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WO2021003712A1 - Procédé de préparation pour batterie à semi-conducteurs, et batterie à semi-conducteurs - Google Patents

Procédé de préparation pour batterie à semi-conducteurs, et batterie à semi-conducteurs Download PDF

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Publication number
WO2021003712A1
WO2021003712A1 PCT/CN2019/095475 CN2019095475W WO2021003712A1 WO 2021003712 A1 WO2021003712 A1 WO 2021003712A1 CN 2019095475 W CN2019095475 W CN 2019095475W WO 2021003712 A1 WO2021003712 A1 WO 2021003712A1
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Prior art keywords
electrode sheet
solid
composite electrolyte
composite
lithium
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Ceased
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PCT/CN2019/095475
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English (en)
Chinese (zh)
Inventor
张健
黄宁
徐斌
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AAC Technologies Holdings Shenzhen Co Ltd
AAC Technologies Holdings Nanjing Co Ltd
Original Assignee
AAC Acoustic Technologies Shenzhen Co Ltd
AAC Technologies Holdings Nanjing Co Ltd
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Application filed by AAC Acoustic Technologies Shenzhen Co Ltd, AAC Technologies Holdings Nanjing Co Ltd filed Critical AAC Acoustic Technologies Shenzhen Co Ltd
Priority to PCT/CN2019/095475 priority Critical patent/WO2021003712A1/fr
Priority to CN201910622388.1A priority patent/CN110534795A/zh
Publication of WO2021003712A1 publication Critical patent/WO2021003712A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

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

Definitions

  • This application relates to the technical field of solid-state batteries, and in particular to a method for preparing solid-state batteries and solid-state batteries.
  • lithium-ion batteries have developed rapidly.
  • the specific energy of the first-generation lithium-ion battery was only 200Wh ⁇ L -1 and 80Wh ⁇ kg -1 , but now its specific energy has reached 560Wh ⁇ L -1 and 210Wh ⁇ kg -1 , or even higher.
  • the safety of lithium-ion batteries has always been a concern.
  • Solid-state batteries assembled with solid electrolytes can effectively solve the safety hazards caused by liquid electrolytes.
  • the solid electrolytes are non-volatile and non-flammable, thus improving the safety performance of lithium-ion batteries; and solid electrolytes can effectively prevent lithium metal dendrites
  • the resulting short circuit problem makes it possible to use lithium metal as the negative electrode of the battery; in addition, the solid electrolyte can work in a wider temperature range, and its electrochemical window is wider, which broadens the use of electrode materials.
  • the composite solid composite electrolyte layer As the core component of the solid secondary lithium battery, the composite solid composite electrolyte layer has the characteristics of high ionic conductivity, high safety performance, high capacity, high mechanical strength, good flexibility, and industrial amplification.
  • Research on composite solid electrolytes at home and abroad is more focused on using inorganic solid electrolytes as polymer solid electrolyte fillers to prepare organic-inorganic composite solid electrolytes.
  • CN201810400093 discloses the preparation of an organic-inorganic composite electrolyte membrane. By adding an inorganic solid electrolyte as a solid filler to an organic polymer electrolyte, the mechanical properties and ionic conductivity of the composite electrolyte membrane are improved.
  • the thickness of the organic-inorganic composite electrolytic film needs to be relatively thick, it is easy to cause the composite electrolyte film to have poor mechanical strength and be pierced by lithium dendrites, which may cause short circuit of the battery.
  • more foreign countries use magnetron sputtering or pulsed laser deposition to prepare. This process has high cost and low production efficiency, making it difficult to realize industrialization. None of these technologies can well solve the problems of easy growth of lithium dendrites, low ion conductivity, and industrialization of composite solid electrolytes.
  • the main technical problem solved by this application is that the single-layer composite solid electrolyte layer is short-circuited and cannot be industrialized due to the growth of lithium dendrites.
  • This application provides a solid state battery and a preparation method thereof, which can be effective Improve the interface contact between the electrode and the electrolyte layer, reduce the interface impedance between the electrode and the solid electrolyte layer, and improve the electrochemical performance of the solid battery.
  • the multi-layer gradient coating solid electrolyte effectively reduces the short circuit risk of the solid battery, has good safety performance and is easy to industrialize.
  • the present application provides a method for preparing a solid-state battery, which includes the following steps: providing a positive electrode sheet, a negative electrode sheet, and a composite electrolyte slurry; forming a composite electrolyte layer in the positive electrode sheet and/or negative electrode sheet Coating the composite electrolyte slurry on one side surface to form at least one composite electrolyte layer, and after curing, a composite positive electrode sheet and/or a composite negative electrode sheet are obtained; the composite positive electrode sheet and the negative electrode sheet are combined by a lamination or winding process Sheet, or the composite negative electrode sheet and the positive electrode sheet, or the composite positive electrode sheet and the composite negative electrode sheet are bonded together, so that the composite electrolyte layer is sandwiched between the pole pieces; rolling or cold, etc.
  • Static pressure is a solid state battery.
  • the components of the composite electrolyte slurry include inorganic solid electrolyte 1% ⁇ 99%, organic lithium ion conductive polymer 1% ⁇ 90%, lithium salt 1% ⁇ 50%, binder 0.5% ⁇ 30% and the balance solvent.
  • the inorganic solid electrolyte is lithium germanium aluminum phosphate, lithium germanium titanium phosphate, lithium lanthanum zirconium tantalum oxide, lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, aluminum oxide, zirconium oxide, Li 2 SA, Li 2 SAB, Li One or more of 2 S-MeS 2 -P 2 S 5 and Li 2 S-MeS 2 -P 2 S 5 -B, where A represents P 2 S 5 , SiS 2 , GeS 2 , B 2 S 3 and One or more of Al 2 S 4 , Me represents one or more of Si, Ge, Sn and Al, and B represents one or more of Cl, Br and I.
  • the organic lithium ion conductive polymer includes one or more of polyethylene oxide, succinonitrile, polyacrylonitrile and polymethyl methacrylate.
  • the lithium salt is one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonimide, and lithium hexafluoroarsenate.
  • the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile and polyisobutylene.
  • the coating method for forming the composite electrolyte layer includes one or more of immersion coating, gradient coating, slot coating, knife coating, extrusion coating, transfer coating and printing coating. kind.
  • the present application also provides a solid-state battery, which is prepared by the above-mentioned method for preparing a solid-state battery.
  • the solid-state battery preparation method and solid-state battery provided in this application can not only effectively improve the interface contact between the electrode and the electrolyte layer, reduce the interface impedance between the pole piece and the solid electrolyte layer, and improve the electrochemical performance of the solid-state battery, but also
  • the multi-layer gradient coating of the solid electrolyte can effectively reduce the short circuit risk of the solid battery and has good safety performance.
  • the preparation method of the present application has the advantage of large-scale amplification.
  • Figure 1 is a schematic structural diagram of a solid-state battery provided by this application.
  • Fig. 2 is a schematic flow chart of the method for preparing the solid-state battery shown in Fig. 1;
  • FIG. 3 is a first charge and discharge curve diagram of the solid-state battery provided in Example 1 of the application;
  • Example 4 is a graph of the first charge and discharge curve of the solid-state battery provided in Example 3 of this application;
  • FIG. 5 is a first charge and discharge curve diagram of the solid-state battery provided in Example 9 of this application.
  • the solid-state battery 100 includes a positive electrode sheet 1, a negative electrode sheet 2, and at least one composite electrolyte layer 3 sandwiched between the positive electrode sheet 1 and the negative electrode sheet 2.
  • the positive electrode sheet 1 serves as the positive electrode of the solid-state battery 100
  • the negative electrode sheet 2 serves as the negative electrode of the solid-state battery 100.
  • the positive electrode sheet 1 is made of positive electrode materials, which use known positive electrode materials. These positive electrode materials include lithium cobalt oxide materials, high-pressure lithium cobalt oxide materials, high-pressure lithium cobalt phosphate materials, ternary nickel cobalt manganese materials, and phosphoric acid. Lithium iron material.
  • the negative electrode sheet 2 is made of negative electrode materials, which use known negative electrode materials. These negative electrode materials include metallic lithium materials, silicon carbon materials, lithium titanate materials, lithium carbon materials, and graphite materials.
  • the composite electrolyte layer 3 is formed on the surface of the positive electrode sheet 1 or the surface of the negative electrode sheet 2 by coating, or is formed on the surfaces of the positive electrode sheet 1 and the negative electrode sheet 2 at the same time.
  • the composite electrolyte layer 3 is formed on the surface of the positive electrode sheet 1 and/or the negative electrode sheet 2 by coating, which can effectively improve the interface contact between the electrode and the electrolyte layer, reduce the interface impedance between the electrode and the solid electrolyte layer, and improve the solid state The electrochemical performance of the battery.
  • the composite electrolyte layer 3 can be set in multiple layers. When multiple layers of the composite electrolyte layer 3 are formed, a layer of composite electrolyte material is first coated on the surface of the positive electrode sheet 1 and/or the negative electrode sheet 2 to be cured. Then, the composite electrolyte material is applied to form another layer of the composite electrolyte layer 3, that is, the composite electrolyte layer 3 needs to be cured before the composite electrolyte material is applied to form the next composite electrolyte layer 3.
  • the use of this multilayer gradient coating solid electrolyte to form a composite electrolyte layer can effectively reduce the short-circuit risk of the solid battery and has good safety performance. At the same time, the process has advantages such as large-scale amplification.
  • the number of layers of the composite electrolyte layer 3 is preferably 1 to 30, and the thickness of each layer is 1 to 50 ⁇ m.
  • the components of the two adjacent composite electrolyte layers 3 are the same, but the content of each component is different.
  • the use of this multilayer gradient coating of the solid electrolyte method can effectively reduce the short circuit risk of the solid battery and has good safety performance.
  • the coating method for forming the composite electrolyte layer 3 includes one of dip coating, ramp coating, slot coating, knife coating, extrusion coating, transfer coating, and printing coating. Many kinds.
  • FIG. 2 Please refer to FIG. 2.
  • This application provides a method for preparing a solid-state battery.
  • the solid-state battery shown in FIG. 1 of the present application is taken as an example for description, which specifically includes the following steps:
  • Step S1 providing positive electrode sheet 1, negative electrode sheet 2 and composite electrolyte slurry
  • the components of the composite electrolyte slurry include inorganic solid electrolyte 1% ⁇ 99%, organic lithium ion conductive polymer 1% ⁇ 90%, lithium salt 1% ⁇ 50%, and binder 0.5% ⁇ 30% and the balance solvent.
  • the inorganic solid electrolyte is lithium germanium aluminum phosphate, lithium germanium titanium phosphate, lithium lanthanum zirconium tantalum oxide, lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, aluminum oxide, zirconium oxide, Li 2 SA, Li 2 SAB, Li 2 S One or more of -MeS 2 -P 2 S 5 and Li 2 S-MeS 2 -P 2 S 5 -B, where A represents P 2 S 5 , SiS 2 , GeS 2 , B 2 S 3 and Al 2 S 4 in one or several, Me represents one or more of Si, Ge, Sn, and Al, B represents one or more Cl, Br and I is.
  • the organic lithium ion conductive polymer includes one or more of polyethylene oxide, succinonitrile, polyacrylonitrile, and polymethyl methacrylate.
  • the lithium salt is one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonimide, and lithium hexafluoroarsenate.
  • the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile and polyisobutylene.
  • the solvent is acetonitrile, N,N dimethylformamide, N,N dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, ethanol, propanol, isopropanol, butanol, One or more of toluene, xylene, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, and diethyl carbonate.
  • the inorganic solid electrolyte, the organic lithium ion conductive polymer, the lithium salt and the binder can be separately dissolved in a solvent to form a mixture, and then the mixtures can be mixed together. Stir uniformly to form the composite electrolyte slurry, or first dissolve two or three of them in a solvent to form a mixture, and then mix each mixture together and stir to form the composite electrolyte slurry.
  • Step S2 coating the composite electrolyte slurry on one surface of the positive electrode sheet 1 and/or the negative electrode sheet 2 to form at least one layer of the composite electrolyte layer 3, and obtaining a composite positive electrode sheet and/or a composite negative electrode sheet after curing ;
  • the composite electrolyte slurry may be coated multiple times to form multiple layers of the composite electrolyte layer 3 on the surface of the positive electrode sheet 1 and/or the negative electrode sheet 2. It is important to note that when forming multiple layers of the composite electrolyte layer 3, a layer of the composite electrolyte slurry is first coated on the surface of the positive electrode sheet 1 and/or the negative electrode sheet 2, and after curing, The composite electrolyte slurry is coated to form another layer of the composite electrolyte layer 3, that is, the composite electrolyte layer 3 needs to be cured before the composite electrolyte slurry is applied to form the next composite electrolyte layer 3
  • the use of this multilayer gradient coating solid electrolyte to form the composite electrolyte layer 3 can effectively reduce the short circuit risk of the solid battery and has good safety performance.
  • the process has advantages such as large-scale amplification.
  • the number of layers of the composite electrolyte layer 3 is preferably 1 to 30, and the thickness of each layer is 1 to 50 ⁇ m.
  • the components of the two adjacent composite electrolyte layers 3 are the same, but the content of each component is different.
  • the use of this multilayer gradient coating of the solid electrolyte method can effectively reduce the short circuit risk of the solid battery and has good safety performance.
  • Step S3 using a lamination or winding process to bond the composite positive electrode sheet and the negative electrode sheet 2, or the composite negative electrode sheet and the positive electrode sheet 1, or the composite positive electrode sheet and the composite negative electrode sheet Together so that the composite electrolyte layer 3 is sandwiched between the positive electrode sheet 1 and the negative electrode sheet 2;
  • step S4 the solid-state battery 100 is obtained by rolling or cold isostatic pressing.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of high-voltage lithium cobalt oxide material
  • the negative electrode sheet is made of metal lithium material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include 75% lithium aluminum germanium phosphate, 15% polyethylene oxide, and polybias.
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile
  • the solid content of the composite electrolyte slurry A is 10%wt
  • the composite electrolyte slurry Material B includes 82% lithium germanium aluminum phosphate, 10% polyethylene oxide, 5% polyvinylidene fluoride, and 3% lithium bistrifluoromethanesulfonimide.
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile.
  • the solid content ratio of the composite electrolyte slurry B is 20%wt.
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N-methylpyrrolidine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to acetonitrile In the solvent, after vigorously stirring to form a colorless transparent viscous liquid, add lithium bis(trifluoromethanesulfonyl)imide and vigorously stir to form a colorless transparent viscous liquid No. 2; add lithium germanium aluminum phosphate Disperse in a mixed solvent of N-methylpyrrolidone and acetonitrile, perform ball milling dispersion, ball milling time is 2h, obtain a uniform milky white suspension; add No. 1 liquid and No. 2 liquid to the milky white lithium aluminum germanium phosphate suspension slurry , The mixed slurry was heated and stirred at 60° C. for 2 hours to obtain a uniform milky white viscous slurry.
  • Step S2 sequentially coating the composite electrolyte slurry on one surface of the positive electrode sheet to form two composite electrolyte layers, and obtaining a composite positive electrode sheet after curing;
  • step S2 the coating thickness of each layer is 20 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed positive electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on the surface of the positive electrode sheet-A, and the baking is continued at 80° C. for 2 hours to remove the excess solvent on the surface to obtain the final composite positive electrode sheet-AB.
  • Step S3 using a lamination or winding process to bond the final composite positive electrode sheet -AB and the negative electrode sheet together, so that the composite electrolyte layer is sandwiched between the electrode sheets;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of ternary nickel cobalt manganese material
  • the negative electrode sheet is made of metal lithium material.
  • the composite electrolyte slurry includes composite electrolyte slurry A, composite electrolyte slurry B, and composite electrolyte slurry C.
  • the raw materials of the composite electrolyte slurry A include 65% lithium germanium aluminum phosphate, polyethylene oxide 20% alkane, 5% polyvinylidene fluoride, 10% lithium bistrifluoromethanesulfonimide, the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile, and the solid content ratio of the composite electrolyte slurry A is 10%wt
  • the composite electrolyte slurry B includes 75% lithium germanium aluminum phosphate, 10% polyethylene oxide, 5% polyvinylidene fluoride, 5% lithium bistrifluoromethanesulfonimide, and the solvent is N-methylpyrrolidone and Acetonitrile mixed solvent, the solid content ratio of the composite electrolyte slurry B is 20%wt, and the composite electrolyte slurry C includes 85% lithium aluminum germanium phosphate, 5% polyethylene oxide, 5% polyvinylidene fluoride, double Lithium trifluorome
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N-methylpyrrolidine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to acetonitrile In the solvent, after vigorously stirring to form a colorless transparent viscous liquid, add lithium bis(trifluoromethanesulfonyl)imide and vigorously stir to form a colorless transparent viscous liquid No. 2; add lithium germanium aluminum phosphate Disperse in a mixed solvent of N-methylpyrrolidone and acetonitrile, perform ball milling dispersion, ball milling time is 2h, obtain a uniform milky white suspension; add No. 1 liquid and No. 2 liquid to the milky white lithium aluminum germanium phosphate suspension slurry , The mixed slurry was heated and stirred at 60° C. for 2 hours to obtain a uniform milky white viscous slurry.
  • step S2 the composite electrolyte slurry is sequentially coated on one surface of the positive electrode sheet to form The three composite electrolyte layers are cured to obtain a composite positive electrode sheet;
  • step S2 the coating thickness of each layer is 10 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed positive electrode sheet-A;
  • Step S22 then coat a layer of the composite electrolyte slurry B on the surface of the positive electrode sheet-A, and continue to bake at 80°C for 2 hours to remove excess solvent on the surface to obtain the final composite positive electrode sheet-AB;
  • Step S23 Finally, a layer of the composite electrolyte slurry C is coated on the surface of the positive electrode sheet-AB, and the baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain the final composite positive electrode sheet-ABC.
  • Step S3 using a lamination or winding process to bond the final composite positive electrode sheet -ABC and the negative electrode sheet together, so that the composite electrolyte layer is sandwiched between the electrode sheets;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of lithium iron phosphate material
  • the negative electrode sheet is made of metal lithium material.
  • the composite electrolyte slurry includes composite electrolyte slurry A, composite electrolyte slurry B, composite electrolyte slurry C, and composite electrolyte slurry D.
  • the raw material of composite electrolyte slurry A includes lithium germanium aluminum phosphate 30%, polyoxyethane 40%, polyvinylidene fluoride 10%, lithium bistrifluoromethanesulfonimide 20%
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile
  • the composite electrolyte slurry A The solid content ratio is 10%wt.
  • the composite electrolyte slurry B includes 40% lithium germanium aluminum phosphate, 30% polyoxyethane, 15% polyvinylidene fluoride, 15% lithium bistrifluoromethanesulfonimide, and solvent Is a mixed solvent of N-methylpyrrolidone and acetonitrile, the solid content of the composite electrolyte slurry B is 20%wt, and the composite electrolyte slurry C includes lithium germanium aluminum phosphate 50%, polyethylene oxide 20%, poly Vinylidene fluoride 20%, bistrifluoromethanesulfonimide lithium 10%, the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile, the solid content of the composite electrolyte slurry C is 30%wt, the composite electrolyte Slurry D includes 60% lithium germanium aluminum phosphate, 15% polyethylene oxide, 15% polyvinylidene fluoride, and 10% lithium bistrifluoromethanesulfonimide.
  • the solvent is a mixed solvent
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N-methylpyrrolidine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to acetonitrile In the solvent, after vigorously stirring to form a colorless transparent viscous liquid, add lithium bis(trifluoromethanesulfonyl)imide and vigorously stir to form a colorless transparent viscous liquid No. 2; add lithium germanium aluminum phosphate Disperse in a mixed solvent of N-methylpyrrolidone and acetonitrile, perform ball milling dispersion, ball milling time is 2h, obtain a uniform milky white suspension; add No. 1 liquid and No. 2 liquid to the milky white lithium aluminum germanium phosphate suspension slurry , The mixed slurry was heated and stirred at 60° C. for 2 hours to obtain a uniform milky white viscous slurry.
  • Step S2 sequentially coating the composite electrolyte slurry on one surface of the positive electrode sheet to form three composite electrolyte layers, and obtaining a composite positive electrode sheet after curing;
  • step S2 the coating thickness of each layer is 5 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed positive electrode sheet-A;
  • Step S22 then coat a layer of the composite electrolyte slurry B on the surface of the positive electrode sheet-A, and continue to bake at 80°C for 2 hours to remove excess solvent on the surface to obtain the final composite positive electrode sheet-AB;
  • Step S23 Finally, a layer of the composite electrolyte slurry C is coated on the surface of the positive electrode sheet-AB, and the baking is continued for 2 hours at 80° C. to remove excess solvent on the surface to obtain the final composite positive electrode sheet-ABC;
  • Step S24 Finally, a layer of the composite electrolyte slurry D is coated on the surface of the positive electrode sheet-ABC, and the baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain the final composite positive electrode sheet-ABCD.
  • Step S3 using a lamination or winding process to bond the final composite positive electrode sheet -ABCD and the negative electrode sheet together, so that the composite electrolyte layer is sandwiched between the pole pieces;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of high-voltage lithium cobalt oxide material
  • the negative electrode sheet is made of graphite material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include 75% lithium aluminum germanium phosphate, 15% polyethylene oxide, and polybias.
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile
  • the solid content of the composite electrolyte slurry A is 10%wt
  • the composite electrolyte slurry Material B includes 82% lithium germanium aluminum phosphate, 10% polyethylene oxide, 5% polyvinylidene fluoride, and 3% lithium bistrifluoromethanesulfonimide.
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile.
  • the solid content ratio of the composite electrolyte slurry B is 20%wt.
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N-methylpyrrolidine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to acetonitrile In the solvent, after vigorously stirring to form a colorless transparent viscous liquid, add lithium bis(trifluoromethanesulfonyl)imide and vigorously stir to form a colorless transparent viscous liquid No. 2; add lithium germanium aluminum phosphate Disperse in a mixed solvent of N-methylpyrrolidone and acetonitrile, perform ball milling dispersion, ball milling time is 2h, obtain a uniform milky white suspension; add No. 1 liquid and No. 2 liquid to the milky white lithium aluminum germanium phosphate suspension slurry , The mixed slurry was heated and stirred at 60° C. for 2 hours to obtain a uniform milky white viscous slurry.
  • Step S2 coating the composite electrolyte slurry on one surface of the negative electrode sheet to form two composite electrolyte layers, and obtaining a composite negative electrode sheet after curing;
  • step S2 the coating thickness of each layer is 20 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the negative electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed negative electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on the surface of the negative electrode sheet-A, and the baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain the final composite negative electrode sheet-AB.
  • Step S3 using a lamination or winding process to bond the final composite negative electrode sheet -AB and the positive electrode sheet together, so that the composite electrolyte layer is sandwiched between the pole pieces;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of high-voltage lithium cobalt oxide material
  • the negative electrode sheet is made of silicon carbon material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include 75% lithium aluminum germanium phosphate, 15% polyethylene oxide, and polybias.
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile
  • the solid content of the composite electrolyte slurry A is 10%wt
  • the composite electrolyte slurry Material B includes 82% lithium germanium aluminum phosphate, 10% polyethylene oxide, 5% polyvinylidene fluoride, and 3% lithium bistrifluoromethanesulfonimide.
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile.
  • the solid content ratio of the composite electrolyte slurry B is 20%wt.
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N-methylpyrrolidine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to acetonitrile In the solvent, after vigorously stirring to form a colorless transparent viscous liquid, add lithium bis(trifluoromethanesulfonyl)imide and vigorously stir to form a colorless transparent viscous liquid No. 2; add lithium germanium aluminum phosphate Disperse in a mixed solvent of N-methylpyrrolidone and acetonitrile, perform ball milling dispersion, ball milling time is 2h, obtain a uniform milky white suspension; add No. 1 liquid and No. 2 liquid to the milky white lithium aluminum germanium phosphate suspension slurry , The mixed slurry was heated and stirred at 60° C. for 2 hours to obtain a uniform milky white viscous slurry.
  • Step S2 coating the composite electrolyte slurry on one surface of the negative electrode sheet to form two composite electrolyte layers, and obtaining a composite negative electrode sheet after curing;
  • step S2 the coating thickness of each layer is 30 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the negative electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed negative electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on the surface of the negative electrode sheet-A, and the baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain the final composite negative electrode sheet-AB.
  • Step S3 using a lamination or winding process to bond the final composite negative electrode sheet -AB and the positive electrode sheet together, so that the composite electrolyte layer is sandwiched between the pole pieces;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of high-voltage lithium cobalt phosphate material
  • the negative electrode sheet is made of lithium titanate material.
  • the composite electrolyte slurry includes composite electrolyte slurry A, composite electrolyte slurry B, and composite electrolyte slurry C.
  • the raw materials of the composite electrolyte slurry A include 75% lithium aluminum titanium phosphate, succinonitrile 15 %, polyvinylidene fluoride 5%, lithium hexafluorophosphate 5%, the solvent is a mixed solvent of N,N dimethylformamide and acetonitrile, the solid content of the composite electrolyte slurry A is 10%wt, the composite electrolyte slurry B includes 40% lithium titanium aluminum phosphate, 30% succinonitrile, 15% polyvinylidene fluoride, 15% lithium hexafluorophosphate, and the solvent is a mixed solvent of N,N dimethylformamide and acetonitrile.
  • the solid content of the composite electrolyte slurry B The ratio is 20%wt.
  • the composite electrolyte slurry C includes 82% lithium aluminum titanium phosphate, 10% succinonitrile, 5% polyvinylidene fluoride, and 3% lithium hexafluorophosphate.
  • the solvent is a mixture of N,N dimethylformamide and acetonitrile. Solvent, the solid content of the composite electrolyte slurry C is 20%wt.
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N,N dimethylformamide solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide Add acetonitrile solvent, and then vigorously stir to form a colorless transparent viscous liquid, then add lithium hexafluorophosphate for vigorous stirring, stir evenly to form a colorless transparent viscous liquid No. 2; disperse lithium titanium aluminum phosphate in N, N In a mixed solvent of methylformamide and acetonitrile, perform ball milling dispersion for 2 hours to obtain a uniform milky white suspension; add No. 1 liquid and No. 2 liquid to the milky white lithium titanium aluminum phosphate suspension slurry, and mix. The slurry was heated and stirred at 60°C for 2h to obtain a uniform milky white viscous slurry.
  • Step S2 sequentially coating the composite electrolyte slurry on one surface of the positive electrode sheet to form three composite electrolyte layers, and obtaining a composite positive electrode sheet after curing;
  • step S2 the coating thickness of each layer is 10 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed positive electrode sheet-A;
  • Step S22 then coat a layer of the composite electrolyte slurry B on the surface of the positive electrode sheet-A, and continue to bake at 80°C for 2 hours to remove excess solvent on the surface to obtain the final composite positive electrode sheet-AB;
  • Step S23 Finally, a layer of the composite electrolyte slurry C is coated on the surface of the positive electrode sheet-AB, and the baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain the final composite positive electrode sheet-ABC.
  • Step S3 using a lamination or winding process to bond the final composite positive electrode sheet -ABC and the negative electrode sheet together, so that the composite electrolyte layer is sandwiched between the electrode sheets;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of high-voltage lithium cobalt oxide material
  • the negative electrode sheet is made of lithium carbon negative electrode material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include 55% lithium lanthanum zirconium oxide, 25% polyethylene oxide, and polytetrafluoroethylene in mass percentage.
  • the composite electrolyte slurry B includes 90% of lithium lanthanum zirconium oxide, 5% of polyethylene oxide, 3% of polytetrafluoroethylene, 2% of lithium bistrifluoromethanesulfonimide, and the solvent is N,N dimethyl A mixed solvent of methyl acetamide and acetonitrile, the solvent is a mixed solvent of N-methylpyrrolidone and acetonitrile, and the solid content of the composite electrolyte slurry B is 20% wt.
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polytetrafluoroethylene into the N,N dimethylacetamide solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide Add acetonitrile solvent, then vigorously stir to form a colorless transparent viscous liquid, then add lithium bistrifluoromethanesulfonimide to vigorously stir, stir evenly to form a colorless transparent viscous liquid No.
  • the zirconium oxide is dispersed in a mixed solvent of N,N dimethylacetamide and acetonitrile, and the ball milling is carried out for 2 hours to obtain a uniform milky white suspension; add one to the milky white lithium lanthanum lithium zirconium oxide suspension slurry No. 2 liquid and No. 2 liquid, the mixed slurry was heated and stirred at 60° C. for 2 hours to obtain a uniform milky white viscous slurry.
  • Step S2 coating the composite electrolyte slurry on one surface of the positive electrode sheet to form two composite electrolyte layers, and obtaining a composite positive electrode sheet after curing;
  • step S2 the coating thickness of each layer is 15 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed positive electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on the surface of the positive electrode sheet-A, and the baking is continued at 80° C. for 2 hours to remove the excess solvent on the surface to obtain the final composite positive electrode sheet-AB.
  • Step S3 using a lamination or winding process to bond the final composite positive electrode sheet -AB and the negative electrode sheet together, so that the composite electrolyte layer is sandwiched between the electrode sheets;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of lithium cobalt oxide material
  • the negative electrode sheet is made of graphite material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include 5% lithium lanthanum zirconium tantalum oxide, 60% polyacrylonitrile, and poly 20% vinyl fluoride, 15% lithium perchlorate
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetone
  • the solid content ratio of the composite electrolyte slurry A is 15%wt
  • the composite electrolyte slurry B includes lithium lanthanum 95% zirconium tantalum oxide, 3% polyacrylonitrile, 2% polyvinylidene fluoride, 1% lithium perchlorate
  • the solvent is a mixed solvent of N-methylpyrrolidone and acetone
  • the solid content ratio of the composite electrolyte slurry B is 30%w
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N-methylpyrrolidine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyacrylonitrile to the acetone solvent Then, after vigorously stirring to form a colorless transparent viscous liquid, add lithium perchlorate for vigorous stirring, and stir evenly to form a colorless transparent viscous liquid No. 2; disperse the lithium lanthanum zirconium tantalum oxide in N-form In the mixed solvent of base pyrrolidone and acetone, ball milling is carried out, and the ball milling time is 2 hours to obtain a uniform milky white suspension; add liquid No. 1 and liquid No. 2 to the milky white lithium lanthanum zirconium tantalum oxide suspension slurry, and mix The slurry was heated and stirred at 60°C for 2 hours to obtain a uniform milky white viscous slurry.
  • Step S2 coating the composite electrolyte slurry on one surface of the positive electrode sheet and one surface of the negative electrode sheet to form a composite electrolyte layer, and obtaining a composite positive electrode sheet and a composite negative electrode sheet after curing;
  • step S2 the coating thickness of each layer is 20 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake at 80° C. for 2 hours to remove excess solvent on the surface to obtain a composite positive electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on one surface of the negative electrode sheet, and baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain a composite negative electrode sheet-B. It should be noted that the order of step S21 and step S22 in this embodiment is not distinguished.
  • step S3 the composite positive electrode sheet-A and the composite negative electrode sheet-B are bonded together using a lamination or winding process, so that the composite electrolyte layer is sandwiched between the pole pieces;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of M-Nb-O material
  • the negative electrode sheet is made of metal lithium material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include 90% lithium lanthanum titanium oxide, 5% polyethylene oxide, and 3% vinyl fluoride, 2% lithium bistrifluoromethanesulfonimide
  • the solvent is a mixed solvent of N-methylpyrrolidone and tetrahydrofuran
  • the solid content of the composite electrolyte slurry A is 30%wt
  • the composite electrolyte slurry Material B includes 30% lithium lanthanum titanium oxide, 40% polyethylene oxide, 10% polyvinylidene fluoride, and 20% lithium bistrifluoromethanesulfonimide.
  • the solvent is a mixed solvent of N-methylpyrrolidone and tetrahydrofuran.
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the N-methylpyrrolidine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to tetrahydrofuran In the solvent, after vigorously stirring to form a colorless transparent viscous liquid, add lithium bis(trifluoromethanesulfonyl)imide and vigorously stir to form a colorless transparent viscous liquid No. 2; add lithium lanthanum titanium oxide Disperse in a mixed solvent of N-methylpyrrolidone and tetrahydrofuran, and carry out ball milling dispersion for 2 hours to obtain a uniform milky white suspension; add liquid No. 1 and liquid No. 2 to the milky white lithium lanthanum titanium oxide suspension slurry , The mixed slurry was heated and stirred at 60° C. for 2 hours to obtain a uniform milky white viscous slurry.
  • Step S2 sequentially coating the composite electrolyte slurry on one surface of the positive electrode sheet to form two composite electrolyte layers, and obtaining a composite negative electrode sheet after curing;
  • step S2 the coating thickness of each layer is 10 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed negative electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on the surface of the positive electrode sheet-A, and the baking is continued at 80° C. for 2 hours to remove the excess solvent on the surface to obtain the final composite negative electrode sheet-AB.
  • Step S3 using a lamination or winding process to bond the final composite positive electrode sheet -AB and the negative electrode sheet together, so that the composite electrolyte layer is sandwiched between the electrode sheets;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of lithium cobalt oxide material
  • the negative electrode sheet is made of metal lithium negative electrode material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include sulfide electrolyte Li 3 PS 4 60% and polyethylene oxide 20%.
  • the solvent is a mixed solvent of xylene and acetonitrile
  • the solid content of the composite electrolyte slurry A is 10%wt
  • the composite electrolyte slurry Material B includes sulfide electrolyte Li 3 PS 4 80%, polyoxyethane 10%, polytetrafluoroethylene 5%, bistrifluoromethanesulfonimide lithium 5%
  • the solvent is a mixed solvent of xylene and acetonitrile.
  • the solid content ratio of the composite electrolyte slurry B is 30%wt.
  • the preparation method of the composite electrolyte slurry is specifically: adding polyvinylidene fluoride to the xylene amine solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to the acetonitrile solvent, Then, after vigorously stirring to form a colorless transparent viscous liquid, add lithium bis(trifluoromethanesulfonyl)imide to vigorously stir and stir to form a colorless transparent viscous liquid No. 2; the sulfide electrolyte Li 3 PS 4 Disperse in a mixed solvent of xylene and acetonitrile, carry out ball milling dispersion, ball milling time is 2h, get a uniform gray suspension; add No. 1 liquid and No. 2 liquid to the gray suspension slurry, the mixed slurry is in Heat and stir at 60°C for 2h to obtain a uniform gray viscous slurry.
  • Step S2 coating the composite electrolyte slurry on one surface of the positive electrode sheet to form two composite electrolyte layers, and obtaining a composite positive electrode sheet after curing;
  • step S2 the coating thickness of each layer is 5 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed positive electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on the surface of the positive electrode sheet-A, and the baking is continued at 80° C. for 2 hours to remove the excess solvent on the surface to obtain the final composite positive electrode sheet-AB.
  • Step S3 using a lamination or winding process to bond the final composite positive electrode sheet -AB and the negative electrode sheet together, so that the composite electrolyte layer is sandwiched between the electrode sheets;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of lithium iron phosphate material
  • the negative electrode sheet is made of silicon carbon material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include sulfide electrolyte Li 7 P 3 S 11 75% and succinonitrile 15%.
  • the composite electrolyte slurry B includes sulfide electrolyte Li 7 P 3 S 11 85%, succinonitrile 10%, polyvinylidene fluoride 4%, bistrifluoromethanesulfonimide lithium 1%, and the solvent is NN-dimethyl A mixed solvent of methyl formamide and acetonitrile, and the solid content of the composite electrolyte slurry B is 40% wt.
  • the preparation method of the composite electrolyte slurry is specifically as follows: adding polyvinylidene fluoride to the NN-dimethylformamide solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyvinylidene fluoride In acetonitrile solvent, then vigorously stir to form a colorless transparent viscous liquid, then add lithium bistrifluoromethanesulfonimide to vigorously stir, stir evenly to form a colorless transparent viscous liquid No.
  • Step S2 respectively coating the composite electrolyte slurry on one surface of the positive electrode sheet and the negative electrode sheet to form a layer of the composite electrolyte layer, and obtaining a composite positive electrode sheet and a composite negative electrode sheet after curing;
  • step S2 the coating thickness of each layer is 50 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the positive electrode sheet, and bake at 80° C. for 2 hours to remove excess solvent on the surface to obtain a composite positive electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on one surface of the negative electrode sheet, and baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain a composite negative electrode sheet-B. It should be noted that the order of step S21 and step S22 in this embodiment is not distinguished.
  • step S3 the composite positive electrode sheet-A and the composite negative electrode sheet-B are bonded together by a lamination or winding process, so that the composite electrolyte layer is sandwiched between the pole pieces;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • a method for preparing a solid-state battery mainly includes the following steps:
  • Step S1 providing a positive electrode sheet, a negative electrode sheet and a composite electrolyte slurry
  • the positive electrode sheet is made of ternary nickel-cobalt-manganese material, and the negative electrode sheet is made of silicon-carbon material.
  • the composite electrolyte slurry includes composite electrolyte slurry A and composite electrolyte slurry B.
  • the raw materials of the composite electrolyte slurry A include sulfide electrolyte Li 10 GeP 2 S 12 80%, polyethylene oxide 10 %, polyvinylidene fluoride-hexafluoropropylene 5%, lithium hexafluorophosphate 5%, the solvent is a mixed solvent of xylene and acetonitrile, the solid content ratio of the composite electrolyte slurry A is 50%wt, and the composite electrolyte slurry B includes Sulfide electrolyte Li 10 GeP 2 S 12 60%, polyethylene oxide 20%, polyvinylidene fluoride-hexafluoropropylene 10%, lithium hexafluorophosphate 10%, the solvent is a mixed solvent of xylene and acetonitrile, the composite electrolyte slurry B is The solid content ratio is 20%wt.
  • the preparation method of the composite electrolyte slurry specifically includes: blending polyvinylidene fluoride-hexafluoropropylene into a xylene solvent, and then vigorously stirring to form the No. 1 colorless transparent viscous liquid; adding polyethylene oxide to acetonitrile In the solvent, vigorously stir to form a colorless transparent viscous liquid, then add lithium hexafluorophosphate for vigorous stirring, and stir to form a colorless transparent viscous liquid No. 2; disperse the sulfide electrolyte Li 10 GeP 2 S 12 in the second In a mixed solvent of toluene and acetonitrile, perform ball milling dispersion for 2 hours to obtain a uniform gray suspension; add No. 1 liquid and No. 2 liquid to the gray suspension slurry, and the mixed slurry is at 60°C Heat and stir for 2 hours to obtain a uniform gray viscous slurry.
  • Step S2 sequentially coating the composite electrolyte slurry on one surface of the negative electrode sheet to form two composite electrolyte layers, and obtaining a composite negative electrode sheet after curing;
  • step S2 the coating thickness of each layer is 5 ⁇ m, which specifically includes the following steps:
  • Step S21 firstly coat a layer of the composite electrolyte slurry A on one surface of the negative electrode sheet, and bake it at 80° C. for 2 hours to remove excess solvent on the surface to obtain a processed negative electrode sheet-A;
  • step S22 a layer of the composite electrolyte slurry B is coated on the surface of the negative electrode sheet-A, and the baking is continued at 80° C. for 2 hours to remove excess solvent on the surface to obtain the final composite negative electrode sheet-AB.
  • Step S3 using a lamination or winding process to bond the final composite negative electrode sheet -AB and the positive electrode sheet together, so that the composite electrolyte layer is sandwiched between the pole pieces;
  • Step S4 rolling or cold isostatic pressing, to obtain a solid battery.
  • FIG. 3 is the first charge and discharge curve of the solid-state battery provided in Example 1 of the application
  • FIG. 4 is the first charge and discharge curve of the solid-state battery provided in Example 3 of the application
  • 5 is the first charge and discharge curve diagram of the solid-state battery provided in Example 9 of this application.
  • the polarization of the solid-state battery is smaller, which indicates that the multilayer gradient coating can effectively improve the interface contact between the electrode and the electrolyte layer, and reduce the electrode and the electrolyte layer.
  • the interface impedance of the solid electrolyte layer improves the electrochemical performance of the solid battery, and the multi-layer gradient coating of the solid electrolyte can effectively reduce the short circuit risk of the solid battery and has good safety performance.
  • the preparation method of the present application has the advantage of large-scale amplification.

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Abstract

Procédé de préparation d'une batterie à semi-conducteurs, comprenant les étapes suivantes consistant à : fournir une plaque d'électrode positive, une plaque d'électrode négative et une suspension d'électrolyte composite ; revêtir une surface de la plaque d'électrode positive et/ou de la plaque d'électrode négative avec la suspension d'électrolyte composite pour former au moins une couche d'électrolyte composite, et réaliser un durcissement pour obtenir une plaque d'électrode positive composite et/ou une plaque d'électrode négative composite ; utiliser un processus de stratification ou d'enroulement pour stratifier la plaque d'électrode positive composite et la plaque d'électrode négative, ou la plaque d'électrode négative composite et la plaque d'électrode positive, ou la plaque d'électrode positive composite et la plaque d'électrode négative composite, de telle sorte que la couche d'électrolyte composite est serrée entre les plaques d'électrode ; et réaliser un laminage ou un pressage isostatique à froid pour obtenir la batterie à semi-conducteurs.
PCT/CN2019/095475 2019-07-10 2019-07-10 Procédé de préparation pour batterie à semi-conducteurs, et batterie à semi-conducteurs Ceased WO2021003712A1 (fr)

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CN108400378A (zh) * 2018-03-15 2018-08-14 清陶（昆山）能源发展有限公司 一种柔性的全固态锂离子电池及其制备方法
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CN109449492A (zh) * 2018-11-01 2019-03-08 中南大学 一种陶瓷基全固态电池及其制备方法

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CN113161606A (zh) * 2021-04-27 2021-07-23 东南大学 超薄复合固态电解质膜及制备方法
CN113690498A (zh) * 2021-07-30 2021-11-23 东莞凯德新能源有限公司 一种复合负极片及包含该负极片的锂离子电池
CN114142099A (zh) * 2021-11-24 2022-03-04 蜂巢能源科技有限公司 一种复合固态电解质膜的制备方法和电化学储能装置
CN115189014A (zh) * 2022-06-20 2022-10-14 上海屹锂新能源科技有限公司 基于钠离子硫化物固态电解质的复合电解质膜的制备及应用
CN115425281A (zh) * 2022-10-10 2022-12-02 宁德新能源科技有限公司 锂离子电池以及电子设备
CN115693018A (zh) * 2022-10-27 2023-02-03 襄阳惠强新能源材料科技有限公司 一种光固化离聚体固态电解质隔膜的制备方法

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