CN112271325A - Three-dimensional solid-state lithium battery and preparation method thereof - Google Patents
Three-dimensional solid-state lithium battery and preparation method thereof Download PDFInfo
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- CN112271325A CN112271325A CN202010967622.7A CN202010967622A CN112271325A CN 112271325 A CN112271325 A CN 112271325A CN 202010967622 A CN202010967622 A CN 202010967622A CN 112271325 A CN112271325 A CN 112271325A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 58
- 239000006260 foam Substances 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 39
- 239000011888 foil Substances 0.000 claims abstract description 37
- 239000003607 modifier Substances 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 polysiloxane Polymers 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011889 copper foil Substances 0.000 claims abstract description 24
- 239000010405 anode material Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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
- 229910001416 lithium ion Inorganic materials 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 40
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000000853 adhesive Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000011267 electrode slurry Substances 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 17
- 239000002033 PVDF binder Substances 0.000 claims description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000007731 hot pressing Methods 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 10
- 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
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process 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
- 239000010406 cathode material Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 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
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000006230 acetylene black 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
- 238000000034 method Methods 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PYUKXGCMRFTISX-UHFFFAOYSA-N [O].[Ta].[Zr].[La].[Li] Chemical compound [O].[Ta].[Zr].[La].[Li] PYUKXGCMRFTISX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material 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
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 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
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000000203 mixture 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
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000002203 sulfidic glass Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 6
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 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 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 230000001351 cycling effect Effects 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
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 238000006467 substitution reaction Methods 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 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 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
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-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
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-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
Landscapes
- 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-state lithium battery and a preparation method thereof, wherein the three-dimensional solid-state lithium battery comprises a negative plate, a positive material, a negative 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 anode material and the solid electrolyte are respectively modified by a surface modifier, and the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkane 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 the conductive capacity of the active substance 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 the system is improved, the short circuit problem caused by the growth of lithium dendrites can be inhibited, the interface resistance is effectively reduced, the stable circulation can be realized under high rate, 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 matching in the IT industry, is supported by the great efforts of national policies on research, development, production and sale, is mature in domestic industrial chain and rapidly grows in the market, but the currently used technology is only limited to the manufacture of the traditional two-dimensional flat plate electrode lithium ion battery. Due to low energy density, the driving electric car has short driving mileage, poor rate capability, long charging time, poor safety performance, short 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 car industry is restricted. In order to break through the bottleneck better, the industry turns to the research of three-dimensional lithium ion batteries in many times, the pole piece carrier foil is subjected to three-dimensional porous treatment, and the three-dimensional foil technology is used for improving the adhesive force between the foil and the active substance. The three-dimension of the pole piece of the lithium ion battery is mainly embodied on the foil, the foil is usually punched or corroded, but the three-dimension of the porous foil is not good, and the adhesion to active substances is not strong.
With the research on solid electrolyte being deepened, a great deal of solid electrolyte materials capable of meeting both high mechanical strength and high ionic conductivity are developed, which lays a key foundation for the research on all-solid-state metal lithium batteries. Although the solid-state battery adopts the solid-state electrolyte to replace the organic electrolyte, the potential safety hazard caused by the problems of leakage of the electrolyte and the like is avoided, so that the safety performance of the battery is greatly improved, moreover, the solid-state battery can better adapt to the positive electrode and the negative electrode with high energy density to meet the requirement of the battery on high energy density, and in addition, the solid-state battery also 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 huge interface resistance, which greatly affects the rate capability of the all-solid-state battery, and the capacity exertion of the material itself is also limited. Among them, the solid-solid interface between the positive electrode side and the solid electrolyte layer has the most significant influence on the performance of the all-solid-state lithium metal battery. In order to reduce the transport resistance of lithium ions at this interface, the positive electrode material or the solid electrolyte needs to be surface-coated. The surfactant is a substance which is added with a small amount of surfactant and can obviously change the interface state of a solution system of the surfactant, has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution, and the surfactant is researched and used for improving the interface difference of the solid-state battery at present. However, the currently used surfactants such as silane coupling agents and polyethylene oxide are not effective enough in improving the interface, and a certain interface difference still exists. Therefore, how to improve the interface difference between the solid lithium batteries is a technical problem to be solved today.
Disclosure of Invention
The invention provides a three-dimensional solid-state lithium battery and a preparation method thereof aiming at the problems. The invention can improve the compactness of the solid-state battery and the compatibility of the system, can inhibit the short circuit problem caused by the growth of lithium dendrite, effectively reduce the interface resistance, realize stable circulation under high multiplying power, has good safety and long service life, and can meet the requirement of quick charge and discharge of the power battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a three-dimensional solid-state lithium battery comprises a negative plate, a positive material, a negative 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 anode material comprises one or more of nickel cobalt lithium aluminate, nickel cobalt lithium manganate, lithium iron phosphate and a lithium-rich manganese-based material, and the cathode material comprises one or more of graphite, mesophase carbon microspheres, a silicon-carbon cathode and silica; the solid electrolyte consists of a polymer matrix, lithium salt and inorganic solid electrolyte filler; the anode material and the solid electrolyte are respectively modified by a surface modifier, and the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkane polysiloxane and alkylphenol polyoxyethylene ether.
Further, the inorganic solid electrolyte filler is selected from one or more 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.
Further, the polymer matrix is one or a mixture of 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.
Furthermore, the mass ratio of ethylene glycol monobutyl ether phosphate sodium salt, the rare earth coupling agent, the polyfluoroalkane 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 bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (difluoro) sulfonimide and lithium bis (trifluoromethyl) sulfonimide.
Furthermore, the three-dimensional foam porous aluminum foil is an aluminum foil with a three-dimensional foam porous structure, the thickness of the aluminum foil is 0.1mm-5mm, the pore diameter of the aluminum foil is 0.05mm-10mm, and the porosity of the 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 excellent electric conduction and heat conduction properties.
Furthermore, the three-dimensional foam porous copper foil is a copper foil with a three-dimensional foam porous structure, which is made of copper foil, and has the thickness of 0.1mm-5mm, the aperture of 0.05mm-10mm and the porosity of 30% -80%. The three-dimensional foam porous copper foil is a metal material with a three-dimensional structure of through holes, a good capillary structure, an ultra-large specific surface area, good mechanical and processing properties and excellent 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 the positive plate: putting the anode material and a surface modifier into a stirring barrel, wherein the addition amount of the surface modifier is 2-4% of the mass of the anode material, uniformly stirring, uniformly mixing the modified anode material with 3-5% of an adhesive and 1-3% of a conductive agent by mass, adding N-methyl pyrrolidone according to the solid content of 60-70%, and uniformly stirring to obtain anode slurry; then the positive electrode slurry is mixed according to the ratio of 50mg/cm2-70mg/cm2The surface density weight is uniformly coated on the three-dimensional foamDrying the porous aluminum foil positive plate by a coating machine oven to obtain a positive plate;
s2, preparing the negative plate: adding the negative electrode material, the adhesive and the conductive agent into a stirring barrel, uniformly stirring, adding N-methylpyrrolidone according to the solid content of 50-60%, and uniformly stirring to obtain negative electrode slurry; the slurry of the negative electrode is mixed according to the proportion of 20mg/cm2-30mg/cm2Uniformly coating the surface density weight on a three-dimensional foam porous copper foil negative plate, and drying the negative plate 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 accounting for 1-3% of the mass of the solid electrolyte, and uniformly stirring to obtain electrolyte slurry;
s4, mixing the electrolyte slurry according to the ratio of 5mg/cm2-10mg/cm2Uniformly coating on the surface of the positive plate, storing at 70-85 deg.C for 12h, storing at normal temperature for 24h, and then at 70-85 deg.C under 1000kg/cm2Hot pressing for 1-2 min, and then at 25 deg.C and normal temperature and pressure of 500-2Cold pressing for 1-2 minutes; preparing a battery core by laminating a negative plate and a positive plate coated with electrolyte by adopting a PVDF diaphragm, and then putting the battery core into a shell at the high temperature of 80 ℃ and the pressure of 500-2Hot pressing for 1-5 min, then at 25 deg.C and normal temperature and pressure of 500-2And (5) performing cold pressing for 1-5 minutes to obtain the three-dimensional solid lithium battery.
Further, the conductive agent is one or more of graphene, electrical graphite, acetylene black and carbon nanotubes.
Further, the adhesive is composed of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerized rubber powder. Preferably, the mass ratio of the polyvinylidene fluoride adhesive to the methacrylic acid ethoxylated bisphenol A diester to the terpene resin is 5-10:1-3:1-3: 3-5.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. 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, the three-dimensional foam porous aluminum foil or the copper foil has a three-dimensional structure with a through hole and a good capillary structure, and the specific surface area is ultra-large, so that the conductive interface and the conductive capacity of an 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, polyfluoroalkane 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 the growth of lithium dendrite can be inhibited, the interface resistance is effectively reduced, the stable circulation can be realized under high multiplying power, the safety is good, the service life is long, and the requirements on quick charge and discharge of.
2. The polyvinylidene fluoride, the methacrylic acid ethoxylated bisphenol A diester, the terpene resin and the vinyl acetate homopolymerized rubber powder are used as the adhesive of the battery, so that the adhesive has good bonding capacity with active substances, and has strong acting force with substances of electrode materials, the stability of an electrode structure of the battery in the charging and discharging processes is ensured, and the defect that the adhesion of the current three-dimensional porous foil to the active substances is not strong is overcome; and the used adhesive also has good dispersibility, is beneficial to the conduction of lithium ions, and improves the multiplying power charge-discharge performance of the electrode.
3. The method provided by the invention combines the modes of hot pressing, cold pressing and multi-gradient temperature rise and fall to prepare the solid lithium battery, so that the internal texture of the electrode material is more uniform during molding, the prepared battery has good mechanical properties, the preparation process is simple, the production efficiency is higher, and the mass production can be better realized.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Example 1
The three-dimensional solid-state lithium battery provided by the embodiment comprises a negative plate, a positive material, a negative material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil which is made of aluminum foil and has 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 which is made of copper foil and has the thickness of 2mm, the aperture of 3mm and the porosity of 58%; the anode material is nickel cobalt lithium aluminate, and the cathode material is graphite; the solid electrolyte consists of polyethylene-vinyl acetate copolymer, aluminum perchlorate and lithium lanthanum zirconium tantalum oxygen solid electrolyte filler in a mass ratio of 1:0.3: 0.2; the anode material and the solid electrolyte are respectively modified by a surface modifier, and the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkane polysiloxane and alkylphenol polyoxyethylene ether in a mass ratio of 2:3:7: 3.
The preparation method comprises the following steps:
s1, preparing the 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, uniformly stirring, uniformly mixing the modified positive electrode material with a binder and a graphene conductive agent, wherein the binder is 3.5% of the mass of the modified positive electrode material, the graphene conductive agent is 2% of the mass of the modified positive electrode material, the binder is composed of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerized 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; then the positive electrode slurry is mixed according to the ratio of 50mg/cm2Uniformly coating the surface density weight on the three-dimensional foam porous aluminum foil positive plate, and drying the three-dimensional foam porous aluminum foil positive plate by using a coating machine drying oven to obtain a positive plate;
s2, preparing the negative plate: adding 95% of graphite, 3% of an adhesive and 2% of a graphene conductive agent into a stirring barrel in a mass ratio, uniformly stirring, adding N-methylpyrrolidone according to a solid content of 50%, and uniformly stirring to obtain a negative electrode slurry; the negative electrode slurry is mixed according to the ratio of 25mg/cm2Uniformly coating the surface density weight on a three-dimensional foam porous copper foil negative plate, and drying the negative plate by a coating machine oven to obtain a negative plate;
s3, dissolving the solid electrolyte in N-methyl pyrrolidone according to 35% of solid content, adding a surface modifier accounting for 2.0% of the solid electrolyte, and uniformly stirring to obtain electrolyte slurry;
s4, mixing the electrolyte slurry according to the ratio of 5mg/cm2Uniformly coating on the surface of the positive plate at 80 deg.CStoring at room temperature for 12h, storing at room temperature for 24h, and then storing at 70 deg.C under 1000kg/cm2Hot pressing for 2 minutes, and then heating at 25 deg.C and normal temperature under 500kg/cm2Cold pressing for 2 minutes; preparing a battery core by laminating a negative plate and a positive plate coated with electrolyte by adopting a PVDF diaphragm, and then putting the battery core into a shell, wherein the temperature is high at 80 ℃ and the pressure is 1000kg/cm2Hot pressing for 3 minutes, and then heating at 25 deg.C and normal temperature under 500kg/cm2And (5) performing cold pressing for 5 minutes to obtain 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 material, a negative material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil which is prepared by 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 which is prepared by copper foil with the thickness of 1mm, the aperture of 5mm and the porosity of 55%; the anode material is lithium cobalt manganese oxide, and the cathode material is a silicon-carbon cathode; the solid electrolyte consists of polyethylene oxide, lithium bis (difluorosulfonimide) and lithium aluminum germanium phosphorus solid electrolyte filler in a mass ratio of 1:0.4: 0.3; the anode material and the solid electrolyte are respectively modified by a surface modifier, and the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkane polysiloxane and alkylphenol polyoxyethylene ether in a mass ratio of 1:4:8: 3.
The preparation method comprises the following steps:
s1, preparing the 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, uniformly stirring, uniformly mixing the modified positive electrode material with a binder and a graphene conductive agent, wherein the binder is 4.0% of the mass of the positive electrode material and 1.5% of the mass of the graphene conductive agent, the binder is composed of polyvinylidene fluoride, ethoxylated bisphenol A diester of methacrylic acid, terpene resin and vinyl acetate homopolymerized rubber powder in a mass ratio of 5:2:1:2, and adding N-methyl pyrrolidone according to 60% of solid content, and uniformly stirring to obtain positive electrode slurry; then the positive electrode slurry is mixed according to the ratio of 60mg/cm2The surface density weight is evenly coated on the three-dimensional foam porous aluminum foil positive plate and coatedDrying in a drying oven to obtain a positive plate;
s2, preparing the negative plate: adding 94.5% of silicon-carbon negative electrode, 2.5% of adhesive and 3% of graphene conductive agent into a stirring barrel in a mass ratio, uniformly stirring, adding 55% of N-methyl pyrrolidone according to solid content, and uniformly stirring to obtain negative electrode slurry; the negative electrode slurry is mixed according to the ratio of 30mg/cm2Uniformly coating the surface density weight on a three-dimensional foam porous copper foil negative plate, and drying the negative plate 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 accounting for 2.5% of the mass of the solid electrolyte, and uniformly stirring to obtain electrolyte slurry;
s4, mixing the electrolyte slurry according to the ratio of 8mg/cm2Uniformly coating on the surface of the positive plate, storing at 75 deg.C for 12h, storing at room temperature for 24h, and then at 80 deg.C under 1000kg/cm2Hot pressing for 2 minutes, and then heating at 25 deg.C and normal temperature under 1000kg/cm2Cold pressing for 1 minute; preparing a battery core by laminating a negative plate and a positive plate coated with electrolyte by adopting a PVDF diaphragm, and then putting the battery core into a shell, wherein the temperature is high at 80 ℃ and the pressure is 500kg/cm2Hot pressing for 5 minutes, and then heating at 25 deg.C and normal temperature under 500kg/cm2And (5) cold pressing for 3 minutes to obtain 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 material, a negative material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil which is prepared by 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 which is prepared by 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 mesocarbon microbeads; 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 anode material and the solid electrolyte are respectively modified by a surface modifier, and the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkane polysiloxane and alkylphenol polyoxyethylene ether in a mass ratio of 1:3:8: 3.
The preparation method comprises the following steps:
s1, preparing the 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 percent of the mass of the lithium iron phosphate, uniformly stirring, uniformly mixing the modified anode material with an adhesive and an acetylene black conductive agent, wherein the adhesive is 4.5 percent of the mass of the modified anode material, the acetylene black conductive agent is 2.8 percent of the mass of the modified anode material, the adhesive is composed of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerized rubber powder in a mass ratio of 9:2:3:4, and then adding N-methyl pyrrolidone according to 60 percent of solid content, and uniformly stirring to obtain anode slurry; then the positive electrode slurry is mixed according to the ratio of 65mg/cm2Uniformly coating the surface density weight on the three-dimensional foam porous aluminum foil positive plate, and drying the three-dimensional foam porous aluminum foil positive plate by using a coating machine drying oven to obtain a positive plate;
s2, preparing the negative plate: adding 95% of mesocarbon microbeads, 2.5% of adhesive and 2.5% of acetylene black conductive agent into a stirring barrel in mass ratio, uniformly stirring, adding 55% of N-methyl pyrrolidone according to solid content, and uniformly stirring to obtain negative electrode slurry; the slurry of the negative electrode is mixed according to the proportion of 20mg/cm2Uniformly coating the surface density weight on a three-dimensional foam porous copper foil negative plate, and drying the negative plate 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 accounting for 2.5% of the mass of the solid electrolyte, and uniformly stirring to obtain electrolyte slurry;
s4, mixing the electrolyte slurry according to the ratio of 10mg/cm2Uniformly coating on the surface of the positive plate, storing at 85 deg.C for 12 hr, storing at room temperature for 24 hr, and then storing at 80 deg.C under 1000kg/cm2Hot pressing for 1 minute, and then heating at 25 deg.C and normal temperature under 1000kg/cm2Cold pressing for 2 minutes; preparing a battery core by laminating a negative plate and a positive plate coated with electrolyte by adopting a PVDF diaphragm, and then putting the battery core into a shell, wherein the temperature is high at 80 ℃ and the pressure is 800kg/cm2Hot pressing for 5 minutes, and then heating at 25 deg.C and normal temperature under 800kg/cm2And (5) cold pressing for 3 minutes to obtain 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 material, a negative material and a solid electrolyte; the positive plate is a three-dimensional foam porous aluminum foil which is prepared by 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 which is prepared by copper foil with the thickness of 1.5mm, the aperture of 0.5mm and the porosity of 60%; the anode material is nickel cobalt lithium aluminate, and the cathode material is a silicon carbon cathode; the solid electrolyte consists of polyvinylidene fluoride-hexafluoropropylene copolymer, lithium bis (oxalato) borate and lithium lanthanum zirconium oxide solid electrolyte filler in a mass ratio of 1:0.2: 0.3; the anode material and the solid electrolyte are respectively modified by a surface modifier, and the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkane polysiloxane and alkylphenol polyoxyethylene ether in a mass ratio of 2:4:8: 3.
The preparation method comprises the following steps:
s1, preparing the 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, uniformly stirring, uniformly mixing the modified positive electrode material with a binder and a calcium carbide ink conductive agent, wherein the binder is 4.5% of the mass of the positive electrode material and 3% of the mass of the positive electrode material, the binder is composed of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerized rubber powder in a mass ratio of 8:3:1:3, and adding N-methyl pyrrolidone according to 65% of solid content, and uniformly stirring to obtain positive electrode slurry; then the positive electrode slurry is mixed according to the proportion of 70mg/cm2Uniformly coating the surface density weight on the three-dimensional foam porous aluminum foil positive plate, and drying the three-dimensional foam porous aluminum foil positive plate by using a coating machine drying oven to obtain a positive plate;
s2, preparing the negative plate: adding 96% of silicon-carbon negative electrode, 2.5% of adhesive and 1.5% of electric ink conductive agent into a stirring barrel in mass ratio, uniformly stirring, adding N-methyl pyrrolidone according to the solid content of 60%, and uniformly stirring to obtain negative electrode slurry; the slurry of the negative electrode is mixed according to the proportion of 20mg/cm2Uniformly coating the surface density weight on a three-dimensional foam porous copper foil negative plate, and drying the negative plate 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 30%, adding a surface modifier with the mass of 3.0%, and uniformly stirring to obtain electrolyte slurry;
s4, mixing the electrolyte slurry according to the ratio of 6mg/cm2Uniformly coating on the surface of the positive plate, storing at 80 deg.C for 12 hr, storing at room temperature for 24 hr, and then at 75 deg.C under 1000kg/cm2Hot pressing for 1 minute, and then heating at 25 deg.C and normal temperature under 1000kg/cm2Cold pressing for 2 minutes; preparing a battery core by laminating a negative plate and a positive plate coated with electrolyte by adopting a PVDF diaphragm, and then putting the battery core into a shell, wherein the temperature is high at 80 ℃ and the pressure is 500kg/cm2Hot pressing for 5 min, and heating at 25 deg.C and 1000kg/cm2And (5) cold pressing for 2 minutes to obtain 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.
Electrochemical performance tests were performed on the three-dimensional solid-state lithium batteries prepared in examples 1 to 4 and comparative examples 1 and 2 according to a conventional method, and the test results are shown in table 1. The test method is to test the multiplying power performance of the battery at 25 ℃, wherein the charging and discharging multiplying power is 5C, and the voltage range is 3.7-4.3V.
Table 1: electrochemical performance test result of three-dimensional solid lithium battery
| Product(s) | Internal resistance (omega) | First discharge capacity (mAhg)-1） | 20 cycles discharge capacity (mAhg)-1） | 100 cycles discharge capacity (mAhg)-1） | 500 cycles 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, is charged and discharged at the multiplying power of 5C, and has the discharge specific capacity as high as 170mAhg-1And the cycling stable capacity is kept above 90% after 500 cycles, and the specific capacity and cycling stability of the battery are obviously improved compared with the battery which is not subjected to surface modification and adopts a common adhesive.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (9)
1. A three-dimensional solid-state lithium battery is characterized in that: the lithium ion battery comprises a negative plate, a positive material, a negative 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 anode material comprises one or more of nickel cobalt lithium aluminate, nickel cobalt lithium manganate, lithium iron phosphate and a lithium-rich manganese-based material, and the cathode material comprises one or more of graphite, mesophase carbon microspheres, a silicon-carbon cathode and silica; the solid electrolyte consists of a polymer matrix, lithium salt and inorganic solid electrolyte filler; the anode material and the solid electrolyte are respectively modified by a surface modifier, and the surface modifier consists of ethylene glycol monobutyl ether phosphate sodium salt, a rare earth coupling agent, polyfluoroalkane polysiloxane and alkylphenol polyoxyethylene ether.
2. The three-dimensional lithium solid state battery of claim 1, wherein: the inorganic solid electrolyte filler is selected from one or more 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.
3. The three-dimensional lithium solid state battery of claim 1, wherein: the polymer matrix is one or a mixture of more of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polysulfone, polyvinylpyrrolidone, polyethylene-vinyl acetate copolymer and polyvinyl butyral.
4. The three-dimensional lithium solid state battery of claim 1, wherein: 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.
5. The three-dimensional lithium solid state battery of claim 1, wherein: in the surface modifier, the mass ratio of ethylene glycol monobutyl ether phosphate sodium salt, the rare earth coupling agent, the polyfluoroalkane polysiloxane and the alkylphenol polyoxyethylene ether is 1-3:3-5:5-10: 3-5.
6. The method of claim 1 for making a three-dimensional solid-state lithium battery, comprising: the method comprises the following steps:
s1, preparing the positive plate: stirring the positive electrode material and the surface modifierThe surface modifier is added in an amount of 2-4% of the mass of the positive electrode material, the positive electrode material is uniformly stirred, the modified positive electrode material is uniformly mixed with 3-5% of adhesive and 1-3% of conductive agent by mass, and then N-methyl pyrrolidone is added according to the solid content of 60-70% and uniformly stirred to obtain positive electrode slurry; then the positive electrode slurry is mixed according to the ratio of 50mg/cm2-70mg/cm2Uniformly coating the surface density weight on the three-dimensional foam porous aluminum foil positive plate, and drying the three-dimensional foam porous aluminum foil positive plate by using a coating machine drying oven to obtain a positive plate;
s2, preparing the negative plate: adding the negative electrode material, the adhesive and the conductive agent into a stirring barrel, uniformly stirring, adding N-methylpyrrolidone according to the solid content of 50-60%, and uniformly stirring to obtain negative electrode slurry; the slurry of the negative electrode is mixed according to the proportion of 20mg/cm2-30mg/cm2Uniformly coating the surface density weight on a three-dimensional foam porous copper foil negative plate, and drying the negative plate 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 accounting for 1-3% of the mass of the solid electrolyte, and uniformly stirring to obtain electrolyte slurry;
s4, mixing the electrolyte slurry according to the ratio of 5mg/cm2-10mg/cm2Uniformly coating on the surface of the positive plate, storing at 70-85 deg.C for 12h, storing at normal temperature for 24h, and then at 70-85 deg.C under 1000kg/cm2Hot pressing for 1-2 min, and then at 25 deg.C and normal temperature and pressure of 500-2Cold pressing for 1-2 minutes; preparing a battery core by laminating a negative plate and a positive plate coated with electrolyte by adopting a PVDF diaphragm, and then putting the battery core into a shell at the high temperature of 80 ℃ and the pressure of 500-2Hot pressing for 1-5 min, then at 25 deg.C and normal temperature and pressure of 500-2And (5) performing cold pressing for 1-5 minutes to obtain the three-dimensional solid lithium battery.
7. The method of manufacturing a three-dimensional lithium solid state battery of claim 6, wherein: the conductive agent is one or a combination of more of graphene, electrical graphite, acetylene black and carbon nanotubes.
8. The method of manufacturing a three-dimensional lithium solid state battery of claim 6, wherein: the adhesive is composed of polyvinylidene fluoride, methacrylic acid ethoxylated bisphenol A diester, terpene resin and vinyl acetate homopolymerized rubber powder.
9. The method of manufacturing a three-dimensional lithium solid state battery of claim 8, wherein: the mass ratio of the polyvinylidene fluoride adhesive to the methacrylic acid ethoxylated bisphenol A diester to the terpene resin is 5-10:1-3:1-3: 3-5.
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