CN113629299A - Solid-state battery and preparation process thereof - Google Patents

Solid-state battery and preparation process thereof Download PDF

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CN113629299A
CN113629299A CN202110786111.XA CN202110786111A CN113629299A CN 113629299 A CN113629299 A CN 113629299A CN 202110786111 A CN202110786111 A CN 202110786111A CN 113629299 A CN113629299 A CN 113629299A
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lithium
solid
electrolyte layer
solvent
gel electrolyte
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李亚迪
胡恒广
闫冬成
张广涛
王博
刘文渊
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Hebei Guangxing Semiconductor Technology Co Ltd
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Hebei Guangxing Semiconductor Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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

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  • General Chemical & Material Sciences (AREA)
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  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
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  • Secondary Cells (AREA)
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Abstract

The utility model relates to a solid-state battery and a preparation process thereof, the process adds gel electrolyte layers between a positive plate and a solid-state electrolyte and/or between a negative plate and the solid-state electrolyte respectively, and softens the gel electrolyte and extends into a positive (negative) pole material layer and/or the solid-state electrolyte layer of the pole piece in a hot pressing way, so that the contact with the solid-state electrolyte and the positive (negative) pole piece is tighter, the contact area between the solid-state electrolyte and the pole piece is increased, the impedance is reduced, and the defect of small contact area caused by the contact between the solid-state electrolyte and the pole piece point in the existing solid-state battery is solved. The prepared solid-state battery has small interface impedance and good rate capability.

Description

Solid-state battery and preparation process thereof
Technical Field
The disclosure relates to the technical field of solid-state batteries, and particularly relates to a solid-state battery and a preparation process thereof.
Background
With the rapid development of human industry, the dependence on energy is gradually increased, the energy situation is more and more severe, and the lithium ion battery as an efficient and clean chemical energy storage device is more and more emphasized by the academic and industrial fields, and a great deal of research and exploration is carried out. In recent years, governments around the world have vigorously promoted the application of lithium ion batteries to automobiles, the lithium ion batteries currently occupy the electric automobile market around the world, and the lithium ion batteries are likely to be applied to the power grid energy storage market on a large scale in the future. In electric vehicles, energy density and safety are important indicators of power battery performance.
The sales volume of new energy electric vehicles around the world is increasing year by year, but the safety accidents are increased, and the safety problem is increasingly highlighted. Safety issues have severely hampered further development and application of lithium ion batteries. The lithium ion battery used by the electric automobile mainly adopts organic liquid electrolyte, the electrochemical window of the lithium ion battery is narrow (< 4.8V), the electrolyte can generate side reaction on the positive electrode side and the negative electrode side, consumes lithium ions and generates more byproducts, the working temperature range of the lithium ion battery is narrow (< 80 ℃), and the lithium ion battery has the defects of low working voltage and difficult use at high temperature. The battery adopting the liquid electrolyte is very likely to have liquid leakage in the production or use process, so that certain potential safety hazard is brought. Meanwhile, the liquid electrolyte contains a plurality of low-melting-point organic solvents, has the defects of low boiling point, low flash point, flammability, volatility and the like, and is one of the main factors influencing the safety performance of the battery.
A solid-state battery is a battery using a solid electrode and a solid electrolyte. Compared with the traditional lithium ion battery, the lithium ion battery has the greatest characteristics that the solid electrolyte is adopted to replace the liquid electrolyte, has the characteristics of high energy density, high safety, good high-temperature performance and the like, and is the development direction of the future lithium battery. (1) The high-energy density and partial solid electrolyte material have a wide electrochemical window, the high strength of the solid electrolyte material can prevent the penetration of lithium dendrites, and the characteristics enable a high-voltage positive electrode material and a lithium metal negative electrode with high gram capacity to be hopefully introduced into a battery, so that the energy density of the whole battery can be improved. (2) The safety is the most outstanding advantage of the solid-state battery, and the inorganic solid-state electrolyte has non-inflammability due to the characteristics of non-volatility and non-leakage of the solid-state electrolyte, so that the potential safety hazards of electrolyte leakage and inflammability are fundamentally eliminated. (3) The high-temperature performance is good, and the solid electrolyte can keep the capability of transmitting ions in a wider temperature range, so that the solid-state battery has a wider working temperature range, especially at high temperature.
However, solid-state batteries face many technical difficulties at present, and commercialization thereof faces many challenges. Wherein, the high interface impedance between the solid electrolyte and the electrode plate is one of the technical difficulties which need to be overcome urgently. The contact mode between the solid electrolyte and the electrode is solid-solid contact, the interface has no wettability, great interface contact resistance is formed, and Li at the interface is reduced+Migration kinetics, which severely affect cell performance.
The current publications show that there are many documents on improving the interfacial resistance of solid-state batteries from the structural aspect. Among them, CN111009682A and CN111834626A propose to improve interface impedance by placing two layers of a first solid electrolyte and a second solid electrolyte having different thicknesses and roughness between a positive electrode sheet and a negative electrode sheet. However, in essence, the solid electrolyte and the pole piece are still in contact with each other between a solid and a solid, and between a point and a point in the schemes, so that the contact area is small, and the interface impedance is still large.
Disclosure of Invention
The purpose of the disclosure is to provide a solid-state battery and a preparation process thereof, wherein the solid-state battery has small interface impedance and good rate capability.
In order to achieve the above object, a first aspect of the present disclosure provides a process for producing a solid-state battery, the process comprising the steps of:
s1, coating a first solution containing a first gel electrolyte on the positive electrode material layer of the positive electrode plate, and removing the first solvent in the first solution to form a first electrode plate coated with the first gel electrolyte layer; coating a second solution containing a second gel electrolyte on the negative electrode material layer of the negative electrode plate, and removing the first solvent in the second solution to form a second electrode plate coated with the second gel electrolyte layer;
and S2, sequentially laminating the first pole piece, the solid electrolyte and the second pole piece, and then carrying out hot pressing treatment.
A second aspect of the present disclosure provides a solid-state battery prepared using the process of the first aspect of the present disclosure.
A third aspect of the present disclosure provides a solid-state battery including a positive electrode sheet, a solid-state electrolyte layer, and a negative electrode sheet that are sequentially stacked; a first gel electrolyte layer is arranged between the positive electrode plate and the solid electrolyte layer, and/or a second gel electrolyte layer is arranged between the solid electrolyte layer and the negative electrode plate;
wherein at least a portion of the first gel electrolyte layer extends into the positive electrode tab and/or the solid electrolyte layer; and/or at least part of the second gel electrolyte layer extends into the negative electrode sheet and/or the solid electrolyte layer.
According to the technical scheme, the gel electrolyte layers are respectively added between the positive plate and the solid electrolyte and/or between the negative plate and the solid electrolyte, and the gel electrolyte is softened and extends into the positive (negative) electrode material layer and/or the solid electrolyte layer of the pole piece in a hot-pressing mode, so that the gel electrolyte is in closer contact with the solid electrolyte and the positive and negative pole pieces, the contact area between the solid electrolyte and the pole piece is increased, the interface impedance is reduced, and the defect that the contact area is small due to the fact that the solid electrolyte of the existing solid battery is in contact with the pole piece and a point is overcome. The prepared solid-state battery has small interface impedance and good rate capability.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is a schematic view of a solid-state battery according to an embodiment of the present application.
Description of the reference numerals
1. Positive electrode sheet 2, first gel electrolyte layer
3. Sheet-like solid electrolyte layer 4, second gel electrolyte layer
5. Negative pole piece 6, first pole piece
7. Second pole piece
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
A first aspect of the present disclosure provides a process for preparing a solid-state battery, the process comprising the steps of:
s1, coating a first solution containing a first gel electrolyte on the positive electrode material layer of the positive electrode plate, and removing the first solvent in the first solution to form a first electrode plate coated with the first gel electrolyte layer; coating a second solution containing a second gel electrolyte on the negative electrode material layer of the negative electrode plate, and removing the first solvent in the second solution to form a second electrode plate coated with the second gel electrolyte layer;
and S2, sequentially laminating the first pole piece, the solid electrolyte and the second pole piece, and then carrying out hot pressing treatment.
According to the solid-state battery, the gel electrolyte layers are respectively added between the positive plate and the solid-state electrolyte and/or between the negative plate and the solid-state electrolyte, and the gel electrolyte is softened and extends into the positive (negative) electrode material layer and/or the solid-state electrolyte layer of the pole piece in a hot-pressing mode, so that the gel electrolyte is in closer contact with the solid-state electrolyte and the positive (negative) pole piece, the contact area between the solid-state electrolyte and the pole piece is increased, the impedance is reduced, and the defect that the contact area is small due to the fact that the solid-state electrolyte and the pole piece are in contact with points in the existing solid-state battery is overcome. The prepared solid-state battery has small interface impedance and good rate capability.
In one embodiment of the present disclosure, in step S1, the first solution and the second solution each independently include an organic polymer, a lithium salt, a first solvent, and an additive; wherein, the component types and contents of the first solution and the second solution are the same or different.
In one embodiment of the present disclosure, the organic polymer is conventional in the art and may include one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylonitrile, polyethylene, polypropylene oxide, polymethyl methacrylate, acrylic resin, polyoxyethylene, and polystyrene; preferably polyvinylidene fluoride-hexafluoropropylene.
In one embodiment of the present disclosure, the lithium salt is conventional in the art and may include one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium hexafluoroarsenate, lithium bis fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium tetrafluoroborate and lithium perchlorate; lithium hexafluorophosphate is preferred.
In one embodiment of the present disclosure, the first solvent is an organic solvent that is conventional in the art, and is capable of dissolving the organic polymer and the lithium salt, and is not particularly limited herein. The first solvent may comprise one or more of N-methyl pyrrolidone, olefin organic solvents, ester organic solvents, ether organic solvents and sulfone organic solvents; specifically, the solvent can comprise one or more of N-methyl pyrrolidone, diethyl carbonate, dimethyl carbonate, propylene carbonate, ethylene carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl propionate, N-dimethylacetamide, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite or crown ether; preferably a mixed solvent of dimethyl carbonate, ethylene carbonate and ethyl methyl carbonate, or a mixed solvent of N-methylpyrrolidone, propylene carbonate, ethylene carbonate and ethyl methyl carbonate.
In one embodiment of the present disclosure, the additive comprises one or more of a film forming agent, a high and low temperature performance improving agent, an overcharge protection agent, a conductive additive and a flame retardant; specifically, it may include fluoroethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfite, methyl chloroformate, propylene sulfite, dimethyl sulfite, diethyl sulfite, dimethyl sulfoxide, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl bromocarbonate, trifluoroethyl phosphonic acid, bromobutyrolactone, vinyl trifluoromethylcarbonate, vinyl chlorocarbonate, phosphate, phosphite, phosphazene, ethanolamine, N-dimethyltrifluoroacetamide, cyclobutyl sulfone, 1, one or more of 3-dioxolane, trifluoroethyl phosphorous acid, succinic anhydride, diphenyl ether, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide and lithium carbonate; preferably ethylene carbonate.
In one embodiment of the present disclosure, the first solution comprises, in terms of mass percent, based on the total mass of the first solution, 1 to 65 wt% of the organic polymer, 1 to 50 wt% of the lithium salt, 10 to 55 wt% of the first solvent, and 0.5 to 10 wt% of the additive; preferably, the organic polymer is contained in an amount of 30 to 50 wt%, the lithium salt is contained in an amount of 10 to 40 wt%, the first solvent is contained in an amount of 29 to 50 wt%, and the additive is contained in an amount of 1 to 5 wt%.
In one embodiment of the present disclosure, the second solution comprises, in terms of mass percent, based on the total mass of the second solution, 1 to 65 wt% of the organic polymer, 1 to 50 wt% of the lithium salt, 10 to 55 wt% of the first solvent, and 0.5 to 10 wt% of the additive; preferably, the organic polymer is contained in an amount of 30 to 50 wt%, the lithium salt is contained in an amount of 10 to 40 wt%, the first solvent is contained in an amount of 29 to 50 wt%, and the additive is contained in an amount of 1 to 5 wt%.
In one embodiment of the present disclosure, in step S2, the conditions of the thermocompression process include: the temperature is 30-150 ℃, the pressure is 0.02-2.0MPa, and the pressure duration is 0.5-5 min; preferably, the conditions of the autoclave process include: the temperature is 80-120 deg.C, the pressure is 0.06-1.6MPa, and the pressure duration is 1-3 min. The assembled battery is subjected to hot-pressing treatment, so that the gel electrolyte can be softened, the viscosity is reduced, the fluidity is enhanced, the gel electrolyte can be infiltrated into the solid electrolyte and the positive and negative electrode plates, and the gel electrolyte is solidified after cooling, so that the solid electrolyte can be well contacted with the positive and negative electrode plates, the interface impedance is reduced, and the performance of the solid battery is improved.
In one embodiment of the present disclosure, in step S2, the first gel electrolyte layer of the first electrode sheet faces the solid electrolyte, and the second gel electrolyte layer of the second electrode sheet faces the solid electrolyte, i.e., a structure of the first gel electrolyte layer-the solid electrolyte-the second gel electrolyte is formed.
In one embodiment of the present disclosure, the first electrode sheet, the solid electrolyte and the second electrode sheet are sequentially stacked in this order and then placed in the battery case, and the battery case is sealed and assembled, and then is subjected to a hot-pressing process. Wherein, the assembling mode is conventional in the field and is not particularly limited.
In one embodiment of the present disclosure, the preparation process further comprises:
uniformly coating the positive electrode slurry containing the second solvent on one side of the first current collector, and removing the second solvent to obtain the positive electrode sheet containing the positive electrode material layer; and uniformly coating the negative electrode slurry containing the third solvent on one side of the second current collector, and removing the third solvent to obtain the negative electrode sheet containing the negative electrode material layer. Wherein the method for removing the second solvent and the third solvent respectively comprises one or more of heating, vacuum and light irradiation. The method is conventional in the art, and no specific requirement is required here, and the purpose of removing the solvent can be achieved, for example, vacuum drying, air-blast heating and the like are adopted, and after the solvent is removed, the pole piece needs to be compacted for standby.
In one embodiment of the present disclosure, the first current collector and the second current collector each independently comprise one or more of an aluminum foil, a copper foil, an iron foil, a nickel foil, a titanium foil, a tin foil, and a zinc foil; preferably, the first current collector is an aluminum foil; the second current collector is a copper foil. This operation is conventional in the art and is not particularly limited herein. Wherein the thickness of the first current collector is 1-25 μm, preferably 8-20 μm; the thickness of the second current collector is 1 to 25 μm, preferably 6 to 15 μm.
In one embodiment of the present disclosure, a positive electrode slurry includes a positive electrode active material, a first conductive agent, a first binder, and a second solvent; the negative electrode slurry includes a negative electrode active material, a second conductive agent, a second binder, and a third solvent.
In one embodiment of the present disclosure, the positive active material includes sulfur, LiCoO2、LiNiO2、LiNixCo1-xO2(0＜x＜1)、LiNi1/3Mn1/3Co1/3O2、LiNi0.6Mn0.2Co0.2O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.85Co0.1Al0.05O2、LiMn2O4、LiNi0.5Mn1.5O4One or more of a lithium-rich manganese-based material and a lithium phosphate salt; wherein the lithium-rich manganese-based material is Li [ Li ]m(MnM)1-m]O2(M is more than 0 and less than 1), wherein M is one or more of Ni, Co and Fe, and lithium phosphate is LiNPO4Wherein N is one or more of Fe and Mn; specifically, the positive active material may be LiCoO2。
In one embodiment of the present disclosure, the negative active material includes one or more of lithium, a lithium alloy, lithium titanate, a carbon-based material, a silicon-based material, and a tin-based material; wherein the lithium alloy is LinY (n is selected from 1,2 or 3), wherein Y is one or more of In, B, Al, Ga, Sn, Si, Ge, Pb, As, Bi, Sb, Cu, Ag and Zn, the carbon-based material comprises artificial graphite, natural graphite, amorphous carbon and mesocarbon microbeads, and the silicon-based material comprises a silicon-carbon material, a silicon-oxygen material and nano silicon; specifically, the negative active material may be artificial graphite.
In one embodiment of the present disclosure, the first conductive agent and the second conductive agent each independently include one or more of acetylene black, carbon nanotubes, graphene, and carbon fibers; specifically, the first conductive agent and the second conductive agent are both carbon black.
In one embodiment of the present disclosure, the first binder and the second binder each independently comprise one or more of polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, and polyacrylic acid; specifically, the first binder is polyvinylidene fluoride, and the second binder is a mixture of styrene butadiene rubber and sodium hydroxymethyl cellulose.
In one embodiment of the present disclosure, the second solvent and the third solvent each independently comprise one or more of water, N-methylpyrrolidone, and ethanol; specifically, the second solvent is N-methylpyrrolidone, and the third solvent is water.
In one embodiment of the present disclosure, the mass ratio of the positive electrode active material, the first conductive agent, the first binder, and the second solvent is 1: (0.005-0.1): (0.005-0.1): (0.1-0.6), preferably 1: (0.005-0.05): (0.005-0.05): (0.2-0.5); the mass ratio of the negative electrode active material to the second conductive agent to the second binder to the third solvent is 1: (0.005-0.1): (0.005-0.1): (0.1-0.6), preferably 1: (0.005-0.05): (0.005-0.05): (0.2-0.5).
In one embodiment of the present disclosure, the solid electrolyte includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, and a polymer solid electrolyte, and may be, for example, lithium aluminum titanium phosphate; the solid electrolyte is preferably in the form of a powder and is pressed into a sheet for use.
In one embodiment of the present disclosure, the thickness of the first pole piece is 5-500 μm, and the thickness of the second pole piece is 5-500 μm; preferably, the thickness of the first pole piece is 60-200 μm, and the thickness of the second pole piece is 50-180 μm.
In one embodiment of the present disclosure, in step S1, the method for removing the first solvent includes one or more of heating, vacuum and light irradiation. This is conventional in the art, and is not specifically required here, and the purpose of removing the solvent may be achieved, and for example, vacuum drying, air-blast heating, or the like may be mentioned.
In one embodiment of the present disclosure, the first solution, the second solution, the positive electrode slurry and the negative electrode slurry are applied by transfer or extrusion coating, respectively; the above-described operations are conventional in the art and are not specifically claimed herein. It should be noted that all the coatings need to be uniformly coated, so that the thicknesses of the formed first gel dielectric layer, the second gel dielectric layer, the positive electrode material layer and the negative electrode material layer are uniform, which is beneficial to improving the performance of the solid-state battery.
A second aspect of the present disclosure provides a solid-state battery manufactured using the manufacturing process according to the first aspect of the present disclosure.
A third aspect of the present disclosure provides a solid-state battery including a positive electrode sheet, a solid-state electrolyte layer, and a negative electrode sheet that are sequentially stacked; a first gel electrolyte layer is arranged between the positive electrode plate and the solid electrolyte layer, and/or a second gel electrolyte layer is arranged between the solid electrolyte layer and the negative electrode plate;
wherein at least a portion of the first gel electrolyte layer extends into the positive electrode tab and/or the solid electrolyte layer; and/or at least part of the second gel electrolyte layer extends into the negative electrode sheet and/or the solid electrolyte layer.
In the present disclosure, "at least a portion of the first gel electrolyte layer extends into the positive electrode sheet and/or the solid electrolyte layer" means that a part or all of the first gel electrolyte layer fills the depressions on the surface of the positive electrode sheet and/or the solid electrolyte layer, and/or fills the pores of the positive electrode sheet and/or the solid electrolyte layer, forming a structure in which the first gel electrolyte layer is incorporated into the positive electrode sheet and/or the solid electrolyte layer. The gel electrolyte layer in the solid-state battery structure is fully contacted with the positive and negative pole pieces and the solid electrolyte layer, so that the interface resistance is reduced, and the multiplying power performance of the battery is improved.
In one embodiment of the present disclosure, a solid-state battery includes a positive electrode sheet, a first gel electrolyte layer, a solid-state electrolyte layer, a second gel electrolyte layer, and a negative electrode sheet, which are sequentially stacked; wherein at least part of the first gel electrolyte layer extends into the positive electrode sheet and the solid electrolyte layer, respectively; at least a portion of the second gel electrolyte layer extends into the negative electrode sheet and the solid electrolyte layer, respectively.
In one embodiment of the present disclosure, the first and second gel electrolyte layers include an organic polymer, a lithium salt, and an additive, respectively.
In one embodiment of the present disclosure, the first gel electrolyte layer contains 15 to 85 wt% of an organic polymer, 10 to 60 wt% of a lithium salt, and 0.5 to 30 wt% of an additive, preferably 40 to 80 wt% of an organic polymer, 15 to 45 wt% of a lithium salt, and 0.5 to 20 wt% of an additive, in terms of mass percentages, based on the total mass of the first gel electrolyte layer.
In one embodiment of the present disclosure, the second gel electrolyte layer contains 15 to 85 wt% of an organic polymer, 10 to 60 wt% of a lithium salt, and 0.5 to 30 wt% of an additive, preferably 40 to 80 wt% of an organic polymer, 15 to 45 wt% of a lithium salt, and 0.5 to 20 wt% of an additive, based on the total mass of the second gel electrolyte layer in terms of mass percentages.
In one embodiment of the present disclosure, the organic polymer is conventional in the art and may include one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylonitrile, polyethylene, polypropylene oxide, polymethyl methacrylate, acrylic resin, polyoxyethylene, and polystyrene; preferably polyvinylidene fluoride-hexafluoropropylene.
In one embodiment of the present disclosure, the lithium salt is conventional in the art and may include one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium hexafluoroarsenate, lithium bis fluorosulfonylimide, lithium bis-trifluoromethylsulfonyl imide, lithium tetrafluoroborate and lithium perchlorate; lithium hexafluorophosphate is preferred.
In one embodiment of the present disclosure, the additive comprises one or more of a film forming agent, a high and low temperature performance improving agent, an overcharge protection agent, a conductive additive and a flame retardant; specifically, it may include fluoroethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfite, methyl chloroformate, propylene sulfite, dimethyl sulfite, diethyl sulfite, dimethyl sulfoxide, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl bromocarbonate, trifluoroethyl phosphonic acid, bromobutyrolactone, vinyl trifluoromethylcarbonate, vinyl chlorocarbonate, phosphate, phosphite, phosphazene, ethanolamine, N-dimethyltrifluoroacetamide, cyclobutyl sulfone, 1, one or more of 3-dioxolane, trifluoroethyl phosphorous acid, succinic anhydride, diphenyl ether, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide and lithium carbonate; specifically, it may be ethylene carbonate.
In one embodiment of the present disclosure, the positive electrode sheet includes a first current collector and a positive electrode material layer, the positive electrode material layer being adjacent to the solid electrolyte layer; the negative plate comprises a second current collector and a negative material layer, and the negative material layer is close to the solid electrolyte layer; namely, a solid-state battery structure of a first current collector, a positive electrode material layer, a first gel electrolyte layer, a solid electrolyte layer, a second gel electrolyte layer, a negative electrode material layer and a second current collector is formed.
In one embodiment of the present disclosure, the solid electrolyte layer includes one or more of an oxide solid electrolyte, a sulfide solid electrolyte, and a polymer solid electrolyte, and may be, for example, lithium aluminum titanium phosphate.
In one embodiment of the present disclosure, the total thickness of the positive electrode sheet and the first gel electrolyte layer is 5 to 500 μm, and the total thickness of the negative electrode sheet and the second gel electrolyte layer is 5 to 500 μm; preferably, the total thickness of the positive electrode sheet and the first gel electrolyte layer is 60 to 200 μm, and the total thickness of the negative electrode sheet and the second gel electrolyte layer is 50 to 180 μm.
In one embodiment of the present disclosure, a positive electrode material layer includes a positive electrode active material, a first conductive agent, a first binder; the negative electrode paste layer includes a negative electrode active material, a second conductive agent, and a second binder.
In one embodiment of the present disclosure, the first current collector and the second current collector each independently comprise one or more of an aluminum foil, a copper foil, an iron foil, a nickel foil, a titanium foil, a tin foil, and a zinc foil; preferably, the first current collector is an aluminum foil; preferably, the second current collector is a copper foil.
In one embodiment of the present disclosure, the thickness of the first current collector is 1 to 25 μm, preferably 8 to 20 μm; the thickness of the second current collector is 1 to 25 μm, preferably 6 to 15 μm.
In one embodiment of the present disclosure, the positive active material includes sulfur, LiCoO2、LiNiO2、LiNixCo1-xO2(0＜x＜1)、LiNi1/3Mn1/3Co1/3O2、LiNi0.6Mn0.2Co0.2O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.85Co0.1Al0.05O2、LiMn2O4、LiNi0.5Mn1.5O4One or more of a lithium-rich manganese-based material and a lithium phosphate salt; wherein the lithium-rich manganese-based material is Li [ Li ]x(MnM)1-x]O2Wherein M is one or more of Ni, Co and Fe, and the lithium phosphate salt is LiNPO4Wherein N is one or more of Fe and Mn; specifically, the positive active material may be LiCoO2。
In one embodiment of the present disclosure, the negative active material includes one or more of lithium, a lithium alloy, lithium titanate, a carbon-based material, a silicon-based material, and a tin-based material; wherein the lithium alloy is LinY (n is selected from 1,2 or 3), wherein Y is one or more of In, B, Al, Ga, Sn, Si, Ge, Pb, As, Bi, Sb, Cu, Ag and Zn, the carbon-based material comprises artificial graphite, natural graphite, amorphous carbon and mesocarbon microbeads, and the silicon-based material comprises a silicon-carbon material, a silicon-oxygen material and nano silicon; specifically, the negative active material may be artificial graphite.
In one embodiment of the present disclosure, the first conductive agent and the second conductive agent each independently include one or more of acetylene black, carbon nanotubes, graphene, and carbon fibers; specifically, the first conductive agent and the second conductive agent are both carbon black.
In one embodiment of the present disclosure, the first binder and the second binder each independently comprise one or more of polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, and polyacrylic acid; specifically, the first binder is polyvinylidene fluoride, and the second binder is a mixture of styrene butadiene rubber and sodium hydroxymethyl cellulose.
In one embodiment of the present disclosure, the mass ratio of the positive electrode active material, the first conductive agent, and the first binder is 1: (0.005-0.1): (0.005-0.1), preferably 1: (0.005-0.05): (0.005-0.05); the molar ratio of the negative electrode active material to the second conductive agent to the second binder is 1: (0.005-0.1): (0.005-0.1), preferably 1: (0.005-0.05): (0.005-0.05).
It should be noted that the first gel electrolyte layer, the second gel electrolyte layer, the positive electrode material layer and the negative electrode material layer are uniform in thickness, which is beneficial to improving the performance of the battery.
In one embodiment of the present disclosure, as shown in fig. 1, the prepared solid-state battery includes a positive electrode sheet 1, a first gel dielectric layer 2, a sheet-like solid-state electrolyte layer 3, a second gel electrolyte layer 4, and a negative electrode sheet 5, which are sequentially stacked, wherein the positive electrode sheet 1 and the first gel dielectric layer 2 constitute a first electrode sheet 6, and the negative electrode sheet 5 and the second gel electrolyte layer 4 constitute a second electrode sheet 7. The positive electrode tab 1 includes a first current collector and a positive electrode material layer (not shown in the drawing) facing the first gel dielectric layer 2, and the negative electrode tab 5 includes a second current collector and a negative electrode material layer (not shown in the drawing) facing the second gel dielectric layer 4.
The following examples 1-6 are provided to illustrate the solid-state battery of the present disclosure and the process for preparing the same.
Example 1
(1) Preparation of Positive plate
LiCoO as positive electrode active material2The first conductive agent carbon black, the first binder polyvinylidene fluoride and the second solvent N-methyl pyrrolidone are as follows: 3: 5: 40, uniformly stirring and mixing, uniformly coating on a 15 mu m aluminum foil, drying in vacuum to remove the solvent, and compacting to obtain the positive plate.
(2) Preparation of negative plate
Mixing a negative electrode material artificial graphite, a second conductive agent carbon black, a second binder styrene butadiene rubber, a second binder sodium carboxymethyl cellulose and a third solvent water according to a ratio of 94: 1.5: 1.5: 3: 40, uniformly stirring and mixing, uniformly coating on a copper foil with the thickness of 8 mu m, drying in vacuum to remove the solvent, and compacting to obtain the negative plate.
(3) Preparation of first solution and second solution
Respectively preparing a first solution and a second solution according to the following mass percentages by taking the total mass of the solutions as a reference: 35% by weight of polyvinylidene fluoride-hexafluoropropylene, 40% by weight of N-methylpyrrolidone, 18% by weight of lithium hexafluorophosphate, 2% by weight of ethylene carbonate, 2% by weight of propylene carbonate, 2% by weight of ethyl methyl carbonate and 1% by weight of ethylene carbonate.
(4) Preparation of solid electrolyte layer
And pressing the lithium titanium aluminum phosphate solid electrolyte powder into a sheet shape to be used as a sheet-shaped solid electrolyte for later use.
(5) Preparation of solid-state batteries
Uniformly coating the first solution on a positive plate, drying at 80 ℃ for 0.5 hour in vacuum to obtain a first plate, and cutting the first plate into a wafer with the diameter of 10mm and the thickness of 80 mu m; and uniformly coating the second solution on a negative pole piece, drying for 0.5 hour at 80 ℃ in vacuum to obtain a second pole piece, and cutting the second pole piece into a wafer with the diameter of 10mm and the thickness of 110 mu m. And stacking the first pole piece, the flaky solid electrolyte and the second pole piece in sequence, placing the stacked first pole piece, flaky solid electrolyte and second pole piece into a button cell shell, and packaging the cell shell by using a sealing machine to complete the assembly of the button cell.
(6) Hot pressing
And after the assembly is finished, carrying out hot pressing treatment on the button cell, wherein the temperature of the hot pressing treatment is 110 ℃, the pressure is 1.0MPa, and the pressure duration is 2 min.
(7) Battery rate test
The operating voltage range of the solid-state battery is set to 3V-4.2V and 0.1C (the current density is 0.15 mA/cm)2) Is charged to 4.2V by constant current, then is cut off by constant voltage to 0.01C, and then is discharged to 3V by 0.1C, 0.2C, 0.5C and 1C currents respectivelyThe gram capacities of the batteries at 0.1C, 0.2C, 0.5C, and 1C rate discharge were obtained, respectively, and the results are shown in table 1.
Example 2
A solid-state battery was manufactured by the same method as in example 1, except that the hot-pressing conditions were: the temperature is 90 deg.C, the pressure is 0.8MPa, and the pressure duration is 3 min. After the preparation, the battery rate test was performed in the same manner as in example 1, and the results are shown in table 1.
Example 3
A solid-state battery was manufactured by the same method as in example 1, except that the hot-pressing conditions were: the temperature is 60 deg.C, the pressure is 0.4MPa, and the pressure duration is 0.5 min. After the preparation, the battery rate test was performed in the same manner as in example 1, and the results are shown in table 1.
Example 4
A solid-state battery was manufactured by the same method as in example 1, except that the hot-pressing conditions were: the temperature is 140 deg.C, the pressure is 0.4MPa, and the pressure duration is 5 min. After the preparation, the battery rate test was performed in the same manner as in example 1, and the results are shown in table 1.
Example 5
A solid-state battery was manufactured by the same method as in example 1, except that the hot-pressing conditions were: the temperature is 60 deg.C, the pressure is 2.0MPa, and the pressure duration is 5 min. After the preparation, the battery rate test was performed in the same manner as in example 1, and the results are shown in table 1.
Example 6
A solid-state battery was manufactured by the same method as in example 1, except that the polyvinylidene fluoride-hexafluoropropylene in the first solution and the second solution was replaced with an equal mass of polyvinylidene fluoride. After the preparation, the battery rate test was performed in the same manner as in example 1. The results are shown in Table 1.
Comparative example 1
A solid-state battery was manufactured in the same manner as in example 1, except that the hot press treatment was not performed after the battery assembly was completed. After the preparation, the battery rate test was performed in the same manner as in example 1. The results are shown in Table 1.
Comparative example 2
A solid-state battery was manufactured in the same manner as in example 1, except that the gel electrolyte layer was not included, but hot pressing was performed after the assembly was completed. After the preparation, the battery rate test was performed in the same manner as in example 1, and the results are shown in table 1.
Comparative example 3
A solid-state battery was produced in the same manner as in example 1 except that no gel electrolyte layer was included and no hot pressing treatment was performed after the assembly was completed. After the preparation, the battery rate test was performed in the same manner as in example 1, and the results are shown in table 1.
TABLE 1
Figure BDA0003159256200000151
According to the data in table 1, the process for preparing the solid-state battery can obviously improve the rate performance of the battery, and the prepared solid-state battery has good interface contact between the solid-state electrolyte and the pole piece and low battery impedance; and in the range of the optimized hot-pressing conditions, namely the temperature is 80-120 ℃, the pressure is 0.06-1.6MPa, the pressure duration is 1-3min, and the rate performance of the solid-state battery is better.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (13)

1. A process for preparing a solid-state battery, comprising the steps of:
s1, coating a first solution containing a first gel electrolyte on the positive electrode material layer of the positive electrode plate, and removing the first solvent in the first solution to form a first electrode plate coated with the first gel electrolyte layer; coating a second solution containing a second gel electrolyte on the negative electrode material layer of the negative electrode plate, and removing the first solvent in the second solution to form a second electrode plate coated with the second gel electrolyte layer;
and S2, sequentially laminating the first pole piece, the solid electrolyte and the second pole piece, and then carrying out hot pressing treatment.
2. The production process according to claim 1, wherein in step S1, the first solution and the second solution each independently include an organic polymer, a lithium salt, a first solvent, and an additive;
optionally, the first solution contains 1-65 wt% of organic polymer, 1-50 wt% of lithium salt, 10-55 wt% of first solvent and 0.5-10 wt% of additive in terms of mass percentage based on the total mass of the first solution;
optionally, the second solution contains 1-65 wt% of organic polymer, 1-50 wt% of lithium salt, 10-55 wt% of first solvent and 0.5-10 wt% of additive in terms of mass percentage based on the total mass of the second solution;
the organic polymer comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylonitrile, polyethylene, polypropylene oxide, polymethyl methacrylate, acrylic resin, polyoxyethylene and polystyrene;
the lithium salt comprises one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium hexafluoroarsenate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium tetrafluoroborate and lithium perchlorate;
the first solvent comprises one or more of N-methyl pyrrolidone, an olefin organic solvent, an ester organic solvent, an ether organic solvent and a sulfone organic solvent;
the additive comprises one or more of a film forming agent, a high-low temperature performance improver, an overcharge protective agent, a conductive additive and a flame retardant.
3. The process of claim 1, wherein in step S2, the conditions of the hot pressing process include: the temperature is 30-150 ℃, the pressure is 0.02-2.0MPa, and the pressure duration is 0.5-5 min;
preferably, the conditions of the hot pressing process include: the temperature is 80-120 deg.C, the pressure is 0.06-1.6MPa, and the pressure duration is 1-3 min.
4. The process of claim 1, wherein in step S2, the first gel electrolyte layer of the first pole piece faces the solid electrolyte and the second gel electrolyte layer of the second pole piece faces the solid electrolyte.
5. The process of claim 1, wherein in step S2, the first electrode sheet, the solid electrolyte and the second electrode sheet are sequentially stacked in this order and placed in a battery case, the battery case is sealed and assembled, and then the hot pressing process is performed.
6. The process of claim 1, wherein the process further comprises:
uniformly coating the positive electrode slurry containing the second solvent on one side of the first current collector, and removing the second solvent to obtain the positive electrode sheet containing the positive electrode material layer; uniformly coating negative electrode slurry containing a third solvent on one side of a second current collector, and removing the third solvent to obtain the negative electrode sheet containing the negative electrode material layer;
the first current collector and the second current collector respectively and independently comprise one or more of an aluminum foil, a copper foil, an iron foil, a nickel foil, a titanium foil, a tin foil and a zinc foil;
preferably, the first current collector is an aluminum foil;
preferably, the second current collector is a copper foil;
the thickness of the first current collector is 1-25 μm, and the thickness of the second current collector is 1-25 μm;
the positive electrode slurry comprises a positive electrode active material, a first conductive agent, a first binder and a second solvent; the negative electrode slurry comprises a negative electrode active material, a second conductive agent, a second binder and a third solvent;
the positive active material includes sulfur, LiCoO2、LiNiO2、LiNixCo1-xO2(0＜x＜1)、LiNi1/3Mn1/3Co1/3O2、LiNi0.6Mn0.2Co0.2O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.85Co0.1Al0.05O2、LiMn2O4、LiNi0.5Mn1.5O4One or more of a lithium-rich manganese-based material and a lithium phosphate salt;
the negative active material comprises one or more of lithium, lithium alloy, lithium titanate, carbon-based material, silicon-based material and tin-based material;
the first conductive agent and the second conductive agent respectively and independently comprise one or more of acetylene black, carbon nanotubes, graphene and carbon fibers;
the first binder and the second binder respectively and independently comprise one or more of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and polyacrylic acid;
the second solvent and the third solvent respectively and independently comprise one or more of water, N-methyl pyrrolidone and ethanol;
optionally, the mass ratio of the positive electrode active material, the first conductive agent, the first binder, and the second solvent is 1: (0.005-0.1): (0.005-0.1): (0.1-0.6); the molar ratio of the negative electrode active material, the second conductive agent, the second binder, and the third solvent is 1: (0.005-0.1): (0.005-0.1): (0.1-0.6);
the solid electrolyte comprises one or more of oxide solid electrolyte, sulfide solid electrolyte and polymer solid electrolyte;
the thickness of the first pole piece is 5-500 μm, and the thickness of the second pole piece is 5-500 μm.
7. The process of claim 6, wherein the removing the first solvent, the removing the second solvent, and the removing the third solvent each independently comprises one or more of heating, vacuum, and light.
8. A solid-state battery prepared by the process of any one of claims 1 to 7.
9. A solid-state battery is characterized by comprising a positive plate, a solid electrolyte layer and a negative plate which are sequentially stacked; a first gel electrolyte layer is arranged between the positive electrode plate and the solid electrolyte layer, and/or a second gel electrolyte layer is arranged between the solid electrolyte layer and the negative electrode plate;
wherein at least a portion of the first gel electrolyte layer extends into the positive electrode tab and/or the solid electrolyte layer; and/or at least part of the second gel electrolyte layer extends into the negative electrode sheet and/or the solid electrolyte layer.
10. The solid-state battery according to claim 9, wherein the solid-state battery comprises the positive electrode tab, the first gel electrolyte layer, the solid-state electrolyte layer, the second gel electrolyte layer, and the negative electrode tab, which are stacked in this order;
wherein at least part of the first gel electrolyte layer extends into the positive electrode sheet and the solid electrolyte layer, respectively; at least a portion of the second gel electrolyte layer extends into the negative electrode sheet and the solid electrolyte layer, respectively.
11. The solid-state battery according to claim 9, wherein the first gel electrolyte layer and the second gel electrolyte layer respectively include an organic polymer, a lithium salt, and an additive;
optionally, the first gel electrolyte layer contains 15-85 wt% of organic polymer, 10-60 wt% of lithium salt and 0.5-30 wt% of additive in terms of mass percentage based on the total mass of the first gel electrolyte layer;
optionally, the second gel electrolyte layer contains 15-85 wt% of organic polymer, 10-60 wt% of lithium salt and 0.5-30 wt% of additive in terms of mass percentage based on the total mass of the second gel electrolyte layer;
the organic polymer comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl chloride, chlorinated polyvinyl chloride, polyacrylonitrile, polyethylene, polypropylene oxide, polymethyl methacrylate, acrylic resin, polyoxyethylene and polystyrene;
the lithium salt comprises one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium oxalyldifluoroborate, lithium hexafluoroarsenate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium tetrafluoroborate and lithium perchlorate;
the additive comprises one or more of a film forming agent, a high-low temperature performance improver, an overcharge protective agent, a conductive additive and a flame retardant.
12. The solid-state battery according to claim 9, wherein the positive electrode sheet includes a first current collector and a positive electrode material layer, the positive electrode material layer being adjacent to the solid-state electrolyte layer; the negative plate comprises a second current collector and a negative material layer, and the negative material layer is close to the solid electrolyte layer;
the solid electrolyte layer comprises one or more of oxide solid electrolyte, sulfide solid electrolyte and polymer solid electrolyte;
the total thickness of the positive electrode plate and the first gel electrolyte layer is 5-500 mu m, and the total thickness of the negative electrode plate and the second gel electrolyte layer is 5-500 mu m.
13. The solid-state battery according to claim 12, wherein the positive electrode material layer includes a positive electrode active material, a first conductive agent, a first binder; the negative electrode material layer includes a negative electrode active material, a second conductive agent, and a second binder;
the first current collector and the second current collector respectively and independently comprise one or more of an aluminum foil, a copper foil, an iron foil, a nickel foil, a titanium foil, a tin foil and a zinc foil;
preferably, the first current collector is an aluminum foil;
preferably, the second current collector is a copper foil;
the thickness of the first current collector is 1-25 μm, and the thickness of the second current collector is 1-25 μm;
the positive active material includes sulfur, LiCoO2、LiNiO2、LiNixCo1-xO2(0＜x＜1)、LiNi1/3Mn1/3Co1/3O2、LiNi0.6Mn0.2Co0.2O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.85Co0.1Al0.05O2、LiMn2O4、LiNi0.5Mn1.5O4One or more of a lithium-rich manganese-based material and a lithium phosphate salt;
the negative active material comprises one or more of lithium, lithium alloy, lithium titanate, carbon-based material, silicon-based material and tin-based material;
the first conductive agent and the second conductive agent respectively and independently comprise one or more of acetylene black, carbon nanotubes, graphene and carbon fibers;
the first binder and the second binder respectively and independently comprise one or more of polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and polyacrylic acid;
the mass ratio of the positive electrode active material, the first conductive agent, and the first binder is 1: (0.005-0.1): (0.005-0.1); the mass ratio of the negative electrode active material, the second conductive agent, and the second binder is 1: (0.005-0.1): (0.005-0.1).
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114156432A (en) * 2021-11-30 2022-03-08 惠州亿纬锂能股份有限公司 Solid-state battery and preparation method thereof
CN114784241A (en) * 2022-04-13 2022-07-22 河北光兴半导体技术有限公司 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11144767A (en) * 1997-11-04 1999-05-28 Tdk Corp Sheet type electrode-electrolyte structure and manufacture thereof
JP2012018932A (en) * 2011-09-12 2012-01-26 Nissan Motor Co Ltd Solid electrolyte cell
CN109659626A (en) * 2018-12-27 2019-04-19 北方奥钛纳米技术有限公司 Battery production method and battery
CN110518283A (en) * 2019-09-12 2019-11-29 深圳先进技术研究院 Solid state secondary battery and its preparation process, electric car
CN111613830A (en) * 2020-07-09 2020-09-01 常州赛得能源科技有限公司 Composite electrolyte and application thereof
CN112103566A (en) * 2020-10-20 2020-12-18 天津市捷威动力工业有限公司 Method for manufacturing lithium ion battery by using gel diaphragm

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11144767A (en) * 1997-11-04 1999-05-28 Tdk Corp Sheet type electrode-electrolyte structure and manufacture thereof
JP2012018932A (en) * 2011-09-12 2012-01-26 Nissan Motor Co Ltd Solid electrolyte cell
CN109659626A (en) * 2018-12-27 2019-04-19 北方奥钛纳米技术有限公司 Battery production method and battery
CN110518283A (en) * 2019-09-12 2019-11-29 深圳先进技术研究院 Solid state secondary battery and its preparation process, electric car
CN111613830A (en) * 2020-07-09 2020-09-01 常州赛得能源科技有限公司 Composite electrolyte and application thereof
CN112103566A (en) * 2020-10-20 2020-12-18 天津市捷威动力工业有限公司 Method for manufacturing lithium ion battery by using gel diaphragm

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114156432A (en) * 2021-11-30 2022-03-08 惠州亿纬锂能股份有限公司 Solid-state battery and preparation method thereof
CN114784241A (en) * 2022-04-13 2022-07-22 河北光兴半导体技术有限公司 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN114784241B (en) * 2022-04-13 2023-11-28 河北光兴半导体技术有限公司 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery

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