WO2024045688A1 - Anti-short-circuit solid-state battery and preparation method therefor - Google Patents

Anti-short-circuit solid-state battery and preparation method therefor Download PDF

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Publication number
WO2024045688A1
WO2024045688A1 PCT/CN2023/093052 CN2023093052W WO2024045688A1 WO 2024045688 A1 WO2024045688 A1 WO 2024045688A1 CN 2023093052 W CN2023093052 W CN 2023093052W WO 2024045688 A1 WO2024045688 A1 WO 2024045688A1
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Prior art keywords
positive electrode
solid
negative electrode
solid electrolyte
coating layer
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PCT/CN2023/093052
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French (fr)
Chinese (zh)
Inventor
翟喜民
高天一
姜涛
别晓非
胡景博
闫晟睿
赵光宇
杨贺捷
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中国第一汽车股份有限公司
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Publication of WO2024045688A1 publication Critical patent/WO2024045688A1/en

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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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • H01M50/593—Spacers; Insulating plates
    • 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

  • One or more embodiments of this specification relate to the technical field of lithium batteries, and in particular, to a short-circuit-proof solid-state battery and a preparation method thereof.
  • all-solid-state batteries usually use pressure to improve the large amount of solid-solid interface contact inside the battery.
  • the applied pressure is large, a short circuit may easily occur inside the battery under the action of pressure.
  • the size difference needs to be set between the negative electrode coating area and the positive electrode coating area, resulting in a gap between the negative electrode coating area and the positive electrode empty foil area.
  • the battery core is pressed, it is easy to cause the electrode piece to break, thereby aggravating the short circuit. happened. Therefore, those skilled in the art have conducted research on short-circuit proof solid-state batteries.
  • Chinese patent application CN107452985A discloses a manufacturing method, a manufacturing device and an all-solid-state battery.
  • the manufacturing method includes: stacking multiple current collector layers, positive electrode mixture layers, solid electrolyte layers and negative electrode mixture layers respectively to obtain a laminated batteries on both end surfaces and side surfaces in the stacking direction; supplying liquid resin to only the side surfaces of the laminated battery; and solidifying the liquid resin.
  • the step of obtaining the laminated battery at least one of the current collector layer, the positive electrode mixture layer, the solid electrolyte layer, and the negative electrode mixture layer is extended longer than the other layers to serve as an extended layer, A plurality of the extension layers extend from the side of the stacked battery.
  • the liquid resin is supplied only to the side surface of the laminated battery, so that the liquid resin penetrates into the gap between one of the extension layers and the other extension layers.
  • Chinese patent application CN111864257A discloses an all-solid-state battery that can more reliably prevent short circuits and a manufacturing method thereof.
  • the all-solid-state battery has a first pole piece in which a first pole active material layer is formed on a first current collector layer, and a second pole active material layer is formed on a second current collector layer.
  • the second pole piece and the bag-shaped solid electrolyte layer housing the first pole piece are stacked so as to overlap when viewed from above, so that the first pole active material
  • the second electrode active material layer and the second electrode active material layer are arranged to face each other with the solid electrolyte layer interposed therebetween.
  • the above-mentioned patented technology still has the following shortcomings: the negative electrode is easily brittle when pressure is applied to the battery, and the battery is prone to short circuit when pressure is applied.
  • one object of the present invention is to provide a short-circuit-proof solid-state battery.
  • an insulating ring is placed in the empty foil area of the positive electrode sheet to fill the gap with the solid electrolyte layer and prevent the negative electrode from fragmenting when pressure is applied to the battery core; the insulating ring bonds the positive electrode sheet to the solid electrolyte layer Knot together to prevent the pole pieces from dislocating; the insulating ring plays an insulating role to prevent battery short circuit; the insulating ring surrounds the pole pieces and acts as a flame retardant.
  • the second object of the present invention is to provide a method for preparing a short-circuit-proof solid-state battery.
  • a short-circuit-proof solid-state battery includes several battery units; the battery unit is composed of a positive electrode plate, an insulating ring, a solid electrolyte layer and a negative electrode plate;
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode coating layer
  • the negative electrode piece includes a negative electrode current collector and a negative electrode coating layer
  • the length*width*height dimensions of the inner ring of the insulation ring are the same as the length*width*height dimensions of the positive electrode coating layer;
  • the insulating ring is set on the edge of the positive electrode piece and surrounds the positive electrode coating layer on all sides;
  • a solid electrolyte layer is provided between the side of the positive electrode piece with the positive electrode coating layer and the negative electrode piece with the negative electrode coating layer;
  • the width L1 of the negative electrode coating layer and the width L2 of the positive electrode coating layer satisfy: 0.05mm ⁇ L1-L2 ⁇ 0.3mm;
  • the length L3 of the negative electrode coating area and the length L4 of the positive electrode coating area satisfy: 0.05mm ⁇ L3-L4 ⁇ 0.3mm.
  • the softening temperature T of the insulating ring is 40°C ⁇ T ⁇ 150°C.
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin includes one or more of PE, PP, PVC, PS, PA, POM, PC, PI, and rubber;
  • a method for preparing a solid-state battery including the following steps:
  • the positive electrode coating film mixed material includes positive electrode active material, conductive agent, binder and solid electrolyte;
  • the negative electrode coating film mixed material includes negative electrode active material, conductive agent, binder and solid electrolyte;
  • the solid electrolyte layer is prepared by independent film formation or transfer film formation; the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte, and a halide electrolyte;
  • the positive active material is lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt manganese aluminate, lithium cobalt oxide, lithium manganate, lithium iron phosphate, lithium-rich manganese one or more base materials.
  • the negative active material is one or more of graphite, hard carbon, lithium titanate, silicon, silicon-carbon composite material or silicon oxide-carbon composite material.
  • the conductive agent is acetylene black (AB), Ketjen black (KB), vaporized carbon fiber (VGCF), carbon nanotube (CNT), carbon nanofiber (CNF), One or more types of graphene or graphite.
  • the binder includes styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), acrylonitrile butadiene rubber (ABR), butadiene rubber (BR) ), one or more of butyl rubber (IIR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyimide (PI).
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • ABR acrylonitrile butadiene rubber
  • BR butadiene rubber
  • IIR butyl rubber
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PI polyimide
  • the solid electrolyte is one or both of an oxide solid electrolyte and a sulfide solid electrolyte.
  • step S4 the transfer film formation transfers the solid electrolyte layer to the negative electrode or the positive electrode.
  • the pressing pressure is 100MPa-1000MPa.
  • step S8 the temperature during pressing is 40°C-100°C.
  • Any range described in the present invention includes the end value and any value between the end value and any subrange formed by the end value or any value between the end value.
  • each raw material in the present invention can be purchased commercially, and the equipment used in the present invention can be carried out using conventional equipment in the field or with reference to the existing technology in the field.
  • the present invention has the following beneficial effects:
  • the insulating ring is placed in the empty foil area of the positive electrode sheet during lamination to fill the gap between the solid electrolyte layer and prevent the negative electrode from breaking when pressure is applied to the battery core;
  • the insulating ring plays an insulating role to prevent battery short circuit
  • the insulating ring surrounds the pole piece and can play a flame retardant role.
  • Figure 1 is a schematic structural diagram of the solid-state battery of the present invention.
  • Figure 2 is an exploded top view of the battery unit in the present invention
  • Figure 3 is a schematic structural diagram of the insulating ring being placed on the positive electrode piece in the present invention.
  • all-solid-state batteries usually use pressure to improve the large amount of solid-solid interface contact inside the battery.
  • the applied pressure is large, a short circuit may easily occur inside the battery under the action of pressure.
  • the size difference needs to be set between the negative electrode coating layer and the positive electrode coating layer, resulting in a gap between the negative electrode coating layer and the positive electrode empty foil area.
  • the battery core is pressed, it is easy to cause the electrode piece to break, thus aggravating the short circuit. happened.
  • a short-circuit proof solid-state battery of the present invention includes a plurality of battery cells 100; the battery cells are composed of a positive electrode plate 10, an insulating ring 20, a solid electrolyte layer 30 and The negative electrode piece 40 is composed of;
  • the positive electrode sheet 10 includes a positive electrode current collector 11 and a positive electrode coating layer 12;
  • the negative electrode sheet 40 includes a negative electrode current collector 41 and a negative electrode coating layer 42;
  • the length*width*thickness dimensions of the inner ring of the insulating ring 20 are the same as the length*width*thickness dimensions of the positive electrode coating layer 12;
  • the insulating ring 20 is sleeved on the edge of the positive electrode piece 10 and matched to surround the positive electrode coating layer 12, as shown in Figure 3;
  • a solid electrolyte layer 30 is provided between the side of the positive electrode piece 10 provided with the positive electrode coating layer 12 and the negative electrode piece 40 provided with the negative electrode coating layer 42;
  • the length L1 of the negative electrode coating layer and the length L2 of the positive electrode coating layer satisfy: 0.05mm ⁇ L1-L2 ⁇ 0.3mm;
  • the width L3 of the negative electrode coating area and the width L4 of the positive electrode coating area satisfy: 0.05mm ⁇ L3-L4 ⁇ 0.3mm.
  • the softening temperature T of the insulating ring is 40°C ⁇ T ⁇ 150°C.
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin includes one or more of PE, PP, PVC, PS, PA, POM, PC, PI, and rubber;
  • the present invention also provides a method for preparing the above-mentioned solid-state battery, which includes the following steps:
  • the positive electrode coating film mixed material includes positive electrode active material, conductive agent, binder and solid electrolyte;
  • the negative electrode coating film mixed material includes negative electrode active material, conductive agent, binder and solid electrolyte;
  • the solid electrolyte layer is prepared by independent film formation or transfer film formation; the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte, and a halide electrolyte;
  • the positive active material is lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium nickel cobalt manganate, lithium cobalt oxide, lithium manganate, lithium iron phosphate, One or more of the lithium-rich manganese-based materials.
  • the negative active material is one or more of graphite, hard carbon, lithium titanate, silicon, silicon-carbon composite material or silicon oxide-carbon composite material.
  • the conductive agent is acetylene black (AB), Ketjen black (KB), vaporized carbon fiber (VGCF), carbon nanotube (CNT), nanocarbon fiber ( CNF), graphene or graphite.
  • the binder in steps S1 and S3, includes styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), acrylonitrile butadiene rubber (ABR), butadiene One or more of rubber (BR), butyl rubber (IIR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyimide (PI).
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • ABR acrylonitrile butadiene rubber
  • BR butadiene
  • IIR butyl rubber
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PI polyimide
  • the solid electrolyte is one or both of an oxide solid electrolyte and a sulfide solid electrolyte.
  • step S4 the transfer film formation transfers the solid electrolyte layer to the negative electrode or the positive electrode.
  • the pressing pressure is 100MPa-1000MPa.
  • step S8 the temperature during pressing is 40°C-100°C.
  • a short-circuit-proof solid-state battery of the present invention includes several battery units 100; the battery unit is composed of a positive electrode piece 10, an insulating ring 20, a solid electrolyte layer 30 and a negative electrode piece 40;
  • the positive electrode sheet 10 includes a positive electrode current collector 11 and a positive electrode coating layer 12;
  • the negative electrode sheet 40 includes a negative electrode current collector 41 and a negative electrode coating layer 42;
  • the length*width*thickness dimensions of the inner ring of the insulating ring 20 are the same as the length*width*thickness dimensions of the positive electrode coating layer 12;
  • the insulating ring 20 is sleeved on the edge of the positive electrode piece 10 and matched to surround the positive electrode coating layer 12, as shown in Figure 3;
  • a solid electrolyte layer 30 is provided between the side of the positive electrode piece 10 provided with the positive electrode coating layer 12 and the negative electrode piece 40 provided with the negative electrode coating layer 42;
  • the length L1 of the negative electrode coating layer and the length L2 of the positive electrode coating layer satisfy: 0.05mm ⁇ L1-L2 ⁇ 0.3mm;
  • the width L3 of the negative electrode coating area and the width L4 of the positive electrode coating area satisfy: 0.05mm ⁇ L3-L4 ⁇ 0.3mm;
  • the softening temperature T of the insulating ring is 40°C ⁇ T ⁇ 150°C;
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PE;
  • a method for preparing a solid-state battery including the following steps:
  • the positive electrode coating film mixed material includes positive electrode active material, conductive agent, binder and solid electrolyte;
  • the negative electrode coating film mixed material includes negative electrode active material, conductive agent, binder and solid electrolyte;
  • the solid electrolyte layer is prepared by independent film formation or transfer film formation; the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte, and a halide electrolyte;
  • the positive active material is lithium nickel cobalt manganate
  • step S3 the negative active material is graphite
  • the conductive agent is acetylene black
  • the binder is styrene-butadiene rubber (SBR);
  • the solid electrolyte is an oxide solid electrolyte
  • step S4 the transfer film formation transfers the solid electrolyte layer to the negative electrode
  • step S8 the pressing pressure is 100MPa
  • step S8 the temperature during pressing is 100°C.
  • the maximum pressure of the product of this embodiment is 400MPa.
  • Example 1 is repeated with the only difference being:
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PP;
  • the positive active material is lithium nickel cobalt aluminate.
  • step S3 the negative active material is hard carbon.
  • the conductive agent is Ketjen black (KB).
  • the binder includes carboxymethylcellulose (CMC).
  • the solid electrolyte is a sulfide solid electrolyte.
  • step S4 the transfer film is used to transfer the solid electrolyte layer to the negative and positive electrodes.
  • step S8 the pressing pressure is 1000MPa.
  • step S8 the temperature during pressing is 100°C.
  • the maximum pressure of the product of this embodiment is 600MPa.
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PVC;
  • Example 1 is repeated with the only difference being:
  • the positive active material is lithium nickel cobalt manganese aluminate.
  • the negative active material is lithium titanate.
  • the conductive agent is vapor phase carbon fiber (VGCF).
  • the binder is acrylonitrile butadiene rubber (ABR).
  • step S8 the pressing pressure is 300MPa.
  • step S8 the temperature during pressing is 50°C.
  • the maximum pressure of the product of this embodiment is 450MPa.
  • Example 1 is repeated with the only difference being:
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PS;
  • the positive active material is lithium cobalt oxide.
  • step S3 the negative active material is silicon.
  • the conductive agent is carbon nanotubes (CNT).
  • the adhesive includes butadiene rubber (BR).
  • step S8 the pressing pressure is 500MPa.
  • step S8 the temperature during pressing is 60°C.
  • the maximum pressure of the product of this embodiment is 500MPa.
  • Example 1 is repeated with the only difference being:
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PA;
  • the positive active material is lithium manganate.
  • the negative active material is a silicon-carbon composite material.
  • the conductive agent is carbon nanofiber (CNF).
  • the binder is polyvinylidene fluoride (PVDF).
  • step S8 the pressing pressure is 700MPa.
  • step S8 the temperature during pressing is 70°C.
  • the maximum pressure of the product of this embodiment is 530MPa.
  • Example 1 is repeated with the only difference being:
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin is POM;
  • the positive active material is lithium iron phosphate.
  • the negative active material is a silicon oxide carbon composite material.
  • the conductive agent is graphene.
  • the binder is polytetrafluoroethylene (PTFE).
  • step S8 the pressing pressure is 800MPa.
  • step S8 the temperature during pressing is 80°C.
  • the maximum pressure of the product of this embodiment is 550MPa.
  • Example 1 is repeated with the only difference being:
  • the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PC;
  • the positive active material is a lithium-rich manganese-based material.
  • the conductive agent is graphite.
  • the binder is polyimide (PI).
  • step S8 the pressing pressure is 900MPa.
  • step S8 the temperature during pressing is 90°C.
  • the maximum pressure of the product of this embodiment is 580MPa.
  • Example 1 is repeated with the only difference being:
  • the maximum pressure of the product of this embodiment is 200MPa.
  • Example 1 is repeated with the only difference being:
  • Example 1 is repeated with the only difference being:
  • Example 1 is repeated with the only difference being:
  • the L3-L4 of the product in this example is 0.03mm. If the data is too low, lithium precipitation may easily occur.
  • Example 1 is repeated with the only difference being:

Abstract

Provided in the present invention is an anti-short-circuit solid-state battery. The battery comprises several battery cells, each of which is composed of a positive electrode sheet, an insulating ring, a solid-state electrolyte layer and a negative electrode sheet, wherein the positive electrode sheet comprises a positive current collector and a positive coating layer; the negative electrode sheet comprises a negative current collector and a negative coating layer; the length * width * height dimension of an inner ring of the insulating ring is the same as the length * width * height dimension of the positive coating layer; the insulating ring is arranged on the edge of the positive electrode sheet and around the positive electrode sheet, and completely encloses the positive coating layer; and the solid-state electrolyte layer is arranged between the side of the positive electrode sheet on which the positive coating layer is provided and the side of the negative electrode sheet on which the negative coating layer is provided. In the present invention, for a solid battery, when lamination is performed, an insulating ring is placed in an empty foil region of a positive electrode sheet to fill a gap between the positive electrode sheet and a solid-state electrolyte layer, such that a negative electrode is prevented from being damaged when pressure is applied to a battery cell; the insulating ring bonds the positive electrode sheet to the solid-state electrolyte layer, thereby preventing misplacement of the electrode sheet; the insulating ring achieves the effect of insulation; and the insulating ring surrounds the electrode sheet, and can thus achieve the effect of fire retardation.

Description

一种防短路固态电池及其制备方法Short-circuit proof solid-state battery and preparation method thereof 技术领域Technical field
本说明书一个或多个实施例涉及锂电池技术领域，尤其是涉及一种防短路固态电池及其制备方法。One or more embodiments of this specification relate to the technical field of lithium batteries, and in particular, to a short-circuit-proof solid-state battery and a preparation method thereof.
背景技术Background technique
与液体电解质不同，全固态电池通常采用压力以改善电池内部大量的固固界面接触。当施加的压力较大时，电池内部易在压力的作用下发生短路。而且，负极涂膜区与正极涂膜区之间需要设定尺寸差异，导致负极涂膜区与正极空箔区存在间隙，在对电芯进行压制时，容易引起极片碎裂，从而加剧短路的发生。因此，本领域技术人员已经在防短路固态电池上进行了研究。Unlike liquid electrolytes, all-solid-state batteries usually use pressure to improve the large amount of solid-solid interface contact inside the battery. When the applied pressure is large, a short circuit may easily occur inside the battery under the action of pressure. Moreover, the size difference needs to be set between the negative electrode coating area and the positive electrode coating area, resulting in a gap between the negative electrode coating area and the positive electrode empty foil area. When the battery core is pressed, it is easy to cause the electrode piece to break, thereby aggravating the short circuit. happened. Therefore, those skilled in the art have conducted research on short-circuit proof solid-state batteries.
例如，中国专利申请CN107452985A公开了全固体电池的制造方法、制造装置及全固体电池，制造方法包括：将集电体层、正极合剂层、固体电解质层及负极合剂层分别层叠多个，得到具有层叠方向两端面和侧面的层叠电池；仅对所述层叠电池的所述侧面供给液状树脂；以及使所述液状树脂固化。在得到所述层叠电池的工序中，使所述集电体层、所述正极合剂层、所述固体电解质层以及所述负极合剂层中的至少一层比其它层延伸出而作为延伸层，从所述层叠电池的所述侧面延伸出多个所述延伸层。在所述树脂的供给中，通过仅对所述层叠电池的所述侧面供给液状树脂，使所述液状树脂渗入一个所述延伸层与其它所述延伸层之间的间隙。For example, Chinese patent application CN107452985A discloses a manufacturing method, a manufacturing device and an all-solid-state battery. The manufacturing method includes: stacking multiple current collector layers, positive electrode mixture layers, solid electrolyte layers and negative electrode mixture layers respectively to obtain a laminated batteries on both end surfaces and side surfaces in the stacking direction; supplying liquid resin to only the side surfaces of the laminated battery; and solidifying the liquid resin. In the step of obtaining the laminated battery, at least one of the current collector layer, the positive electrode mixture layer, the solid electrolyte layer, and the negative electrode mixture layer is extended longer than the other layers to serve as an extended layer, A plurality of the extension layers extend from the side of the stacked battery. In the supply of the resin, the liquid resin is supplied only to the side surface of the laminated battery, so that the liquid resin penetrates into the gap between one of the extension layers and the other extension layers.
再例如，中国专利申请CN111864257A公开了能够更可靠地防止短路的全固态电池及其制造方法。全固态电池具有在第一集电体层上形成第一极活性物质层而成的第一极片、在第二集电体层上形成第二极活性物质层而成的 第二极片、以及收容第一极片的袋状的固体电解质层，第二极片和收容于袋状的固体电解质层的第一极片层叠成俯视时重叠，由此第一极活性物质层和第二极活性物质层隔着固体电解质层对置配置。As another example, Chinese patent application CN111864257A discloses an all-solid-state battery that can more reliably prevent short circuits and a manufacturing method thereof. The all-solid-state battery has a first pole piece in which a first pole active material layer is formed on a first current collector layer, and a second pole active material layer is formed on a second current collector layer. The second pole piece and the bag-shaped solid electrolyte layer housing the first pole piece are stacked so as to overlap when viewed from above, so that the first pole active material The second electrode active material layer and the second electrode active material layer are arranged to face each other with the solid electrolyte layer interposed therebetween.
但是，上述专利技术仍然存在如下缺陷：在对电芯施压时容易负极脆裂，施压时电池容易短路等问题。However, the above-mentioned patented technology still has the following shortcomings: the negative electrode is easily brittle when pressure is applied to the battery, and the battery is prone to short circuit when pressure is applied.
发明内容Contents of the invention
有鉴于此，本发明的目的之一在于提供一种防短路固态电池。该固态电池在叠片时将绝缘环置于正极极片空箔区，填补与固态电解质层间空隙，预防在对电芯施压时负极碎裂；绝缘环将正极极片与固态电解质层粘结在一起，防止极片错位；绝缘环起到绝缘作用，预防电池短路；绝缘环包围在极片四周，可起到阻燃作用。In view of this, one object of the present invention is to provide a short-circuit-proof solid-state battery. When stacking the solid-state battery, an insulating ring is placed in the empty foil area of the positive electrode sheet to fill the gap with the solid electrolyte layer and prevent the negative electrode from fragmenting when pressure is applied to the battery core; the insulating ring bonds the positive electrode sheet to the solid electrolyte layer Knot together to prevent the pole pieces from dislocating; the insulating ring plays an insulating role to prevent battery short circuit; the insulating ring surrounds the pole pieces and acts as a flame retardant.
本发明的目的之二在于提供一种防短路固态电池的制备方法。The second object of the present invention is to provide a method for preparing a short-circuit-proof solid-state battery.
基于上述第一个目的，本发明提供如下技术方案：Based on the above first purpose, the present invention provides the following technical solutions:
一种防短路固态电池，包括若干电池单元；所述电池单元由正极极片、绝缘环、固态电解质层和负极极片构成；A short-circuit-proof solid-state battery includes several battery units; the battery unit is composed of a positive electrode plate, an insulating ring, a solid electrolyte layer and a negative electrode plate;
所述正极极片包括正极集流体和正极涂膜层；The positive electrode sheet includes a positive electrode current collector and a positive electrode coating layer;
所述负极极片包括负极集流体和负极涂膜层；The negative electrode piece includes a negative electrode current collector and a negative electrode coating layer;
所述绝缘环内环的长*宽*高的尺寸与正极涂膜层长*宽*高尺寸相同；The length*width*height dimensions of the inner ring of the insulation ring are the same as the length*width*height dimensions of the positive electrode coating layer;
所述绝缘环套设在正极极片的边缘并四方包围住正极涂膜层；The insulating ring is set on the edge of the positive electrode piece and surrounds the positive electrode coating layer on all sides;
在正极极片设有正极涂膜层的一侧和负极极片设有负极涂膜层之间设置固态电解质层；A solid electrolyte layer is provided between the side of the positive electrode piece with the positive electrode coating layer and the negative electrode piece with the negative electrode coating layer;
所述负极涂膜层宽度L1与正极涂膜层宽度L2满足：0.05mm＜L1-L2＜0.3mm；The width L1 of the negative electrode coating layer and the width L2 of the positive electrode coating layer satisfy: 0.05mm<L1-L2<0.3mm;
所述负极涂膜区长度L3与正极涂膜区长度L4满足：0.05mm＜L3-L4＜0.3mm。 The length L3 of the negative electrode coating area and the length L4 of the positive electrode coating area satisfy: 0.05mm<L3-L4<0.3mm.
作为一种实施方式，所述绝缘环软化温度T为40℃＜T＜150℃。As an implementation manner, the softening temperature T of the insulating ring is 40°C<T<150°C.
作为一种实施方式，所述绝缘环由热塑性树脂制成，所述热塑性树脂包括PE、PP、PVC、PS、PA、POM、PC、PI、橡胶中一种或多种；As an embodiment, the insulating ring is made of thermoplastic resin, and the thermoplastic resin includes one or more of PE, PP, PVC, PS, PA, POM, PC, PI, and rubber;
基于上述第二个目的，本发明提供如下技术方案：Based on the above second purpose, the present invention provides the following technical solutions:
一种固态电池的制备方法，包括如下步骤：A method for preparing a solid-state battery, including the following steps:
S1、制备正极极卷S1. Preparation of positive electrode roll
将正极涂膜混合材料涂在正极集流体上，形成正极涂膜层，正极涂膜混合材料包括正极活性物质、导电剂、粘结剂和固态电解质；Coating the positive electrode coating film mixed material on the positive electrode current collector to form a positive electrode coating film layer, the positive electrode coating film mixed material includes positive electrode active material, conductive agent, binder and solid electrolyte;
S2、将绝缘环通过转印或压制的方法粘结到正极集流体并四方包围住正极涂膜层；S2. Bond the insulating ring to the positive electrode current collector by transfer or pressing and surround the positive electrode coating layer in all directions;
S3、制备负极极卷S3. Preparation of negative electrode roll
将负极涂膜混合材料涂在负极集流体上，负极涂膜混合材料包括负极活性物质、导电剂、粘结剂和固态电解质；Coating the negative electrode coating film mixed material on the negative electrode current collector, the negative electrode coating film mixed material includes negative electrode active material, conductive agent, binder and solid electrolyte;
S4、制备固态电解质层S4. Preparation of solid electrolyte layer
通过独立成膜或转印成膜的方式制备固态电解质层；所述固态电解质包括氧化物型固态电解质、硫化物型固态电解质、聚合物电解质、卤化物电解质中的一种或多种；The solid electrolyte layer is prepared by independent film formation or transfer film formation; the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte, and a halide electrolyte;
S5、按设计尺寸要求将正极极卷、绝缘环、固态电解质层和负极极卷进行分切；S5. Cut the positive electrode roll, insulating ring, solid electrolyte layer and negative electrode roll according to the design size requirements;
S6、从下到上将正极极卷、固态电解质层和负极极卷叠片；S6. Laminate the positive electrode roll, solid electrolyte layer and negative electrode roll from bottom to top;
S7、将所述叠片进行封装；S7. Package the stacked sheets;
S8、对封装好的叠片进行压制，得到产品。S8. Press the packaged laminates to obtain the product.
作为一种实施方式，步骤S1中，所述正极活性物质为镍钴锰酸锂、镍钴铝酸锂、镍钴锰铝酸锂、钴酸锂、锰酸锂、磷酸铁锂、富锂锰基材料中的一种或多种。 As an embodiment, in step S1, the positive active material is lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt manganese aluminate, lithium cobalt oxide, lithium manganate, lithium iron phosphate, lithium-rich manganese one or more base materials.
作为一种实施方式，步骤S3中，所述负极活性物质为石墨、硬碳、钛酸锂、硅、硅碳复合材料或氧化硅碳复合材料中的一种或多种。As an embodiment, in step S3, the negative active material is one or more of graphite, hard carbon, lithium titanate, silicon, silicon-carbon composite material or silicon oxide-carbon composite material.
作为一种实施方式，步骤S1和S3中，所述导电剂为乙炔黑(AB)、科琴黑(KB)、气相法碳纤维(VGCF)、碳纳米管(CNT)、纳米碳纤维(CNF)、石墨烯或石墨中的一种或多种。As an embodiment, in steps S1 and S3, the conductive agent is acetylene black (AB), Ketjen black (KB), vaporized carbon fiber (VGCF), carbon nanotube (CNT), carbon nanofiber (CNF), One or more types of graphene or graphite.
作为一种实施方式，步骤S1和S3中，所述粘结剂包括丁苯橡胶(SBR)、羧甲基纤维素(CMC)、丙烯腈丁二烯橡胶(ABR)、丁二烯橡胶(BR)、丁基橡胶(IIR)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚酰亚胺(PI)中的一种或多种。As an embodiment, in steps S1 and S3, the binder includes styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), acrylonitrile butadiene rubber (ABR), butadiene rubber (BR) ), one or more of butyl rubber (IIR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyimide (PI).
作为一种实施方式，步骤S1和S3中，所述固态电解质为氧化物型固态电解质、硫化物型固态电解质中的一种或两种。As an embodiment, in steps S1 and S3, the solid electrolyte is one or both of an oxide solid electrolyte and a sulfide solid electrolyte.
作为一种实施方式，步骤S4中，所述转印成膜将固态电解质层转印至负极或正极上。As an implementation manner, in step S4, the transfer film formation transfers the solid electrolyte layer to the negative electrode or the positive electrode.
作为一种实施方式，步骤S8中，所述压制压力为100MPa-1000MPa。As an embodiment, in step S8, the pressing pressure is 100MPa-1000MPa.
作为一种实施方式，步骤S8中，所述压制时温度为40℃-100℃。As an embodiment, in step S8, the temperature during pressing is 40°C-100°C.
本发明所记载的任何范围包括端值以及端值之间的任何数值以及端值或者端值之间的任意数值所构成的任意子范围。Any range described in the present invention includes the end value and any value between the end value and any subrange formed by the end value or any value between the end value.
如无特殊说明，本发明中的各原料均可通过市售购买获得，本发明中所用的设备可采用所属领域中的常规设备或参照所属领域的现有技术进行。Unless otherwise specified, each raw material in the present invention can be purchased commercially, and the equipment used in the present invention can be carried out using conventional equipment in the field or with reference to the existing technology in the field.
与现有技术相比较，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1)本发明在叠片时将绝缘环置于正极极片空箔区，填补与固态电解质层间空隙，预防对电芯施压时负极碎裂；1) In the present invention, the insulating ring is placed in the empty foil area of the positive electrode sheet during lamination to fill the gap between the solid electrolyte layer and prevent the negative electrode from breaking when pressure is applied to the battery core;
2)绝缘环将正极极片与固态电解质层粘结在一起，防止极片错位；2) The insulating ring bonds the positive electrode piece and the solid electrolyte layer together to prevent the electrode piece from dislocating;
3)绝缘环起到绝缘作用，预防电池短路；3) The insulating ring plays an insulating role to prevent battery short circuit;
4)绝缘环包围在极片四周，可起到阻燃作用。 4) The insulating ring surrounds the pole piece and can play a flame retardant role.
附图说明Description of drawings
图1为本发明固态电池的结构示意图；Figure 1 is a schematic structural diagram of the solid-state battery of the present invention;
图2为本发明中电池单元***俯视图；Figure 2 is an exploded top view of the battery unit in the present invention;
图3为本发明中绝缘环套在正极极片上的结构示意图。Figure 3 is a schematic structural diagram of the insulating ring being placed on the positive electrode piece in the present invention.
具体实施方式Detailed ways
为使本公开的目的、技术方案和优点更加清楚明白，以下结合具体实施例，对本公开进一步详细说明。In order to make the purpose, technical solutions and advantages of the present disclosure clearer, the present disclosure will be further described in detail below with reference to specific embodiments.
需要说明的是，除非另外定义，本说明书一个或多个实施例使用的技术术语或者科学术语应当为本公开所属领域内具有一般技能的人士所理解的通常意义。本说明书一个或多个实施例中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。“包括”或者“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。It should be noted that, unless otherwise defined, the technical terms or scientific terms used in one or more embodiments of this specification should have the usual meanings understood by those with ordinary skills in the field to which this disclosure belongs. The "first", "second" and similar words used in one or more embodiments of this specification do not indicate any order, quantity or importance, but are only used to distinguish different components. Words such as "include" or "comprising" mean that the elements or things appearing before the word include the elements or things listed after the word and their equivalents, without excluding other elements or things.
目前，与液体电解质不同，全固态电池通常采用压力以改善电池内部大量的固固界面接触。当施加的压力较大时，电池内部易在压力的作用下发生短路。而且，负极涂膜层与正极涂膜层之间需要设定尺寸差异，导致负极涂膜层与正极空箔区存在间隙，在对电芯进行压制时，容易引起极片碎裂，从而加剧短路的发生。Currently, unlike liquid electrolytes, all-solid-state batteries usually use pressure to improve the large amount of solid-solid interface contact inside the battery. When the applied pressure is large, a short circuit may easily occur inside the battery under the action of pressure. Moreover, the size difference needs to be set between the negative electrode coating layer and the positive electrode coating layer, resulting in a gap between the negative electrode coating layer and the positive electrode empty foil area. When the battery core is pressed, it is easy to cause the electrode piece to break, thus aggravating the short circuit. happened.
基于此，参见图1所示，作为本发明的一个方面，本发明一种防短路固态电池，包括若干电池单元100；所述电池单元由正极极片10、绝缘环20、固态电解质层30和负极极片40构成；Based on this, as shown in Figure 1, as one aspect of the present invention, a short-circuit proof solid-state battery of the present invention includes a plurality of battery cells 100; the battery cells are composed of a positive electrode plate 10, an insulating ring 20, a solid electrolyte layer 30 and The negative electrode piece 40 is composed of;
所述正极极片10包括正极集流体11和正极涂膜层12；The positive electrode sheet 10 includes a positive electrode current collector 11 and a positive electrode coating layer 12;
所述负极极片40包括负极集流体41和负极涂膜层42；The negative electrode sheet 40 includes a negative electrode current collector 41 and a negative electrode coating layer 42;
所述绝缘环20内环的长*宽*厚的尺寸与正极涂膜层12长*宽*厚尺寸相同； The length*width*thickness dimensions of the inner ring of the insulating ring 20 are the same as the length*width*thickness dimensions of the positive electrode coating layer 12;
所述绝缘环20套在正极极片10的边缘并匹配套设包围住正极涂膜层12，如图3所示；The insulating ring 20 is sleeved on the edge of the positive electrode piece 10 and matched to surround the positive electrode coating layer 12, as shown in Figure 3;
在正极极片10设有正极涂膜层12的一侧和负极极片40设有负极涂膜层42之间设置固态电解质层30；A solid electrolyte layer 30 is provided between the side of the positive electrode piece 10 provided with the positive electrode coating layer 12 and the negative electrode piece 40 provided with the negative electrode coating layer 42;
所述负极涂膜层长度L1与正极涂膜层长度L2满足：0.05mm＜L1-L2＜0.3mm；The length L1 of the negative electrode coating layer and the length L2 of the positive electrode coating layer satisfy: 0.05mm<L1-L2<0.3mm;
所述负极涂膜区宽度L3与正极涂膜区宽度L4满足：0.05mm＜L3-L4＜0.3mm。The width L3 of the negative electrode coating area and the width L4 of the positive electrode coating area satisfy: 0.05mm<L3-L4<0.3mm.
作为一种实施方式，所述绝缘环软化温度T为40℃＜T＜150℃。As an implementation manner, the softening temperature T of the insulating ring is 40°C<T<150°C.
作为一种实施方式，所述绝缘环由热塑性树脂制成，所述热塑性树脂包括PE、PP、PVC、PS、PA、POM、PC、PI、橡胶中一种或多种；As an embodiment, the insulating ring is made of thermoplastic resin, and the thermoplastic resin includes one or more of PE, PP, PVC, PS, PA, POM, PC, PI, and rubber;
作为本发明的另一个方面，参见图2所示，本发明还提供了上述固态电池的制备方法，包括如下步骤：As another aspect of the present invention, as shown in Figure 2, the present invention also provides a method for preparing the above-mentioned solid-state battery, which includes the following steps:
S1、制备正极极卷S1. Preparation of positive electrode roll
将正极涂膜混合材料涂在正极集流体上，形成正极涂膜层，正极涂膜混合材料包括正极活性物质、导电剂、粘结剂和固态电解质；Coating the positive electrode coating film mixed material on the positive electrode current collector to form a positive electrode coating film layer, the positive electrode coating film mixed material includes positive electrode active material, conductive agent, binder and solid electrolyte;
S2、将绝缘环通过转印或压制的方法粘结到正极集流体并四方包围住正极涂膜层；S2. Bond the insulating ring to the positive electrode current collector by transfer or pressing and surround the positive electrode coating layer in all directions;
S3、制备负极极卷S3. Preparation of negative electrode roll
将负极涂膜混合材料涂在负极集流体上，负极涂膜混合材料包括负极活性物质、导电剂、粘结剂和固态电解质；Coating the negative electrode coating film mixed material on the negative electrode current collector, the negative electrode coating film mixed material includes negative electrode active material, conductive agent, binder and solid electrolyte;
S4、制备固态电解质层S4. Preparation of solid electrolyte layer
通过独立成膜或转印成膜的方式制备固态电解质层；所述固态电解质包括氧化物型固态电解质、硫化物型固态电解质、聚合物电解质、卤化物电解质中的一种或多种； The solid electrolyte layer is prepared by independent film formation or transfer film formation; the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte, and a halide electrolyte;
S5、按设计尺寸要求将正极极卷、绝缘环、固态电解质层和负极极卷进行分切；S5. Cut the positive electrode roll, insulating ring, solid electrolyte layer and negative electrode roll according to the design size requirements;
S6、从下到上将正极极卷、固态电解质层和负极极卷叠片；S6. Laminate the positive electrode roll, solid electrolyte layer and negative electrode roll from bottom to top;
S7、将所述叠片进行封装；S7. Package the stacked sheets;
S8、对封装好的叠片进行压制，得到产品。S8. Press the packaged laminates to obtain the product.
根据本发明的某些实施例，步骤S1中，所述正极活性物质为镍钴锰酸锂、镍钴铝酸锂、镍钴锰铝酸锂、钴酸锂、锰酸锂、磷酸铁锂、富锂锰基材料中的一种或多种。According to some embodiments of the present invention, in step S1, the positive active material is lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium nickel cobalt manganate, lithium cobalt oxide, lithium manganate, lithium iron phosphate, One or more of the lithium-rich manganese-based materials.
根据本发明的某些实施例，步骤S3中，所述负极活性物质为石墨、硬碳、钛酸锂、硅、硅碳复合材料或氧化硅碳复合材料中的一种或多种。According to some embodiments of the present invention, in step S3, the negative active material is one or more of graphite, hard carbon, lithium titanate, silicon, silicon-carbon composite material or silicon oxide-carbon composite material.
根据本发明的某些实施例，步骤S1和S3中，所述导电剂为乙炔黑(AB)、科琴黑(KB)、气相法碳纤维(VGCF)、碳纳米管(CNT)、纳米碳纤维(CNF)、石墨烯或石墨中的一种或多种。According to some embodiments of the present invention, in steps S1 and S3, the conductive agent is acetylene black (AB), Ketjen black (KB), vaporized carbon fiber (VGCF), carbon nanotube (CNT), nanocarbon fiber ( CNF), graphene or graphite.
根据本发明的某些实施例，步骤S1和S3中，所述粘结剂包括丁苯橡胶(SBR)、羧甲基纤维素(CMC)、丙烯腈丁二烯橡胶(ABR)、丁二烯橡胶(BR)、丁基橡胶(IIR)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚酰亚胺(PI)中的一种或多种。According to some embodiments of the present invention, in steps S1 and S3, the binder includes styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), acrylonitrile butadiene rubber (ABR), butadiene One or more of rubber (BR), butyl rubber (IIR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyimide (PI).
根据本发明的某些实施例，步骤S1和S3中，所述固态电解质为氧化物型固态电解质、硫化物型固态电解质中的一种或两种。According to some embodiments of the present invention, in steps S1 and S3, the solid electrolyte is one or both of an oxide solid electrolyte and a sulfide solid electrolyte.
根据本发明的某些实施例，步骤S4中，所述转印成膜将固态电解质层转印至负极或正极上。According to some embodiments of the present invention, in step S4, the transfer film formation transfers the solid electrolyte layer to the negative electrode or the positive electrode.
根据本发明的某些实施例，步骤S8中，所述压制压力为100MPa-1000MPa。According to some embodiments of the present invention, in step S8, the pressing pressure is 100MPa-1000MPa.
根据本发明的某些实施例，步骤S8中，所述压制时温度为40℃-100℃。According to some embodiments of the present invention, in step S8, the temperature during pressing is 40°C-100°C.
实施例1 Example 1
本发明一种防短路固态电池，包括若干电池单元100；所述电池单元由正极极片10、绝缘环20、固态电解质层30和负极极片40构成；A short-circuit-proof solid-state battery of the present invention includes several battery units 100; the battery unit is composed of a positive electrode piece 10, an insulating ring 20, a solid electrolyte layer 30 and a negative electrode piece 40;
所述正极极片10包括正极集流体11和正极涂膜层12；The positive electrode sheet 10 includes a positive electrode current collector 11 and a positive electrode coating layer 12;
所述负极极片40包括负极集流体41和负极涂膜层42；The negative electrode sheet 40 includes a negative electrode current collector 41 and a negative electrode coating layer 42;
所述绝缘环20内环的长*宽*厚的尺寸与正极涂膜层12长*宽*厚尺寸相同；The length*width*thickness dimensions of the inner ring of the insulating ring 20 are the same as the length*width*thickness dimensions of the positive electrode coating layer 12;
所述绝缘环20套在正极极片10的边缘并匹配套设包围住正极涂膜层12，如图3所示；The insulating ring 20 is sleeved on the edge of the positive electrode piece 10 and matched to surround the positive electrode coating layer 12, as shown in Figure 3;
在正极极片10设有正极涂膜层12的一侧和负极极片40设有负极涂膜层42之间设置固态电解质层30；A solid electrolyte layer 30 is provided between the side of the positive electrode piece 10 provided with the positive electrode coating layer 12 and the negative electrode piece 40 provided with the negative electrode coating layer 42;
所述负极涂膜层长度L1与正极涂膜层长度L2满足：0.05mm＜L1-L2＜0.3mm；The length L1 of the negative electrode coating layer and the length L2 of the positive electrode coating layer satisfy: 0.05mm<L1-L2<0.3mm;
所述负极涂膜区宽度L3与正极涂膜区宽度L4满足：0.05mm＜L3-L4＜0.3mm；The width L3 of the negative electrode coating area and the width L4 of the positive electrode coating area satisfy: 0.05mm<L3-L4<0.3mm;
所述绝缘环软化温度T为40℃＜T＜150℃；The softening temperature T of the insulating ring is 40°C<T<150°C;
所述绝缘环由热塑性树脂制成，所述热塑性树脂为PE；The insulating ring is made of thermoplastic resin, and the thermoplastic resin is PE;
一种固态电池的制备方法，包括如下步骤：A method for preparing a solid-state battery, including the following steps:
S1、制备正极极卷S1. Preparation of positive electrode roll
将正极涂膜混合材料涂在正极集流体上，形成正极涂膜层，正极涂膜混合材料包括正极活性物质、导电剂、粘结剂和固态电解质；Coating the positive electrode coating film mixed material on the positive electrode current collector to form a positive electrode coating film layer, the positive electrode coating film mixed material includes positive electrode active material, conductive agent, binder and solid electrolyte;
S2、将绝缘环通过转印或压制的方法粘结到正极集流体并四方包围住正极涂膜层；S2. Bond the insulating ring to the positive electrode current collector by transfer or pressing and surround the positive electrode coating layer in all directions;
S3、制备负极极卷S3. Preparation of negative electrode roll
将负极涂膜混合材料涂在负极集流体上，负极涂膜混合材料包括负极活性物质、导电剂、粘结剂和固态电解质； Coating the negative electrode coating film mixed material on the negative electrode current collector, the negative electrode coating film mixed material includes negative electrode active material, conductive agent, binder and solid electrolyte;
S4、制备固态电解质层S4. Preparation of solid electrolyte layer
通过独立成膜或转印成膜的方式制备固态电解质层；所述固态电解质包括氧化物型固态电解质、硫化物型固态电解质、聚合物电解质、卤化物电解质中的一种或多种；The solid electrolyte layer is prepared by independent film formation or transfer film formation; the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte, and a halide electrolyte;
S5、按设计尺寸要求将正极极卷、绝缘环、固态电解质层和负极极卷进行分切；S5. Cut the positive electrode roll, insulating ring, solid electrolyte layer and negative electrode roll according to the design size requirements;
S6、从下到上将正极极卷、固态电解质层和负极极卷叠片；S6. Laminate the positive electrode roll, solid electrolyte layer and negative electrode roll from bottom to top;
S7、将所述叠片进行封装；S7. Package the stacked sheets;
S8、对封装好的叠片进行压制，得到产品；S8. Press the packaged laminations to obtain the product;
步骤S1中，所述正极活性物质为镍钴锰酸锂；In step S1, the positive active material is lithium nickel cobalt manganate;
步骤S3中，所述负极活性物质为石墨；In step S3, the negative active material is graphite;
步骤S1和S3中，所述导电剂为乙炔黑；In steps S1 and S3, the conductive agent is acetylene black;
步骤S1和S3中，所述粘结剂为丁苯橡胶(SBR)；In steps S1 and S3, the binder is styrene-butadiene rubber (SBR);
步骤S1和S3中，所述固态电解质为氧化物型固态电解质；In steps S1 and S3, the solid electrolyte is an oxide solid electrolyte;
步骤S4中，所述转印成膜将固态电解质层转印至负极上；In step S4, the transfer film formation transfers the solid electrolyte layer to the negative electrode;
步骤S8中，所述压制压力为100MPa；In step S8, the pressing pressure is 100MPa;
步骤S8中，所述压制时温度为100℃。In step S8, the temperature during pressing is 100°C.
经检测，本实施例产品的最大承受压力为400MPa。After testing, the maximum pressure of the product of this embodiment is 400MPa.
实施例2Example 2
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述固态电池中，所述绝缘环由热塑性树脂制成，所述热塑性树脂为PP；In the solid-state battery, the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PP;
步骤S1中，所述正极活性物质为镍钴铝酸锂。In step S1, the positive active material is lithium nickel cobalt aluminate.
步骤S3中，所述负极活性物质为硬碳。In step S3, the negative active material is hard carbon.
步骤S1和S3中，所述导电剂为科琴黑(KB)。In steps S1 and S3, the conductive agent is Ketjen black (KB).
步骤S1和S3中，所述粘结剂包括羧甲基纤维素(CMC)。 In steps S1 and S3, the binder includes carboxymethylcellulose (CMC).
步骤S1和S3中，所述固态电解质为硫化物型固态电解质。In steps S1 and S3, the solid electrolyte is a sulfide solid electrolyte.
步骤S4中，所述转印成膜将固态电解质层转印至负正极上。In step S4, the transfer film is used to transfer the solid electrolyte layer to the negative and positive electrodes.
步骤S8中，所述压制压力为1000MPa。In step S8, the pressing pressure is 1000MPa.
步骤S8中，所述压制时温度为100℃。In step S8, the temperature during pressing is 100°C.
经检测，本实施例产品的最大承受压力为600MPa。After testing, the maximum pressure of the product of this embodiment is 600MPa.
实施例3Example 3
所述固态电池中，所述绝缘环由热塑性树脂制成，所述热塑性树脂为PVC；In the solid-state battery, the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PVC;
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
步骤S1中，所述正极活性物质为镍钴锰铝酸锂。In step S1, the positive active material is lithium nickel cobalt manganese aluminate.
步骤S3中，所述负极活性物质为钛酸锂。In step S3, the negative active material is lithium titanate.
步骤S1和S3中，所述导电剂为气相法碳纤维(VGCF)。In steps S1 and S3, the conductive agent is vapor phase carbon fiber (VGCF).
步骤S1和S3中，所述粘结剂为丙烯腈丁二烯橡胶(ABR)。In steps S1 and S3, the binder is acrylonitrile butadiene rubber (ABR).
步骤S8中，所述压制压力为300MPa。In step S8, the pressing pressure is 300MPa.
步骤S8中，所述压制时温度为50℃。In step S8, the temperature during pressing is 50°C.
经检测，本实施例产品的最大承受压力为450MPa。After testing, the maximum pressure of the product of this embodiment is 450MPa.
实施例4Example 4
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述固态电池中，所述绝缘环由热塑性树脂制成，所述热塑性树脂为PS；In the solid-state battery, the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PS;
步骤S1中，所述正极活性物质为钴酸锂。In step S1, the positive active material is lithium cobalt oxide.
步骤S3中，所述负极活性物质为硅。In step S3, the negative active material is silicon.
步骤S1和S3中，所述导电剂为碳纳米管(CNT)。In steps S1 and S3, the conductive agent is carbon nanotubes (CNT).
步骤S1和S3中，所述粘结剂包括丁二烯橡胶(BR)。In steps S1 and S3, the adhesive includes butadiene rubber (BR).
步骤S8中，所述压制压力为500MPa。In step S8, the pressing pressure is 500MPa.
步骤S8中，所述压制时温度为60℃。 In step S8, the temperature during pressing is 60°C.
经检测，本实施例产品的最大承受压力为500MPa。After testing, the maximum pressure of the product of this embodiment is 500MPa.
实施例5Example 5
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述固态电池中，所述绝缘环由热塑性树脂制成，所述热塑性树脂为PA；In the solid-state battery, the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PA;
步骤S1中，所述正极活性物质为锰酸锂。In step S1, the positive active material is lithium manganate.
步骤S3中，所述负极活性物质为硅碳复合材料。In step S3, the negative active material is a silicon-carbon composite material.
步骤S1和S3中，所述导电剂为纳米碳纤维(CNF)。In steps S1 and S3, the conductive agent is carbon nanofiber (CNF).
步骤S1和S3中，所述粘结剂为聚偏二氟乙烯(PVDF)。In steps S1 and S3, the binder is polyvinylidene fluoride (PVDF).
步骤S8中，所述压制压力为700MPa。In step S8, the pressing pressure is 700MPa.
步骤S8中，所述压制时温度为70℃。In step S8, the temperature during pressing is 70°C.
经检测，本实施例产品的最大承受压力为530MPa。After testing, the maximum pressure of the product of this embodiment is 530MPa.
实施例6Example 6
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述固态电池中，所述绝缘环由热塑性树脂制成，所述热塑性树脂为POM；In the solid-state battery, the insulating ring is made of thermoplastic resin, and the thermoplastic resin is POM;
步骤S1中，所述正极活性物质为磷酸铁锂。In step S1, the positive active material is lithium iron phosphate.
步骤S3中，所述负极活性物质为氧化硅碳复合材料。In step S3, the negative active material is a silicon oxide carbon composite material.
步骤S1和S3中，所述导电剂为石墨烯。In steps S1 and S3, the conductive agent is graphene.
步骤S1和S3中，所述粘结剂为聚四氟乙烯(PTFE)。In steps S1 and S3, the binder is polytetrafluoroethylene (PTFE).
步骤S8中，所述压制压力为800MPa。In step S8, the pressing pressure is 800MPa.
步骤S8中，所述压制时温度为80℃。In step S8, the temperature during pressing is 80°C.
经检测，本实施例产品的最大承受压力为550MPa。After testing, the maximum pressure of the product of this embodiment is 550MPa.
实施例7Example 7
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述固态电池中，所述绝缘环由热塑性树脂制成，所述热塑性树脂为PC； In the solid-state battery, the insulating ring is made of thermoplastic resin, and the thermoplastic resin is PC;
步骤S1中，所述正极活性物质为富锂锰基材料。In step S1, the positive active material is a lithium-rich manganese-based material.
步骤S1和S3中，所述导电剂为石墨。In steps S1 and S3, the conductive agent is graphite.
步骤S1和S3中，所述粘结剂聚酰亚胺(PI)。In steps S1 and S3, the binder is polyimide (PI).
步骤S8中，所述压制压力为900MPa。In step S8, the pressing pressure is 900MPa.
步骤S8中，所述压制时温度为90℃。In step S8, the temperature during pressing is 90°C.
经检测，本实施例产品的最大承受压力为580MPa。After testing, the maximum pressure of the product of this embodiment is 580MPa.
对比例1Comparative example 1
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
没有在正极极片和固态电解质层间设置绝缘环。There is no insulating ring between the positive electrode plate and the solid electrolyte layer.
经检测，本实施例产品的最大承受压力为200MPa。After testing, the maximum pressure of the product of this embodiment is 200MPa.
对比例2Comparative example 2
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述负极涂膜层长度L1与正极涂膜层长度L2满足：L1-L2＝0.02mm。The length L1 of the negative electrode coating layer and the length L2 of the positive electrode coating layer satisfy: L1-L2=0.02mm.
经检测，本实施例产品的L1-L2＝0.02mm，数据过低易产生析锂。After testing, the product of this example has L1-L2 = 0.02mm. If the data is too low, lithium precipitation will easily occur.
对比例3Comparative example 3
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述负极涂膜层长度L1与正极涂膜层长度L2满足：L1-L2＝0.5mm。The length L1 of the negative electrode coating layer and the length L2 of the positive electrode coating layer satisfy: L1-L2=0.5mm.
经检测，本实施例产品的L1-L2＝0.5mm，数据过高会降低能量密度。After testing, the product of this embodiment has L1-L2 = 0.5mm. If the data is too high, the energy density will be reduced.
对比例4Comparative example 4
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述负极涂膜区宽度L3与正极涂膜区宽度L4满足：L3-L4＝0.03mm。The width L3 of the negative electrode coating area and the width L4 of the positive electrode coating area satisfy: L3-L4=0.03mm.
经检测，本实施例产品的L3-L4＝0.03mm，数据过低易产生析锂。After testing, the L3-L4 of the product in this example is 0.03mm. If the data is too low, lithium precipitation may easily occur.
对比例5Comparative example 5
重复实施例1，其不同之处仅在于：Example 1 is repeated with the only difference being:
所述负极涂膜区宽度L3与正极涂膜区宽度L4满足：L3-L4＝0.6mm。 The width L3 of the negative electrode coating area and the width L4 of the positive electrode coating area satisfy: L3-L4=0.6mm.
经检测，本实施例产品的L3-L4＝0.6mm，数据过高会降低能量密度。After testing, the product of this embodiment has L3-L4=0.6mm. If the data is too high, the energy density will be reduced.
上述对本说明书特定实施例进行了描述。其它实施例在所附权利要求书的范围内。在一些情况下，在权利要求书中记载的动作或步骤可以按照不同于实施例中的顺序来执行并且仍然可以实现期望的结果。另外，在说明书中描绘的过程不一定要求示出的特定顺序或者连续顺序才能实现期望的结果。在某些实施方式中，多任务处理和并行处理也是可以的或者可能是有利的。The foregoing describes specific embodiments of this specification. Other embodiments are within the scope of the appended claims. In some cases, the actions or steps recited in the claims can be performed in a different order than in the embodiments and still achieve desired results. Additionally, the processes depicted in the specification do not necessarily require the specific order shown, or sequential order, to achieve desirable results. Multitasking and parallel processing are also possible or may be advantageous in certain implementations.
所属领域的普通技术人员应当理解：以上任何实施例的讨论仅为示例性的，并非旨在暗示本公开的范围(包括权利要求)被限于这些例子；在本公开的思路下，以上实施例或者不同实施例中的技术特征之间也可以进行组合，步骤可以以任意顺序实现，并存在如上所述的本说明书一个或多个实施例的不同方面的许多其它变化，为了简明它们没有在细节中提供。Those of ordinary skill in the art should understand that the discussion of any above embodiments is only illustrative, and is not intended to imply that the scope of the present disclosure (including the claims) is limited to these examples; under the spirit of the present disclosure, the above embodiments or Technical features in different embodiments can also be combined, steps can be implemented in any order, and there are many other variations in different aspects of one or more embodiments of this specification as described above, which are not included in the details for the sake of simplicity. supply.
另外，为简化说明和讨论，在阐述了具体细节以描述本公开的示例性实施例的情况下，对本领域技术人员来说显而易见的是，可以在没有这些具体细节的情况下或者这些具体细节有变化的情况下实施本说明书一个或多个实施例。因此，这些描述应被认为是说明性的而不是限制性的。In addition, to simplify illustration and discussion, where specific details are set forth to describe the exemplary embodiments of the present disclosure, it will be apparent to those skilled in the art that the specific details may be practiced without or with the specific details. One or more embodiments of this specification may be implemented with variations. Accordingly, these descriptions should be considered illustrative rather than restrictive.
尽管已经结合了本公开的具体实施例对本公开进行了描述，但是根据前面的描述，这些实施例的很多替换、修改和变型对本领域普通技术人员来说将是显而易见的。Although the present disclosure has been described in conjunction with specific embodiments thereof, many alternatives, modifications, and variations of these embodiments will be apparent to those of ordinary skill in the art from the foregoing description.
本说明书一个或多个实施例旨在涵盖落入所附权利要求的宽泛范围之内的所有这样的替换、修改和变型。因此，凡在本说明书一个或多个实施例的精神和原则之内，所做的任何省略、修改、等同替换、改进等，均应包含在本公开的保护范围之内。 This description of one or more embodiments is intended to embrace all such alternatives, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of one or more embodiments of this specification shall be included in the protection scope of this disclosure.

Claims (12)

  1. 一种防短路固态电池，包括若干电池单元；其特征在于：所述电池单元由正极极片、绝缘环、固态电解质层和负极极片构成；A short-circuit-proof solid-state battery includes several battery units; it is characterized in that: the battery unit is composed of a positive electrode plate, an insulating ring, a solid electrolyte layer and a negative electrode plate;
    所述正极极片包括正极集流体和正极涂膜层；The positive electrode sheet includes a positive electrode current collector and a positive electrode coating layer;
    所述负极极片包括负极集流体和负极涂膜层；The negative electrode piece includes a negative electrode current collector and a negative electrode coating layer;
    所述绝缘环内环的长*宽*高的尺寸与正极涂膜层长*宽*高尺寸相同；The length*width*height dimensions of the inner ring of the insulation ring are the same as the length*width*height dimensions of the positive electrode coating layer;
    所述绝缘环套设在正极极片的边缘并四方包围住正极涂膜层；The insulating ring is set on the edge of the positive electrode piece and surrounds the positive electrode coating layer on all sides;
    在正极极片设有正极涂膜层的一侧和负极极片设有负极涂膜层之间设置固态电解质层；A solid electrolyte layer is provided between the side of the positive electrode piece with the positive electrode coating layer and the negative electrode piece with the negative electrode coating layer;
    所述负极涂膜层宽度L1与正极涂膜层宽度L2满足：0.05mm＜L1-L2＜0.3mm；The width L1 of the negative electrode coating layer and the width L2 of the positive electrode coating layer satisfy: 0.05mm<L1-L2<0.3mm;
    所述负极涂膜区长度L3与正极涂膜区长度L4满足：0.05mm＜L3-L4＜0.3mm。The length L3 of the negative electrode coating area and the length L4 of the positive electrode coating area satisfy: 0.05mm<L3-L4<0.3mm.
  2. 根据权利要求1所述的防短路固态电池，其特征在于：所述绝缘环软化温度T为40℃＜T＜150℃。The anti-short-circuit solid-state battery according to claim 1, characterized in that the softening temperature T of the insulating ring is 40°C<T<150°C.
  3. 根据权利要求1所述的防短路固态电池，其特征在于：所述绝缘环由热塑性树脂制成，所述热塑性树脂包括PE、PP、PVC、PS、PA、POM、PC、PI、橡胶中一种或多种。The anti-short-circuit solid-state battery according to claim 1, characterized in that: the insulating ring is made of thermoplastic resin, and the thermoplastic resin includes one of PE, PP, PVC, PS, PA, POM, PC, PI, and rubber. Kind or variety.
  4. 根据权利要求1-3中任一所述固态电池的制备方法，其特征在于，包括如下步骤：The method for preparing a solid-state battery according to any one of claims 1-3, characterized in that it includes the following steps:
    S1、制备正极极卷S1. Preparation of positive electrode roll
    将正极涂膜混合材料涂在正极集流体上，形成正极涂膜层，正极涂膜混合材料包括正极活性物质、导电剂、粘结剂和固态电解质；Coating the positive electrode coating film mixed material on the positive electrode current collector to form a positive electrode coating film layer, the positive electrode coating film mixed material includes positive electrode active material, conductive agent, binder and solid electrolyte;
    S2、将绝缘环通过转印或压制的方法粘结到正极集流体并四方包围住正 极涂膜层；S2. Bond the insulating ring to the positive electrode current collector by transfer printing or pressing and surround the positive electrode in all directions. extremely coating layer;
    S3、制备负极极卷S3. Preparation of negative electrode roll
    将负极涂膜混合材料涂在负极集流体上，负极涂膜混合材料包括负极活性物质、导电剂、粘结剂和固态电解质；Coating the negative electrode coating film mixed material on the negative electrode current collector, the negative electrode coating film mixed material includes negative electrode active material, conductive agent, binder and solid electrolyte;
    S4、制备固态电解质层S4. Preparation of solid electrolyte layer
    通过独立成膜或转印成膜的方式制备固态电解质层；所述固态电解质包括氧化物型固态电解质、硫化物型固态电解质、聚合物电解质、卤化物电解质中的一种或多种；The solid electrolyte layer is prepared by independent film formation or transfer film formation; the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, a polymer electrolyte, and a halide electrolyte;
    S5、按设计尺寸要求将正极极卷、绝缘环、固态电解质层和负极极卷进行分切；S5. Cut the positive electrode roll, insulating ring, solid electrolyte layer and negative electrode roll according to the design size requirements;
    S6、从下到上将正极极卷、固态电解质层和负极极卷叠片；S6. Laminate the positive electrode roll, solid electrolyte layer and negative electrode roll from bottom to top;
    S7、将所述叠片进行封装；S7. Package the stacked sheets;
    S8、对封装好的叠片进行压制，得到产品。S8. Press the packaged laminates to obtain the product.
  5. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S1中，所述正极活性物质为镍钴锰酸锂、镍钴铝酸锂、镍钴锰铝酸锂、钴酸锂、锰酸锂、磷酸铁锂、富锂锰基材料中的一种或多种。The preparation method of a solid-state battery according to claim 4, characterized in that: in step S1, the positive active material is lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt manganese aluminate, lithium cobalt oxide, One or more of lithium manganate, lithium iron phosphate, and lithium-rich manganese-based materials.
  6. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S3中，所述负极活性物质为石墨、硬碳、钛酸锂、硅、硅碳复合材料或氧化硅碳复合材料中的一种或多种。The preparation method of a solid-state battery according to claim 4, characterized in that: in step S3, the negative active material is graphite, hard carbon, lithium titanate, silicon, silicon-carbon composite material or silicon oxide-carbon composite material. one or more.
  7. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S1和S3中，所述导电剂为乙炔黑、科琴黑、气相法碳纤维、碳纳米管、纳米碳纤维、石墨烯或石墨中的一种或多种。The preparation method of solid-state battery according to claim 4, characterized in that: in steps S1 and S3, the conductive agent is acetylene black, Ketjen black, gas phase carbon fiber, carbon nanotube, nano carbon fiber, graphene or graphite one or more of them.
  8. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S1和S3中，所述粘结剂包括丁苯橡胶、羧甲基纤维素、丙烯腈丁二烯橡胶、丁二烯橡胶、丁基橡胶、聚偏二氟乙烯、聚四氟乙烯、聚酰亚胺中的一种或多种。 The preparation method of a solid-state battery according to claim 4, characterized in that: in steps S1 and S3, the binder includes styrene-butadiene rubber, carboxymethyl cellulose, acrylonitrile butadiene rubber, butadiene rubber , butyl rubber, one or more of polyvinylidene fluoride, polytetrafluoroethylene, and polyimide.
  9. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S1和S3中，所述固态电解质为氧化物型固态电解质、硫化物型固态电解质中的一种或两种。The method for preparing a solid-state battery according to claim 4, wherein in steps S1 and S3, the solid electrolyte is one or both of an oxide solid electrolyte and a sulfide solid electrolyte.
  10. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S4中，所述转印成膜将固态电解质层转印至负极或正极上。The preparation method of a solid-state battery according to claim 4, characterized in that in step S4, the transfer film transfer transfers the solid electrolyte layer to the negative electrode or the positive electrode.
  11. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S8中，所述压制压力为100MPa-1000MPa。The method for preparing a solid-state battery according to claim 4, characterized in that in step S8, the pressing pressure is 100MPa-1000MPa.
  12. 根据权利要求4所述的固态电池的制备方法，其特征在于：步骤S8中，所述压制时温度为40℃-100℃。 The method for preparing a solid-state battery according to claim 4, characterized in that in step S8, the temperature during pressing is 40°C-100°C.
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