CN109786817A - Solid-state lithium battery and its application and method for preparing non-woven reinforced solid-state electrolyte membrane - Google Patents
Solid-state lithium battery and its application and method for preparing non-woven reinforced solid-state electrolyte membrane Download PDFInfo
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- CN109786817A CN109786817A CN201910063972.8A CN201910063972A CN109786817A CN 109786817 A CN109786817 A CN 109786817A CN 201910063972 A CN201910063972 A CN 201910063972A CN 109786817 A CN109786817 A CN 109786817A
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- solid
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- woven fabrics
- electrolyte membrane
- lithium
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- 239000012528 membrane Substances 0.000 title claims abstract description 118
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000003792 electrolyte Substances 0.000 title claims description 84
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 147
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 125
- 239000007787 solid Substances 0.000 claims abstract description 109
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 82
- 239000000853 adhesive Substances 0.000 claims description 73
- 230000001070 adhesive effect Effects 0.000 claims description 73
- 239000002904 solvent Substances 0.000 claims description 53
- 239000002131 composite material Substances 0.000 claims description 43
- 239000004020 conductor Substances 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 32
- 239000007773 negative electrode material Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011268 mixed slurry Substances 0.000 claims description 25
- 229910000614 lithium tin phosphorous sulfides (LSPS) Inorganic materials 0.000 claims description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- 239000007774 positive electrode material Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 18
- -1 Sc 2 O 3 Inorganic materials 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011889 copper foil Substances 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000002103 nanocoating Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 229910013188 LiBOB Inorganic materials 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 8
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 8
- 229910000846 In alloy Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002134 carbon nanofiber Substances 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 229910052706 scandium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 229910010941 LiFSI Inorganic materials 0.000 claims description 6
- 229910013398 LiN(SO2CF2CF3)2 Inorganic materials 0.000 claims description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 6
- 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 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 2
- 229910012258 LiPO Inorganic materials 0.000 claims 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910018068 Li 2 O Inorganic materials 0.000 claims 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims 1
- 229910010093 LiAlO Inorganic materials 0.000 claims 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 claims 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 239000011888 foil Substances 0.000 claims 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 238000007790 scraping Methods 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 abstract description 96
- 230000008569 process Effects 0.000 abstract description 36
- 210000001787 dendrite Anatomy 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 72
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 27
- 238000000576 coating method Methods 0.000 description 22
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 21
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 15
- 239000005030 aluminium foil Substances 0.000 description 15
- 238000005098 hot rolling Methods 0.000 description 15
- 238000010586 diagram Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000002356 single layer Substances 0.000 description 10
- 229910003327 LiNbO3 Inorganic materials 0.000 description 9
- 238000005253 cladding Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 9
- 229910001290 LiPF6 Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 230000003139 buffering effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 210000000170 cell membrane Anatomy 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 4
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920005573 silicon-containing polymer Polymers 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000002305 electric material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 description 2
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- 229910012761 LiTiS2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- YMDRKQVJDIXFSZ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxirane Chemical compound C1CO1.CC(=C)C(O)=O YMDRKQVJDIXFSZ-UHFFFAOYSA-N 0.000 description 1
- 206010011968 Decreased immune responsiveness Diseases 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 1
- 229910008920 Li2O—ZrO2 Inorganic materials 0.000 description 1
- 229910010848 Li6PS5Cl Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000002362 energy-dispersive X-ray chemical map Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910009160 xLi2S 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of method of solid state lithium battery and its application and the solid electrolyte membrane for preparing non-woven fabrics enhancing, which includes solid electrolyte membrane, anode, cathode and the buffer layer of non-woven fabrics enhancing.The solid electrolyte membrane mechanical strength with higher and thermal stability of non-woven fabrics enhancing described herein, do not occur positive and negative anodes short circuit in the assembling and use process of solid state battery simultaneously, power is prepared into very high, and in the use process of battery, the phenomenon that dendrite through electrode, significantly reduces, it is well suited for large-scale industrial production, there is significant commerciality.
Description
Technical field
The present invention relates to technical field of lithium batteries, in particular to a kind of solid state lithium battery and its application and prepare non-woven fabrics increasing
The method of strong solid electrolyte membrane.
Background technique
In recent years, people generally use vehicle to mitigate the air pollution of facing mankind and global warming crisis.For mesh
The lithium battery that vehicle in front uses, technology are state-of-the-art technologies in the industry.However, lithium battery technology is in safety and aspect of performance
There are many disadvantages: on the one hand, due to using inflammable and having corrosive liquid electrolyte, easy thermal runaway causes explosion；One
Aspect, because need to use a large amount of battery protection systems there are above-mentioned hidden danger, cause the total energy density of battery low；On the one hand,
Since the chemical degradation of the formation of Li dendrite, liquid electrolyte and electrode surface will lead to the poor circulation of battery.
Recently, it is developed the safer solid state lithium battery with high-energy density.Solid state lithium battery is liquid lithium
Most of technical disadvantages of battery provide remedial measure.Lithium ion battery (LiB) and fuel cell (FC) are that vehicle is answered at present
The benchmark energy.However, state-of-the-art LiB technology there are problems that can't get rid of in the industry, predominantly safety and mileage problem.
In order to solve these problems, people have paid great efforts in terms of developing for vehicle and the solid state lithium battery of other application.
However, because short circuit during assembling, the formation of dendrite during use, can not high yield production and production efficiency it is low while lacking machine
The problems such as tool intensity is high, substance is evenly distributed and telescopic diaphragm, so that the large-scale production and commercialization of solid state lithium battery
Also it cannot achieve.In addition, using having low total impedance and the sulfide solid electrolyte in high circulation service life to manufacture solid state lithium battery,
And realize that there are still limitations in terms of large scale with retractable electrode, variable collector.
Therefore, the existing technology for preparing solid state lithium battery is further improved.
Summary of the invention
In view of this, the present invention is directed to propose a kind of solid state lithium battery and its application and prepare non-woven fabrics enhancing solid-state electricity
The method for solving plasma membrane, with solve existing solid state lithium battery easily occur during assembly short circuit, easily form dendrite during use, can not
Large-scale industrial production is evenly distributed and the problem of telescopic diaphragm without high mechanical strength, substance.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of solid state lithium battery, the lithium battery include: solid electrolyte membrane, anode, cathode and the buffering of non-woven fabrics enhancing
Layer.
Further, the solid electrolyte membrane of the non-woven fabrics enhancing includes: the first solid sulfide electrolyte, non-woven fabrics
And first adhesive.
Further, the anode includes aluminium foil and anode composite, and the anode composite includes: positive electrode active materials, receives
Rice coating material, the second solid sulfide electrolyte, the first conductive material and second adhesive, the nano-coating material cladding
On the surface of the positive electrode active materials.
Further, the cathode includes collector and negative electrode material, and the collector is copper foil or nickel foil, the cathode
Material is lithium or indium or lithium-indium alloy or composite negative pole.
Further, the composite negative pole includes: negative electrode active material, solid electrolyte, the second conductive material and third
Adhesive.
Further, the tensile strength of the solid electrolyte membrane of the non-woven fabrics enhancing is 100-10000N/cm2, elongation
Rate is 0-50%.
Further, the non-woven fabrics enhancing solid electrolyte membrane in, the first solid sulfide electrolyte with
The non-woven fabrics, the first adhesive mass ratio be 80-97:0.01-20:3-10.
Further, the non-woven fabrics be PP based nonwoven, PE based nonwoven, PET based nonwoven, PAN based nonwoven,
At least one of PTFE based nonwoven, Celgard non-woven fabrics.
Further, the grammes per square metre of the non-woven fabrics is 1-10g/m2, porosity 50-95%, with a thickness of 10-50 μm, drawing
Stretching intensity is 200-4500N/cm2。
Further, the first adhesive is ethylene oxide quasi polymer, polyvinyls, vinylidene Type of Collective
At least one of object, styrenic polymer, butadiene polymer.
Further, the molecular weight of the first adhesive is 100000-1000000.
Further, the first lithium salts, first lithium salts are further included in the solid electrolyte of the non-woven fabrics enhancing
For selected from LiTFSI, LiFSI, LiN (SO2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2、LiBOB、
At least one of LiODFB.
Further, in the anode composite, the positive electrode active materials and the second solid sulfide electrolyte,
First conductive material, the second adhesive mass ratio be 50-95:10-45:0-10:0-20.
Further, the positive electrode active materials are selected from lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, ferric phosphate
Lithium, LiMn2O4, cobalt phosphate lithium, lithium nickel manganese oxide, cobalt acid lithium, LiTiS2、LiNiO2, elemental sulfur, in sulphur carbon mix at least
One of.
Further, the nano-coating material is selected from Li3PO4, Al2O3, LiNbO3, LiAlO2, Li3BO3, Li2O-
ZrO2、MgO、HfO2, Li2SiO3、B2O3、Li2O、Nb2O5、P2O5、SiO2、Sc2O3、TiO2、ZrO2At least one of.
Further, the second adhesive is selected from polyvinyls, styrenic polymer, butadiene type polymerization
At least one of object.
Further, the molecular weight of the second adhesive is 1000-1000000.
Further, the molecular weight of the second adhesive is 5000-300000.
Further, in the composite negative pole, the negative electrode active material is led with the solid electrolyte, described second
Electric material, the third adhesive mass ratio be 40-85:15-60:0-10:0-20.
Further, the negative electrode active material is the graphite of graphite or siliceous/Si oxide nano particle.
Further, the first solid sulfide electrolyte, the second solid sulfide electrolyte, the third are solid
State sulfide electrolyte is separately selected from LPS, LPSCl, LGPS, LSPS, LPSO and LPS or LPSCl or LGPS or LSPS
Or LPSO has at least one of the variant of Si, Ta, Hf, Sc dopant.
Further, first conductive material and second conductive material be separately selected from Super P,
At least one of VGCF, carbon nanotube, acetylene black, Ketjen black, conductive graphene.
Further, the third adhesive is selected from ethylene oxide quasi polymer, polyvinyls, styrene polymer
Close at least one of object, butadiene polymer.
Further, the molecular weight of the third adhesive is 1000-1000000.
Further, the molecular weight of the third adhesive is 5000-300000.
Further, the buffer layer with a thickness of 5-50 μm.
Further, the buffer layer includes polymer and third conductive material, and the polymer is selected from poly- methyl-prop
At least one of olefin(e) acid ethylene oxide, polysiloxanes, dimethyl silicone polymer, the third conductive material are selected from the second lithium
At least one of salt, nano ceramics oxide, nano ceramics sulfide.
Further, the mass ratio of the polymer and the third conductive material is 50-95:5-50.
Further, second lithium salts is selected from LiTFSI, LiFSI, LiN (SO2CF2CF3)2、LiCF3SO3、LiPF6、
LiClO4、LiBF4、LiPO2F2, at least one of LiBOB, LiODFB.
Further, the buffer layer less than 5v voltage under stablize, at -30-150 DEG C stablize, at room temperature from
Subconductivity rate is greater than 10-4S/cm。
Compared with the existing technology, solid state lithium battery of the present invention has the advantage that
Solid state lithium battery of the present invention has the solid electrolyte membrane of non-woven fabrics enhancing can by using non-woven fabrics
The mechanical strength and scalable rate of significant enhancing solid electrolyte membrane, while the solid electrolyte membrane that non-woven fabrics can be made to enhance is still
Ionic conductivity with higher, and large scale can be fabricated to；Simultaneous buffering layer can reduce interface internal resistance, and uniform current is close
The volume change that degree is electrode in charge and discharge process provides cushion space.By largely testing discovery, the nothing of the application
The solid state lithium battery mechanical strength with higher and thermal stability of woven fabric enhancing, while in the assembling and use process of battery
There is not positive and negative anodes short circuit, is prepared into power with very high, and in the use process of battery, dendrite through electrode
Phenomenon significantly reduces, and is well suited for large-scale industrial production, has significant commerciality.
Another object of the present invention is to propose a kind of vehicle, to solve the safety of existing vehicle and mileage is shorter asks
Topic.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of vehicle, the vehicle include above-mentioned solid state lithium battery.
Compared with the existing technology, vehicle of the present invention has the advantage that because the vehicle uses above-mentioned solid-state
There is the solid electrolyte membrane of non-woven fabrics enhancing can significantly enhance by using non-woven fabrics for lithium battery, the solid state lithium battery
The mechanical strength of state electrolyte and scalable rate, while the solid electrolyte membrane ion still with higher that non-woven fabrics can be made to enhance
Electric conductivity, and large scale can be fabricated to；Simultaneous buffering layer can reduce interface internal resistance, and uniform current density is electrode in charge and discharge
Volume change in electric process provides cushion space.By largely testing discovery, the solid-state lithium of the non-woven fabrics enhancing of the application
Battery mechanical strength with higher and thermal stability, at the same it is positive and negative extremely short without occurring in the assembling and use process of battery
The phenomenon that road is prepared into power with very high, and in the use process of battery, dendrite through electrode significantly reduces, very
It is suitble to large-scale industrial production, there is significant commerciality.Therefore, so that vehicle is because the possibility of safety problem occurs in battery
Property greatly reduce, meanwhile, because the solid state lithium battery can it is in large size production and have preferable ionic conductivity, can be effective
Extend the mileage of vehicle.
Another object of the present invention is a kind of method for proposing solid electrolyte membrane for preparing above-mentioned non-woven fabrics enhancing,
The solid electrolyte membrane of the non-woven fabrics enhancing is the solid electrolyte membrane of above-mentioned non-woven fabrics enhancing, to solve existing solid-state lithium electricity
The problem of mechanical strength of solid electrolyte membrane, elongation are too low in pond, cannot achieve large scale production.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
By the first solid sulfide electrolyte and first adhesive, the first solvent mixed grinding, to obtain mixed slurry；
Mixed slurry is stated and non-woven fabrics is applied to substrate surface for described, to form membrane layer in substrate surface, and
The membrane layer is scratched under atmosphere of inert gases, to obtain diaphragm；
By the vacuum dried rear progress hot rolling of the diaphragm, the solid electrolyte membrane of the non-woven fabrics enhancing is obtained.
Compared with the existing technology, the method for the solid electrolyte membrane of the present invention for preparing above-mentioned non-woven fabrics enhancing has
Following advantage: first adhesive is dissolved in the first solvent, is thus conducive to improve the first solid sulfide electrolyte and the first bonding
The mixed effect of agent and the first solvent.After dry and hot rolling, the first solvent volatilization, so that the solid electrolyte of non-woven fabrics enhancing
The first solid-state vulcanization electrolyte and first adhesive are uniformly distributed in film.First adhesive is conducive to improve consolidating for non-woven fabrics enhancing
The mechanical strength of state dielectric film and scalable rate, and make the first solid sulfide electrolyte distribution more uniform.Non-woven fabrics
It can further improve the mechanical strength and scalable rate of the solid electrolyte membrane of non-woven fabrics enhancing, while non-woven fabrics can be made to enhance
Solid electrolyte membrane ionic conductivity still with higher, and the solid electrolyte membrane that non-woven fabrics is enhanced can be fabricated to big ruler
It is very little.Entire simple process is easy to commercially produce.
Further, it is mixed by the first solid sulfide electrolyte and the first adhesive, first solvent
The first solid sulfide electrolyte is washed with the second solvent before closing grinding, and the first solid sulfide after washing is electric
It is dry under vacuum environment to solve matter.
Further, the first solid sulfide electrolyte and the first adhesive, first solvent are existed
Mixed grinding 0.5-1h under 100-300rpm.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the structural schematic diagram of the solid state lithium battery of one embodiment of the invention；
Fig. 2 is the method flow schematic diagram of the solid electrolyte membrane for preparing non-woven fabrics enhancing of one embodiment of the invention；
Fig. 3 is the method flow signal of the solid electrolyte membrane for preparing non-woven fabrics enhancing of further embodiment of the present invention
Figure；
Fig. 4 is the structural schematic diagram of single layer solid state lithium battery in the embodiment of the present invention 1；
Fig. 5 is state diagram after the solid electrolyte membrane mechanical strength test of non-woven fabrics enhancing in the embodiment of the present invention 1；
Fig. 6 is the SEM image of the solid electrolyte membrane of non-woven fabrics enhancing in the embodiment of the present invention 1；
Fig. 7 is the ionic conductivity of the solid electrolyte membrane of non-woven fabrics enhancing in the embodiment of the present invention 1；
Fig. 8 is to contain LiNbO in the embodiment of the present invention 13The SEM detection image of coating NCM811；
Fig. 9 is to contain LiNbO in the embodiment of the present invention 13The EDX detection image of coating NCM811；
Figure 10 is the structural schematic diagram of single layer solid state lithium battery in the embodiment of the present invention 2；
Figure 11 is the structural schematic diagram of two-layer solid-state lithium battery in the embodiment of the present invention 3；
Figure 12 is the structural schematic diagram of two-layer solid-state lithium battery in the embodiment of the present invention 4.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
In one aspect of the invention, the invention proposes a kind of solid state lithium batteries, according to an embodiment of the invention, with reference to
Fig. 1, the lithium battery include: solid electrolyte membrane 100, anode 200, cathode 300 and the buffer layer 400 of non-woven fabrics enhancing.
According to an embodiment of the invention, non-woven fabrics enhancing solid electrolyte membrane include: the first solid sulfide electrolyte,
Non-woven fabrics and first adhesive.Inventors have found that first adhesive is conducive to improve the solid electrolyte membrane of non-woven fabrics enhancing
Mechanical strength and scalable rate, and make the first solid sulfide electrolyte distribution more uniform.Non-woven fabrics can further improve
The mechanical strength and scalable rate of the solid electrolyte membrane of non-woven fabrics enhancing, while the solid electrolyte membrane that non-woven fabrics can be made to enhance
Ionic conductivity still with higher, and the solid electrolyte membrane that non-woven fabrics is enhanced can be fabricated to large scale.Entire technique
Simply, it is easy to commercially produce.
According to one embodiment of present invention, the tensile strength of the solid electrolyte membrane of non-woven fabrics enhancing is 100-
10000N/cm2, elongation 0-50%.The solid electrolyte membrane of the non-woven fabrics enhancing in the application is relative to existing solid as a result,
State dielectric film tensile strength with higher and elongation are conducive to the solid state electrolysis for being fabricated to large-sized non-woven fabrics enhancing
Plasma membrane improves the energy density of battery, commercially producing and using convenient for solid state lithium battery.
Still another embodiment in accordance with the present invention, in the solid electrolyte membrane of non-woven fabrics enhancing, the first solid sulfide
The mass ratio of electrolyte and non-woven fabrics, first adhesive can be 80-97:0.01-20:3-10.Inventors have found that non-woven fabrics and
The ionic conductivity decline that the too high levels of first binder will lead to solid electrolyte membrane is very big, and if non-woven fabrics or first viscous
The content of mixture is too low, cannot provide enough dielectric film intensity.
According to still another embodiment of the invention, the first solid sulfide electrolyte can selected from LPS, LPSCl, LGPS,
At least one of LSPS, LPSO.Wherein, LPS xLi2S·(1-x)P2S5, LPSCl Li6PS5Cl, LGPS are
Li10GeP2S12, LSPS Li10SnP2S12, LPSO 70Li2S·29P2S5·1P2O5.It should be noted that the first solid-state sulphur
Compound electrolyte can also be the change with dopants such as Si, Ta, Hf, Sc in LPS or LPSCl or LGPS or LSPS or LPSO
Body.
According to still another embodiment of the invention, non-woven fabrics be PP based nonwoven, PE based nonwoven, PET based nonwoven,
At least one of PAN based nonwoven, PTFE based nonwoven, Celgard non-woven fabrics.Inventors have found that the nonwoven of the above-mentioned type
Cloth has lower negative effect for the ionic conductivity of the first solid sulfide electrolyte, can improve the vulcanization of the first solid-state
While the mechanical strength of object electrolyte, tensile strength and elongation so that the first solid sulfide electrolyte still have it is higher
Ionic conductivity.
According to still another embodiment of the invention, the grammes per square metre of non-woven fabrics can be 1-10g/m2, porosity can be 50-
95%, thickness can be 10-50 μm, and tensile strength can be 200-4500N/cm2.Inventors have found that the surface density of non-woven fabrics
Too small, porosity is excessively high, and thickness is too small, then tensile strength can be too small；And surface density is excessive, porosity is too low, thickness is excessive then
Will lead to the first solid sulfide electrolyte can not permeate non-woven fabrics film forming.
According to still another embodiment of the invention, first adhesive can be ethylene oxide polymer, ethylenic polymer
At least one of object, vinylidene fluoride polymer, styrenic polymer, butadiene polymer.Inventors have found that above-mentioned
The first adhesive of type can improve the first solid sulfide electricity in the solid electrolyte membrane of non-woven fabrics enhancing to a certain extent
The distributing homogeneity of matter is solved, the ionic conductivity of the solid electrolyte membrane of non-woven fabrics enhancing is improved, while can further improve nothing
The mechanical strength of the solid electrolyte membrane of woven fabric enhancing.
According to still another embodiment of the invention, the molecular weight of first adhesive can be 100000-1000000.Invention
People's discovery, the too low then viscosity of the molecular weight of binder is poor, excessively high, is not easily dissolved in organic solvent.
It according to still another embodiment of the invention, can also include the first lithium salts in the solid electrolyte of non-woven fabrics enhancing,
First lithium salts can be for selected from LiTFSI, LiFSI, LiN (SO2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、
LiPO2F2, at least one of LiBOB, LiODFB.It should be noted that the first lithium salts need to be with the first solid sulfide electrolyte
With good compatibility.In the actual process, it can be selected by following method: the first lithium salts and the first solid-state are vulcanized
Simultaneously dry-pressing is in blocks for the mixing of object electrolyte, obtains sheet sulfide electrolyte containing lithium salt, measures under the pressure of 100-400MPa
The AC impedance and cyclic voltammetric impedance of the sheet sulfide electrolyte containing lithium salt, if sheet sulfide electrolyte containing lithium salt
AC impedance and cyclic voltammetric impedance and it is not added with the AC that the first solid sulfide electrolyte sheet of lithium salts is measured under similarity condition
The difference of impedance and cyclic voltammetric impedance is smaller, then shows that selected first lithium salts has with the first solid sulfide electrolyte
Good compatibility.The addition of first lithium salts helps to improve the ionic conductivity of the solid electrolyte membrane of non-woven fabrics enhancing.
According to an embodiment of the invention, anode 200 includes aluminium foil 210 and anode composite 220, anode composite includes: anode
Active material, nano-coating material, the second solid sulfide electrolyte, the first conductive material and second adhesive, nano coating
Material is coated on the surface of positive electrode active materials.Specifically, in solid state lithium battery, when battery is single layer battery, i.e. battery
When only including an anode and a cathode, only anode composite need to be coated in the side of aluminium foil；And when battery is bilayer or multilayer
When battery, i.e., when battery includes two or more anodes and two or more cathode, it can be coated in the two sides of aluminium foil compound
Anode, realizes sharing for aluminium foil, improves the energy density of battery, reduces cell body product, under same battery capacity convenient for business
Change application.For above-mentioned anode, following method can be used and prepared: nano-coating material is coated on positive electrode active materials table
Face obtains positive electrode active materials containing coating；By above-mentioned positive electrode active materials containing coating and the second solid sulfide electrolyte, second
Adhesive, the first conductive material, third solvent Wet blend-milling, obtain positive mixed slurry；Resulting positive mixed slurry is applied
Cloth is vacuum dried on aluminium foil, obtains positive plate；Above-mentioned positive plate is subjected to roll-in, obtains anode.The carbon-coating of aluminium foil used
Thickness is not more than 1 μm, and blocked up carbon-coating will affect the conductivity of anode.Temperature when roll-in can be 50-70 degrees Celsius, roll-in
Temperature is too low to be unfavorable for positive densification, excessively high to destroy the second binder.Further, coating positive electrode active materials will contained
It, can be first by when with the second solid sulfide electrolyte, second adhesive, the first conductive material, third solvent Wet blend-milling
Then it is living will to contain coating anode again for two solid sulfide electrolyte and second adhesive, third solvent Wet blend-milling long period
Property material and the first conductive material be added the Wet blend-milling short period.It so can avoid damage surface of positive electrode active material containing coating
Coating.Above-mentioned third solvent is organic solvent, and third solvent can dissolve second adhesive, while to the second solid sulfide
Electrolyte has lesser negative effect.It should be noted that concrete type those skilled in the art of third solvent can be
Selected in real process according to the second solid sulfide electrolyte and second adhesive, for example, can for ketone, amine,
At least one of esters, ethers, alkanes.Inventors have found that being thus conducive to mention because second adhesive is dissolved in third solvent
High second solid sulfide electrolyte and second adhesive, third solvent, positive electrode active materials containing coating, the first conductive agent it is mixed
Close effect.After drying, third solvent volatilizees, so that positive electrode active materials containing coating, the second solid sulfide in anode composite
Electrolyte, the first conductive agent and first adhesive are evenly distributed, and are conducive to the energy density for improving anode, improve the circulation of battery
Service life.Whole preparation process simple process simultaneously, it is easy to accomplish large scale production is easy to be commercialized.Inventors have found that receiving
Rice coating material has high dielectric constant, can prevent positive electrode active materials from reacting with the second solid sulfide electrolyte, no
It will limit the diffusion of lithium ion, qualitative response will not be electrolysed with the second solid sulfide.
According to one embodiment of present invention, in anode composite, positive electrode active materials and the second solid sulfide are electrolysed
Matter, the first conductive material, second adhesive mass ratio can be 50-95:10-45:0-10:0-20.It should be noted that just
Pole active material and the second solid sulfide electrolyte, the first conductive material, second adhesive specific proportion art technology
Personnel can select and optimize according to actual needs.
Still another embodiment in accordance with the present invention, positive electrode active materials can be lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxygen
Compound, LiFePO4, LiMn2O4, cobalt phosphate lithium, lithium nickel manganese oxide, cobalt acid lithium, LiTiS2、LiNiO2, elemental sulfur, sulphur carbon it is mixed
Close at least one of object.Specifically, positive electrode active materials can be elemental sulfur or sulphur carbon mix when containing lithium in cathode.
According to still another embodiment of the invention, nano-coating material can be Li3PO4, Al2O3, LiNbO3, LiAlO2,
Li3BO3, Li2O-ZrO2、MgO、HfO2, Li2SiO3、B2O3、Li2O、Nb2O5、P2O5、SiO2、Sc2O3、TiO2、ZrO2In at least
One of.
According to still another embodiment of the invention, the second solid sulfide electrolyte can for LPS, LPSCl, LGPS,
LSPS, LPSO and LPS or LPSCl or LGPS or LSPS or LPSO have in the variant of Si, Ta, Hf, Sc dopant at least it
One.
According to still another embodiment of the invention, the first conductive material can for selected from Super P, VGCF, carbon nanotube,
At least one of acetylene black, Ketjen black, conductive graphene.According to still another embodiment of the invention, second adhesive can be with
For at least one of polyvinyls, styrenic polymer, butadiene polymer.The molecular weight of second adhesive can
Think 1000-1000000, preferably 5000-300000.
According to an embodiment of the invention, cathode 300 includes collector 310 and negative electrode material 320, collector is copper foil or nickel
Foil, negative electrode material are lithium or indium or lithium-indium alloy or composite negative pole.Specifically, in solid state lithium battery, when battery is single layer electricity
When Chi Shi, i.e. battery only include an anode and a cathode, only composite negative pole need to be coated in the side of collector；And work as battery
It, i.e., can be in collector when battery includes two or more anodes and two or more cathode when for bilayer or multilayer battery
Two sides are coated with composite negative pole, realize sharing for collector, improve the energy density of battery, electricity is reduced under same battery capacity
Pond body product, is convenient for commercial applications.
According to one embodiment of present invention, when negative electrode material is composite negative pole, composite negative pole includes: negative electrode active material
Material, solid electrolyte, the second conductive material and third adhesive.For cathode, following method can be used and prepared: by cathode
Active material and solid electrolyte, the second conductive material, third adhesive, the 4th solvent mixed grinding, it is mixed to obtain cathode
Close slurry；On a current collector by the coating of cathode mixed slurry, negative electrode tab is obtained after vacuum drying；Negative electrode tab is subjected to roll-in, with
Just cathode is obtained.The temperature of roll-in can be 50-60 degrees Celsius.By negative electrode active material and solid electrolyte, second conductive
When material, third adhesive, the 4th solvent mixed grinding, first third adhesive can be dissolved in the 4th solvent, then again
Negative electrode active material and solid electrolyte, the second conductive material is added.Above-mentioned 4th solvent is organic solvent, and the 4th solvent can
Third adhesive is dissolved, while there is lesser negative effect to solid electrolyte.It should be noted that the 4th solvent is specific
Type those skilled in the art can select according to solid electrolyte and third adhesive in the actual process, for example, can
Think at least one of ketone, amine, esters, ethers, alkanes.Inventors have found that because to be dissolved in the 4th molten for third adhesive
Thus agent is conducive to improve negative electrode active material and solid electrolyte, the second conductive material, third adhesive and the 4th solvent
Mixed effect.After drying, the 4th solvent volatilizees, so that negative electrode active material is led with solid electrolyte, second in composite negative pole
Electric material and third adhesive distribution are uniform, are conducive to the energy density for improving cathode, improve the service life cycle of battery.Together
When whole preparation process simple process, it is easy to accomplish large scale production, be easy to be commercialized.
Still another embodiment in accordance with the present invention, in composite negative pole, negative electrode active material is led with solid electrolyte, second
Electric material, third adhesive mass ratio can be 40-85:15-60:0-10:0-20.
According to still another embodiment of the invention, negative electrode active material can be graphite or siliceous/Si oxide nanometer
The graphite of grain.Inventors have found that adding silicon/Si oxide nano particle in graphite can be improved the specific volume of negative electrode active material
It measures while it being made to keep relatively good cycle performance.
According to still another embodiment of the invention, solid electrolyte can be poly- for third solid sulfide electrolyte and solid-state
At least one of polymer electrolyte, wherein third solid sulfide electrolyte can for LPS, LPSCl, LGPS, LSPS,
LPSO and LPS or LPSCl or LGPS or LSPS or LPSO has at least one of the variant of Si, Ta, Hf, Sc dopant.Gu
State polymer dielectric can be at least one of PEO, PPC, PVDF.
According to still another embodiment of the invention, the second conductive material can be Super P, VGCF, carbon nanotube, acetylene
At least one of black, Ketjen black, conductive graphene.According to still another embodiment of the invention, third adhesive can be ring
At least one of oxidative ethane quasi polymer, polyvinyls, styrenic polymer, butadiene polymer.Third is viscous
The molecular weight of mixture is 1000-1000000, preferably 5000-300000.
According to an embodiment of the invention, buffer layer includes polymer and third conductive material, polymer can be for selected from poly-
At least one of methacrylic acid ethylene oxide, polysiloxanes, dimethyl silicone polymer, third conductive material can be for selected from the
At least one of dilithium salt, nano ceramics oxide, nano ceramics sulfide.Wherein, the second lithium salts and the first solid-state vulcanize
Object electrolyte and/or the second solid sulfide electrolyte and/or solid electrolyte are stablized.Buffer layer can be coated to anode composite
In upper and/or negative electrode material, to separate the solid electrolyte membrane of anode composite and/or negative electrode material and non-woven fabrics enhancing.In reality
In the cell assembling processes of border, the specific coating method of buffer layer is answered so that entire battery has lower interface impedance and is easy
Assembly is principle.Nano ceramics oxide can be LLZO (Li7La3Zr2O12)、LATP(Li1.4Al0.4Ti1.6(PO4)3), nanometer
Ceramic sulfide can be LGPS (Li10GeP2S12), LPSO etc., nano ceramics oxide and nano ceramics sulfide and polymer
Synergistic effect can significantly be turned up buffer layer ionic conductivity.Buffer layer can use dry or wet system as a tunic
At.Specifically, dry method are as follows: mix polymer and third conductive material, buffer layer mixed material is obtained, by resulting buffer layer
Mixed material carries out hot rolling, obtains buffer layer.Wherein it is possible to be clipped in inviscid by buffer layer mixed material and mixed with buffer layer
Hot rolling is carried out between the film of material anergy, hot rolling can carry out under conditions of 35-45 degrees Celsius.Wet process are as follows: by polymer
It is dissolved in the 5th solvent with third conductive material, to obtain buffer layer mixed slurry, resulting buffer layer mixed slurry is applied
It overlays on matrix, after vacuum dried, by under the buffering synusia blade coating in collective, obtains buffer layer.It should be noted that when negative
Mixed slurry, can directly be coated on cathode by extremely lithium or indium or when lithium indium alloy.Inventors have found that buffer layer can reduce
Interface internal resistance, the volume change that uniform current density is electrode in charge and discharge process provide cushion space.
According to one embodiment of present invention, in buffer layer, the mass ratio of polymer and third conductive material can be
95-50:5-50.Inventors have found that the mass ratio of polymer and third conductive material within the above range when may make buffer layer
With preferably ionic conductivity, thermal stability and mechanical performance.
Still another embodiment in accordance with the present invention, the thickness of buffer layer can be 5-50 μm.Inventors have found that buffer layer is too
The thin effect for not having buffering, the performances such as too thick multiplying power that will affect battery.
According to still another embodiment of the invention, the second lithium salts can be LiTFSI, LiFSI, LiN (SO2CF2CF3)2、
LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2, at least one of LiBOB, LiODFB.
According to still another embodiment of the invention, buffer layer is stablized under the voltage less than 5v, steady at -30-150 DEG C
Fixed, ionic conductivity at room temperature is greater than 10-4S/cm.Buffer layer i.e. in the application has high voltage withstanding, wider thermostabilization
Property and certain ionic conductivity, the chemical property and cycle performance of battery can be improved in buffer layer as a result,.
According to an embodiment of the invention, above-mentioned solid state lithium battery has the solid electrolyte membrane of non-woven fabrics enhancing, by adopting
It with non-woven fabrics, can significantly enhance the mechanical strength and scalable rate of solid electrolyte membrane, while consolidating for non-woven fabrics enhancing can be made
State dielectric film ionic conductivity still with higher, and large scale can be fabricated to；Simultaneous buffering layer can reduce interface internal resistance,
The volume change that uniform current density is electrode in charge and discharge process provides cushion space.By largely testing discovery, this
The solid state lithium battery mechanical strength with higher and thermal stability of the non-woven fabrics enhancing of application, while in the assembling of battery and making
With not occurring positive and negative anodes short circuit in the process, it is prepared into power with very high, and in the use process of battery, dendrite is worn
The phenomenon that transflective electrode, significantly reduces, and is well suited for large-scale industrial production, has significant commerciality.
In another aspect of the invention, the invention proposes a kind of vehicles, according to an embodiment of the invention, the vehicle packet
Containing above-mentioned enhancing solid state lithium battery.Inventors have found that solid state lithium battery has nonwoven because vehicle uses above-mentioned solid state lithium battery
The solid electrolyte membrane of cloth enhancing can significantly increase the mechanical strength of solid electrolyte membrane and scalable by using non-woven fabrics
Rate, while the solid electrolyte membrane ionic conductivity still with higher that non-woven fabrics can be made to enhance, and large scale can be fabricated to；Together
When buffer layer can reduce interface internal resistance, the volume change that uniform current density is electrode in charge and discharge process provides buffering
Space.By largely testing discovery, the solid state lithium battery mechanical strength with higher and heat of the non-woven fabrics enhancing of the application
Stability, while positive and negative anodes short circuit do not occur in the assembling and use process of battery, have it is very high be prepared into power, and
And in the use process of battery, the phenomenon that dendrite through electrode, is significantly reduced, and is well suited for large-scale industrial production, is had aobvious
The commerciality of work.Therefore, so that vehicle is because battery a possibility that safety problem occurs and greatly reduces, meanwhile, because this is solid
State lithium battery in large size can make and have preferable ionic conductivity, can effectively extend the mileage of vehicle.
In an additional aspect of the present invention, the invention proposes a kind of solid electrolyte membranes for preparing above-mentioned non-woven fabrics enhancing
Method, according to an embodiment of the invention, with reference to Fig. 2, this method comprises:
S100: by the first solid sulfide electrolyte and first adhesive, the first solvent mixed grinding
In the step, by the first solid sulfide electrolyte and first adhesive, the first solvent mixed grinding, to obtain
Mixed slurry.It further, can also include the first lithium salts in first binder.First adhesive dissolves in the first solvent,
And when containing the first lithium salts in first adhesive, the first lithium salts is also dissolved in the first solvent, and the first solvent is organic solvent,
And first solvent to the first solid sulfide electrolyte have lesser negative effect.It should be noted that the tool of the first solvent
Body type those skilled in the art can carry out according to the first solid sulfide electrolyte and first adhesive in the actual process
Selection, for example, can be at least one of ketone, amine, esters, ethers, alkanes.Table 1 lists four kind of first solid-state
Conductivity of the sulfide electrolyte through methyl phenyl ethers anisole under mild 80 degrees Celsius of length before and after the processing, as shown in Table 1, at normal temperature, benzene
The conductivity decline 1% of methyl ether treated LPSCl, the conductivity decline 24% of methyl phenyl ethers anisole treated LGPS, at methyl phenyl ethers anisole
The conductivity of LSPS after reason rises 15%, the conductivity decline 46% of methyl phenyl ethers anisole treated LPSO；At 80 degrees celsius, benzene
The conductivity decline 24% of methyl ether treated LPSCl, the conductivity of methyl phenyl ethers anisole treated LGPS rise 26%, at methyl phenyl ethers anisole
The conductivity decline 32% of LSPS after reason, the conductivity decline 81% of methyl phenyl ethers anisole treated LPSO.I.e. when the first solid-state sulphur
When compound electrolyte is LPSO, it is affected when using methyl phenyl ethers anisole as the first solvent to LPSO, is not suitable as LPSO's
Mating processing solvent uses.
Conductivity of the 1 four kind of first solid sulfide electrolyte of table through methyl phenyl ethers anisole under mild 80 degrees Celsius of length before and after the processing
Inventors have found that by by the first solid sulfide electrolyte and first adhesive, the first solvent mixed grinding,
Middle first adhesive is dissolved in the first solvent, is conducive to improve the first solid sulfide electrolyte and first adhesive and the first solvent
Mixed effect.So that the first solid sulfide electrolyte is uniformly distributed with first binder, the first solvent in mixed slurry, have
Conducive to the ionic conductivity for the solid electrolyte membrane for improving non-woven fabrics enhancing.First adhesive is conducive to improve non-woven fabrics enhancing
The mechanical strength of solid electrolyte membrane and scalable rate, and make the first solid sulfide electrolyte distribution more uniform.
According to one embodiment of present invention, the first solid sulfide electrolyte and first adhesive, the first solvent are existed
Mixed grinding 0.5-1h under 100-300rpm.It is mixed not inventors have found that mixed grinding revolving speed is too low with time too short will lead to
Uniformly；Grinding revolving speed is excessively high and overlong time will lead to material particles and be destroyed.
S200: mixed slurry and non-woven fabrics are applied to substrate surface
In the step, mixed slurry and non-woven fabrics are applied to substrate surface, to form membrane layer in substrate surface, and
Membrane layer is scratched under atmosphere of inert gases, to obtain diaphragm.Specifically, being applied to by mixed slurry and non-woven fabrics
When substrate surface, it is coated after can directly mixing non-woven fabrics with mixed slurry in substrate surface and/or is put down in mixed slurry
Spread layer of non-woven fabric.Inventors have found that non-woven fabrics can further improve the mechanical strength of the solid electrolyte membrane of non-woven fabrics enhancing
With scalable rate, while the solid electrolyte membrane ionic conductivity still with higher that non-woven fabrics can be made to enhance and makes nonwoven
The solid electrolyte membrane of cloth enhancing can be fabricated to large scale.
S300: by the vacuum dried rear progress hot rolling of diaphragm
In the step, by the vacuum dried rear progress hot rolling of diaphragm, the solid electrolyte membrane of non-woven fabrics enhancing is obtained.Hair
Bright people's discovery, after dry and hot rolling, the first solvent volatilization, so that the first solid-state sulphur in the solid electrolyte membrane of non-woven fabrics enhancing
Change electrolyte and first adhesive is uniformly distributed.After hot rolling, the solid electrolyte membrane structure of non-woven fabrics enhancing is finer and close, has
Conducive to the volume for the solid electrolyte membrane for reducing non-woven fabrics enhancing.
According to one embodiment of present invention, the temperature of hot rolling can be 60-80 DEG C, and the time can be 0.5-2 hours.
According to an embodiment of the invention, the method for preparing the solid electrolyte membrane of above-mentioned non-woven fabrics enhancing, because of the first bonding
Agent is dissolved in the first solvent, is thus conducive to the mixing for improving the first solid sulfide electrolyte and first adhesive and the first solvent
Effect.After dry and hot rolling, the first solvent volatilization, so that the first solid-state vulcanization electricity in the solid electrolyte membrane of non-woven fabrics enhancing
Solution matter and first adhesive are uniformly distributed.The machinery that first adhesive is conducive to improve the solid electrolyte membrane of non-woven fabrics enhancing is strong
Degree and scalable rate, and make the first solid sulfide electrolyte distribution more uniform.Non-woven fabrics can further improve non-woven fabrics
The mechanical strength of the solid electrolyte membrane of enhancing and scalable rate, while the solid electrolyte membrane that non-woven fabrics can be made to enhance still has
Higher ionic conductivity, and the solid electrolyte membrane that non-woven fabrics is enhanced can be fabricated to large scale.Entire simple process, easily
In commercially producing.
According to an embodiment of the invention, with reference to Fig. 3, by the first solid sulfide electrolyte and first adhesive, first
Can further comprise before solvent mixed grinding:
S400: the first solid sulfide electrolyte is washed with the second solvent, and by the first solid sulfide after washing
Electrolyte is dry under vacuum environment
In the step, the first solid sulfide electrolyte is washed with the second solvent, and by the first solid-state sulphur after washing
Compound electrolyte is dry under vacuum environment, thus can get that surface is clean and even-grained first solid sulfide electrolysis
Matter is conducive to the ionic conductivity for improving the solid electrolyte membrane of non-woven fabrics enhancing.Specifically, the second solvent is organic solvent,
And second solvent to the first solid sulfide electrolyte have lesser negative effect.It should be noted that the tool of the second solvent
Body type those skilled in the art can select according to the first solid sulfide electrolyte in the actual process, for example, can
Think at least one of ketone, amine, esters, ethers, alkanes.
It should be noted that the property and feature of the solid electrolyte membrane of above-mentioned non-woven fabrics enhancing are preparing non-woven fabrics enhancing
Solid electrolyte membrane in equally leave, details are not described herein.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
Embodiment 1
A kind of single layer solid state lithium battery, structural schematic diagram as shown in figure 4, successively include: that copper foil 310 is (thick from top to bottom
Degree is 8 μm), lithium titanate cathode material 320 (with a thickness of 50 μm), buffer layer 400 (with a thickness of 25 μm), the solid state electrolysis of non-woven fabrics enhancing
Plasma membrane 100 (with a thickness of 80 μm), anode composite 220 (with a thickness of 100 μm) and aluminium foil 210 (with a thickness of 6 μm).
Wherein:
Buffer layer includes polymethylacrylic acid ethylene oxide and LiTSFI, the quality of polymethylacrylic acid ethylene oxide and LITFSI
Than for 4:1.
The solid electrolyte membrane of non-woven fabrics enhancing includes LPSCl, PP based nonwoven (grammes per square metre 1g/m2, porosity is
95%, with a thickness of 10 μm, tensile strength 1000N/cm2) and polyethylene oxide (molecular weight 100000), LPSCl, PP base without
The mass ratio of woven fabric and polyethylene oxide be 95:2:3, the non-woven fabrics enhancing solid electrolyte membrane the preparation method comprises the following steps: first will
LPSCl and polyethylene oxide, CHO grind 0.5h at 100 rpm, obtain mixed slurry；Then by above-mentioned mixed slurry and PP base
Non-woven fabrics is applied to substrate surface, to form membrane layer in substrate surface, and scratches above-mentioned membrane layer under argon atmosphere,
Obtain diaphragm；Hot rolling is carried out after the diaphragm is dried in vacuo about 14 hours at 80 degrees celsius, obtains non-woven fabrics enhancing
The solid electrolyte membrane that the non-woven fabrics enhances is placed between 2 stainless steel pistons by solid electrolyte membrane through mechanical strength test
The high pressure for applying 200MPa still will not tear or perforate, and the solid electrolyte membrane of the non-woven fabrics enhancing after test is as shown in Figure 5.
The SEM image of the solid electrolyte membrane of non-woven fabrics enhancing is as shown in Figure 6.Its ionic conductivity is as shown in Figure 7.Non-woven fabrics enhancing
Solid electrolyte membrane tensile strength be 1000N/m2, elongation 20%.
Anode composite includes: LiNbO3NCM811, LPSCl, SP+VGCF and PVDF1&B2 of cladding, LiNbO3Cladding
The mass ratio of NCM811 and LPSCl, SP+VGCF and PVDF1&B2 are 60:32:3:5.LiNbO3The NCM811 of cladding is carried out respectively
SEM detection and EDX detection, as a result as follows: its SEM image is as shown in figure 8, by Fig. 8 (a-c) it is found that LiNbO3Cladding
The average particle size particle size of NCM811 is 14 μm, by Fig. 8 (d) it is found that in LiNbO3On the NCM811 particle of cladding, LiNbO3Coating
Thickness be less than 10nm.Its EDX map, can be further by Fig. 9 and table 2 as shown in figure 9, specific element data is as shown in table 2
Prove that NCM811 particle surface has LiNbO3Coating.
2 LiNbO of table3The EDX of the NCM811 particle of coating analyzes data
| Element | Linear-type | Key parameter | Absorption/corrigendum | Mass fraction % | ∑ (%) |
| O | K | 2.028 | 1.00 | 40.77 | 0.13 |
| Mn | K | 1.144 | 1.00 | 6.76 | 0.05 |
| Co | K | 1.175 | 1.00 | 6.12 | 0.05 |
| Ni | K | 1.151 | 1.00 | 43.67 | 0.12 |
| Nb | L | 1.799 | 1.00 | 2.68 | 0.08 |
By by cathode, buffer layer, the solid electrolyte membrane of non-woven fabrics enhancing, the positive roll-in at 60 degrees Celsius, 5MPa
Molding, obtains single layer solid state lithium battery, during roll-in, the high-molecular compound in each substance serves as binder, makes to bear
The side of lithium titanate cathode material layer and buffer layer in extremely bonds, the solid electrolyte membrane of the other side of buffer layer and non-woven fabrics enhancing
Side bonding, non-woven fabrics enhancing solid electrolyte membrane the other side and anode in anode composite bond.The single layer solid-state
There is not positive and negative anodes short circuit in assembling and use process in lithium battery, is prepared into power with very high, and in battery
In use process, the phenomenon that dendrite through electrode, is significantly reduced, and is well suited for large-scale industrial production, has significant business
Property.
Embodiment 2
A kind of single layer solid state lithium battery, structural schematic diagram is as shown in Figure 10, from top to bottom successively includes: that copper foil 310 is (thick
Degree is 8 μm), composite negative pole 320 (with a thickness of 120), buffer layer 400 (with a thickness of 35 μm), the solid electrolyte of non-woven fabrics enhancing
Film 100 (with a thickness of 100), anode composite 220 (with a thickness of 80) and aluminium foil 210 are with a thickness of 6 μm.Wherein:
Composite negative pole includes: graphite, LGPS, SP and PEO, and the mass ratio of graphite and LGPS, SP and PEO are 70:25:3:2.
Buffer layer includes polysiloxanes and LiBOB, and the mass ratio of polysiloxanes and LiBOB are 75:25.
The solid electrolyte membrane of non-woven fabrics enhancing includes LGPS, PE based nonwoven (grammes per square metre 3g/m2, porosity 80%,
With a thickness of 20 μm, tensile strength 1000N/cm2) and polyethylene oxide (molecular weight 600000), LGPS, PE based nonwoven and
The mass ratio of polyethylene oxide is 90:5:5, the solid electrolyte membrane of non-woven fabrics enhancing the preparation method comprises the following steps: first by LGPS and
Polyethylene oxide, CHO grind 0.6h at 200 rpm, obtain mixed slurry；Then by above-mentioned mixed slurry and PE based nonwoven
Be applied to substrate surface, to form membrane layer in substrate surface, and scratch above-mentioned membrane layer under argon atmosphere, obtain every
Diaphragm；Hot rolling is carried out after the diaphragm is dried in vacuo about 14 hours under 75 degrees Celsius, obtains the solid-state electricity of non-woven fabrics enhancing
Solve plasma membrane.
Anode composite includes: SiO2NCM622, LGPS, SP+CNT and PVDF2 of cladding, SiO2The NCM622 of cladding,
The mass ratio of LGPS, SP+CNT and PVDF2 are 82:15:1:2.
By by cathode, buffer layer, the solid electrolyte membrane of non-woven fabrics enhancing, the positive roll-in at 70 degrees Celsius, 5MPa
Molding, obtains single layer solid state lithium battery, during roll-in, the high-molecular compound in each substance serves as binder, makes to bear
The side of composite negative pole and buffer layer in extremely bonds, and the one of the solid electrolyte membrane of the other side of buffer layer and non-woven fabrics enhancing
Side bonding, the other side and the anode composite in anode of the solid electrolyte membrane of non-woven fabrics enhancing bond.The single layer solid-state lithium electricity
There is not positive and negative anodes short circuit in assembling and use process in pond, is prepared into power with very high, and in the use of battery
In the process, the phenomenon that dendrite through electrode, significantly reduces, and is well suited for large-scale industrial production, has significant commerciality.
Embodiment 3
A kind of bilayer cells of shared copper foil, structural schematic diagram is as shown in figure 11, from top to bottom successively includes: aluminium foil
The solid-state that 210 (with a thickness of 8 μm), anode composite 220 (with a thickness of 90 μm), buffer layer 400 (with a thickness of 45 μm), non-woven fabrics enhance
Dielectric film 100 (with a thickness of 75 μm), indium negative electrode material 320 (with a thickness of 50 μm), copper foil 310 (with a thickness of 6 μm), indium cathode material
Expect 320 (with a thickness of 50 μm), the solid electrolyte membrane 100 (with a thickness of 75 μm) of non-woven fabrics enhancing, buffer layer 400 (with a thickness of 45 μ
M), anode composite 220 (with a thickness of 90 μm), aluminium foil 210 (with a thickness of 8 μm).
Anode composite includes: Li3PO4The LiNiO of cladding2, LSPS, Ketjen black+conductive graphene and PVDF3, Li3PO4Packet
The LiNiO covered2, LSPS, Ketjen black+conductive graphene and PVDF3 mass ratio be 65:30:3:2.
Buffer layer includes polysiloxanes and LiPF6, polysiloxanes with and LiPF6Mass ratio be 80:20.
The solid electrolyte membrane of non-woven fabrics enhancing includes LSPS, PET based nonwoven (grammes per square metre 6g/m2, porosity is
90%, with a thickness of 35 μm, tensile strength 2500N/cm2) and polyethylene oxide (molecular weight 800000), LSPS, PET base without
The mass ratio of woven fabric and polyethylene oxide be 92:5:3, the non-woven fabrics enhancing solid electrolyte membrane the preparation method comprises the following steps: first will
LSPS and polyethylene oxide, cyclohexanone grind 1h at 300 rpm, obtain mixed slurry；Then by above-mentioned mixed slurry and PET
Based nonwoven is applied to substrate surface, to form membrane layer in substrate surface, and scrapes above-mentioned membrane layer under argon atmosphere
It applies, obtains diaphragm；Hot rolling is carried out after the diaphragm is dried in vacuo about 13 hours at 80 degrees celsius, obtains non-woven fabrics enhancing
Solid electrolyte membrane.
The two sides of copper foil are indium negative electrode materials.
By anode, buffer layer, non-woven fabrics enhancing solid electrolyte membrane, cathode, non-woven fabrics enhancing solid electrolyte membrane,
Buffer layer, anode roll-forming at 80 degrees Celsius, 5MPa obtain two-layer solid-state lithium battery, in roll-in by sharing copper foil
In the process, the high-molecular compound in each substance serves as binder, bonds the side of the anode composite and buffer layer in anode,
The side of the solid electrolyte membrane of the other side of buffer layer and non-woven fabrics enhancing bonds, the solid electrolyte membrane of non-woven fabrics enhancing
Composite negative pole in the other side and cathode bonds.The bilayer cells for sharing copper foil occur just in assembling with no in use process
The phenomenon that cathode short circuit is prepared into power with very high, and in the use process of battery, dendrite through electrode is significantly dropped
It is low, it is well suited for large-scale industrial production, there is significant commerciality.
Embodiment 4
A kind of bilayer cells of shared aluminium foil, structural schematic diagram is as shown in figure 12, from top to bottom successively includes: copper foil
310 (with a thickness of 5 μm), lithium indium alloy negative electrode material 320 (with a thickness of 40 μm), the solid electrolyte membrane 100 of non-woven fabrics enhancing are (thick
Degree is 60 μm), it is buffer layer 400 (with a thickness of 30 μm), anode composite 220 (with a thickness of 90 μm), aluminium foil 210 (with a thickness of 6 μm), multiple
Close the 100 (thickness of solid electrolyte membrane that positive 220 (with a thickness of 100 μm), buffer layer 400 (with a thickness of 40 μm), non-woven fabrics enhance
Be 70 μm), lithium indium alloy negative electrode material 320 (with a thickness of 40 μm), copper foil 310 (with a thickness of 10 μm).
The two sides of copper foil are lithium indium negative electrode materials.
The solid electrolyte membrane of non-woven fabrics enhancing includes LPSO, PTFE based nonwoven (grammes per square metre 10g/m2, porosity is
95%, with a thickness of 50 μm, tensile strength 4500N/cm2) and polyethylene oxide (900000), LPSO, PTFE based nonwoven and
The mass ratio of polyethylene oxide is 94:3:3, the solid electrolyte membrane of non-woven fabrics enhancing the preparation method comprises the following steps: first by LPSO and
Polyethylene oxide, hexamethylene grind 0.8h at 250rpm, obtain mixed slurry；Then by above-mentioned mixed slurry and PTFE base without
Woven fabric is applied to substrate surface, to form membrane layer in substrate surface, and scratches above-mentioned membrane layer under argon atmosphere, obtains
To diaphragm；Hot rolling is carried out after the diaphragm is dried in vacuo about 14 hours at 80 degrees celsius, obtains consolidating for non-woven fabrics enhancing
State dielectric film.
Buffer layer includes dimethyl silicone polymer and LiPF6, dimethyl silicone polymer and LiPF6Mass ratio be 5:1.
Anode composite includes: carbon coating elemental sulfur, LPSO, carbon black and PVDF4, carbon coating elemental sulfur, LPSO, carbon black and
The mass ratio of PVDF4 is 50:45:2.5:2.5.
Cathode, the solid electrolyte membrane of non-woven fabrics enhancing, buffer layer, anode, buffer layer, the solid-state of non-woven fabrics enhancing is electric
Plasma membrane, cathode roll-forming at 80 degrees Celsius, 5MPa are solved, by sharing aluminium foil, two-layer solid-state lithium battery is obtained, in roll-in
In the process, the high-molecular compound in each substance serves as binder, increases lithium indium alloy negative electrode material and non-woven fabrics in cathode
The side of strong solid electrolyte membrane bonds, and the other side of the solid electrolyte membrane of non-woven fabrics enhancing and the side of buffer layer are viscous
Knot, the other side and the anode composite in anode of buffer layer bond.This shares the bilayer cells of aluminium foil in assembling and use process
In there is not positive and negative anodes short circuit, have it is very high be prepared into power, and in the use process of battery, dendrite through electrode
The phenomenon that significantly reduce, be well suited for large-scale industrial production, there is significant commerciality.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
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