CN114361711A - Composite coating diaphragm of metal lithium battery, preparation method of composite coating diaphragm and corresponding lithium battery - Google Patents
Composite coating diaphragm of metal lithium battery, preparation method of composite coating diaphragm and corresponding lithium battery Download PDFInfo
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- CN114361711A CN114361711A CN202111680978.3A CN202111680978A CN114361711A CN 114361711 A CN114361711 A CN 114361711A CN 202111680978 A CN202111680978 A CN 202111680978A CN 114361711 A CN114361711 A CN 114361711A
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- solid electrolyte
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 152
- 238000000576 coating method Methods 0.000 title claims abstract description 136
- 239000011248 coating agent Substances 0.000 title claims abstract description 128
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 title description 28
- 239000002184 metal Substances 0.000 title description 28
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 68
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 210000001787 dendrite Anatomy 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 11
- 239000001989 lithium alloy Substances 0.000 claims abstract description 11
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 44
- 239000010410 layer Substances 0.000 claims description 22
- 239000011787 zinc oxide Substances 0.000 claims description 22
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 239000002562 thickening agent Substances 0.000 claims description 17
- 239000000080 wetting agent Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910010252 TiO3 Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- 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 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 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 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 3
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims description 3
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims description 3
- 229910000614 lithium tin phosphorous sulfides (LSPS) Inorganic materials 0.000 claims description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- PBRODHRUIYBSBN-UHFFFAOYSA-N COCCCC(OC)F Chemical compound COCCCC(OC)F PBRODHRUIYBSBN-UHFFFAOYSA-N 0.000 claims description 2
- PSGNUMDAWJFHJQ-UHFFFAOYSA-N COCCCCCC(OC)F Chemical compound COCCCCCC(OC)F PSGNUMDAWJFHJQ-UHFFFAOYSA-N 0.000 claims description 2
- NIQAXIMIQJNOKY-UHFFFAOYSA-N ethyl 2,2,2-trifluoroethyl carbonate Chemical compound CCOC(=O)OCC(F)(F)F NIQAXIMIQJNOKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 16
- -1 sodium alkyl sulfate Chemical class 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000006255 coating slurry Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- LWHQXUODFPPQTL-UHFFFAOYSA-M sodium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LWHQXUODFPPQTL-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910009515 Li1.5Al0.5Ti1.5(PO4)3 Inorganic materials 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000002355 dual-layer Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to a composite coating diaphragm for a lithium battery, a preparation method of the composite coating diaphragm and the corresponding lithium battery. The composite coating membrane includes: a base film; a solid electrolyte coating disposed on the base film; and, a lithium-philic oxide coating disposed on the solid electrolyte coating; wherein the solid electrolyte coating comprises a solid electrolyte capable of reacting with lithium dendrites and the lithiophilic oxide coating comprises a lithiophilic oxide capable of forming a lithium alloy with lithium metal by an in situ electrochemical or chemical reaction. According to the composite coating diaphragm, the specific paired coatings are set on the diaphragm, so that the lithium ion flow is homogenized, the growth of lithium dendrites is effectively inhibited, the safety of the battery is improved, and the preparation method is simple and is easy for industrial popularization and production. When the fluorine-containing electrolyte is adopted in the lithium battery, the coating and the fluorine-containing electrolyte are combined, so that the lithium battery has an extremely excellent safe and quick charging effect.
Description
Technical Field
The invention relates to the field of metal lithium batteries, in particular to a composite coating diaphragm for a metal lithium battery, a method for preparing the composite coating diaphragm and the metal lithium battery comprising the composite coating diaphragm.
Background
Lithium batteries, as a class of electrochemical energy storage devices, have the advantages of no memory effect, high energy density, long cycle life, and the like, and are widely used in a plurality of fields, such as portable electronic devices and electric vehicles. Among them, lithium metal has high theoretical energy density and low electrochemical potential to increase the energy density of the whole battery, and simultaneously, a series of core problems are brought by ultrahigh chemical reaction activity and uneven lithium deposition. In particular, the high chemical reactivity causes the metallic lithium to easily react with the electrolyte, causing consumption of the electrolyte; non-uniform lithium deposition can lead to the formation of lithium dendrites that easily penetrate the separator causing short circuits and can detach from the root during delithiation, forming "dead lithium" causing irreversible capacity loss. Due to the characteristics of lithium deposition, the metal lithium battery has poor dynamic performance, particularly the fast charging performance. The rapid charging process is particularly easy to generate lithium dendrites, which hinders the practical application of the metal lithium battery.
Today, much research is focused on solving the problem of lithium dendrite growth. For example, it has been reported that materials such as inorganic lithium ion conductors and lithium salts are coated on a separator to induce uniform distribution of lithium ions during lithium deposition (see, for example, CN 108365152B, CN 108695473A, CN 107819097A, CN 108777282 a, etc.). And another method adopts in-situ generation of uniformly dispersed lithium alloy and/or lithium nitride on the surface of the lithium negative electrode to enhance lithium-philic sites, improve lithium ion diffusion capacity and inhibit lithium dendrite generation (for example, see CN 107910496B). However, in the above two methods, lithium precipitation occurs on the surface of the negative electrode to form dendritic metallic lithium, which may pierce the separator, resulting in short-circuiting and combustion explosion of the lithium battery.
Another report takes the form of a composite coating that first places a silica coating on the surface of the separator substrate and then places a boehmite coating on the silica coating. Thus inhibiting lithium dendrites by SiOx + yLi + ye → Si + LiyOx and yLi + SiOx → LiySiOxIncrease (see for example CN 111211278A). However, SiO in such a process2The theoretical equilibrium potential of the reaction with lithium is low, the reaction is easy to be carried out together with the decomposition reaction of the electrolyte to generate SEI mainly containing organic components, and the SEI mainly containing inorganic components and containing lithium-philic sites is not favorable to be formed in advance to solve the problem of uneven deposition of metal lithium, and the lithium/electrolyte interface of the former is unstable.
In addition, there are also proposals (such as CN 201910707142.4) to provide a coating layer of a polymer material (such as CN202110308553.3), an inorganic and organic composite coating layer, and the like.
In addition to the above-described method of applying a coating, Xiaoge Hao et al ("structuring Multifunctional Interphase between Li)1.4Al0.4Ti1.6(PO4)3and Li Metal by Magnetron Sputtering for high hly Stable Solid-State Lithium Metal Batteries, Advanced Energy Materials, 2019) construct an ultrathin ZnO layer on the surface of LATP particles through Magnetron Sputtering, and react with Li in situ to form a Solid electrolyte interface phase (SEI) to reduce the interface resistance and inhibit side reactions, thereby inhibiting the growth of Lithium dendrites. However, the existing magnetron sputtering technology has complex process and harsh environmental conditions, which brings great improvement on the operation cost and the production cost.
Therefore, a simple and effective strategy is needed to solve the problems caused by lithium dendrites in the lithium metal battery, and further improve the electrochemical performance of the lithium battery.
Disclosure of Invention
In view of the defects and shortcomings of the prior art, the present invention aims to provide a composite coating separator for a lithium battery, a preparation method thereof and a corresponding metal lithium battery. According to the invention, the specific paired coatings are arranged on the diaphragm, so that the lithium ion flow is homogenized, the growth of lithium dendrites is effectively inhibited, and the safety of the battery is improved.
In a first aspect, the present invention provides a composite separator for a lithium metal battery, comprising:
a base film;
a solid electrolyte coating disposed on the base film; and the number of the first and second groups,
a lithium-philic oxide coating disposed on the solid electrolyte coating,
wherein the solid electrolyte coating is in the form of a single layer or multiple layers comprising a solid electrolyte capable of reacting with lithium dendrites; the lithiophilic oxide coating is in the form of a single layer or multiple layers and comprises a lithiophilic oxide capable of forming a lithium alloy with lithium metal through an in situ electrochemical or chemical reaction.
In some embodiments, wherein the total thickness of the solid electrolyte coating and the lithiophilic oxide coating is 0.1 μm to 10 μm. Wherein the thickness of the solid electrolyte coating is 0.05-5 μm, and the thickness of the lithium-philic oxide coating is 0.05-5 μm.
In some embodiments, the solid electrolyte capable of reacting with lithium dendrites is selected from one or more of LIPON-type electrolytes, NASICON-type electrolytes, garnet-type electrolytes, perovskite-type electrolytes, anti-perovskite-type electrolytes, and LISICON-type electrolytes; in particular from lithium aluminium titanium phosphate Li1+xAlxTi2-x(PO4)3Lithium aluminum germanium phosphate Li1+yAlyGe2-y(PO4)3Lithium lanthanum titanyl LizLa2/3-z/3TiO3Lithium lanthanum zirconium oxygen Li7La3Zr2O12And Li10GeP2S12，Li10SnP2S12Wherein 0 is<x≤1.5，0<y≤1，0<z≤1.5。
In some embodiments, the lithiophilic oxide capable of forming a lithium alloy (having a suitable intercalation potential) with lithium metal by an in situ electrochemical or chemical reaction is generally one that reacts with lithium with a Gibbs free energy of from-150 to-350 mol-1In particular from zinc oxide, manganous-manganic oxide, ferrous oxide, V2O3、Cr2O3、Cr3O4One or more of the above.
In some embodiments, the solid electrolyte coating further comprises a dispersant, a thickener, a binder and a wetting agent, and the preferred mass ratio of the solid electrolyte to the dispersant, the thickener, the binder and the wetting agent is 100 (0.3-0.8): 1-9): 3-10): 0.4-1.2; and/or the lithium-philic oxide coating further comprises a dispersing agent, a thickening agent, a binder and a wetting agent, and the preferable mass ratio of the lithium-philic oxide to the dispersing agent, the thickening agent, the binder and the wetting agent is 100 (0.3-0.8): 1-9): 3-10: (0.4-1.2).
In some embodiments, the binder used may be selected from one or more of polyacrylate, styrene-butadiene rubber, styrene-acrylic emulsion, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyurethane, polyethyleneimine, and the invention is not limited thereto.
In some embodiments, the thickener used may be selected from one or more of carboxyethyl cellulose, sodium carboxymethyl cellulose, polyacrylamide, sodium alginate, and the invention is not limited thereto.
In some embodiments, the wetting agent used may be selected from one or more of sodium perfluorooctanoate, nonylphenol polyoxyethylene ether, chloroalkylmethoxyethanol ether, polyoxyethylenealkylamine, butyl tea sodium sulfonate, aryl naphthalene sodium sulfonate, sodium dodecylbenzene sulfonate, or sodium alkyl sulfate, and the present invention is not limited thereto.
In some embodiments, the dispersant used may be selected from one or more of polyethylene glycol, polyacrylic acid, sodium polyacrylate, and the present invention is not limited thereto.
In some embodiments, the solid electrolyte coating is in the form of a plurality of layers and the lithiophilic oxide coating is in the form of a plurality of layers, wherein the number of layers of the solid electrolyte coating and the lithiophilic oxide are the same and are arranged alternately. The effects of inhibiting lithium dendrites and accelerating lithium ion conduction of the composite coating can be enhanced by designing a multi-layer coating scheme. For example, a first solid electrolyte coating disposed on the base film is designed to react with lithium dendrites to a greater extent, a first lithiophilic oxide coating disposed on the first solid electrolyte coating is used in combination with a less lithiophilic oxide, a second solid electrolyte coating disposed on the first lithiophilic oxide coating is used with a solid electrolyte having a higher ionic conductivity, and a second lithiophilic oxide coating disposed on the second solid electrolyte coating is used with a more lithiophilic oxide. In some embodiments, both sides of the base film are provided with a solid electrolyte coating and a lithiophilic oxide coating.
Furthermore, the multi-layer overlapping coating design can control the thickness difference of each layer to strengthen the synergistic effect, for example, the thickness of the coating from the first solid electrolyte coating to the second lithium-philic oxide coating is reduced progressively, so that the interface contacting with the metal lithium is lithium-philic and has strong lithium-conducting capability, and the interface close to the basement membrane can effectively eliminate the effect of lithium dendrite; this design may also induce diffusion deposition of lithium ions to the lithium metal interface.
In a second aspect, the present invention provides a method of making a composite coated separator for a lithium battery. The method comprises the following steps:
mixing and stirring a solid electrolyte capable of reacting with lithium dendrite with an optional thickening agent, a binder, a wetting agent, a dispersing agent and a solvent, and performing sand milling and dispersion to obtain solid electrolyte coating slurry;
mixing and stirring lithium-philic oxide capable of forming lithium alloy with lithium metal through in-situ electrochemistry or chemistry with an optional thickening agent, a bonding agent, a wetting agent, a dispersing agent and a solvent, and performing sand grinding and dispersion to obtain lithium-philic oxide coating slurry; and
coating the solid electrolyte coating slurry on the surface of the base film, and drying to obtain a solid electrolyte coating; and
and overlapping the lithium-philic oxide coating slurry on the solid electrolyte coating, and drying to obtain the composite coating diaphragm.
In some embodiments, the total thickness of the resulting coating is 0.1 to 10 μm, preferably 1 to 5 μm. Wherein the thickness of the first layer is 0.05-5 μm, and the thickness of the second layer is 0.05-5 μm.
In some embodiments, the coating is applied using a coater microgravure coating.
In some embodiments, the drying is performed after the coating by the coater micro-gravure coating, and the coating and the drying are performed simultaneously, so that the production efficiency is improved.
In some embodiments, the sanding dispersion is performed for 0-10 hours by using a sand mill to sand the raw material to an average particle size of 0.05-1 μm.
In some embodiments, the solvent used may be selected from one or more of water, ethanol, DMAC, DMF, NMP, acetonitrile, but the present invention is not limited thereto.
In a third aspect, the invention provides a lithium metal battery comprising a composite coated separator as described above or a composite coated separator prepared according to the method described above.
In the lithium metal battery according to the present invention, a fluorine-containing electrolyte may be particularly used, wherein the solvent contains fluorine, so that the lithium metal battery has an excellent effect of safe and fast charge. The fluorine-containing electrolyte component includes, but is not limited to, common fluorinated solvents such as fluoroethylene carbonate (FEC), methyl trifluoroethyl carbonate, ethyl trifluoroethyl carbonate, Hydrofluoroether (HFE), fluoro 1, 6-dimethoxyhexane, fluoro 1, 4-dimethoxybutane, and also includes, but is not limited to, common lithium salts such as LiPF6、LiBF4Lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium difluoro (oxalato) borate (liddob), lithium difluoro (phosphorodioxy) phosphate, and other additives, including but not limited to lithium bis (oxalato) borate (LiBOB).
In the invention, by arranging the specific paired coatings, the complex procedure of conventional modification of the lithium metal cathode and harsh environmental conditions are avoided. And the first coating of the invention comprises a solid electrolyte which can react with lithium dendrites, on one hand, the growth of the lithium dendrites is restrained, and on the other hand, the lithium ion transfer is facilitated, and the lithium ion flow is homogenized. The second coating of the invention is selected from lithium-philic oxides with suitable lithium insertion potential, which can form lithium alloys by in-situ electrochemical or chemical reactions, forming a stable electrode/electrolyte interface with a predominant inorganic component. By overlaying the second coating on the first coating, the reaction of the solid electrolyte with the lithium negative electrode before lithium dendrite formation is avoided.
Thus, the dual layer design of the present invention exerts a synergistic effect. The inorganic property cannot be realized without suitable lithium-philic oxidesThe stable electrode/electrolyte interface with the main component is constructed, and the lithium ion conductivity parallel to the pole piece direction cannot be improved while the lithium dendrite is eliminated without a proper inorganic solid electrolyte containing variable-valence transition metal elements, so that the island-shaped deposition of the metal lithium on the surface of the pole piece is realized. For lithiophilic oxides, the degree of lithiophilization is too great (e.g., Gibbs free energy of reaction of the oxide with lithium<-350kJ mol-1) Is not beneficial to the lithium ion conduction in the plane direction of the pole piece, and the degree of lithium affinity is too small (such as Gibbs free energy of the reaction of oxide and lithium>-150kJ mol-1) The lithium dendrites easily overflow the lithium-philic layer if the inorganic solid electrolyte reacts excessively with the lithium dendrites (e.g., Li)0.5La0.5TiO3Middle Ti4+Higher content and total conversion to Ti0) It is not favorable for the lithium ion conduction in the planar direction of the electrode sheet, if the reaction between the inorganic solid electrolyte and the lithium dendrite is too small (e.g. Li)7La3Zr2O12Middle Zr4+Low content and not easily reduced by lithium), it is not favorable to eliminate lithium dendrite; the electrolyte wettability of the composite diaphragm is obviously improved by adopting the overlapping design.
In the present invention, the lithium metal battery includes a battery in which a negative electrode is pure lithium metal and a battery in which a negative electrode is a lithium alloy.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are illustrative only and are not limiting upon the scope of the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The composite coating diaphragm provided by the invention can be a double-layer coating diaphragm, wherein the second coating far away from the base film is a lithium-philic oxide (such as an electrode/electrolyte interface which is about 1.0-1.5V higher than the theoretical potential of lithium deposition) which can form a lithium alloy through in-situ electrochemical or chemical reaction and has a proper lithium-embedding theoretical equilibrium potential, and a stable electrode/electrolyte interface mainly containing inorganic components is generated, so that the lithium deposition is homogenized, and the metallic lithium deposition is effectively prevented from being dendritic; the first coating layer close to the base film is a solid electrolyte capable of reacting with lithium dendrites, and on one hand, the solid electrolyte has high ionic conductivity, is beneficial to lithium ion transfer and homogenizes lithium ion flow; on the other hand, once the lithium dendrites penetrate through the second coating of the separator, the lithium dendrites react with the second coating to inhibit further growth of the lithium dendrites, so that the safety of the battery is improved.
The method for preparing the composite coating diaphragm mainly comprises the following steps: step 1, mixing and stirring inorganic solid electrolyte, a thickening agent, a binder, a wetting agent, a dispersing agent and a solvent, and performing sanding dispersion to obtain first coating slurry; step 2, mixing and stirring the lithium-philic oxide, the thickening agent, the binder, the wetting agent, the dispersing agent and the solvent, and performing sanding dispersion to obtain second coating slurry; step 3, coating the first coating slurry on the surface of the base film, and drying; and 4, overlapping the second coating slurry on the first coating, and drying to obtain the composite coating diaphragm.
In the present invention, the base film may be one or more of a polyethylene film, a polypropylene film, a polyethylene/polypropylene double-layer film, a polyethylene/polypropylene/polyethylene triple-layer film, a polypropylene/polyethylene/polypropylene triple-layer film, a polyimide, a glass cellulose membrane, and a non-woven fabric film, and is preferably a polyethylene film, and the surface of the base film may be coated with high temperature resistant ceramic particles, such as alumina (Al) on the surface2O3). The invention is not so limited.
In the invention, the rotation speed of the sand grinding dispersion in the step 1 can be 100-2000 r/min, such as 1500r/min, and the sand grinding time can be 0-10 h, such as 3 h. The particles have a size of 0.05 to 1 μm, for example 600 nm.
The rotational speed of sanding dispersion in the step 2 can be 100-2000 r/min, such as 1500r/min, and the sanding time is 0-10 h, such as 3 h. The particles have a size of 0.05 to 1 μm, for example 400 nm.
The coating process of the step 3 and the step 4 can be one or two of dip coating, blade coating, spray coating and the like. Preferably, the coating process of steps 3 and 4 may be micro-gravure coating.
The drying in step 3 and step 4 may be coating machine drying, for example, the temperature of forced air drying is 20 ℃ to 60 ℃, for example, 40 ℃, etc.; the drying time is 1-5 min, for example 2 min.
It should be understood that when the coating is in the form of multiple layers, the corresponding steps described above are repeated.
The invention is further detailed by means of several specific embodiments. In addition, unless otherwise specified, materials and instruments used in the following examples are all conventionally commercially available.
Example 1
Step 1, 100 parts by weight of LATP, i.e. lithium aluminum titanium phosphate Li1.5Al0.5Ti1.5(PO4)30.5 parts by weight of sodium polyacrylate, 2 parts by weight of sodium carboxymethylcellulose, 5 parts by weight of polyacrylate, 0.6 parts by weight of sodium perfluorooctanoate and a proper amount of water are mixed as a solvent, stirred and subjected to sanding dispersion treatment at 1500r/min for 3 hours to obtain a first coating slurry, wherein the LATP particle size is about 600 nm.
And 2, mixing 100 parts by weight of zinc oxide, 0.5 part by weight of sodium polyacrylate, 2 parts by weight of sodium carboxymethylcellulose, 5 parts by weight of polyacrylate, 0.6 part by weight of sodium perfluorooctanoate and a proper amount of water as solvents, stirring, and performing sanding dispersion treatment at 1500r/min for 3 hours to obtain second coating slurry, wherein the particle size of zinc oxide particles is about 400 nm.
Step 3, selecting polyethylene with aluminum oxide coatings on two sides, coating the first coating slurry on the surface of the base film through micro-gravure coating, and then carrying out air-blast drying treatment for 5min at 40 ℃;
and 4, overlaying the second coating slurry on the first coating by blade coating, and then carrying out forced air drying treatment for 5min at the temperature of 40 ℃ to obtain the composite coating diaphragm.
The lithium battery composite diaphragm prepared by the method comprises a base film and a composite coating; the thickness of the base film is 2+9+2 μm measured by a micrometer;
the thickness of the composite coating is 1+1 mu m;
lithium battery composite separator prepared by the methodThe membrane is used for assembling a lithium battery, the battery structure is an LFP metal lithium soft package battery, the composite coating faces to the negative side, the prepared lithium battery is subjected to electrochemical test, and the electrolyte is EC + EMC (3:7)/LiPF6(1M)/VC (2%). Specific electrochemical performance test results are shown in Table 1
Example 2
The parameters were the same as in example 1, except that the cell structure was LCO | | | metallic lithium and the particle diameter ratio of lithium-philic oxide as solid electrolyte was 600nm: 500 nm.
Example 3
The parameters were the same as in example 1, except that the battery structure was NCM | | | lithium metal and the particle diameter ratio of lithium-philic oxide as solid electrolyte was 600nm to 600 nm.
Example 4
The parameters were the same as in example 1 except that zinc oxide was replaced with MnO and the cell structure was NCM | | | metallic lithium.
Example 5
Except that zinc oxide is replaced by Mn3O4The battery structure is NCM metal lithium, the particle diameter ratio of the lithium-philic oxide as the solid electrolyte is 600nm to 700nm, and other parameters are the same as those in the embodiment 1.
Example 6
The parameters were the same as in example 1 except that zinc oxide was replaced with FeO, the cell structure was NCM | | | metallic lithium, and the particle diameter ratio of the lithium-philic oxide as the solid electrolyte was 600nm to 300 nm.
Example 7
Except that the lithiophilic oxide zinc oxide is replaced by V2O3The battery structure is NCM metal lithium, the particle diameter ratio of the lithium-philic oxide of the solid electrolyte is 700nm to 400nm, and other parameters are the same as those of the embodiment 1.
Example 8
Except that zinc oxide is replaced by Cr2O3The battery structure is NCM metal lithium, the particle diameter ratio of the lithium-philic oxide as the solid electrolyte is not more than 500nm and 400nm, and other parameters are the same as those in the embodiment 1.
Example 9
Except that zinc oxide is replaced by Cr3O4The battery structure is that besides NCM | | | metallic lithium,the other parameters were the same as in example 1.
Example 10
Except that LATP is replaced by LATP and LAGP (Li)1.5Al0.5Ge1.5(PO4)3) The battery structure was the same as that of example 1 except that the battery structure was metal lithium (NCM | |) (mass ratio 1: 1).
Example 11
Except that LATP is replaced by LATP and LLTO (Li)0.5La0.5TiO3) The battery structure was the same as that of example 1 except that the battery structure was metal lithium (NCM | |) (mass ratio 1: 1).
Example 12
Except that zinc oxide is replaced by ZnO and Al2O3The battery structure was the same as that of example 1 except that the battery structure was metal lithium (NCM | |) (mass ratio 1: 1).
Example 13
The parameters were the same as in example 1, except that zinc oxide was replaced with a mixture of ZnO and FeO (mass ratio 1:1), and the cell structure was NCM | | metallic lithium.
Example 14
The parameters were the same as in example 1, except that the LATP particle size was controlled to 300nm, the ZnO particle size was controlled to 700nm, and the cell structure was NCM | | metallic lithium.
Example 15
The parameters were the same as in example 1, except that the thickness of the LATP coating was 2 μm, the thickness of the ZnO coating was 2 μm, and the cell structure was NCM | | metallic lithium.
Example 16
Except that the composite coating is coated on both sides, the thickness of the single side is 1+1 mu m, the battery structure is NCM metal lithium, and other parameters are the same as those of the embodiment 1.
Example 17
The polyethylene base film without the alumina coating is used, the composite coating is designed into four layers, LLTO, MnO, LATP and ZnO are arranged in sequence from the part close to the base film, the particle size is controlled to be 600nm, the thickness of the composite coating is 1+1+1+1 mu m, the battery structure is NCM metal lithium, and other parameters are the same as those in the embodiment 1.
Example 18
The polyethylene base film without the alumina coating is used, the composite coating is designed into four layers, LLTO, MnO, LATP and ZnO are arranged in sequence from the part close to the base film, the particle size is controlled to be 600nm, the thickness of the composite coating is 3+2+1+1 mu m, the battery structure is NCM metal lithium, and other parameters are the same as those in the embodiment 1.
Example 19
The parameters were the same as in example 1, except that the battery structure was NCM | | | metallic lithium and EC was replaced with FEC in the electrolyte.
Comparative example 1
Without the composite coating, a polyethylene-based film without an alumina coating was used, with the other parameters being the same as in example 1.
Comparative example 2
Without the composite coating, a polyethylene-based film with a single-sided 2 μm alumina coating (coating facing the negative side) was used, and the cell structure was LCO | | | metallic lithium, with the other parameters being the same as in example 1.
Comparative example 3
The battery structure is NCM metal lithium without a composite coating, and other parameters are the same as those in the embodiment 1.
Comparative example 4
The structure of the battery is NCM | | | metallic lithium without the lithium-philic oxide coating, and other parameters are the same as those in the embodiment 1.
Comparative example 5
The solid electrolyte coating uses LAGP instead of LATP without a lithium-philic oxide coating, and the battery structure is NCM metal lithium, with other parameters as in example 1.
Comparative example 6
The lithium-philic oxide coating is not used, the solid electrolyte coating uses LLTO to replace LATP, the battery structure is NCM | | metallic lithium, and other parameters are the same as those in the embodiment 1.
Comparative example 7
The battery structure is NCM metal lithium without a solid electrolyte coating, and other parameters are the same as those of the embodiment 1.
Comparative example 8
The lithium-philic oxide ZnO is replaced by AgO, the battery structure is NCM | | | metallic lithium, and other parameters are the same as those in the embodiment 1.
Comparative example 9
The lithium-philic oxide ZnO is replaced by CaO, the battery structure is NCM | | | metallic lithium, and other parameters are the same as those in the embodiment 1.
Comparative example 10
The solid electrolyte component LATP was replaced with LLTO, the cell structure was NCM | | | metallic lithium, and the other parameters were the same as in example 1.
Comparative example 11
The solid electrolyte component LATP is replaced with LLZO (Li)7La3Zr2O12) The battery structure is NCM metal lithium, and other parameters are the same as those in embodiment 1.
Comparative example 12
The solid electrolyte coating and the lithium-philic oxide coating are exchanged, namely the lithium-philic oxide coating is close to the base film, the solid electrolyte coating is close to the metal lithium, the battery structure is NCM | | | metal lithium, and other parameters are the same as those of the embodiment 1.
Performance testing
The 10Ah pouch cells assembled by the separators obtained in the above examples and comparative examples were tested. The respective parameters of the batteries obtained in the respective examples and comparative examples were determined according to a test method well known in the art. The results obtained are shown in table 1 below.
TABLE 1 summary of parameters of the batteries obtained in examples and comparative examples
It can be seen from table 1 that the double-layer design of the present invention solves the problems of uneven deposition of lithium metal in the metal lithium battery in the prior art, precipitation of lithium dendrites, large surface area of the lithium dendrites, and side reaction with the electrolyte, which leads to gas generation and capacity reduction of the battery, and further, the lithium dendrites may pierce the separator, which leads to short circuit and combustion explosion of the lithium battery. The electrochemical performance of the diaphragm is improved, and further the rate capability of the lithium battery is enhanced and the cycle life of the lithium battery is prolonged. Examples 1 to 19 of the present invention have excellent electrochemical properties as compared with comparative examples. The capacity retention rate of the lithium battery obtained by the invention in 50 weeks and 1.5C quick charge cycle can reach 94%, and no obvious overcharge phenomenon, namely no obvious dendritic crystal growth situation, occurs.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (10)
1. A composite coated separator for a lithium battery comprising:
a base film;
a solid electrolyte coating disposed on the base film; and the number of the first and second groups,
a lithium-philic oxide coating disposed on the solid electrolyte coating;
wherein the solid electrolyte coating is in the form of a single layer or multiple layers comprising a solid electrolyte capable of reacting with lithium dendrites; the lithiophilic oxide coating is in the form of a single layer or multiple layers and comprises a lithiophilic oxide capable of forming a lithium alloy with lithium metal through an in situ electrochemical or chemical reaction.
2. The composite coated separator according to claim 1, wherein the solid electrolyte reactive with lithium dendrites is selected from one or more of LIPON-type electrolyte, NASICON-type electrolyte, garnet-type electrolyte, perovskite-type electrolyte, anti-perovskite-type electrolyte, and LISICON-type electrolyte; in particular from lithium aluminium titanium phosphate Li1+xAlxTi2-x(PO4)3Lithium aluminum germanium phosphate Li1+yAlyGe2-y(PO4)3Lithium lanthanum titanyl LizLa2/3-z/3TiO3Lithium lanthanum zirconium oxygen Li7La3Zr2O12And Li10GeP2S12，Li10SnP2S12Wherein 0 is<x≤1.5，0<y≤1，0<z≤1.5；
The compound can form lithium complex with lithium metal through in-situ electrochemical or chemical reactionThe lithium-philic oxide of gold reacts with lithium with Gibbs free energy of-150 to-350 mol-1In particular from zinc oxide, manganous-manganic oxide, ferrous oxide, V2O3、Cr2O3、Cr3O4One or more of the above.
3. The composite coated separator according to claim 2, wherein the solid electrolyte coating further comprises a dispersant, a thickener, a binder and a wetting agent, and the preferred mass ratio of the solid electrolyte to the dispersant, the thickener, the binder and the wetting agent is 100 (0.3-0.8): 1-9): 3-10): 0.4-1.2;
the lithium-philic oxide coating further comprises a dispersing agent, a thickening agent, a binder and a wetting agent, and the preferable mass ratio of the lithium-philic oxide to the dispersing agent, the thickening agent, the binder and the wetting agent is 100 (0.3-0.8): 1-9): 3-10: (0.4-1.2).
4. The composite coated separator according to any one of claims 1 to 3, wherein the total thickness of the solid electrolyte coating and the lithiophilic oxide coating is 0.1 to 10 μm; wherein the thickness of the solid electrolyte coating is 0.05-5 μm, and the thickness of the lithium-philic oxide coating is 0.05-5 μm.
5. The composite coated separator according to any one of claims 1 to 4, wherein the solid electrolyte coating is in the form of a plurality of layers and the lithium-philic oxide coating is in the form of a plurality of layers;
wherein the number of layers of the solid electrolyte coating and the lithium-philic oxide are the same and are alternately arranged; wherein the ionic conductance of each of the multi-layered form of solid electrolyte coatings increases with increasing distance of the layer from the base film, and the degree of lithium affinity of each of the multi-layered form of lithium-philic oxide coatings increases with increasing distance of the layer from the base film.
6. A method of making a composite coated separator for a lithium battery comprising:
mixing and stirring a solid electrolyte capable of reacting with lithium dendrite with an optional thickening agent, a binder, a wetting agent, a dispersing agent and a solvent, and performing sand milling and dispersion to obtain solid electrolyte slurry;
mixing and stirring lithium-philic oxide capable of forming lithium alloy with lithium metal through in-situ electrochemical or chemical reaction with optional thickening agent, binder, wetting agent, dispersant and solvent, and performing sand milling and dispersion to obtain lithium-philic oxide slurry; and
coating the solid electrolyte slurry on the surface of a base film by using a coating machine, and drying to obtain a solid electrolyte coating; and
and overlapping the lithium-philic oxide slurry on the solid electrolyte coating, and drying to obtain the composite coating diaphragm.
7. The method of claim 6, wherein the solid electrolyte reactive with lithium dendrites is selected from one or more of a LIPON-type electrolyte, a NASICON-type electrolyte, a garnet-type electrolyte, a perovskite-type electrolyte, an anti-perovskite-type electrolyte, and a LISICON-type electrolyte; in particular from lithium aluminium titanium phosphate Li1+xAlxTi2-x(PO4)3Lithium aluminum germanium phosphate Li1+yAlyGe2-y(PO4)3Lithium lanthanum titanyl LizLa2/3-z/3TiO3Lithium lanthanum zirconium oxygen Li7La3Zr2O12And Li10GeP2S12，Li10SnP2S12Wherein 0 is<x≤1.5，0<y≤1，0<z≤1.5；
The lithium-philic oxide capable of forming lithium alloy by in-situ electrochemical or chemical reaction with lithium metal has Gibbs free energy of reaction with lithium of-150 to-350 mol-1In particular from zinc oxide, manganous-manganic oxide, ferrous oxide, V2O3、Cr2O3、Cr3O4One or more of the above.
8. A method according to claim 6 or 7, wherein the preferred mass ratio of the solid electrolyte to the dispersant, thickener, binder and wetting agent is 100 (0.3-0.8): 1-9): 3-10): 0.4-1.2; and the preferable mass ratio of the lithium-philic oxide to the dispersing agent, the thickening agent, the binder and the wetting agent is 100 (0.3-0.8): (1-9): 3-10): 0.4-1.2.
9. A lithium metal battery comprising a composite coated separator according to any one of claims 1 to 5 or obtained by the method according to any one of claims 6 to 8.
10. The metallic lithium battery of claim 9, wherein the electrolyte used is a fluorine-containing electrolyte, and the components of the fluorine-containing electrolyte comprise fluoroethylene carbonate (FEC), methyl trifluoroethyl carbonate, ethyl trifluoroethyl carbonate, Hydrofluoroether (HFE), fluoro 1, 6-dimethoxyhexane, fluoro 1, 4-dimethoxybutane, LiPF6、LiBF4Lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium difluoro (oxalato) borate (liddob), and lithium difluorophosphate.
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| CN114976217A (en) * | 2022-05-11 | 2022-08-30 | 北京科技大学 | Method for modifying LATP solid electrolyte and solid electrolyte thereof |
| CN115332725A (en) * | 2022-08-22 | 2022-11-11 | 珠海冠宇动力电池有限公司 | Diaphragm and battery |
| FR3137217A1 (en) * | 2022-06-28 | 2023-12-29 | Saft | MEMBRANE FOR ELECTROCHEMICAL CELL COMPRISING A LITHIOPHILE LAYER |
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| CN112968254A (en) * | 2021-01-29 | 2021-06-15 | 东莞维科电池有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery |
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| CN114976217A (en) * | 2022-05-11 | 2022-08-30 | 北京科技大学 | Method for modifying LATP solid electrolyte and solid electrolyte thereof |
| CN114843705A (en) * | 2022-05-16 | 2022-08-02 | 武汉中原长江科技发展有限公司 | Lithium metal battery diaphragm and preparation method and application thereof |
| FR3137217A1 (en) * | 2022-06-28 | 2023-12-29 | Saft | MEMBRANE FOR ELECTROCHEMICAL CELL COMPRISING A LITHIOPHILE LAYER |
| CN115332725A (en) * | 2022-08-22 | 2022-11-11 | 珠海冠宇动力电池有限公司 | Diaphragm and battery |
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