CN116169366A - Solid-state lithium battery, preparation method thereof and electric equipment - Google Patents
Solid-state lithium battery, preparation method thereof and electric equipment Download PDFInfo
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- CN116169366A CN116169366A CN202211680855.4A CN202211680855A CN116169366A CN 116169366 A CN116169366 A CN 116169366A CN 202211680855 A CN202211680855 A CN 202211680855A CN 116169366 A CN116169366 A CN 116169366A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 104
- 238000011065 in-situ storage Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- -1 polyfluoroethylene carbonate Polymers 0.000 claims description 23
- 239000000084 colloidal system Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 16
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical group [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000005266 casting Methods 0.000 claims 1
- 238000010952 in-situ formation Methods 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 238000002156 mixing Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- 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 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of lithium batteries, and particularly relates to a solid-state lithium battery, a preparation method thereof and electric equipment. The solid lithium battery comprises a positive electrode plate, a high-voltage-resistant solid electrolyte, a lithium-philic solid electrolyte and a negative electrode plate; the high-pressure-resistant solid electrolyte is formed on the positive electrode plate in situ; the lithium-philic solid electrolyte is formed on the negative electrode plate in situ. According to the method, the high-pressure-resistant solid electrolyte and the lithium-philic solid electrolyte are respectively formed on the surfaces of the positive electrode plate and the negative electrode plate in situ, the ion conducting channel is formed on the interfaces of the positive electrode plate and the negative electrode plate in situ, the interface impedance is reduced, and the circularity and the stability of the battery are improved.
Description
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a solid-state lithium battery, a preparation method thereof and electric equipment.
Background
Solid-state lithium batteries have been widely studied for their advantages of high safety, high energy density, wide use temperature, long cycle life, etc., and conventional liquid electrolytes present the risk of explosion and fire, and in all-solid batteries, there is no liquid flammable electrolyte present, so they have high energy density and high safety. The lithium ion battery is expected to replace the traditional lithium ion battery to become the next generation electrochemical energy storage device. The solid electrolyte refers to a substance having lithium ion conductive properties that exists as a solid at room temperature, and the requirements for the solid electrolyte are: (1) has higher lithium ion conductivity; (2) excellent oxidation-reduction resistance and wide electrochemical window; (3) excellent chemical stability; (4) Does not have side reaction with anode and cathode materials and has low interface resistance.
The electrolyte with stable high voltage is easy to be reduced, the electrolyte with stable low voltage is easy to be oxidized by the high voltage positive electrode, so far, no single solid electrolyte can simultaneously meet the stability requirement of the surface of the positive electrode and the negative electrode, namely, the electrolyte cannot simultaneously be compatible with the positive electrode materials with high voltage, such as positive electrode materials of lithium cobaltate, lithium-rich manganese base and the like, and the metal lithium negative electrode with low potential.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a solid lithium battery, a preparation method thereof and electric equipment, wherein the solid lithium battery is provided with a double-layer solid electrolyte, the high-voltage-resistant solid electrolyte is matched with an anode, and the lithium-philic solid electrolyte is matched with a cathode, so that the double-layer solid electrolyte has a wider electrochemical window and more stable cycle performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a solid lithium battery comprises a positive electrode plate, a high-voltage resistant solid electrolyte, a lithium-philic solid electrolyte and a negative electrode plate; the high-pressure-resistant solid electrolyte is formed on the positive electrode plate in situ; the lithium-philic solid electrolyte is formed on the negative electrode plate in situ.
The high-pressure-resistant solid electrolyte comprises the following components in parts by mass: 5-20 parts of inorganic filler, 10-90 parts of high-pressure resistant polymer matrix, 5-40 parts of first lithium salt and 5-50 parts of high-pressure resistant organic solvent;
preferably, the composition comprises the following components in parts by mass: 5-10 parts of inorganic filler, 30-40 parts of high-pressure resistant polymer matrix, 5-30 parts of first lithium salt and 30-45 parts of high-pressure resistant organic solvent.
The inorganic filler is one or more of lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum titanium oxide, aluminum doped lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, aluminum doped lithium lanthanum zirconium oxide, tantalum doped lithium lanthanum zirconium oxide, niobium doped lithium lanthanum zirconium oxide, aluminum oxide, silicon dioxide or titanium dioxide;
preferably, the high pressure resistant polymer matrix is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinyl carbonate, polystyrene, styrene-acrylonitrile copolymer or polyfluorocarbon ethylene ester;
preferably, the high-pressure resistant organic solvent is one or more of fluoroethylene carbonate, chloroethylene carbonate, difluoroethylene carbonate, trifluoromethyl ethylene carbonate, propylene carbonate or nitrile compound;
preferably, the first lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide or lithium bisfluorosulfonyl imide.
The lithium-philic solid electrolyte comprises the following components in parts by mass: 10-95 parts of a lithium-philic polymer matrix and 5-70 parts of a second lithium salt;
30-90 parts of a lithium-philic polymer matrix and 10 parts of a second lithium salt;
preferably, the lithium-philic solid electrolyte consists of the following components in parts by mass: 10-95 parts of a lithium-philic polymer matrix and 5-70 parts of a second lithium salt.
The lithium-philic polymer matrix comprises one or more of polyethylene oxide, polypropylene carbonate, poly (ethylene glycol) dimethyl ether, polyacrylamide, poly (N-isopropyl acrylamide), polyvinyl alcohol or polyethylene glycol;
preferably, the second lithium salt is one or a mixture of more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide or lithium bisfluorosulfonyl imide.
The positive electrode plate is an electrode plate formed by coating a positive electrode active material on a positive electrode current collector;
preferably, the positive active material is one or more of lithium cobaltate, lithium-rich manganese-based material, nickel cobalt lithium manganate, lithium iron phosphate or lithium manganese iron phosphate;
preferably, the positive current collector comprises an alloy of one or more of copper, stainless steel, aluminum, nickel, titanium;
preferably, the positive electrode current collector includes an irregular coating layer on a surface thereof;
preferably, the positive current collector is one or more of a film, sheet, foil, mesh, porous structure or foam structure;
preferably, the negative electrode plate is an electrode plate with a negative electrode active material coated on a negative electrode current collector, or a negative electrode current collector without a negative electrode active material;
preferably, the negative electrode active material is one or more of natural graphite, artificial graphite, silicon oxide, lithium metal or lithium alloy;
preferably, the negative current collector comprises an alloy of one or more components of copper, stainless steel, aluminum, nickel or titanium;
preferably, the negative electrode current collector includes an irregular coating on its surface;
preferably, the negative current collector is one or a combination of more of a film, sheet, foil, mesh, porous structure or foam structure.
The high-pressure-resistant solid electrolyte is formed on the positive electrode plate in situ by the following method: dispersing raw material components of the high-pressure-resistant solid electrolyte in a first solvent to obtain a mixed colloid; then, pouring the mixed colloid on a die taking the positive electrode plate as a substrate, and forming the high-pressure-resistant solid electrolyte on the positive electrode plate in situ after the first solvent volatilizes; preferably, the first solvent is one or more of acetonitrile, N-methyl pyrrolidone and acetone;
preferably, the high-pressure-resistant solid electrolyte is coated on the positive electrode plate;
preferably, the lithium-philic solid electrolyte is formed in situ on the negative electrode sheet by: dispersing a lithium-philic solid electrolyte raw material in a second solvent to obtain a mixed colloid; then, pouring the mixed colloid on a die taking the negative electrode plate as a substrate, and forming the lithium-philic solid electrolyte on the negative electrode plate in situ after the second solvent is exerted; preferably, the second solvent is one or more of acetonitrile, N-methyl pyrrolidone and acetone;
preferably, the lithium-philic solid electrolyte is coated on the negative electrode plate;
preferably, the first solvent or the second solvent volatilizes in a manner of heating and drying under vacuum or heating and drying under inert atmosphere;
preferably, the heating temperature is 30-80 ℃, preferably, the heating temperature is 45-60 ℃;
preferably, the drying time is 3-24 hours, preferably, the drying time is 12 hours.
The invention also comprises a preparation method of the solid-state lithium battery, which comprises the following steps:
1) Forming a high-pressure-resistant solid electrolyte on the positive electrode plate in situ;
2) The lithium-philic solid electrolyte is formed on the negative electrode plate in situ;
3) Assembling the products obtained in the step 1) and the step 2) to obtain the solid-state lithium battery.
Step 1) comprises: dispersing raw material components of the high-pressure-resistant solid electrolyte in a first solvent to obtain a mixed colloid; then, pouring the mixed colloid on a die taking the positive electrode plate as a substrate, and forming the high-pressure-resistant solid electrolyte on the positive electrode plate in situ after the first solvent volatilizes; preferably, the first solvent is one or more of acetonitrile, N-methyl pyrrolidone and acetone;
preferably, the high-pressure-resistant solid electrolyte is coated on the positive electrode plate;
preferably, step 2) comprises: dispersing a lithium-philic solid electrolyte raw material in a second solvent to obtain a mixed colloid; then, pouring the mixed colloid on a die taking the negative electrode plate as a substrate, and forming the lithium-philic solid electrolyte on the negative electrode plate in situ after the second solvent is exerted; preferably, the second solvent is one or more of acetonitrile, N-methyl pyrrolidone and acetone;
preferably, the high-pressure-resistant solid electrolyte is coated on the positive electrode plate;
preferably, the volatilization mode of the first solvent and the second solvent comprises heating and drying under vacuum condition or heating and drying under inert atmosphere;
preferably, the heating temperature is 30-80 ℃, preferably, the heating temperature is 45-60 ℃;
preferably, the drying time is 3-24 hours, preferably, the drying time is 12 hours.
The invention also comprises electric equipment and uses the solid-state lithium battery.
Compared with the prior art, the invention has the beneficial effects that:
the surfaces of the positive electrode plate and the negative electrode plate of the solid lithium battery respectively form the high-pressure resistant solid electrolyte and the lithium-philic solid electrolyte in situ, and the interfaces of the positive electrode plate and the negative electrode plate form ion conducting channels in situ, so that the interface impedance is reduced, and the circularity and the stability of the battery are improved.
The preparation method of the solid-state lithium battery provided by the invention has the advantages that the solid electrolyte is formed on the positive electrode plate and the negative electrode plate in situ, the preparation process is simple, the solid-state lithium battery is suitable for large-scale production, and a new development direction is brought for the development of the solid-state battery in the future.
Drawings
FIG. 1 is a schematic structural view of embodiment 1 of the present application;
fig. 2 is a schematic structural view of comparative example 1 of the present application;
fig. 3 is a graph comparing cycle performance of example 1 and comparative example 1 of the present application.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and preferred embodiments, so that those skilled in the art can better understand the technical solutions of the present invention.
Example 1: a preparation method of a solid-state lithium battery comprises the following steps:
(1) Preparing a positive electrode plate: mixing lithium cobaltate, acetylene black, lithium bis (fluorosulfonyl) imide and PVDF (polyvinylidene fluoride) according to the mass ratio of 90:3:4:3, adding an N-methyl pyrrolidone solvent, fully grinding for 30min, uniformly coating the mixture on an aluminum foil, then vacuum drying the mixture at 90 ℃ for 10h, and rolling the mixture to obtain the positive electrode plate.
(2) Preparing a high-pressure-resistant solid electrolyte coated positive electrode plate: mixing polyvinylidene fluoride-hexafluoropropylene, lithium bis (trifluoromethylsulfonyl) imide, lithium lanthanum zirconium oxide and fluoroethylene carbonate according to a mass ratio of 30:15:10:45, adding 100mL of acetonitrile solvent, uniformly mixing, continuously stirring for 5 hours at 30 ℃, pouring colloid into a die taking the positive electrode plate obtained in the step (1) as a substrate, and drying at 60 ℃ for 12 hours in an inert atmosphere to obtain the high-pressure-resistant solid electrolyte coated positive electrode plate;
(3) Preparation of a lithium-philic solid electrolyte coated negative electrode piece: and (3) dissolving poly (ethylene glycol) dimethyl ether and lithium bis (trifluoromethylsulfonyl) imide in the mass ratio of 3:1 in N-methylpyrrolidone, stirring for 24 hours at room temperature to obtain a mixed solution, pouring the mixed solution into a mold with copper foil as a substrate, and vacuum drying at 45 ℃ for 24 hours to obtain the lithium-philic solid electrolyte coated negative electrode plate.
(4) And placing a lithium cobalt oxide positive electrode sheet coated by a high-pressure-resistant solid electrolyte into the positive electrode shell, attaching a lithium-philic solid electrolyte coated negative electrode sheet above the positive electrode sheet, hot-pressing for 300 seconds at 60 ℃ and 0.6MPa, placing an elastic sheet and a gasket, assembling the solid lithium battery in an inert atmosphere, and aging for 10 hours at 60 ℃, wherein the cycle performance of the solid lithium battery prepared in the embodiment is detected as shown in figure 3. Test conditions: the current is 0.1C and the voltage is in the range of 3.0V-4.4V.
The mode of the embodiment in the application is that a form of a high-pressure-resistant solid electrolyte is arranged on one side of a positive electrode plate, and a lithium-philic solid electrolyte is arranged on one side of a negative electrode plate is shown in fig. 1; the mode is more suitable for button cells, and for soft package cells, the mode that high-voltage resistant solid electrolytes are arranged on both sides of the positive electrode plate, and lithium-philic solid electrolytes are arranged on both sides of the negative electrode plate can be adopted;
this application is illustrated in the form of a side set-up in fig. 1.
Example 2: a preparation method of a solid-state lithium battery comprises the following steps:
(1) Preparing a positive electrode plate: mixing lithium cobaltate, acetylene black, lithium bis (fluorosulfonyl) imide and PVDF according to the mass ratio of 90:3:4:3, adding an N-methyl pyrrolidone solvent, fully grinding for 30min, uniformly coating the mixture on an aluminum foil, then vacuum drying at 90 ℃ for 10h, and rolling to obtain the positive pole piece.
(2) Preparing a high-pressure-resistant solid electrolyte coated positive electrode plate: mixing poly fluoroethylene carbonate, lithium bis (trifluoromethylsulfonyl) imide, titanium dioxide and fluoroethylene carbonate according to a mass ratio of 40:5:10:45, adding 100mL of acetonitrile solvent, uniformly mixing, continuously stirring for 5 hours at 30 ℃, pouring colloid into a die taking a positive electrode plate as a substrate, and drying for 12 hours at 60 ℃ in an inert atmosphere to obtain the high-pressure-resistant solid electrolyte coated positive electrode plate.
(3) Preparation of a lithium-philic solid electrolyte coated negative electrode piece: and (3) dissolving polyethylene oxide and lithium bis (trifluoromethylsulfonyl) imide in N-methylpyrrolidone according to a mass ratio of 5:1, stirring for 24 hours at room temperature to obtain a mixed solution, pouring the mixed solution into a mold taking copper foil as a substrate, and vacuum drying for 24 hours at 45 ℃ to obtain the lithium-philic solid electrolyte coated negative electrode plate.
(4) A lithium cobalt oxide positive electrode sheet coated by high-pressure-resistant solid electrolyte is placed in a positive electrode shell, a negative electrode sheet coated by lithium-philic solid electrolyte is attached above the positive electrode sheet, an elastic sheet and a gasket are placed after hot pressing for 300 seconds at 60 ℃ and 0.6MPa, a solid lithium battery is assembled in an inert atmosphere, and then aging is carried out for 10 hours at 60 ℃, so that the cycle performance of the solid lithium battery prepared in the embodiment is detected as shown in figure 1. Test conditions: the current is 0.1C and the voltage is in the range of 3.0V-4.4V.
Example 3: a preparation method of a solid-state lithium battery comprises the following steps:
(1) Preparing a positive electrode plate: mixing lithium cobaltate, acetylene black, lithium bis (fluorosulfonyl) imide and PVDF according to the mass ratio of 90:3:4:3, adding an N-methyl pyrrolidone solvent, fully grinding for 30min, uniformly coating the mixture on an aluminum foil, then vacuum drying at 90 ℃ for 10h, and rolling to obtain the positive pole piece.
(2) Preparing a high-pressure-resistant solid electrolyte coated positive electrode plate: mixing polystyrene, lithium bis (trifluoromethylsulfonyl) imide, lithium titanium aluminum phosphate and fluoroethylene carbonate according to a mass ratio of 35:25:10:30, adding 100mL of acetonitrile solvent, continuously stirring at 30 ℃ for 5 hours, pouring the colloid into a die taking the positive electrode plate as a substrate, and drying at 60 ℃ for 12 hours in an inert atmosphere to obtain the high-pressure-resistant solid electrolyte coated positive electrode plate.
(3) Preparation of a lithium-philic solid electrolyte coated negative electrode piece: and (3) dissolving polyvinyl alcohol and lithium bis (trifluoromethylsulfonyl) imide in N-methylpyrrolidone according to a mass ratio of 7:1, stirring for 24 hours at room temperature to obtain a mixed solution, pouring the mixed solution into a mold taking copper foil as a substrate, and vacuum drying for 24 hours at 45 ℃ to obtain the lithium-philic solid electrolyte coated negative electrode plate.
(4) A lithium cobalt oxide positive electrode sheet coated by high-pressure-resistant solid electrolyte is placed in a positive electrode shell, a negative electrode sheet coated by lithium-philic solid electrolyte is attached above the positive electrode sheet, an elastic sheet and a gasket are placed after hot pressing for 300 seconds at 60 ℃ and 0.6MPa, a solid lithium battery is assembled in an inert atmosphere, and then aging is carried out for 10 hours at 60 ℃, so that the cycle performance of the solid lithium battery prepared in the embodiment is detected as shown in figure 1. Test conditions: the current is 0.1C and the voltage is in the range of 3.0V-4.4V.
Example 4: a preparation method of a solid-state lithium battery comprises the following steps:
(1) Preparing a positive electrode plate: mixing lithium cobaltate, acetylene black, lithium bis (fluorosulfonyl) imide and PVDF according to the mass ratio of 90:3:4:3, adding an N-methyl pyrrolidone solvent, fully grinding for 30min, uniformly coating the mixture on an aluminum foil, then vacuum drying at 90 ℃ for 10h, and rolling to obtain the positive pole piece.
(2) Preparing a high-pressure-resistant solid electrolyte coated positive electrode plate: mixing polyvinyl carbonate, lithium bis (trifluoromethylsulfonyl) imide, lithium titanium aluminum phosphate and fluoroethylene carbonate according to a mass ratio of 30:30:5:35, adding 100mL of acetonitrile solvent, continuously stirring at 30 ℃ for 5 hours, pouring the colloid into a die taking the positive electrode plate as a substrate, and drying at 60 ℃ for 12 hours in an inert atmosphere to obtain the high-pressure-resistant solid electrolyte coated positive electrode plate.
(3) Preparation of a lithium-philic solid electrolyte coated negative electrode piece: and (3) dissolving polyvinyl alcohol and lithium bis (trifluoromethylsulfonyl) imide in N-methylpyrrolidone according to a mass ratio of 9:1, stirring for 24 hours at room temperature to obtain a mixed solution, pouring the mixed solution into a mold taking copper foil as a substrate, and vacuum drying for 24 hours at 45 ℃ to obtain the lithium-philic solid electrolyte coated negative electrode plate.
(4) A lithium cobalt oxide positive electrode sheet coated by high-pressure-resistant solid electrolyte is placed in a positive electrode shell, a negative electrode sheet coated by lithium-philic solid electrolyte is attached above the positive electrode sheet, an elastic sheet and a gasket are placed after hot pressing for 300 seconds at 60 ℃ and 0.6MPa, a solid lithium battery is assembled in an inert atmosphere, and then aging is carried out for 10 hours at 60 ℃, so that the cycle performance of the solid lithium battery prepared in the embodiment is detected as shown in figure 1. Test conditions: the current is 0.1C and the voltage is in the range of 3.0V-4.4V.
Comparative example 1: a preparation method of a solid-state lithium battery comprises the following steps:
(1) Preparing a positive electrode plate: mixing lithium cobaltate, acetylene black, lithium bis (fluorosulfonyl) imide and PVDF according to the mass ratio of 90:3:4:3, adding an N-methyl pyrrolidone solvent, fully grinding for 30min, uniformly coating the mixture on an aluminum foil, then vacuum drying at 90 ℃ for 10h, and rolling to obtain the positive pole piece.
(2) Preparation of high-pressure resistant solid electrolyte: mixing polyvinylidene fluoride-hexafluoropropylene, lithium bis (trifluoromethylsulfonyl) imide, lithium lanthanum zirconium oxide and fluoroethylene carbonate according to a mass ratio of 30:15:10:45, adding 100mL of acetonitrile solvent, continuously stirring at 30 ℃ for 5 hours, pouring the colloid into a mold, and drying at 50 ℃ for 12 hours in an inert atmosphere to obtain the high-pressure-resistant solid electrolyte.
(3) Preparation of a lithium-philic solid electrolyte: and (3) dissolving poly (ethylene glycol) dimethyl ether and lithium bis (trifluoromethylsulfonyl) imide in the mass ratio of 3:1 in N-methylpyrrolidone, stirring for 24 hours at room temperature to obtain a mixed solution, pouring the colloid into a mold, and drying at 50 ℃ for 24 hours in an inert atmosphere to obtain the lithium-philic solid electrolyte.
(4) And sequentially placing a lithium cobaltate positive electrode plate, a high-pressure-resistant solid electrolyte, a lithium philic solid electrolyte and a negative electrode plate in a positive electrode shell, hot-pressing for 300 seconds at 60 ℃ under 0.6MPa, then placing an elastic sheet and a gasket, placing the elastic sheet and the gasket, assembling the solid lithium battery in an inert atmosphere, then aging for 10 hours at 60 ℃, and detecting the cycle performance of the solid lithium battery prepared in the comparative example as shown in figure 3. Test conditions: the current is 0.1C and the voltage is in the range of 3.0V-4.4V.
A schematic structure of a solid-state lithium battery thereof is shown in fig. 2; the positive electrode plate coated with the high-pressure-resistant solid electrolyte is characterized in that the high-pressure-resistant solid electrolyte is arranged on both sides of the positive electrode plate, and the negative electrode plate coated with the lithium-philic solid electrolyte is characterized in that the lithium-philic solid electrolyte is arranged on both sides of the negative electrode plate; the side in contact with the positive electrode sheet is exemplarily shown in fig. 2 provided with a high-voltage-resistant solid electrolyte. Comparative example 1 a schematic diagram of a solid lithium battery was compared with the schematic diagram obtained in example 1 of fig. 1, and it can be seen that the positive electrode tab was unevenly contacted with the high-voltage-resistant solid electrolyte interface. The interface contact between the negative electrode plate and the lithium-philic solid electrolyte is uneven.
Table 1 shows the specific discharge capacity results at 0.1C at the first week of the solid-state lithium batteries prepared in examples 1 to 4 and comparative example 1. The first gram of capacity of example 1 is higher because the electrolyte fully penetrates into the pores of the positive electrode sheet and the solid electrolyte has the optimal ion conductivity. The lower initial gram capacity of example 2 may be due to lower lithium salt concentration, poorer ionic conductivity of the solid state electrolyte, and higher internal resistance of the battery. Examples 3 and 4 have lower gram capacity, possibly higher lithium salt concentration and lower proportion of organic solvent, and the electrolyte has high viscosity and poor fluidity before solidification, and the electrolyte cannot fully permeate into the gaps of the positive electrode plate, so that the interface impedance is increased. The lowest first week gram capacity of comparative example 1 is caused by uneven contact of the double-layer electrolyte with the positive and negative pole pieces and higher interface impedance.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Specific discharge capacity (mAh/g) of 0.1C | 170.5 | 155.3 | 165.7 | 168.6 | 150.3 |
The cycling performance of the solid lithium batteries of example 1 and comparative example 1 versus, for example, fig. 3 shows that the capacity retention rate of comparative example 1 decays rapidly as the cycle progresses, with a capacity retention rate of 47.55% at 50 cycles. The capacity retention was 88.95% for 50 cycles of example 1, and similarly, the capacity retention was between 80% and 90% for 50 cycles of examples 2-4. Similarly, comparative example 2, comparative example 3 and comparative example 4 were prepared in a similar manner to comparative example 1. The results show that comparative example 2 has different levels of attenuation in capacity retention relative to example 2, comparative example 3 relative to example 3, and comparative example 4 relative to example 4.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
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