CN115832195A - Porous composite foil, positive pole piece, negative pole piece, semi-solid lithium ion battery and preparation method - Google Patents
Porous composite foil, positive pole piece, negative pole piece, semi-solid lithium ion battery and preparation method Download PDFInfo
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- CN115832195A CN115832195A CN202211367853.XA CN202211367853A CN115832195A CN 115832195 A CN115832195 A CN 115832195A CN 202211367853 A CN202211367853 A CN 202211367853A CN 115832195 A CN115832195 A CN 115832195A
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- Prior art keywords
- porous composite
- binder
- pole piece
- composite foil
- layer
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- 239000002131 composite material Substances 0.000 title claims abstract description 140
- 239000011888 foil Substances 0.000 title claims abstract description 133
- 239000007787 solid Substances 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 76
- 238000000576 coating method Methods 0.000 claims abstract description 63
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- 239000006258 conductive agent Substances 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 230000000149 penetrating effect Effects 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 121
- 239000011230 binding agent Substances 0.000 claims description 71
- 239000002002 slurry Substances 0.000 claims description 71
- 239000010416 ion conductor Substances 0.000 claims description 41
- 239000007774 positive electrode material Substances 0.000 claims description 37
- 239000007773 negative electrode material Substances 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- -1 polyethylene Polymers 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 239000011889 copper foil Substances 0.000 claims description 22
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 17
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 238000005524 ceramic coating Methods 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000004745 nonwoven fabric Substances 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002174 Styrene-butadiene Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000004642 Polyimide Substances 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 229920001721 polyimide Polymers 0.000 claims description 9
- 239000004800 polyvinyl chloride Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 4
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- PHDNGVHIVIYFJP-UHFFFAOYSA-N [Zr].[La].[Li] Chemical compound [Zr].[La].[Li] PHDNGVHIVIYFJP-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 claims description 2
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims 3
- 150000002500 ions Chemical class 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 11
- 239000011244 liquid electrolyte Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000006255 coating slurry Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 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 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
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Abstract
The invention discloses a porous composite foil, which comprises a porous composite foil current collector; the porous composite foil current collector comprises a high polymer insulating layer and two metal conducting layers; the upper side and the lower side of the polymer insulating layer are respectively provided with a layer of metal conducting layer in a covering manner; a plurality of through holes are arranged on the porous composite foil current collector in a penetrating manner; and the outer side surface of each metal conducting layer in the porous composite foil current collector is coated with a mixed bottom coating respectively. The invention also provides a positive pole piece, a negative pole piece, a semi-solid lithium ion battery and a preparation method. Aiming at the problem of high internal resistance of the original composite foil, the invention improves the adhesive force of an active material and a current collector by introducing a mixed bottom coating which contains a conductive agent and an inorganic oxide solid electrolyte and has good electronic conduction and ionic conduction on the surface of the porous composite foil, constructs a complete ion and electron transmission channel, reduces the internal resistance of the battery and improves the multiplying power performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a porous composite foil, a positive pole piece, a negative pole piece, a semi-solid lithium ion battery and a preparation method thereof.
Background
With the rapid development of electric vehicles and the large-scale energy storage field, higher requirements are put forward on the safety and the energy density of the battery.
In terms of energy density, the energy density of the battery determines the cruising ability of the electric vehicle, including the volumetric energy density and the mass energy density. The anode and cathode materials are active energy storage materials of the lithium battery, and the aluminum foil and the copper foil are carriers of the anode and cathode active materials and are collecting and conducting bodies of anode and cathode electrons. The energy density of the battery can be further improved by increasing the unit gram capacity of the positive electrode active material on one hand and reducing the weight of the inactive substances on the other hand, wherein the weight of the foil is reduced.
In the aspect of safety, the conventional lithium ion battery adopts an organic liquid electrolyte, so that when other abnormal working states such as overcharge and internal short circuit occur, a large amount of generated heat can cause the electrolyte to be rapidly vaporized, and the anode material releases oxygen, thereby possibly causing safety problems such as battery explosion, electric automobile ignition and spontaneous combustion, and the like.
At present, PET (polyethylene terephthalate) composite aluminum foils and copper foils have the characteristics of small density, thin thickness, high tensile strength and the like, and in addition, the PET composite aluminum foils and the copper foils have good conductivity and are good substitute materials of current collectors (aluminum foils and copper foils) of traditional lithium batteries. The PET composite foil can reduce the weight of the material under the condition that partial metal is replaced by high polymer, thereby increasing the energy density of the battery.
At present, lithium battery foils are gradually developing towards the direction of ultra-thinness. The thinner the lithium battery foil is, the more easily the problems of edge tearing, tape breakage, wrinkling and the like occur, and great challenges are caused to the safety of the battery cell. The PET composite foil is more easily fused when short circuit occurs in the lithium battery due to the characteristics of thin conducting layer, non-conducting base film and the like, so that short circuit current is cut off, heat generated during short circuit is reduced, thermal runaway is prevented, and the safety performance of the battery is improved. In addition, the consumption of metal in the PET composite foil is only 1/3-1/5 of that of the original pure metal foil, if the manufacturing cost can be controlled, the theoretical cost of the composite foil is lower than that of the metal foil, and the cost reduction space of the material is larger.
However, at present, the composite foil is a micron-sized composite foil with a sandwich structure of metal layer-polymer layer-metal layer, and the polymer material layer is adopted in the middle of the composite foil, so that the metal coatings on two sides cannot realize electronic conduction, current conduction in the battery is hindered, internal resistance of the battery is high, and rate performance of the battery is affected.
Therefore, there is an urgent need to develop a technology capable of solving the above technical problems.
Disclosure of Invention
The invention aims to provide a porous composite foil, a positive pole piece, a negative pole piece, a semi-solid lithium ion battery and a preparation method thereof, aiming at the technical defects in the prior art.
Therefore, the invention provides a porous composite foil, which is applied to a battery pole piece and comprises a porous composite foil current collector;
the porous composite foil current collector comprises a high polymer insulating layer and two metal conducting layers;
the upper side and the lower side of the polymer insulating layer are respectively provided with a layer of metal conducting layer in a covering manner;
a plurality of through holes are arranged on the porous composite foil current collector in a penetrating manner;
and the outer side surface of each metal conducting layer in the porous composite foil current collector is respectively coated with a mixed bottom coating.
Preferably, when the porous composite foil current collector is applied to the positive electrode plate, both the two metal conductive layers are aluminum foils, and the porous composite foil current collector at the moment is defined as a composite porous aluminum foil current collector;
when the porous composite foil current collector is applied to a negative pole piece, the two metal conductive layers are both copper foils, and the porous composite foil current collector at the moment is defined as a composite porous copper foil current collector.
Preferably, the thickness of the high-molecular insulating layer is 2-10 μm;
the thickness of each metal conductive layer is 1-5 μm;
the aperture of the through hole is between 0.2 and 3 mu m;
the porosity on the porous composite foil current collector is 10% -40%;
the thickness of each mixed primer layer is 2-10 microns.
Preferably, the material of the polymer insulating layer includes any one of polyethylene, polypropylene, polyvinyl chloride, polyimide, polyacrylonitrile and polyethylene terephthalate;
a mixed base coat comprising the following components in mass percent:
10% -40% of conductive agent, 50% -85% of oxide solid electrolyte and 5% -10% of binder;
for the hybrid undercoat, the conductive agent includes at least one of carbon black, ketjen black, conductive graphite, conductive fibers, carbon nanotubes, and graphene;
an oxide solid electrolyte comprising at least one of lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, and lithium lanthanum zirconium thallium oxygen;
the binder comprises one or a mixture of more than two of polytetrafluoroethylene, polyvinylidene fluoride, acrylic acid, polyethylene oxide, sodium carboxymethyl cellulose, styrene-butadiene rubber, hydroxypropyl methyl cellulose, carboxylic styrene-butadiene latex and polyvinyl alcohol.
In addition, the invention provides a positive pole piece, which comprises the porous composite foil;
the outer side of each mixed bottom coating in the porous composite foil is respectively coated with a positive material layer;
the positive electrode material layer comprises a positive electrode active material, an oxide solid electrolyte, a conductive agent and a binder;
the mass ratio of the positive electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (84-96): 1-5): 2-6;
for the positive electrode material layer, the positive electrode active material specifically comprises at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium iron phosphate and lithium iron manganese phosphate;
the conductive agent comprises at least one of conductive carbon black, conductive graphite, carbon nanotubes, carbon nanofibers and graphene;
the oxide solid electrolyte comprises at least one of LATP, LAGP, LLZO, LLTO, and LLZTO;
the binder includes at least one of PVDF, SBR, CMC, and PTFE.
In addition, the invention provides a negative pole piece, which comprises the porous composite foil;
the outer side of each mixed bottom coating in the porous composite foil is respectively coated with a negative material layer;
the negative electrode material layer comprises a negative electrode active material, an oxide solid electrolyte, a conductive agent and a binder;
the mass ratio of the negative electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (83-97): 1-5): 1-7;
for the negative electrode material layer, the negative electrode active material comprises one or more of simple substance silicon, silicon oxide, artificial graphite, natural graphite, composite graphite, soft carbon and hard carbon;
for the negative electrode material layer, the conductive agent comprises at least one of conductive carbon black, conductive graphite, carbon nano tubes, carbon nano fibers and graphene;
for the anode material layer, the oxide solid electrolyte includes at least one of LATP, LAGP, LLZO, LLTO, and LLZTO;
for the negative electrode material layer, the binder includes any one of SBR, PAA, and PTFE.
In addition, the invention also provides a semi-solid lithium ion battery, which comprises a battery pole group;
the battery pole group comprises the positive pole piece, the ionic conductor diaphragm and the negative pole piece;
the ion conductor diaphragm is positioned between the positive pole piece and the negative pole piece;
electrolyte is injected into the battery pole group;
an ion conductor separator comprising a base film, a first coating layer, and a second coating layer;
the first coating and the second coating are respectively positioned on the surface of one side of the base film close to the positive pole piece and the surface of one side of the base film close to the negative pole;
the base film comprises any one of a polyethylene base film, a polyethylene non-woven fabric base film, a polypropylene non-woven fabric base film, a polypropylene composite base film, a polyimide non-woven fabric base film, a polytetrafluoroethylene non-woven fabric base film, a polyvinyl chloride base film and a polyvinyl chloride non-woven fabric base film;
the first coating is a ceramic coating, and the ceramic coating comprises ceramic powder and an aqueous emulsion binder of an acrylate system;
in the ceramic coating, the ceramic powder accounts for 90-99% by mass, and the binder accounts for 1-10% by mass;
the ceramic powder adopted by the ceramic coating comprises at least one of alumina, zirconia, boehmite, magnesium hydroxide, barium sulfate, silicon oxide, aluminum nitride, magnesia, titanium dioxide, yttrium oxide and cerium oxide;
the second coating is a fast ion conductor coating which comprises fast ion conductor powder and an acrylic acid aqueous emulsion binder;
in the fast ion conductor coating, the fast ion conductor powder accounts for 90-99% by mass, and the binder accounts for 1-10% by mass;
the fast ion conductor powder adopted by the fast ion conductor coating comprises LATP powder or LLTO powder.
In addition, the invention also provides a preparation method of the positive pole piece, which comprises the following steps:
step one, preparing a porous composite foil of a positive pole piece with a mixed bottom coating: mixing and uniformly stirring a conductive agent, an oxide solid electrolyte and a binder according to a preset mass percentage, dissolving the mixture in a solvent NMP (N-methyl pyrrolidone) for dispersion to obtain mixed primer slurry, adjusting the solid content of the mixed primer slurry to 10-30% or the viscosity of the slurry to 1000-4000cp by adjusting the amount of an added solvent, then respectively coating a layer of mixed primer slurry on the upper side and the lower side of the composite porous aluminum foil current collector, drying at the temperature of 80-120 ℃, and drying to obtain a porous composite foil material of the positive pole piece with the mixed primer, namely the composite porous aluminum foil;
in the first step, the preset mass percentages among the conductive agent, the oxide solid electrolyte and the binder are as follows:
10% -40% of a conductive agent, 50% -85% of an oxide solid electrolyte and 5% -10% of a binder, namely the mass percentage of each component included in the solute of the mixed undercoat slurry;
step two, preparing anode substance slurry: mixing and uniformly stirring a positive electrode active material, an oxide solid electrolyte, a conductive agent and a binder according to a preset mass ratio, dissolving the mixture in a solvent NMP for dispersion to obtain a positive electrode substance slurry, and adjusting the solid content of the positive electrode substance slurry to be 60-75% or the viscosity of the slurry to be 6000-8000cp by adjusting the amount of an added solvent;
in the second step, the mass ratio of the positive electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (84-96): 1-5: (2-6);
and thirdly, respectively coating a layer of the positive electrode substance slurry obtained in the second step on the upper side and the lower side of the composite porous aluminum foil obtained in the first step, drying at the temperature of 80-120 ℃, rolling after drying to obtain a rolled positive electrode piece, and then cutting the rolled positive electrode piece to a specified size to finally obtain a finished positive electrode piece.
In addition, the invention also provides a preparation method of the negative pole piece, which comprises the following steps:
step one, preparing a porous composite foil of a negative pole piece with a mixed bottom coating: mixing and uniformly stirring a conductive agent, an oxide solid electrolyte and a binder according to a preset mass percentage, dissolving the mixture in solvent deionized water for dispersion to obtain mixed undercoat slurry, adjusting the amount of an added solvent to adjust the solid content of the mixed undercoat slurry to 10-30% or the viscosity of the slurry to 1000-4000cp, then respectively coating a layer of mixed undercoat slurry on the upper side and the lower side of the composite porous copper foil current collector, drying at the temperature of 80-120 ℃, and drying to obtain a porous composite foil material, namely a composite porous aluminum foil, of the negative pole piece with the mixed undercoat;
in the first step, the preset mass percentages among the conductive agent, the oxide solid electrolyte and the binder are as follows:
10% -40% of conductive agent, 50% -85% of oxide solid electrolyte and 5% -10% of binder;
step two, preparing anode substance slurry: mixing and uniformly stirring a negative electrode active material, an oxide solid electrolyte, a conductive agent and a binder according to a preset mass ratio, dissolving the mixture in solvent deionized water for dispersing to obtain negative electrode substance slurry, and adjusting the solid content of the negative electrode substance slurry to be 40-50% or the viscosity of the slurry to be 3000-5000cp by adjusting the amount of the added solvent;
in the second step, specifically, the mass ratio of the negative electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (83-97): 1-5: (1-7);
and thirdly, respectively coating a layer of the negative electrode substance slurry obtained in the second step on the upper side and the lower side of the composite porous copper foil obtained in the first step, drying at the temperature of 80-120 ℃, rolling after drying to obtain a rolled negative electrode plate, and then cutting the rolled negative electrode plate to a specified size to finally obtain a finished negative electrode plate.
In addition, the invention also provides a preparation method of the semisolid lithium ion battery, which comprises the following steps:
firstly, stacking and assembling the positive pole piece, the ion conductor diaphragm and the negative pole piece in sequence, and then injecting electrolyte after packaging to prepare a soft-package, round or square and semi-solid lithium ion battery;
and secondly, the semi-solid lithium ion battery is subjected to standing, clamp pre-charging, degassing, formation, aging and grading processes in sequence to complete the preparation of the battery and the basic electrical performance test.
Compared with the prior art, the technical scheme provided by the invention has the advantages that the design is scientific, and aiming at the problem of high internal resistance of the original composite foil, the mixed bottom coating which contains a conductive agent and an inorganic oxide solid electrolyte and has good electronic conduction and ionic conduction is introduced to the surface of the porous composite foil, so that the adhesive force of an active material and a current collector is improved, a complete ion and electron transmission channel is constructed, the transfer efficiency of electronic conduction and lithium ions is improved, the polarization of the battery is inhibited, the thermal effect is reduced, the internal resistance of the battery is reduced, the multiplying power performance is improved, and the preparation method has great practical significance.
In addition, in the invention, the solid electrolyte is introduced into the positive and negative porous composite foils, the positive and negative materials, the positive and negative material layers and the diaphragm, so that the amount of liquid electrolyte in the semi-solid battery system can be effectively reduced by introducing the solid electrolyte material, and the safety performance of the high-specific-energy battery is further improved.
Drawings
Fig. 1 is a schematic cross-sectional view of a porous composite foil provided by the present invention, when no mixed primer is applied, that is, a schematic cross-sectional view of a porous composite foil current collector;
fig. 2 is a schematic top-view structural diagram of a porous composite foil provided by the present invention, when the porous composite foil is not coated with the upper hybrid primer layer, that is, a schematic top-view structural diagram of a porous composite foil current collector;
FIG. 3 is a schematic cross-sectional view of a positive electrode plate according to the present invention;
FIG. 4 is a schematic cross-sectional view of a negative electrode plate according to the present invention;
fig. 5 is a schematic cross-sectional structure view of a battery pole group of a semi-solid lithium ion battery provided by the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the following detailed description of the present invention is provided in conjunction with the accompanying drawings and embodiments.
Referring to fig. 1 and fig. 2, the present invention provides a porous composite foil, which is applied to a battery pole piece (the battery pole piece includes a positive pole piece and a negative pole piece), and includes a porous composite foil current collector;
the porous composite foil current collector comprises a high polymer insulating layer 102 and two metal conducting layers 101;
a layer of the metal conductive layer 101 is respectively arranged on the upper side and the lower side of the polymer insulating layer 102 in a covering manner;
a plurality of through holes 103 are arranged on the porous composite foil current collector in a penetrating manner;
it should be noted that each of the through holes 103 vertically penetrates through one polymer insulating layer 102 and the two metal conductive layers 101 on both sides of the polymer insulating layer 102.
The outer side surface of each metal conductive layer 101 in the porous composite foil current collector is coated with a mixed bottom coating layer 104.
In the present invention, in a specific implementation, the material of the polymer insulating layer 102 includes any one of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyimide (PI), polyacrylonitrile (PAN), and polyethylene terephthalate (PET);
in the present invention, the thickness of the polymer insulating layer 102 is 2-10 μm;
the thickness of each metal conductive layer 101 is 1-5 μm.
In the invention, in a specific implementation, when the porous composite foil current collector is applied to a positive electrode plate, the two metal conductive layers 101 are both aluminum foils, and the porous composite foil current collector at the moment is defined as a composite porous aluminum foil current collector;
when the porous composite foil current collector is applied to a negative electrode plate, the two metal conductive layers 101 are both copper foils, and the porous composite foil current collector at this time is defined as a composite porous copper foil current collector.
In the present invention, the metal conductive layers are compounded on two sides of the polymer insulating layer 102, and the compounding on two sides of the polymer insulating layer is to coat on two sides of the polymer insulating layer, specifically: the metal conductor layers are coated on the two sides of the polymer insulating layer by adopting methods such as evaporation, sputtering, chemical plating and the like on the two sides of the polymer insulating layer.
In the present invention, in a specific implementation, the shape of the through hole 103 may include at least one of a circle, an ellipse, a diamond, and a triangle, and may be other polygons.
In the present invention, the aperture of the through hole 103 is between 0.2-3 μm;
in the invention, the porosity on the porous composite foil current collector is 10-40%.
In the present invention, in a specific implementation, the method for forming the through hole 103 includes any one of puncturing, hole pressing, and laser etching.
In the present invention, in a specific implementation, the mixed primer layer 104 includes the following components by mass percent:
10-40% of conductive agent, 50-85% of oxide solid electrolyte and 5-10% of binder.
Specifically, the prepared mixed bottom coating slurry (the solute of the mixed bottom coating slurry comprises a conductive agent, an oxide solid electrolyte and a binder, NMP is used as a solvent when the mixed bottom coating is used for preparing a positive pole piece, deionized water is used as a solvent when the mixed bottom coating is used for preparing a negative pole piece, and the solid content of the mixed bottom coating slurry is 10% -30%, and the viscosity of the slurry is 1000-4000 cp) is coated on the porous composite foil.
In a specific implementation, the thickness of each mixed primer layer 104 is 2-10 microns;
specifically, for the mixed primer layer 104, the conductive agent includes at least one of carbon black, ketjen black, conductive graphite, conductive fibers, carbon nanotubes, and graphene;
an oxide solid state electrolyte comprising at least one of Lithium Aluminum Titanium Phosphate (LATP), lithium Aluminum Germanium Phosphate (LAGP), lithium Lanthanum Zirconium Oxide (LLZO), lithium Lanthanum Titanium Oxide (LLTO), and Lithium Lanthanum Zirconium Thallium Oxide (LLZTO);
a binder including one or a mixture of two or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), acrylic Acid (AA), polyethylene oxide (PEO), sodium carboxymethyl cellulose (PTFE), styrene-butadiene rubber (SBR), hydroxypropyl methyl cellulose (HPMC), carboxylated styrene-butadiene latex (XSBRL), and polyvinyl alcohol (PVA);
referring to fig. 3, the present invention also provides a positive electrode plate, which comprises the porous composite foil as described above;
the outer side of each mixed bottom coating layer 104 in the porous composite foil is respectively coated with a positive material layer 105 (namely a positive active material layer);
referring to fig. 4, the present invention also provides a negative electrode plate, which comprises the porous composite foil;
the outer side of each mixed bottom coating layer 104 in the porous composite foil is respectively coated with a negative material layer 205 (namely a negative active material layer);
in the present invention, the positive electrode material layer 105 includes a positive electrode active material, an oxide solid electrolyte, a conductive agent, and a binder;
the mass ratio of the positive electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (84-96): 1-5)/(2-6);
for the positive electrode material layer 105, the positive electrode active material specifically includes at least one of Lithium Cobaltate (LCO), lithium Manganate (LMO), lithium nickel manganese cobalt (NCM), lithium Nickel Cobalt Aluminate (NCA), lithium iron phosphate (LFP), and lithium manganese iron phosphate (LMFP);
the positive active material is at least one of Lithium Cobaltate (LCO), lithium Manganate (LMO), lithium Nickel Cobalt Manganese (NCM), lithium Nickel Cobalt Aluminate (NCA), lithium iron phosphate (LFP) and lithium manganese iron phosphate (LMFP), and the surface of these materials can be coated with a solid electrolyte (i.e., coated with an oxide solid electrolyte located outside the positive active material), which is a material with a core-shell structure, and the solid electrolyte is an outer coating layer.
For the positive electrode material layer 105, the conductive agent includes at least one of conductive carbon black, conductive graphite, carbon nanotubes, carbon nanofibers, and graphene;
for the positive electrode material layer 105, the oxide solid electrolyte includes at least one of LATP, LAGP, LLZO, LLTO, and LLZTO;
for positive electrode material layer 105, the binder includes at least one of PVDF, SBR, CMC, and PTFE.
In particular, the surface density of the positive electrode material layer 105 is 10-50mg/cm 2 。
In the present invention, the negative electrode material layer 205 includes a negative electrode active material, an oxide solid electrolyte, a conductive agent, and a binder;
the mass ratio of the negative electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (83-97): 1-5): 1-7.
For the negative electrode material layer 205, the negative electrode active material includes one or more of elemental silicon, silicon oxide, artificial graphite, natural graphite, composite graphite, soft carbon, and hard carbon;
for the negative electrode material layer 205, the conductive agent includes at least one of conductive carbon black, conductive graphite, carbon nanotubes, carbon nanofibers, and graphene;
for the anode material layer 205, the oxide solid electrolyte includes at least one of LATP, LAGP, LLZO, LLTO, and LLZTO;
for negative electrode material layer 205, the binder includes any one of SBR, PAA, and PTFE.
In particular, the surface density of the negative electrode material layer 205 is 5-30mg/cm 2 ；
Referring to fig. 5, the present invention also provides a semi-solid lithium ion battery, which includes a battery pole group;
the battery pole group comprises the positive pole piece 1, the ionic conductor diaphragm 3 and the negative pole piece 2;
the ion conductor diaphragm 3 is positioned between the positive pole piece 1 and the negative pole piece 2;
electrolyte is injected into the battery pole group; namely, the electrolyte is filled in the gaps among the positive pole piece 1, the ion conductor diaphragm 3 and the negative pole piece 2;
the ion conductor diaphragm 3 comprises a base film 301, a first coating 302 and a second coating 303;
a first coating layer and a second coating layer respectively positioned on the surface of the base film close to the side of the positive pole piece and the surface of the base film close to the side of the negative pole, such as the upper side surface and the lower side surface shown in FIG. 5;
the base membrane comprises any one of a polyethylene base membrane, a polyethylene non-woven fabric base membrane, a polypropylene non-woven fabric base membrane, a polypropylene/polyethylene/polypropylene (PP/PE/PP) composite base membrane, a Polyimide (PI) base membrane, a polyimide non-woven fabric base membrane, a Polytetrafluoroethylene (PTFE) membrane, a polytetrafluoroethylene non-woven fabric base membrane, a polyvinyl chloride (PVC) base membrane and a polyvinyl chloride non-woven fabric base membrane;
the first coating is a ceramic coating, and ceramic powder adopted by the ceramic coating comprises at least one of alumina, zirconia, boehmite, magnesium hydroxide, barium sulfate, silicon oxide, aluminum nitride, magnesium oxide, titanium dioxide, yttrium oxide and cerium oxide (the materials are all powder);
in particular, the ceramic coating comprises ceramic powder and an aqueous emulsion binder of an acrylate system;
in the ceramic coating, the ceramic powder accounts for 90-99% by mass, and the binder accounts for 1-10% by mass. The ceramic coating diaphragm is a lithium battery diaphragm which is mature and applied in the existing battery industry.
In particular, the grain diameter of the ceramic powder is 0.01-2um.
The second coating is a fast ion conductor coating, and fast ion conductor powder (also called solid electrolyte) adopted by the fast ion conductor coating comprises LATP powder or LLTO powder;
in particular, the fast ion conductor coating comprises fast ion conductor powder and an acrylic acid aqueous emulsion binder;
in the fast ion conductor coating, the fast ion conductor powder accounts for 90-99% by mass, and the binder accounts for 1-10% by mass.
In concrete implementation, the particle size of the fast ion conductor powder is 0.01-2um, so that the influence on the density and the bonding effect of the coating due to too large particle size is avoided, and the influence on ion transmission is avoided.
In the present invention, the thickness of the ceramic coating is, in particular, 0.1 to 5 μm;
in the invention, the electrolyte comprises lithium salt, solvent and additive;
wherein the lithium salt comprises lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (fluorosulfonylimide) (LiFSI), lithium bis (trifluoromethanesulfonylimide) (LiTFSI), and lithium tetrafluoroborate (LiBF) 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluorophosphate (LiPO) 2 F 2 ) And lithium difluoroborate (LiDFOB), and the like;
the solvent comprises at least one of Propylene Carbonate (PC), ethylene Carbonate (EC), dimethyl carbonate (DMC), ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), phthalate (DMP), dimethyl maleate (DMM), ethylene glycol dimethyl ether (DME) and Tetrahydrofuran (TH) F;
the additive comprises at least one of Vinylene Carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), propane Sultone (PS), propylene Sultone (PST), vinyl sulfate (DTD) and difluoroethylene carbonate (DFEC).
Specifically, the electrolyte injection amount of each semi-solid battery is 0.5-1.5g/Ah;
specifically, the molar concentration of the lithium salt is 0.5-2mol/L;
in the invention, the semi-solid battery is a soft-package semi-solid battery prepared by a lamination process.
In addition, the invention also provides a preparation method of the positive pole piece, which comprises the following steps:
step one, preparing a porous composite foil of a positive pole piece with a mixed bottom coating: mixing and uniformly stirring a conductive agent, an oxide solid electrolyte and a binder according to a preset mass percentage, dissolving the mixture in a solvent NMP (N-methyl pyrrolidone) for dispersion to obtain mixed primer slurry, adjusting the solid content of the mixed primer slurry to 10-30% or the viscosity of the slurry to 1000-4000cp by adjusting the amount of an added solvent, then respectively coating a layer of mixed primer slurry on the upper side and the lower side of the composite porous aluminum foil current collector, drying (putting into an oven) at the temperature of 80-120 ℃, and drying to obtain a porous composite foil material of the positive pole piece with the mixed primer, namely the composite porous aluminum foil;
in the first step, specifically, the preset mass percentages among the conductive agent, the oxide solid electrolyte and the binder are as follows:
10% -40% of a conductive agent, 50% -85% of an oxide solid electrolyte and 5% -10% of a binder, that is, mass percentages of respective components included in a solute of the mixed undercoat slurry.
Step two, preparing anode substance slurry: mixing and uniformly stirring a positive electrode active material, an oxide solid electrolyte, a conductive agent and a binder according to a preset mass ratio, dissolving the mixture in a solvent NMP for dispersion to obtain a positive electrode substance slurry, and adjusting the solid content of the positive electrode substance slurry to be 60-75% or the viscosity of the slurry to be 6000-8000cp by adjusting the amount of an added solvent;
in the second step, the mass ratio among the positive electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (84-96): 1-5: (2-6).
And thirdly, respectively coating a layer of the positive electrode substance slurry obtained in the second step on the upper side and the lower side of the composite porous aluminum foil obtained in the first step, drying (putting in a drying oven) at the temperature of 80-120 ℃, rolling after drying to obtain a rolled positive electrode piece, and then cutting the rolled positive electrode piece to a specified size to finally obtain a finished positive electrode piece.
In addition, the invention also provides a preparation method of the negative pole piece, which comprises the following steps:
step one, preparing a porous composite foil of a negative pole piece with a mixed bottom coating: mixing and uniformly stirring a conductive agent, an oxide solid electrolyte and a binder according to a preset mass percentage, dissolving the mixture in solvent deionized water for dispersion to obtain mixed undercoat slurry, adjusting the amount of an added solvent to adjust the solid content of the mixed undercoat slurry to 10-30% or the viscosity of the slurry to 1000-4000cp, then respectively coating a layer of mixed undercoat slurry on the upper side and the lower side of the composite porous copper foil current collector, drying (putting into an oven) at the temperature of 80-120 ℃, and drying to obtain a porous composite foil material of a negative pole piece with a mixed undercoat, namely a composite porous aluminum foil;
in the first step, specifically, the preset mass percentages among the conductive agent, the oxide solid electrolyte and the binder are as follows:
10% -40% of a conductive agent, 50% -85% of an oxide solid electrolyte and 5% -10% of a binder, that is, mass percentages of respective components included in a solute of the mixed undercoat slurry.
Step two, preparing anode substance slurry: mixing and uniformly stirring a negative electrode active material, an oxide solid electrolyte, a conductive agent and a binder according to a preset mass ratio, dissolving the mixture in solvent deionized water for dispersion to obtain negative electrode substance slurry, and adjusting the solid content of the negative electrode substance slurry to be 40-50% or the viscosity of the slurry to be 3000-5000cp by adjusting the amount of the added solvent;
in the second step, the mass ratio among the negative electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (83-97): (1-5): (1-7).
And thirdly, respectively coating a layer of the negative electrode substance slurry obtained in the second step on the upper side and the lower side of the composite porous copper foil obtained in the first step, drying (putting into a drying oven) at the temperature of 80-120 ℃, rolling after drying to obtain a rolled negative electrode piece, and then cutting the rolled negative electrode piece to a specified size to finally obtain a finished negative electrode piece.
In addition, the invention provides a preparation method of the semisolid lithium ion battery, which comprises the following steps:
firstly, sequentially stacking and assembling the prepared positive pole piece, the prepared ion conductor diaphragm and the prepared negative pole piece (namely, assembling by applying the existing lamination process), and then injecting electrolyte after packaging (for example, packaging by an aluminum plastic film) to prepare a soft-package, round or square semi-solid lithium ion battery;
secondly, the semi-solid lithium ion battery is subjected to conventional (namely the existing) standing, clamp pre-charging, degas (degassing), formation, aging, capacity grading and other processes in sequence to complete the preparation of the battery and the basic electrical performance test;
wherein, the pressure of the clamp for pre-charging, formation and partial volume is 500-1500 kgf, the temperature is 25-45 ℃, and the multiplying power is 0.1-1C.
It should be noted that the operations of pre-charging, formation, capacity grading and the like of the clamp adopted in the present invention are conventional operations in the charging and discharging processes of the battery in the lithium battery industry, and are not described herein again.
It should be noted that, for the technical scheme of the present invention, a mixed primer layer containing a conductive agent and an inorganic oxide solid electrolyte and having good electronic conduction and ionic conduction is introduced on the porous composite foil, so as to improve the adhesion of the positive and negative electrode slurry and the current collector foil, construct a complete ion and electron transmission channel between the active material in the electrode plate and the current collector foil, reduce the impedance of the electrode plate, and improve the performance of the battery. Meanwhile, solid electrolyte is introduced into the positive and negative porous composite foils, the positive and negative materials, the positive and negative material layers and the diaphragm, so that a good ion diffusion network is established, the liquid electrolyte amount in the semi-solid battery can be effectively reduced, and the safety performance of the battery is further improved.
It should be noted that, the semi-solid battery is a compromise solution between the liquid lithium ion battery and the all-solid lithium battery, and the mass or volume of the solid electrolyte in the single body accounts for half of the total mass or volume of the electrolyte in the single body, compared with the solid electrolyte in the semi-solid battery, the solid electrolyte in the semi-solid battery is nonflammable, high temperature resistant, non-corrosive, non-volatile, and the amount of the liquid electrolyte is greatly reduced, so that when the semi-solid battery is damaged or punctured, the conditions of spontaneous combustion or explosion and the like are effectively avoided.
In order to more clearly understand the technical solution of the present invention, the technical solution of the present invention is described below by specific examples.
Examples
1. And preparing the positive pole piece.
Firstly, adding 30 mass percent of conductive carbon black, 60 mass percent of solid electrolyte LATP and 10 mass percent of binder PVDF into solvent NMP to obtain mixed primer slurry, adjusting the solid content of the slurry to be 20 percent and the viscosity to be 3000cp, coating the prepared mixed primer slurry on holes and two side surfaces of a porous composite aluminum foil with the thickness of 12 mu m (wherein, the thickness of a PET layer is 9 mu m, the thickness of an aluminum metal layer as the surface of a metal conductive layer is 1.5 mu m, the aperture of a circular through hole is 1 mu m, and the porosity is 20 percent) and the thickness is 3 mu m, and then drying at the temperature of 90 ℃ to obtain the composite porous aluminum foil with the mixed primer;
then, mixing 90% by mass of a positive electrode active material (specifically, LATP surface-coated ternary NCM, ni% = 90%), 3% of a solid electrolyte LATP, 3% of a conductive agent Super P, and 4% of a binder PVDF to prepare positive electrode material slurry;
then, the positive electrode material slurry is coated on the front and back surfaces of the composite porous aluminum foil with the mixed bottom coating, and the surface density of the positive electrode coating is 40mg/cm 2 And after drying, rolling and slitting to obtain the positive pole piece.
As shown in fig. 1 and fig. 2, when the porous composite foil is a porous composite aluminum foil, the foil includes a polymer insulating layer 102 that is a PET layer, metal conductive layers 101 on two sides of the polymer insulating layer 102 are aluminum metal layers (i.e., aluminum foils), and the porous composite aluminum foil is provided with a plurality of through holes 103;
referring to fig. 3, the positive electrode plate includes a porous composite aluminum foil having a mixed bottom coating 104 on the upper and lower sides thereof, and a positive electrode material layer 105 is coated on the outer side of each mixed bottom coating 104;
2. and preparing a negative pole piece.
Firstly, uniformly mixing 30% by mass of conductive carbon black, 60% by mass of solid electrolyte LATP, 5% by mass of binder SBR and 5% by mass of CMC, adding deionized water to obtain mixed undercoat slurry, adjusting the solid content of the slurry to be 20% and the viscosity to be 2000cp, coating the prepared mixed slurry on holes and two side surfaces of a porous composite copper foil with the thickness of 6.5 mu m (wherein the thickness of a PET layer is 4.5 mu m, the thickness of a surface copper metal layer serving as a metal conductive layer is 1 mu m, the aperture of a circular through hole is 1 mu m, and the porosity is 20%) and the thickness is 3 mu m, and then drying at the temperature of 90 ℃ to obtain the composite porous copper foil with the mixed undercoat;
then, mixing 92% of negative active material (specifically, a mixture of graphite coated on the surface of LATP and silica), 3% of solid electrolyte LATP, 2% of conductive agent Super P and 3% of binder PAA by mass percent to prepare negative material slurry;
then, the negative electrode material slurry was coated on both sides of the composite porous copper foil with the mixed primer layer, and the surface density of the positive electrode coating layer was 20mg/cm 2 And after drying, rolling and slitting to obtain the negative pole piece.
Referring to fig. 4, the negative electrode tab includes a porous composite copper foil having a mixed primer layer 104 on each of the upper and lower sides thereof, and a negative electrode material layer 205 is coated on the outer side of each mixed primer layer 104.
3. And preparing the semi-solid lithium ion battery.
Firstly, stacking a negative pole piece, an ion conductor diaphragm and a positive pole in sequence, and preparing the soft package semi-solid battery through a lamination process, wherein the thickness of the ion conductor diaphragm is 16 mu m, the thickness of the PE base film is 12 mu m, and the surface close to the positive pole side is coated with Al 2 O 3 The ceramic coating of (2) has a coating thickness of 2 μm, and the surface close to the negative electrode side is coated with a LATP fast ion conductor coating having a coating thickness of 2 μm.
Then, the battery is packaged by an aluminum-plastic film, and then the electrolyte is injected according to the injection coefficient of 1.5g/Ah, the high-temperature standing, the clamp pre-charging, degassing, formation, aging, capacity grading and other procedures are carried out, so that the battery preparation and the basic electrical property test are completed. Wherein the pre-charging, the formation and the volume division are carried out under the pressure of 1000kgf, the ambient temperature of 25 ℃ and the multiplying power of 0.2C.
The schematic structural diagram of a cell (i.e., a battery pole group) of the semisolid lithium ion battery is shown in fig. 5, and includes a positive pole piece 1, a negative pole piece 2, and an ion conductor diaphragm 3,
the battery pole group comprises the positive pole piece 1, the ionic conductor diaphragm 3 and the negative pole piece 2;
the ion conductor diaphragm 3 is positioned between the positive pole piece 1 and the negative pole piece 2;
electrolyte is injected into the battery pole group; namely, the electrolyte is filled in the gaps among the positive pole piece 1, the ion conductor diaphragm 3 and the negative pole piece 2;
the ion conductor separator 3 includes a base film 301, a surface coating layer (i.e., a first coating layer 302) near the positive electrode side, and a surface coating layer (i.e., a second coating layer 30) near the negative electrode side.
Comparative example 1.
Comparative example 1 is substantially the same as example except for the following:
1. the positive electrode material slurry is directly coated on two sides of a 12-micron-thick PET composite aluminum foil (namely a composite porous aluminum foil), and the negative electrode material slurry is directly coated on two sides of a 6-micron-thick PET composite copper foil;
2. and the battery core is injected with electrolyte with the injection coefficient of 2.0 g/Ah. The rest is the same as the preparation process of the embodiment.
Comparative example 2:
comparative example 2 is substantially the same as the example except that:
1. the positive electrode material slurry is directly coated on two sides of a 12-micron-thick porous PET composite aluminum foil, and the negative electrode material slurry is directly coated on two sides of a 6-micron-thick porous PET composite copper foil;
2. and the battery core is injected with electrolyte with the injection coefficient of 2.0 g/Ah. The rest is the same as the preparation process of the example.
The energy density, internal resistance and rate capability of the examples were compared with those of the two comparative examples, and the comparison results are shown in table 1.
Table 1:
compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the porous composite foil used in the invention can reduce the weight ratio of the current collector in the battery, and can effectively improve the energy density of the battery;
2. according to the invention, the mixed bottom coating which contains a conductive agent and an inorganic oxide solid electrolyte and has good electronic conduction and ionic conduction is introduced into the holes and the surface of the porous composite foil, and an ion and electron rapid transmission channel is constructed, so that the polarization of the battery can be inhibited, the internal resistance of the battery is reduced, and the rate capability is improved;
3. according to the invention, the solid electrolyte is introduced into the positive and negative electrode porous composite foil, the positive and negative electrode active materials, the positive and negative electrode material layers and the diaphragm, so that a good ion diffusion network is established, the liquid electrolyte amount in the semi-solid battery can be effectively reduced, and the safety performance of the battery is further improved.
In summary, compared with the prior art, the porous composite foil, the positive electrode plate, the negative electrode plate, the semi-solid lithium ion battery and the preparation method thereof provided by the invention have scientific design, and have great practical significance in that a mixed primer layer containing a conductive agent and an inorganic oxide solid electrolyte and having good electronic conduction and ion conduction is introduced to the surface of the porous composite foil to improve the adhesive force of an active material and a current collector, and a complete ion and electron transmission channel is constructed, so that the electronic conduction and the migration efficiency of lithium ions are improved, the polarization of the battery is inhibited, the thermal effect is reduced, the internal resistance of the battery is reduced, and the rate capability is improved.
In addition, in the invention, the solid electrolyte is introduced into the positive and negative porous composite foils, the positive and negative materials, the positive and negative material layers and the diaphragm, so that the amount of liquid electrolyte in the semi-solid battery system can be effectively reduced by introducing the solid electrolyte material, and the safety performance of the high-specific-energy battery is further improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A porous composite foil is applied to a battery pole piece and is characterized by comprising a porous composite foil current collector;
the porous composite foil current collector comprises a high polymer insulating layer (102) and two metal conducting layers (101);
the upper side and the lower side of the polymer insulating layer (102) are respectively provided with a layer of the metal conducting layer (101) in a covering manner;
a plurality of through holes (103) are arranged on the porous composite foil current collector in a penetrating manner;
the outer side surface of each metal conductive layer (101) in the porous composite foil current collector is coated with a mixed bottom coating (104).
2. The porous composite foil of claim 1, wherein when the porous composite foil current collector is applied to a positive electrode plate, both metal conductive layers (101) are aluminum foils, and the porous composite foil current collector is defined as a composite porous aluminum foil current collector;
when the porous composite foil current collector is applied to a negative pole piece, the two metal conducting layers (101) are both copper foils, and the porous composite foil current collector at the moment is defined as a composite porous copper foil current collector.
3. The porous composite foil according to claim 1, wherein the polymeric insulating layer (102) has a thickness of 2-10 μm;
the thickness of each metal conductive layer (101) is 1-5 μm;
the aperture of the through hole (103) is between 0.2 and 3 mu m;
the porosity on the porous composite foil current collector is 10% -40%;
each mixed primer layer (104) has a thickness of 2-10 microns.
4. The porous composite foil material of claim 1, wherein the material of the polymer insulating layer (102) comprises any one of polyethylene, polypropylene, polyvinyl chloride, polyimide, polyacrylonitrile and polyethylene terephthalate;
a hybrid base coat (104) comprising the following components in mass percent:
10% -40% of conductive agent, 50% -85% of oxide solid electrolyte and 5% -10% of binder;
for the hybrid primer layer (104), the conductive agent includes at least one of carbon black, ketjen black, conductive graphite, conductive fibers, carbon nanotubes, and graphene;
the oxide solid electrolyte comprises at least one of lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen and lithium lanthanum zirconium thallium oxygen;
the binder comprises one or a mixture of more than two of polytetrafluoroethylene, polyvinylidene fluoride, acrylic acid, polyethylene oxide, sodium carboxymethyl cellulose, styrene-butadiene rubber, hydroxypropyl methyl cellulose, carboxylic styrene-butadiene latex and polyvinyl alcohol.
5. A positive electrode sheet comprising the porous composite foil according to any one of claims 1 to 4;
the outer side of each mixed bottom coating (104) in the porous composite foil is respectively coated with a positive material layer (105);
a positive electrode material layer (105) including a positive electrode active material, an oxide solid electrolyte, a conductive agent, and a binder;
the mass ratio of the positive electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (84-96): 1-5): 2-6;
for the positive electrode material layer (105), the positive electrode active material specifically comprises at least one of lithium cobaltate, lithium manganate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium iron phosphate and lithium manganese iron phosphate;
the conductive agent comprises at least one of conductive carbon black, conductive graphite, carbon nanotubes, carbon nanofibers and graphene;
the oxide solid electrolyte comprises at least one of LATP, LAGP, LLZO, LLTO, and LLZTO;
the binder includes at least one of PVDF, SBR, CMC, and PTFE.
6. A negative electrode sheet comprising the porous composite foil according to any one of claims 1 to 4;
the outer side of each mixed bottom coating (104) in the porous composite foil is respectively coated with a negative material layer (205);
a negative electrode material layer (205) including a negative electrode active material, an oxide solid electrolyte, a conductive agent, and a binder;
the mass ratio of the negative electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (83-97): 1-5): 1-7;
for the negative electrode material layer (205), the negative electrode active material comprises one or more of simple substance silicon, silicon oxide, artificial graphite, natural graphite, composite graphite, soft carbon and hard carbon;
for the negative electrode material layer (205), the conductive agent comprises at least one of conductive carbon black, conductive graphite, carbon nanotubes, carbon nanofibers and graphene;
for the anode material layer (205), the oxide solid electrolyte comprises at least one of LATP, LAGP, LLZO, LLTO, and LLZTO;
for the negative electrode material layer (205), the binder includes any one of SBR, PAA, and PTFE.
7. A semi-solid lithium ion battery is characterized by comprising a battery pole group;
the battery pole group comprises the positive pole piece of claim 5, the ion conductor diaphragm (3) and the negative pole piece of claim 6;
the ion conductor diaphragm (3) is positioned between the positive pole piece and the negative pole piece;
electrolyte is injected into the battery pole group;
an ion conductor separator (3) including a base film (301), a first coating layer (302), and a second coating layer (303);
the first coating and the second coating are respectively positioned on the surface of one side of the base film close to the positive pole piece and the surface of one side of the base film close to the negative pole;
the base film comprises any one of a polyethylene base film, a polyethylene non-woven fabric base film, a polypropylene non-woven fabric base film, a polypropylene composite base film, a polyimide non-woven fabric base film, a polytetrafluoroethylene non-woven fabric base film, a polyvinyl chloride base film and a polyvinyl chloride non-woven fabric base film;
the first coating is a ceramic coating, and the ceramic coating comprises ceramic powder and an aqueous emulsion binder of an acrylate system;
in the ceramic coating, the ceramic powder accounts for 90-99% by mass, and the binder accounts for 1-10% by mass;
the ceramic powder adopted by the ceramic coating comprises at least one of alumina, zirconia, boehmite, magnesium hydroxide, barium sulfate, silicon oxide, aluminum nitride, magnesia, titanium dioxide, yttrium oxide and cerium oxide;
the second coating is a fast ion conductor coating which comprises fast ion conductor powder and an acrylic acid aqueous emulsion binder;
in the fast ion conductor coating, the fast ion conductor powder accounts for 90-99% by mass, and the binder accounts for 1-10% by mass;
the fast ion conductor powder adopted by the fast ion conductor coating comprises LATP powder or LLTO powder.
8. The preparation method of the positive pole piece according to claim 5, characterized by comprising the following steps:
step one, preparing a porous composite foil of a positive pole piece with a mixed bottom coating: mixing and uniformly stirring a conductive agent, an oxide solid electrolyte and a binder according to a preset mass percentage, dissolving the mixture in a solvent NMP (N-methyl pyrrolidone) for dispersion to obtain mixed primer slurry, adjusting the solid content of the mixed primer slurry to 10-30% or the viscosity of the slurry to 1000-4000cp by adjusting the amount of an added solvent, then respectively coating a layer of mixed primer slurry on the upper side and the lower side of the composite porous aluminum foil current collector, drying at the temperature of 80-120 ℃, and drying to obtain a porous composite foil material of the positive pole piece with the mixed primer, namely the composite porous aluminum foil;
in the first step, the preset mass percentages among the conductive agent, the oxide solid electrolyte and the binder are as follows:
10% -40% of conductive agent, 50% -85% of oxide solid electrolyte and 5% -10% of binder;
step two, preparing anode substance slurry: mixing and uniformly stirring a positive electrode active material, an oxide solid electrolyte, a conductive agent and a binder according to a preset mass ratio, dissolving the mixture in a solvent NMP for dispersion to obtain a positive electrode substance slurry, and adjusting the solid content of the positive electrode substance slurry to be 60-75% or the viscosity of the slurry to be 6000-8000cp by adjusting the amount of an added solvent;
in the second step, the mass ratio of the positive electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (84-96): 1-5: (2-6);
and thirdly, respectively coating a layer of the positive electrode substance slurry obtained in the second step on the upper side and the lower side of the composite porous aluminum foil obtained in the first step, drying at the temperature of 80-120 ℃, rolling after drying to obtain a rolled positive electrode piece, and then cutting the rolled positive electrode piece to a specified size to finally obtain a finished positive electrode piece.
9. The preparation method of the negative electrode plate of claim 6, characterized by comprising the following steps:
step one, preparing a porous composite foil of a negative pole piece with a mixed bottom coating: mixing and uniformly stirring a conductive agent, an oxide solid electrolyte and a binder according to a preset mass percentage, dissolving the mixture in solvent deionized water for dispersion to obtain mixed undercoat slurry, adjusting the amount of an added solvent to adjust the solid content of the mixed undercoat slurry to 10-30% or the viscosity of the slurry to 1000-4000cp, then respectively coating a layer of mixed undercoat slurry on the upper side and the lower side of the composite porous copper foil current collector, drying at the temperature of 80-120 ℃, and drying to obtain a porous composite foil material, namely a composite porous aluminum foil, of the negative pole piece with the mixed undercoat;
in the first step, the preset mass percentages among the conductive agent, the oxide solid electrolyte and the binder are as follows:
10% -40% of conductive agent, 50% -85% of oxide solid electrolyte and 5% -10% of binder;
step two, preparing anode substance slurry: mixing and uniformly stirring a negative electrode active material, an oxide solid electrolyte, a conductive agent and a binder according to a preset mass ratio, dissolving the mixture in solvent deionized water for dispersing to obtain negative electrode substance slurry, and adjusting the solid content of the negative electrode substance slurry to be 40-50% or the viscosity of the slurry to be 3000-5000cp by adjusting the amount of the added solvent;
in the second step, specifically, the mass ratio of the negative electrode active material, the oxide solid electrolyte, the conductive agent and the binder is (83-97): 1-5: (1-7);
and thirdly, respectively coating a layer of the negative electrode substance slurry obtained in the second step on the upper side and the lower side of the composite porous copper foil obtained in the first step, drying at the temperature of 80-120 ℃, rolling after drying to obtain a rolled negative electrode plate, and then cutting the rolled negative electrode plate to a specified size to finally obtain a finished negative electrode plate.
10. A preparation method of a semisolid lithium ion battery is characterized by comprising the following steps:
the method comprises the following steps of firstly, sequentially stacking and assembling the positive pole piece of claim 5, the ion conductor diaphragm and the negative pole piece of claim 6, and then injecting electrolyte after packaging to prepare a soft-package, round or square and semi-solid lithium ion battery;
and secondly, the semi-solid lithium ion battery is subjected to standing, clamp pre-charging, degassing, formation, aging and grading processes in sequence to complete the preparation of the battery and the basic electrical performance test.
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