CN112271325B - Three-dimensional solid lithium battery and preparation method thereof - Google Patents
Three-dimensional solid lithium battery and preparation method thereof Download PDFInfo
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- CN112271325B CN112271325B CN202010967622.7A CN202010967622A CN112271325B CN 112271325 B CN112271325 B CN 112271325B CN 202010967622 A CN202010967622 A CN 202010967622A CN 112271325 B CN112271325 B CN 112271325B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 54
- 239000006260 foam Substances 0.000 claims abstract description 43
- 239000003607 modifier Substances 0.000 claims abstract description 37
- 239000011888 foil Substances 0.000 claims abstract description 31
- -1 polysiloxane Polymers 0.000 claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011889 copper foil Substances 0.000 claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- MPFVDKFRCLZQKV-UHFFFAOYSA-L disodium;2-butoxyethyl phosphate Chemical compound [Na+].[Na+].CCCCOCCOP([O-])([O-])=O MPFVDKFRCLZQKV-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 42
- 239000000853 adhesive Substances 0.000 claims description 25
- 230000001070 adhesive effect Effects 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000002033 PVDF binder Substances 0.000 claims description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 16
- 239000006258 conductive agent Substances 0.000 claims description 14
- 238000007731 hot pressing Methods 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 13
- 239000010405 anode material Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000011267 electrode slurry Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 150000003505 terpenes Chemical class 0.000 claims description 9
- 235000007586 terpenes Nutrition 0.000 claims description 9
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006256 anode slurry Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 6
- 239000006257 cathode slurry Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- PYUKXGCMRFTISX-UHFFFAOYSA-N [O].[Ta].[Zr].[La].[Li] Chemical compound [O].[Ta].[Zr].[La].[Li] PYUKXGCMRFTISX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000002203 sulfidic glass Substances 0.000 claims description 2
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 abstract description 6
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- BVPMZCWLVVIHKO-UHFFFAOYSA-N lithium cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Co+2].[Li+] BVPMZCWLVVIHKO-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- VOEUMFXKYRCDKK-UHFFFAOYSA-N FS(=N)F.FS(=N)F.[Li] Chemical compound FS(=N)F.FS(=N)F.[Li] VOEUMFXKYRCDKK-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- DGQGEJIVIMHONW-UHFFFAOYSA-N [O-2].[Ta+5].[Zr+4].[La+3].[Li+] Chemical compound [O-2].[Ta+5].[Zr+4].[La+3].[Li+] DGQGEJIVIMHONW-UHFFFAOYSA-N 0.000 description 1
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a three-dimensional solid lithium battery and a preparation method thereof, wherein the three-dimensional solid lithium battery comprises a negative plate, a positive electrode material, a negative electrode material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil, and the negative plate is a three-dimensional foam porous copper foil; the positive electrode material and the solid electrolyte are respectively modified by a surface modifier, wherein the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether. The three-dimensional foam porous aluminum foil or copper foil adopted by the invention can increase the conductive interface and conductive capacity of active substances of the lithium ion battery, and then the positive electrode material and the solid electrolyte are treated by the surface modifier, so that the compactness of the solid battery is improved, the compatibility of a system is improved, the short circuit problem caused by growth of lithium dendrites can be inhibited, the interface resistance is effectively reduced, stable circulation under high multiplying power is realized, the safety is good, and the service life is long.
Description
Technical Field
The invention relates to the technical field of electrodes, in particular to a three-dimensional solid-state lithium battery and a preparation method thereof.
Background
The lithium ion battery is a high and new technology product, is mainly used in the fields of mine cars, electric automobiles, electric bicycles, electric motorcycles, electric field vehicles, clean energy storage and the like except for being matched with IT industry, is greatly supported by national policies in research, development, production and sales, is mature in domestic industry chain and rapidly grows in market, and the currently used technology is limited to the traditional two-dimensional flat electrode lithium ion battery manufacturing. Due to the low energy density, the driving trolley is short in endurance mileage, poor in multiplying power performance, long in charging time, poor in safety performance, short in cycle life and the like, and the development of the two-dimensional flat electrode lithium ion battery in the aspects of energy output and electric automobile industry is restricted. In order to better break through the bottleneck, the industry is turned to the research of three-dimensional lithium ion batteries, the pole piece carrier foil is subjected to three-dimensional porosification, and the three-dimensional foil technology is used for improving the adhesive force of the foil and active substances. The three-dimensional property of the pole piece of the lithium ion battery is mainly embodied on the foil, and is usually punched or corroded by the foil, but the three-dimensional property of the porous foil is not good, and the adhesion to active substances is not strong.
With the gradual deep research of solid electrolyte, solid electrolyte materials capable of simultaneously meeting high mechanical strength and high ion conductivity are greatly developed, which lays a key foundation for the research of all-solid-state metal lithium batteries. The solid-state battery adopts the solid electrolyte to replace organic electrolyte, so that potential safety hazards caused by problems such as leakage of the electrolyte are avoided, the safety performance of the battery is greatly improved, the solid-state battery can be better adapted to positive and negative electrodes with high energy density, the requirement of the battery on high energy density is met, and in addition, the solid-state battery has the advantages of wider electrochemical window, no memory effect, good thermal stability and the like. However, the solid-solid interface in the solid-state metal lithium battery brings about a huge interface resistance, greatly influences the rate performance of the all-solid-state battery, and the capacity exertion of the material itself is limited. Wherein, the solid interface between the positive electrode side and the solid electrolyte layer has the most obvious influence on the performance of the all-solid-state metal lithium battery. In order to reduce the transmission resistance of lithium ions at the interface, the surface of the positive electrode material or the solid electrolyte is coated. The surfactant is a substance which can obviously change the interface state of a solution system by adding a small amount, has fixed hydrophilic and lipophilic groups and is directionally arranged on the surface energy of the solution, and the surfactant is studied to improve the interface difference of the solid-state battery. However, the surfactant such as silane coupling agent and polyethylene oxide used at present has an insufficient effect of improving the interface, and a certain interface difference still exists. Therefore, how to improve the interface difference between solid-state lithium batteries is a technical problem that needs to be solved today.
Disclosure of Invention
The invention aims at the problems and provides a three-dimensional solid-state lithium battery and a preparation method thereof. The invention can improve the compactness of the solid-state battery and the compatibility of the system, inhibit the short circuit problem caused by the growth of lithium dendrite, effectively reduce the interface resistance, realize stable circulation under high multiplying power, and have good safety and long service life, and can meet the requirement of rapid charge and discharge of the power battery.
In order to achieve the above object, the present invention adopts the following technical scheme:
a three-dimensional solid-state lithium battery comprises a negative plate, a positive electrode material, a negative electrode material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil, and the negative plate is a three-dimensional foam porous copper foil; the positive electrode material comprises one or more of nickel cobalt lithium aluminate, nickel cobalt lithium manganate, lithium iron phosphate and lithium-rich manganese-based materials, and the negative electrode material comprises one or more of graphite, mesophase carbon microspheres, silicon carbon negative electrode and silicon oxygen; the solid electrolyte consists of a polymer matrix, lithium salt and inorganic solid electrolyte filler; the positive electrode material and the solid electrolyte are respectively modified by a surface modifier, wherein the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether.
Further, the inorganic solid electrolyte filler is selected from one or more of lithium lanthanum zirconium oxide solid electrolyte, lithium lanthanum zirconium tantalum oxide solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, lithium aluminum titanium phosphorus solid electrolyte and sulfide solid electrolyte.
Further, the polymer matrix polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polysulfone, polyvinylpyrrolidone, polyethylene-vinyl acetate copolymer and polyvinyl butyral.
Further, the mass ratio of the polymer matrix, the lithium salt and the inorganic solid electrolyte filler in the solid electrolyte is 1:0.1-0.5:0.1-0.3.
Further, the mass ratio of the ethylene glycol monobutyl ether phosphate sodium salt, the rare earth coupling agent, the polyfluoroalkyl polysiloxane and the alkylphenol polyoxyethylene ether in the surface modifier is 1-3:3-5:5-10:3-5.
Further, the lithium salt is selected from one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfimide and lithium bistrifluoromethylsulfonimide.
Further, the three-dimensional foam porous aluminum foil is a three-dimensional foam porous structural aluminum foil which is manufactured by aluminum foil, the thickness of the three-dimensional foam porous structural aluminum foil is 0.1mm-5mm, the aperture of the three-dimensional foam porous aluminum foil is 0.05mm-10mm, and the porosity of the three-dimensional foam porous structural aluminum foil is 30% -80%. The three-dimensional foam porous aluminum foil is a metal material with a three-dimensional structure with through holes, a good capillary structure, an ultra-large specific surface area, good mechanical and processing properties and good electric conduction and heat conduction properties.
Further, the three-dimensional foam porous copper foil is a three-dimensional foam porous structure copper foil made of copper foil, the thickness of the three-dimensional foam porous structure copper foil is 0.1mm-5mm, the aperture of the three-dimensional foam porous structure copper foil is 0.05mm-10mm, and the porosity of the three-dimensional foam porous structure copper foil is 30% -80%. The three-dimensional foam porous copper foil is a metal material with a three-dimensional structure with through holes, a good capillary structure, an ultra-large specific surface area, good mechanical and processing properties and good electric conduction and heat conduction properties.
Another object of the present invention is to provide a method for preparing a three-dimensional solid-state lithium battery, comprising the steps of:
s1, preparing a positive plate: placing the anode material and the surface modifier into a stirring barrel, wherein the addition amount of the surface modifier is 2-4% of the mass of the anode material, stirring uniformly, mixing the anode material after modification with 3-5% of adhesive and 1-3% of conductive agent uniformly, and adding N-methyl pyrrolidone according to the solid content of 60-70%, and stirring uniformly to obtain anode slurry; the positive electrode slurry was then mixed at a concentration of 50mg/cm 2 -70mg/cm 2 The surface density and weight are uniformly coated on a three-dimensional foam porous aluminum foil positive plate, and the positive plate is obtained through baking in a baking oven of a coating machine;
s2, preparing a negative plate: adding the anode material, the adhesive and the conductive agent into a stirring barrel, stirring uniformly, and then adding N-methyl pyrrolidone according to the solid content of 50-60%, and stirring uniformly to obtain anode slurry; the cathode slurry was prepared at a concentration of 20mg/cm 2 -30mg/cm 2 Uniformly coating the surface density and weight on a three-dimensional foam porous copper foil negative plate, and drying by a coating machine oven to obtain a negative plate;
s3, dissolving the solid electrolyte in N-methyl pyrrolidone according to the solid content of 20-40%, adding a surface modifier with the mass of 1-3%, and uniformly stirring to obtain electrolyte slurry;
s4, electrolyte slurry is processed according to 5mg/cm 2 -10mg/cm 2 Uniformly coating the surface of the positive plate, storing for 12 hours at a high temperature of 70-85 ℃ and 24 hours at normal temperature, and then storing for 1000kg/cm at a high temperature of 70-85 DEG C 2 Hot-pressing for 1-2 min, and then heating at 25deg.C under 500-1000kg/cm 2 Cold pressing for 1-2 minutes; preparing a battery cell by laminating a cathode plate and an electrolyte-coated anode plate by adopting a PVDF diaphragm, and then placing the battery cell into a shell, wherein the pressure is 500-1000kg/cm at the high temperature of 80 DEG C 2 Hot-pressing for 1-5 min at 25deg.C under 500-1000kg/cm 2 Cold pressing for 1-5 min to obtain the three-dimensional solid lithium battery.
Further, the conductive agent is one or more of graphene, electrographite, acetylene black and carbon nano tubes.
Further, the adhesive is composed of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homo-polymer rubber powder. Preferably, the mass ratio of the adhesive polyvinylidene fluoride, the methacrylic acid ethoxylated bisphenol A diester and the terpene resin is 5-10:1-3:1-3:3-5.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the positive electrode material and the negative electrode material are respectively loaded on the three-dimensional foam porous aluminum foil and the three-dimensional foam porous copper foil, and the three-dimensional foam porous aluminum foil or the three-dimensional foam porous aluminum foil has a three-dimensional structure with through holes and a good capillary structure, so that the conductive interface and the conductive capacity of the active substance of the lithium ion battery can be increased, the positive electrode material and the solid electrolyte are treated by the surface modifier consisting of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether, the compactness of the solid battery is improved, the compatibility of the system is improved, the short circuit problem caused by growth of lithium dendrites can be restrained, the interface resistance is effectively reduced, the stable circulation under high multiplying power is realized, the safety is good, the service life is long, and the rapid charge and discharge requirements of the power battery can be met.
2. The invention selects polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homo-polymer rubber powder as the adhesive of the battery, has good bonding capability with active substances, has strong acting force with each substance of electrode materials, ensures the stability of the electrode structure of the battery in the charging and discharging process, and overcomes the defect of weak adhesive force of the current three-dimensional porous foil to the active substances; the adhesive also has good dispersibility, is favorable for conducting lithium ions, and improves the multiplying power charge-discharge performance of the electrode.
3. The method combines the hot pressing, cold pressing and multi-gradient temperature rising and reducing modes to prepare the solid lithium battery, so that the internal texture of the electrode material is more uniform during molding, and the prepared battery has good mechanical properties, simple preparation process and higher production efficiency, and can better realize mass production.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its applications.
Example 1
The three-dimensional solid-state lithium battery provided by the embodiment comprises a negative plate, a positive electrode material, a negative electrode material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil with the thickness of 3mm, the aperture of 3mm and the porosity of 58%, and the negative plate is a three-dimensional foam porous copper foil with the thickness of 2mm, the aperture of 3mm and the porosity of 58%; the positive electrode material is nickel cobalt lithium aluminate, and the negative electrode material is graphite; the solid electrolyte consists of polyethylene-vinyl acetate copolymer and aluminum perchlorate and lithium lanthanum zirconium tantalum oxygen solid electrolyte filler in a mass ratio of 1:0.3:0.2; the positive electrode material and the solid electrolyte are respectively modified by a surface modifier, wherein the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether in a mass ratio of 2:3:7:3.
The preparation method comprises the following steps:
s1, preparing a positive plate: putting nickel cobalt lithium aluminate and a surface modifier into a stirring barrel, wherein the addition amount of the surface modifier is 3% of the mass of the nickel cobalt lithium aluminate, stirring uniformly, and mixing the modified positive electrode material with 3.5% of adhesive and 2% of the mass of the positive electrode materialUniformly mixing a graphene conductive agent, wherein the adhesive consists of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homo-polymer rubber powder in a mass ratio of 7:2:2:4, and adding N-methyl pyrrolidone according to a solid content of 65%, and uniformly stirring to obtain positive electrode slurry; the positive electrode slurry was then mixed at a concentration of 50mg/cm 2 The surface density and weight are uniformly coated on a three-dimensional foam porous aluminum foil positive plate, and the positive plate is obtained through baking in a baking oven of a coating machine;
s2, preparing a negative plate: adding 95% of graphite, 3% of adhesive and 2% of graphene conductive agent into a stirring barrel, stirring uniformly, and adding N-methylpyrrolidone according to the solid content of 50%, and stirring uniformly to obtain negative electrode slurry; the cathode slurry was prepared at a concentration of 25mg/cm 2 Uniformly coating the surface density and weight on a three-dimensional foam porous copper foil negative plate, and drying by a coating machine oven to obtain a negative plate;
s3, dissolving the solid electrolyte in N-methyl pyrrolidone according to the solid content of 35%, adding a surface modifier with the mass of 2.0%, and uniformly stirring to obtain electrolyte slurry;
s4, electrolyte slurry is processed according to 5mg/cm 2 Uniformly coating the surface of the positive plate, storing for 12 hours at a high temperature of 80 ℃ and 24 hours at normal temperature, and then storing at a high temperature of 70 ℃ and a pressure of 1000kg/cm 2 Hot-pressing for 2 min, and then heating at 25deg.C under 500kg/cm 2 Cold pressing for 2 minutes; preparing a battery cell by laminating a cathode plate and an electrolyte-coated anode plate by adopting a PVDF diaphragm, and then placing the battery cell into a shell, wherein the temperature is 80 ℃ and the pressure is 1000kg/cm 2 Hot-pressing for 3 min, and then heating at 25deg.C under 500kg/cm 2 Cold pressing for 5 minutes to prepare the three-dimensional solid lithium battery.
Example 2
The three-dimensional solid-state lithium battery provided by the embodiment comprises a negative plate, a positive electrode material, a negative electrode material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil with the thickness of 2mm, the aperture of 5mm and the porosity of 65%, and the negative plate is a three-dimensional foam porous copper foil with the thickness of 1mm, the aperture of 5mm and the porosity of 55%; the positive electrode material is lithium cobalt manganate, and the negative electrode material is a silicon-carbon negative electrode; the solid electrolyte consists of polyethylene oxide, lithium bis (difluoro-sulfonyl imide) and lithium aluminum germanium phosphorus solid electrolyte filler in a mass ratio of 1:0.4:0.3; the positive electrode material and the solid electrolyte are respectively modified by a surface modifier, wherein the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether with the mass ratio of 1:4:8:3.
The preparation method comprises the following steps:
s1, preparing a positive plate: putting lithium cobalt manganese oxide and a surface modifier into a stirring barrel, wherein the addition amount of the surface modifier is 3.2% of the mass of the lithium cobalt manganese oxide, stirring uniformly, mixing the modified anode material with an adhesive with the mass of 4.0% and a graphene conductive agent with the mass of 1.5%, wherein the adhesive consists of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerization rubber powder with the mass ratio of 5:2:1:2, and adding N-methyl pyrrolidone according to the solid content of 60%, and stirring uniformly to obtain anode slurry; the positive electrode slurry was then subjected to a treatment at 60mg/cm 2 The surface density and weight are uniformly coated on a three-dimensional foam porous aluminum foil positive plate, and the positive plate is obtained through baking in a baking oven of a coating machine;
s2, preparing a negative plate: adding 94.5% of silicon-carbon negative electrode, 2.5% of adhesive and 3% of graphene conductive agent into a stirring barrel, uniformly stirring, and adding N-methyl pyrrolidone according to the solid content of 55%, and uniformly stirring to obtain negative electrode slurry; the cathode slurry was prepared at a concentration of 30mg/cm 2 Uniformly coating the surface density and weight on a three-dimensional foam porous copper foil negative plate, and drying by a coating machine oven to obtain a negative plate;
s3, dissolving the solid electrolyte in N-methyl pyrrolidone according to the solid content of 25%, adding a surface modifier with the mass of 2.5%, and uniformly stirring to obtain electrolyte slurry;
s4, electrolyte slurry is mixed according to 8mg/cm 2 Uniformly coating the surface of the positive plate, storing for 12 hours at a high temperature of 75 ℃ and 24 hours at normal temperature, and then storing for 1000kg/cm at a high temperature of 80 DEG C 2 Hot-pressing for 2 min at 25deg.C under a pressure of 1000kg/cm 2 Cold pressing for 1 minute; preparing a battery cell by laminating a cathode plate and an electrolyte-coated anode plate by adopting a PVDF diaphragm, and then placing the battery cell into a shell, wherein the pressure is 500kg/cm at the high temperature of 80 DEG C 2 Hot-pressing for 5 min, and then heating at 25deg.C under 500kg/cm 2 Cold pressing for 3 minutes to prepare the three-dimensional solid lithium battery.
Example 3
The three-dimensional solid-state lithium battery provided by the embodiment comprises a negative plate, a positive electrode material, a negative electrode material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil with the thickness of 2.5mm, the aperture of 0.5mm and the porosity of 40%, and the negative plate is a three-dimensional foam porous copper foil with the thickness of 1.5mm, the aperture of 0.5mm and the porosity of 40%; the anode material is lithium iron phosphate, and the cathode material is mesophase carbon microsphere; the solid electrolyte consists of polymethyl methacrylate, lithium hexafluorophosphate and lithium lanthanum germanium phosphorus solid electrolyte filler in a mass ratio of 1:0.5:0.2; the positive electrode material and the solid electrolyte are respectively modified by a surface modifier, wherein the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether with the mass ratio of 1:3:8:3.
The preparation method comprises the following steps:
s1, preparing a positive plate: putting lithium iron phosphate and a surface modifier into a stirring barrel, wherein the addition amount of the surface modifier is 2.7% of the mass of the lithium iron phosphate, stirring uniformly, mixing the modified anode material with 4.5% of adhesive and 2.8% of acetylene black conductive agent uniformly, wherein the adhesive consists of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerization rubber powder in a mass ratio of 9:2:3:4, and adding N-methyl pyrrolidone according to the solid content of 60%, and stirring uniformly to obtain anode slurry; the positive electrode slurry was then subjected to a treatment of 65mg/cm 2 The surface density and weight are uniformly coated on a three-dimensional foam porous aluminum foil positive plate, and the positive plate is obtained through baking in a baking oven of a coating machine;
s2, preparing a negative plate: 95% of mesocarbon microbeads, 2.5% of adhesive, and the like,Adding 2.5% of acetylene black conductive agent into a stirring barrel, uniformly stirring, and then adding N-methyl pyrrolidone according to the solid content of 55%, and uniformly stirring to obtain negative electrode slurry; the cathode slurry was prepared at a concentration of 20mg/cm 2 Uniformly coating the surface density and weight on a three-dimensional foam porous copper foil negative plate, and drying by a coating machine oven to obtain a negative plate;
s3, dissolving the solid electrolyte in N-methyl pyrrolidone according to the solid content of 25%, adding a surface modifier with the mass of 2.5%, and uniformly stirring to obtain electrolyte slurry;
s4, electrolyte slurry is mixed according to 10mg/cm 2 Uniformly coating the surface of the positive plate, storing for 12 hours at a high temperature of 85 ℃ and 24 hours at normal temperature, and then storing for 1000kg/cm at a high temperature of 80 DEG C 2 Hot-pressing for 1 min at 25deg.C under a pressure of 1000kg/cm 2 Cold pressing for 2 minutes; preparing a battery cell by laminating a cathode plate and an electrolyte-coated anode plate by adopting a PVDF diaphragm, and then placing the battery cell into a shell, wherein the temperature is 80 ℃ and the pressure is 800kg/cm 2 Hot-pressing for 5 min, and then at 25deg.C and normal temperature under 800kg/cm 2 Cold pressing for 3 minutes to prepare the three-dimensional solid lithium battery.
Example 4
The three-dimensional solid-state lithium battery provided by the embodiment comprises a negative plate, a positive electrode material, a negative electrode material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil with the thickness of 2mm, the aperture of 0.5mm and the porosity of 60%, and the negative plate is a three-dimensional foam porous copper foil with the thickness of 1.5mm, the aperture of 0.5mm and the porosity of 60%; the positive electrode material is nickel cobalt lithium aluminate, and the negative electrode material is a silicon-carbon negative electrode; the solid electrolyte consists of polyvinylidene fluoride-hexafluoropropylene copolymer, lithium bisoxalato borate and lithium lanthanum zirconium oxide solid electrolyte filler in a mass ratio of 1:0.2:0.3; the positive electrode material and the solid electrolyte are respectively modified by a surface modifier, wherein the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether in a mass ratio of 2:4:8:3.
The preparation method comprises the following steps:
s1, preparing a positive plate: putting nickel cobalt lithium aluminate and a surface modifier into a stirring barrel, wherein the addition amount of the surface modifier is 2.5% of the mass of the nickel cobalt lithium aluminate, stirring uniformly, mixing the modified anode material with 4.5% of an adhesive and 3% of an ink-jet conductive agent uniformly, wherein the adhesive consists of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homo-polymer rubber powder in a mass ratio of 8:3:1:3, and adding N-methyl pyrrolidone according to a solid content of 65%, and stirring uniformly to obtain anode slurry; the positive electrode slurry was then mixed at a concentration of 70mg/cm 2 The surface density and weight are uniformly coated on a three-dimensional foam porous aluminum foil positive plate, and the positive plate is obtained through baking in a baking oven of a coating machine;
s2, preparing a negative plate: adding 96% of silicon-carbon negative electrode, 2.5% of adhesive and 1.5% of graphite conductive agent into a stirring barrel, uniformly stirring, and then adding N-methyl pyrrolidone according to the solid content of 60%, and uniformly stirring to obtain negative electrode slurry; the cathode slurry was prepared at a concentration of 20mg/cm 2 Uniformly coating the surface density and weight on a three-dimensional foam porous copper foil negative plate, and drying by a coating machine oven to obtain a negative plate;
s3, dissolving solid electrolyte in N-methyl pyrrolidone according to the solid content of 30%, adding a surface modifier with the mass of 3.0%, and uniformly stirring to obtain electrolyte slurry;
s4, electrolyte slurry is mixed according to 6mg/cm 2 Uniformly coating the surface of the positive plate, storing for 12 hours at a high temperature of 80 ℃ and 24 hours at normal temperature, and then storing for 1000kg/cm at a high temperature of 75 DEG C 2 Hot-pressing for 1 min at 25deg.C under a pressure of 1000kg/cm 2 Cold pressing for 2 minutes; preparing a battery cell by laminating a cathode plate and an electrolyte-coated anode plate by adopting a PVDF diaphragm, and then placing the battery cell into a shell, wherein the pressure is 500kg/cm at the high temperature of 80 DEG C 2 Hot-pressing for 5 min at 25deg.C under a pressure of 1000kg/cm 2 Cold pressing for 2 minutes to prepare the three-dimensional solid lithium battery.
Comparative example 1
This example differs from example 4 in that: the positive electrode material and the solid electrolyte are not modified by a surface modifier.
Comparative example 2
This example differs from example 4 in that: the binder used was polyvinylidene fluoride.
The three-dimensional solid-state lithium batteries prepared in examples 1 to 4 and comparative examples 1 and 2 were subjected to electrochemical performance test according to a conventional method, and the test results are shown in table 1. The testing method is to test the multiplying power performance of the battery at 25 ℃, the charging and discharging multiplying power is 5 ℃, and the voltage range is 3.7-4.3V.
Table 1: electrochemical performance test result of three-dimensional solid-state lithium battery
| Product(s) | Internal resistance (omega) | First discharge capacity (mAhg) -1 ） | 20-turn discharge capacity (mAhg) -1 ） | 100 cycles discharge capacity (mAhg) -1 ） | 500-turn discharge capacity (mAhg) -1 ） |
| Example 1 | 9 | 196 | 193 | 186 | 178 |
| Example 2 | 11 | 189 | 187 | 183 | 174 |
| Example 3 | 13 | 172 | 168 | 161 | 159 |
| Example 4 | 10 | 185 | 181 | 175 | 167 |
| Comparative example 1 | 18 | 166 | 160 | 142 | 124 |
| Comparative example 2 | 16 | 173 | 167 | 151 | 138 |
From the test results, the three-dimensional solid lithium battery prepared by the invention has small internal resistance, and can be charged and discharged at the multiplying power of 5 ℃ with the discharge specific capacity of up to 170mAhg -1 The battery has the advantages that the stable capacity after 500 circles is kept above 90%, and compared with the battery without surface modification and with the common adhesive, the battery has obviously improved specific capacity and cycle stability.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention.
Claims (5)
1. A three-dimensional solid state lithium battery, characterized by: comprises a negative plate, a positive electrode material, a negative electrode material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil, and the negative plate is a three-dimensional foam porous copper foil; the positive electrode material comprises one or more of nickel cobalt lithium aluminate, nickel cobalt lithium manganate, lithium iron phosphate and lithium-rich manganese-based materials, and the negative electrode material comprises one or more of graphite, mesophase carbon microspheres, silicon carbon negative electrode and silicon oxygen; the solid electrolyte consists of a polymer matrix, lithium salt and inorganic solid electrolyte filler; the positive electrode material and the solid electrolyte are respectively modified by a surface modifier, wherein the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkyl polysiloxane and alkylphenol polyoxyethylene ether;
the inorganic solid electrolyte filler is selected from one or a plurality of combinations of lithium lanthanum zirconium oxygen solid electrolyte, lithium lanthanum zirconium tantalum oxygen solid electrolyte, lithium aluminum germanium phosphorus solid electrolyte, lithium aluminum titanium phosphorus solid electrolyte and sulfide solid electrolyte;
the polymer matrix polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polysulfone, polyvinylpyrrolidone, polyethylene-vinyl acetate copolymer and polyvinyl butyral;
the mass ratio of the polymer matrix, the lithium salt and the inorganic solid electrolyte filler in the solid electrolyte is 1:0.1-0.5:0.1-0.3;
the mass ratio of the ethylene glycol monobutyl ether phosphate sodium salt, the rare earth coupling agent, the polyfluoroalkyl polysiloxane and the alkylphenol polyoxyethylene ether in the surface modifier is 1-3:3-5:5-10:3-5.
2. The method for preparing the three-dimensional solid-state lithium battery according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
s1, preparing a positive plate: placing the anode material and the surface modifier into a stirring barrel, wherein the addition amount of the surface modifier is 2-4% of the mass of the anode material, stirring uniformly, mixing the anode material after modification with 3-5% of adhesive and 1-3% of conductive agent uniformly, and adding N-methyl pyrrolidone according to the solid content of 60-70%, and stirring uniformly to obtain anode slurry; the positive electrode slurry was then mixed at a concentration of 50mg/cm 2 -70mg/cm 2 The surface density and weight are uniformly coated on a three-dimensional foam porous aluminum foil positive plate, and the positive plate is obtained through baking in a baking oven of a coating machine;
s2, preparing a negative plate: adding the anode material, the adhesive and the conductive agent into a stirring barrel, stirring uniformly, and then adding N-methyl pyrrolidone according to the solid content of 50-60%, and stirring uniformly to obtain anode slurry; the cathode slurry was prepared at a concentration of 20mg/cm 2 -30mg/cm 2 Uniformly coating the surface density and weight on a three-dimensional foam porous copper foil negative plate, and drying by a coating machine oven to obtain a negative plate;
s3, dissolving the solid electrolyte in N-methyl pyrrolidone according to the solid content of 20-40%, adding a surface modifier with the mass of 1-3%, and uniformly stirring to obtain electrolyte slurry;
s4, electrolyte slurry is processed according to 5mg/cm 2 -10mg/cm 2 Uniformly coating the surface of the positive plate, storing for 12 hours at a high temperature of 70-85 ℃ and 24 hours at normal temperature, and then storing for 1000kg/cm at a high temperature of 70-85 DEG C 2 Hot-pressing for 1-2 min at 25 deg.C under 500-1000kg/cm 2 Cold pressing for 1-2 minutes; by usingThe PVDF diaphragm is used for preparing a battery cell by laminating a negative electrode sheet and an electrolyte-coated positive electrode sheet, and then the battery cell is placed into a shell, and the battery cell is subjected to high temperature of 80 ℃ and pressure of 500-1000kg/cm 2 Hot-pressing for 1-5 min at 25deg.C under 500-1000kg/cm 2 Cold pressing for 1-5 min to obtain the three-dimensional solid lithium battery.
3. The method for preparing a three-dimensional solid-state lithium battery according to claim 2, wherein: the conductive agent is one or more of graphene, electrographite, acetylene black and carbon nano tubes.
4. The method for preparing a three-dimensional solid-state lithium battery according to claim 2, wherein: the adhesive consists of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerization rubber powder.
5. The method for preparing a three-dimensional solid-state lithium battery according to claim 4, wherein: the mass ratio of the adhesive polyvinylidene fluoride, the methacrylic acid ethoxylated bisphenol A diester and the terpene resin is 5-10:1-3:1-3:3-5.
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