lithium ion conductivity of a system and reduce interface impedance.

Description

Solid 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 the nonflammable solid electrolyte to replace the flammable organic liquid electrolyte, so that the safety of the battery system is greatly improved, meanwhile, the high-energy anode and the high-energy 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 industrialization, which has become a consensus of industry and scientific community.
At present, the solid-state lithium battery is generally prepared by adopting an interface improvement mode by mixing an inorganic oxide electrolyte or a polymer electrolyte with a liquid electrolyte, but as the ion conductivity of the inorganic oxide electrolyte and the ion conductivity of the polymer electrolyte are lower, more liquid electrolytes are needed to be added to improve the internal resistance and the conductivity of the whole battery, and the addition of more liquid electrolytes is not beneficial to the improvement of the overall safety of the solid-state lithium battery. In theory, an all-solid-state lithium battery without any electrolyte component has the highest safety, but the solid-state system has a relatively large interface problem as a whole due to solid-solid connection among particles formed by all inorganic particles, and very large pressure needs to be applied to directly influence the use condition, the battery multiplying power and the cycle performance of the battery. How to improve the interface while maintaining high safety has therefore 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, rapidly improve lithium ion conductivity of a system and reduce interface impedance aiming at the defects and the shortcomings of the existing solid-state battery interface fusion technology.
In order to achieve the above object, an aspect of the present invention provides a solid lithium battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer between the positive electrode and the negative electrode, the positive electrode comprising a positive electrode current collector and a solid positive electrode active material layer formed on the positive electrode current collector, wherein an active material in the solid positive electrode active material layer is selected from LiMO 2 M is selected from one or more of Co, ni and Mn; the solid electrolyte layer contains sulfide and a binder; the negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector, and at least 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 cathode active material layer contains 60 to 85 wt% of the cathode 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 carbon-coated aluminum foil.
Preferably, the LiMO 2 Is LiCoO 2 、LiNi 1/3 Mn 1/3 Co 1/3 O 2 One 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, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
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, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
Preferably, the solid electrolyte layer contains 90 to 99 wt% of sulfide and 1 to 10 wt% of a second binder.
Preferably, the second binder is one or more of polyvinylidene fluoride and a rubber-based binder.
Preferably, the anode active material layer includes an anode active material, a third binder, a lithium salt, a second conductive agent, and an organic solvent.
Preferably, the anode active material layer contains 40 to 90 wt% of an anode active material, 1 to 15% of a second binder, 1 to 15% of a lithium salt, 1 to 10% of a second conductive agent, and 10 to 20% of an organic solvent.
Preferably, the negative electrode active material is one or more of graphite, silicon oxide, 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, liDFOB, liPF 6 、LiBF 4 、LiClO 4 And 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 preparing 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, 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-state anode active material layer on at least one side of the anode with a fourth solvent to obtain a gel-state anode active material layer;
5) First pressing the positive electrode and the solid electrolyte layer to form a positive electrode/solid electrolyte layer assembly, then laminating the gel-state negative electrode active material layer of the positive electrode/solid electrolyte layer assembly and the gel-state negative electrode active material layer of the negative electrode and performing second pressing,
wherein the positive electrode active material is selected from LiMO 2 M 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 to 600 parts by weight with respect 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 carbon-coated aluminum foil.
Preferably, the LiMO 2 Is LiCoO 2 、LiNi 1/3 Mn 1/3 Co 1/3 O 2 One 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, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
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 content of the sulfide is 90 to 99% by weight and the content of the second binder is 1 to 10% by weight, based on the total amount of the sulfide and the second binder.
Preferably, the second solvent is used in an amount of 100 to 600 parts by weight with respect to 100 parts by weight of the total amount of sulfide and second binder.
Preferably, the sulfide is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
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 anode 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 anode active material, the third binder, the lithium salt, and the second conductive agent.
Preferably, the third solvent is used in an amount of 100 to 600 parts by weight with respect 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 electrode active material is one or more of graphite, silicon oxide, 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, liDFOB, liPF 6 、LiBF 4 、LiClO 4 And 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-state 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: the isostatic pressure is 50-550Mpa, the dwell time is 10-30min, and the temperature is 15-100 ℃.
Preferably, the conditions of the second pressing include: the temperature isostatic pressure is 100-550Mpa, the pressure maintaining time is 10-30min, and the temperature is 15-100 ℃.
Through the technical scheme, the novel solid-state lithium battery can improve interface contact, can rapidly improve lithium ion conductivity of a system and reduce interface impedance.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to 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 electrolyte layer formed on the positive electrode current collector, a negative electrode, and a solid-state electrolyte layer between the positive electrode and the negative electrodeA solid positive electrode active material layer, wherein the active material in the solid positive electrode active material layer is selected from LiMO 2 M is selected from one or more of Co, ni and Mn; the solid electrolyte layer contains sulfide and a binder; the negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector, and at least 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 invention, by using a specific sulfide solid-state electrolyte layer and making the anode active material layer in contact with the solid-state electrolyte layer a gel-state anode active material layer, not only can the battery interface contact be improved, but also the lithium ion conductivity of the system can be rapidly improved and the interface resistance can be reduced.
According to the present invention, it is preferable that the solid-state positive electrode active material layer contains 60 to 85% by weight of a positive electrode active material, 2 to 5% by weight of a first conductive agent, 10 to 30% by weight of a sulfide electrolyte, and 1 to 5% by weight of a first binder, in view of being capable of further rapidly improving the lithium ion conductivity of the system and reducing the interface resistance; more preferably, the solid-state positive electrode active material layer contains 70 to 85 wt% of a positive electrode active material, 3 to 5 wt% of a first conductive agent, 15 to 30 wt% of a sulfide electrolyte, and 2 to 4 wt% of a first binder; further preferably, the solid cathode active material layer contains 75 to 80 wt% of a cathode active material, 3 to 4 wt% of a first conductive agent, 15 to 20 wt% of a sulfide electrolyte, and 2 to 3 wt% of a first binder.
In a particularly preferred embodiment of the present invention, the solid-state 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 metal sheets commonly used as positive electrode current collectors in the art may be used. Preferably, the positive electrode current collector is carbon-coated aluminum foil.
According to the invention, preference is given toThe LiMO is 2 Is LiCoO 2 、LiNi 1/3 Mn 1/3 Co 1/3 O 2 One or more of NCM523, NCM622, and NCM 811. 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 commonly 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 present invention, preferably, the sulfide electrolyte is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following; more preferably, the sulfide is Li 10 GeP 2 S 12 、Li 6 PS 5 Cl and Li 2 S-P 2 S 5 One or more of the following.
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. In addition, the molecular weight of the first binder is preferably 20 to 500 ten thousand.
According to the invention, the solid electrolyte layer contains a sulfide and a second binder. Preferably, the sulfide is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following; more preferably, the sulfide is Li 10 GeP 2 S 12 、Li 6 PS 5 Cl and Li 2 S-P 2 S 5 One or more of (a)A kind of module is assembled in the module and the module is assembled in the module.
According to the present invention, preferably, the solid electrolyte layer contains 90 to 99 wt% of sulfide and 1 to 10 wt% of a second binder; more preferably, the solid electrolyte layer contains 95 to 99 wt% sulfide and 1 to 2 wt% second binder.
In a particularly preferred embodiment of the invention, the solid electrolyte layer contains 98 wt.% sulfide and 2 wt.% secondary 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. In addition, the weight average molecular weight of the second binder is preferably 20 to 500 ten thousand.
According to the present invention, the anode active material layer includes an anode active material, a third binder, a lithium salt, a second conductive agent, and an organic solvent. Preferably, the anode active material layer contains 40 to 90 wt% of an anode 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 anode active material layer contains 40 to 90 wt% of an anode 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 anode active material layer contains 40 to 90 wt% of an anode 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 anode active material layer contains 60 to 90 wt% of an anode 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 anode active material layer contains 65 to 75 wt% of an anode 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 anode active material is one or more of graphite, silicon oxide, elemental silicon, carbon-coated silicon, and graphene-coated silicon; more preferably, the negative active material is one or more of graphite, silicon oxide, and elemental silicon.
According to the present invention, the negative electrode current collector is not particularly limited, and various metal sheets commonly 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. In addition, the 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 commonly used in the art for lithium batteries. Preferably, the lithium salt is LiTFSI, liFSI, liDFOB, liPF 6 、LiBF 4 、LiClO 4 And LiBOB: more preferably, the lithium salt is one or more of LiTFSI, liFSI and lidaob.
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 preparing 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, 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-state anode active material layer on at least one side of the anode with a fourth solvent to obtain a gel-state anode active material layer;
5) First pressing the positive electrode and the solid electrolyte layer to form a positive electrode/solid electrolyte layer assembly, then laminating the gel-state negative electrode active material layer of the positive electrode/solid electrolyte layer assembly and the gel-state negative electrode active material layer of the negative electrode and performing second pressing,
wherein the positive electrode active material is selected from LiMO 2 M 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% by weight, the content of the first conductive agent is 2 to 5% by weight, the content of the sulfide electrolyte is 10 to 30% by weight, and the content of the first binder is 1 to 5% by weight, 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 wt%, the content of the first conductive agent is 4 wt%, the content of the sulfide electrolyte is 15 wt%, and the content of the first binder is 2 wt%, 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 to 600 parts by weight, more preferably 150 to 500 parts by weight, still more preferably 200 to 400 parts by weight, particularly preferably 200 to 300 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.
According to the present invention, the positive electrode current collector is not particularly limited, and various metal sheets commonly used as positive electrode current collectors in the art may be used. Preferably, the positive electrode current collector is carbon-coated aluminum foil.
According to the present invention, preferably, the LiMO 2 Is LiCoO 2 、LiNi 1/3 Mn 1/3 Co 1/3 O 2 One or more of NCM523, NCM622, and NCM 811. 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 commonly 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 present invention, preferably, the sulfide electrolyte is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following; more preferably, the sulfide is Li 10 GeP 2 S 12 、Li 6 PS 5 Cl and Li 2 S-P 2 S 5 One or more of the following.
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. In addition, 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 a method of applying the first paste on the positive electrode current collector and drying, various methods and conditions commonly used in the art may be employed, and will not be described again.
Step 2)
According to the present invention, preferably, in the second slurry, the content of the sulfide is 90 to 99% by weight, and the content of the second binder is 1 to 10% by weight, based on the total amount of the sulfide and the second binder; preferably, the sulfide is contained in an amount of 95 to 99 wt% and the second binder is contained in an amount of 1 to 5 wt%.
In a particularly preferred embodiment of the invention, the sulphide content is 98% by weight and the second binder content 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 second solvent is used in an amount of 200 to 600 parts by weight, more preferably 300 to 500 parts by weight, still more preferably 350 to 500 parts by weight, particularly preferably 400 to 500 parts by weight, relative to 100 parts by weight of the total amount of sulfide and second binder.
According to the present invention, preferably, the sulfide is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following; more preferably, the sulfide is Li 10 GeP 2 S 12 、Li 6 PS 5 Cl and Li 2 S-P 2 S 5 One or more of the following.
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. In addition, 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.
The method of preparing the second slurry containing sulfide, the second binder and the second solvent into the solid electrolyte layer according to the present invention may employ methods and conditions generally used in the art, for example, a method of coating the second slurry containing sulfide, the second binder and the second solvent on an aluminum foil and drying the same may be used.
Step 3)
According to the present invention, preferably, in the third slurry, the content of the anode 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 anode active material, the third binder, the lithium salt, and the second conductive agent; preferably, the content of the anode 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 anode active material, the third binder, the lithium salt, and the second conductive agent; further preferably, the content of the anode 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 anode active material, the third binder, the lithium salt, and the second conductive agent; further preferably, the content of the anode 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 anode 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 to 600 parts by weight, more preferably 100 to 300 parts by weight, still more preferably 100 to 200 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.
According to the present invention, preferably, the anode active material is one or more of graphite, silicon oxide, elemental silicon, carbon-coated silicon, and graphene-coated silicon; more preferably, the negative active material is one or more of graphite, silicon oxide, and elemental silicon.
According to the present invention, the negative electrode current collector is not particularly limited, and various metal sheets commonly 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. In addition, 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 commonly used in the art for lithium batteries. Preferably, the lithium salt is LiTFSI, liFSI, liDFOB, liPF 6 、LiBF 4 、LiClO 4 And LiBOB: more preferably, the lithium salt is one or more of LiTFSI, liFSI and lidaob.
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.
The method and conditions for applying the third slurry on the negative electrode current collector and drying the same according to the present invention may employ methods and conditions generally used in the art, and will not be described here.
Step 4)
According to the present invention, in order to obtain the gel-state anode active material layer, the solid-state anode active material layer is brought into contact with the fourth solvent, and the manner of contact is not particularly limited, and may be, for example, spray coating, dip coating, and drop coating. The binder in the anode is swelled to form a gel state by contacting the solid anode active material layer with a fourth solvent.
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-state anode active material layer; more preferably, the fourth solvent is used in an amount of 5 to 20 parts by weight with respect to 100 parts by weight of the solid-state 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-state 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 press is preferably an isostatic press. Preferably, the conditions of the first pressing include: the isostatic pressure is 50-550Mpa, the dwell time is 10-30min, and the temperature is 15-100 ℃.
According to the invention, the second press is preferably an isostatic press. Preferably, the conditions of the second pressing include: the temperature isostatic 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 by way of examples, but the present invention is not limited to the following examples.
Example 1
1) A first slurry containing a positive electrode active material, a conductive agent, a sulfide electrolyte, a first binder and a first solvent is coated on a carbon-coated copper foil of a positive electrode current collector, and dried to obtain a positive electrode, wherein the coating amount is 35mg/cm 2 The 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 the aluminum foil, drying, and removing the aluminum foil to obtain a solid electrolyte layer, wherein the coating amount is 60mg/cm 2 The 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, lithium salt, a conductive agent and a third solvent on a carbon-coated copper foil of a negative electrode current collector, and drying to obtain a negative electrode plate, wherein the coating amount is 10mg/cm 2 The drying temperature was 80℃and the drying time was 600 minutes.
4) And contacting the solid-state anode active material layer on one side of the anode with a fourth solvent to obtain a gel-state anode active material layer.
5) And carrying out isostatic pressing on the positive electrode and the solid electrolyte layer for 500MPa and 10min at the temperature of 25 ℃ to form a positive electrode/solid electrolyte layer assembly, and then laminating the gel-state negative electrode active material layers of the positive electrode/solid electrolyte layer assembly/solid electrolyte layer and the negative electrode, and carrying out isostatic pressing on the gel-state negative electrode active material layers for 100MPa and 5min to obtain the solid-state battery A1.
The raw materials and the amounts thereof 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) A first slurry containing a positive electrode active material, a conductive agent, a sulfide electrolyte, a first binder and a first solvent is coated on a carbon-coated copper foil of a positive electrode current collector, and dried to obtain a positive electrode, wherein the coating amount is 30mg/cm 2 The 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 the aluminum foil, drying, and removing the aluminum foil to obtain a solid electrolyte layer, wherein the coating amount is 58mg/cm 2 The 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, lithium salt, a conductive agent and a third solvent on a carbon-coated copper foil of a negative electrode current collector, and drying to obtain a negative electrode plate, wherein the coating amount is 11mg/cm 2 The drying temperature was 80℃and the drying time was 600 minutes.
4) And contacting the solid-state anode active material layer on one side of the anode with a fourth solvent to obtain a gel-state anode active material layer.
5) And carrying out isostatic pressing on the positive electrode and the solid electrolyte layer for 500MPa and 10min at the temperature of 25 ℃ to form a positive electrode/solid electrolyte layer assembly, and then laminating the gel-state negative electrode active material layers of the positive electrode/solid electrolyte layer assembly/solid electrolyte layer and the negative electrode, and carrying out isostatic pressing on the gel-state negative electrode active material layers for 100MPa and 5min to obtain the solid-state battery bare core A2.
The raw materials and the amounts thereof 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) A first slurry containing a positive electrode active material, a conductive agent, a sulfide electrolyte, a first binder and a first solvent is coated on a carbon-coated aluminum foil of a positive electrode current collector, and dried to obtain a positive electrode, wherein the coating amount is 33mg/cm 2 The 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 the aluminum foil, drying, and removing the aluminum foil to obtain a solid electrolyte layer, wherein the coating amount is 55mg/cm 2 The 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, 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 amount is 12mg/cm 2 The drying temperature was 80℃and the drying time was 600 minutes.
4) And contacting the solid-state anode active material layer on one side of the anode with a fourth solvent to obtain a gel-state anode active material layer.
5) And carrying out isostatic pressing on the positive electrode and the solid electrolyte layer for 500MPa and 10min at the temperature of 25 ℃ to form a positive electrode/solid electrolyte layer assembly, and then laminating the gel-state negative electrode active material layers of the positive electrode/solid electrolyte layer assembly/solid electrolyte layer and the negative electrode, and carrying out isostatic pressing on the gel-state negative electrode active material layers for 100MPa and 5min to obtain the solid-state battery A3.
The raw materials and the amounts thereof 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) Comprises positive electrode active material, conductive agent, sulfide electrolyte, first binder and first solventThe first sizing agent of the anode current collector is coated on carbon-coated aluminum foil and dried to obtain the anode, wherein the coating amount is 40mg/cm 2 The 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 into a solid electrolyte layer. 4g of sulfide, 0.2g of second binder, 8g of second solvent are stirred into a slurry, coated on an aluminum foil, dried at 80 ℃ for 600 minutes.
3) Coating a third slurry containing a negative electrode active material, a third binder, 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 amount is 15mg/cm 2 The drying temperature was 80℃and the drying time was 600 minutes.
4) And contacting the solid-state anode active material layer on one side of the anode with a fourth solvent to obtain a gel-state anode active material layer.
5) And carrying out isostatic pressing on the positive electrode and the solid electrolyte layer for 500MPa and 10min at the temperature of 25 ℃ to form a positive electrode/solid electrolyte layer assembly, and then laminating the gel-state negative electrode active material layers of the positive electrode/solid electrolyte layer assembly/solid electrolyte layer and the negative electrode, and carrying out isostatic pressing on the gel-state negative electrode active material layers for 100MPa and 5min to obtain the solid-state battery A4.
The raw materials and the amounts thereof 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 process was conducted in accordance with example 1, except that a third slurry containing a negative electrode active material, a third binder, a lithium salt, a conductive agent and a third solvent was coated on a negative electrode current collector, and dried to obtain a negative electrode sheet, wherein the coating amount was 10mg/cm 2 The drying temperature was 80 deg.c and the drying time 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 thereof 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 that: "parts" means "parts by weight"
TABLE 2
Figure BDA0002655465340000211
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Note that: "%" means "% by weight"%;
test case
The solid-state batteries obtained in examples 1 to 4 and comparative example 1 were each mounted in a 3Mpa battery holder, tested at 70C, and subjected to a 0.1C,0.3C rate cycle test (1c=380 mAh) with a cut-off voltage of 1V to 4.25V. The results are shown in Table 3.
TABLE 3 Table 3
Figure BDA0002655465340000212
It can be seen from table 3 that the discharge capacity of the solid-state batteries A1, A2, A3 and A4 at different rates is far higher than that of the solid-state battery of comparative example D1, and in addition, the rate performance of 0.3C/0.1C is also greatly improved, so that by the technical scheme of the invention, the interface contact can be improved, the lithium ion conductivity of the system can be rapidly improved, and the interface impedance can be reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (43)

1. A solid-state lithium battery comprising a positive electrode, a negative electrode, and a solid electrolyte layer between the positive electrode and the negative electrode, the positive electrode comprising a positive electrode current collector and a solid positive electrode active material layer formed on the positive electrode current collector, characterized in that,
the active material in the solid positive electrode active material layer is selected from LiMO 2 M is selected from one or more of Co, ni and Mn;
the solid electrolyte layer contains 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, wherein the negative electrode active material layer contacted with the solid electrolyte layer is a gel-state negative electrode active material layer,
the anode active material layer contains 40-90 wt% of anode active material, 1-15 wt% of third binder, 1-15 wt% of lithium salt, 1-10 wt% of second conductive agent and 10-20 wt% of organic solvent,
The negative electrode active material is one or more of graphite, silicon oxide, simple substance silicon, carbon coated silicon and graphene coated silicon.
2. The solid state lithium battery of claim 1, wherein the solid state positive electrode active material layer contains 60-85 wt% of positive electrode active material, 2-5 wt% of first conductive agent, 10-30 wt% of sulfide electrolyte, and 1-5 wt% of first binder.
3. The solid state lithium battery of claim 1, wherein the positive electrode current collector is a carbon coated aluminum foil.
4. The solid state lithium battery of claim 1, wherein the LiMO 2 Is LiCoO 2 、LiNi 1/3 Mn 1/3 Co 1/3 O 2 One or more of NCM523, NCM622, and NCM 811.
5. The solid state lithium battery of claim 2, wherein the first conductive agent is one or more of SP, CNT, VGCF, silver powder, and aluminum powder.
6. The solid state lithium battery of claim 2, wherein the sulfide electrolyte is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
7. The solid state lithium battery of claim 2, wherein the first binder is one or more of polyvinylidene fluoride and a rubber-based binder.
8. The solid state lithium battery of claim 1 or 2, wherein the solid state electrolyte layer contains a sulfide and a second binder.
9. The solid state lithium battery of claim 8, wherein the sulfide is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
10. The solid state lithium battery of claim 8, wherein the solid state electrolyte layer contains 90-99 wt% sulfide and 1-10 wt% second binder.
11. The solid state lithium battery of claim 10, wherein the second binder is one or more of polyvinylidene fluoride and a rubber-based binder.
12. The solid state lithium battery of claim 1, wherein the negative current collector is a carbon coated copper foil.
13. The solid state lithium battery of claim 1, wherein the third binder is one or more of polyvinylidene fluoride and a rubber-based binder.
14. The solid state lithium battery of claim 1, wherein the lithium salt is LiTFSI, liFSI, liDFOB, liPF 6 、LiBF 4 、LiClO 4 And LiBOB.
15. The solid state lithium battery of claim 1, wherein the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder.
16. The solid state lithium battery of claim 1, wherein the organic solvent is one or more of an alkane solvent, a benzene solvent, and a ketone solvent.
17. The solid state lithium battery of claim 1, wherein 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.
18. A method for preparing a solid-state lithium battery is characterized by comprising the following steps,
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, 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-state anode active material layer on at least one side of the anode with a fourth solvent to obtain a gel-state anode active material layer;
5) First pressing the positive electrode and the solid electrolyte layer to form a positive electrode/solid electrolyte layer assembly, then laminating the gel-state negative electrode active material layer of the positive electrode/solid electrolyte layer assembly and the gel-state negative electrode active material layer of the negative electrode and performing second pressing,
Wherein the positive electrode active material is selected from LiMO 2 M is selected from one or more of Co, ni and Mn.
19. The method according to claim 18, 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.
20. The method according to claim 19, wherein the first solvent is used in an amount of 100 to 600 parts by weight with respect 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.
21. The method of claim 19, wherein the positive current collector is a carbon-coated aluminum foil.
22. The method of claim 19, wherein the LiMO 2 Is LiCoO 2 、LiNi 1/3 Mn 1/3 Co 1/3 O 2 One or more of NCM523, NCM622, and NCM 811.
23. The method of claim 19, wherein the first conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder.
24. The method of claim 19, wherein the sulfide electrolyte is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
25. The method of claim 19, wherein the first binder is one or more of polyvinylidene fluoride and a rubber-based binder.
26. The method of claim 19, wherein the first solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane, and methyl formamide.
27. The method of any of claims 18-26, wherein the sulfide is present in the second slurry in an amount of 90-99 wt% and the second binder is present in an amount of 1-10 wt%, based on the total amount of sulfide and second binder.
28. The method of claim 27, wherein the second solvent is used in an amount of 100-600 parts by weight with respect to 100 parts by weight of the total amount of sulfide and second binder.
29. The method of claim 27, wherein the sulfide is thio-LISICON, li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 10 SnP 2 S 12 、Li 2 S-P 2 S 5 、Li 2 S-SiS 2 And Li (lithium) 2 S-B 2 S 3 One or more of the following.
30. The method of claim 27, wherein the second binder is one or more of polyvinylidene fluoride and a rubber-based binder.
31. The process of claim 27, wherein 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.
32. The method according to any one of claims 18 to 26, wherein in the third slurry, the content of the anode 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 anode active material, the third binder, the lithium salt, and the second conductive agent.
33. The method according to claim 32, wherein the third solvent is used in an amount of 100 to 600 parts by weight with respect 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.
34. The method of claim 32, wherein the negative electrode active material is one or more of graphite, silicon oxide, elemental silicon, carbon-coated silicon, and graphene-coated silicon.
35. The method of claim 32, wherein the negative current collector is a carbon coated copper foil.
36. The method of claim 32, wherein the third binder is one or more of polyvinylidene fluoride and a rubber-based binder.
37. The method of claim 32, wherein the lithium salt is LiTFSI, liFSI, liDFOB, liPF 6 、LiBF 4 、LiClO 4 And LiBOB.
38. The method of claim 32, wherein the second conductive agent is one or more of SP, CNT, AB, VGCF, silver powder, and aluminum powder.
39. The process of claim 32, wherein 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.
40. The method according to any one of claims 18 to 26, wherein 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-state anode active material layer.
41. The process of claim 40 wherein the fourth solvent is one or more of n-hexane, n-heptane, toluene, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane, and methyl formamide.
42. The method of any of claims 18-26, wherein the first pressing conditions comprise: the isostatic pressure is 50-550Mpa, the dwell time is 10-30min, and the temperature is 15-100 ℃.
43. The method of claim 42, wherein the second pressing conditions comprise: the temperature isostatic pressure is 100-550Mpa, the pressure maintaining time is 10-30min, and the temperature is 15-100 ℃.
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