CN113451580A - Interface layer and lithium ion battery comprising same - Google Patents
Interface layer and lithium ion battery comprising same Download PDFInfo
- Publication number
- CN113451580A CN113451580A CN202110741435.1A CN202110741435A CN113451580A CN 113451580 A CN113451580 A CN 113451580A CN 202110741435 A CN202110741435 A CN 202110741435A CN 113451580 A CN113451580 A CN 113451580A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid electrolyte
- metal
- negative electrode
- interface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 144
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 132
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- -1 Lithium halide Chemical class 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002923 metal particle Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims description 15
- 229910001507 metal halide Inorganic materials 0.000 claims description 12
- 150000005309 metal halides Chemical class 0.000 claims description 12
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 11
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- 229940096017 silver fluoride Drugs 0.000 claims description 7
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RMSOEGBYNWXXBG-UHFFFAOYSA-N 1-chloronaphthalen-2-ol Chemical compound C1=CC=CC2=C(Cl)C(O)=CC=C21 RMSOEGBYNWXXBG-UHFFFAOYSA-N 0.000 claims description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 239000002203 sulfidic glass Substances 0.000 claims description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 2
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 claims description 2
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 43
- 239000000243 solution Substances 0.000 description 35
- 239000000843 powder Substances 0.000 description 28
- 238000002156 mixing Methods 0.000 description 23
- 239000013543 active substance Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 18
- 238000003825 pressing Methods 0.000 description 18
- 238000005245 sintering Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000005096 rolling process Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 229910009515 Li1.5Al0.5Ti1.5(PO4)3 Inorganic materials 0.000 description 7
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 239000012456 homogeneous solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000003618 dip coating Methods 0.000 description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000003273 ketjen black Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910011244 Li3xLa2/3-xTiO3 Inorganic materials 0.000 description 3
- 229910011245 Li3xLa2/3−xTiO3 Inorganic materials 0.000 description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000002227 LISICON Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910012742 LiNi0.5Co0.3Mn0.2O2 Inorganic materials 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910006243 Li1+xGe2-xAlx(PO4)3 Inorganic materials 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910009225 Li2S—P2S5—GeS2 Inorganic materials 0.000 description 1
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910011671 Li4-xGe1-xPxS4 Inorganic materials 0.000 description 1
- 229910011572 Li4−xGe1−xPxS4 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 description 1
- 229910006180 NixCoyAl1-x-yO2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-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
- NKLLZZNEDKQOOB-UHFFFAOYSA-N [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] Chemical compound [O-2].[Mg+2].[Ti+4].[Ni+2].[Li+] NKLLZZNEDKQOOB-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to an interface layer and a lithium ion battery comprising the same. Lithium halide generated by in-situ reaction at the interface of the solid electrolyte and the metallic lithium negative electrode in the invention can optimize interface contact and interface wettability and provide a rapid ion diffusion path. The metal particles generated by the in-situ reaction at the interface of the solid electrolyte and the lithium metal cathode can guide the electric field to be uniformly distributed, regulate and control the uniform deposition of the lithium metal in the circulation process, and inhibit the formation and growth of lithium dendrites. The lithium ion battery can effectively stabilize the interface between the electrode and the electrolyte, reduce the chemical reaction activity of the metal lithium cathode, and avoid the occurrence of side reactions at the interface, and the lithium ion battery shows higher cycle stability and coulombic efficiency in continuous charge-discharge cycles.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an interface layer between a solid electrolyte and a metal lithium negative electrode and a lithium ion battery comprising the interface layer.
Background
The lithium ion battery has a plurality of excellent performances of small volume, light weight, high specific energy, no pollution, small self-discharge, long service life and the like, so the lithium ion battery is rapidly developed in the fields of notebooks, mobile phones, digital products and the like. Nowadays, a lithium ion battery with high energy density and high power is becoming a core technology applied to the field of new energy automobiles, but has higher requirements on the structure and performance of the lithium ion battery, and the anode and cathode materials in the lithium ion battery face new challenges.
At present, the lithium ion battery taking graphite as a negative electrode is difficult to meet the requirement of increasing specific energy, so that the metal lithium negative electrode with the advantage of high specific capacity enters the field of researchers. The specific capacity of the metallic lithium is 3860mAh/g, the electrochemical potential is-3.04V (vs standard hydrogen electrode), and the lithium ion battery cathode material is very ideal. However, lithium metal as a negative electrode still has problems in many aspects such as safety, volume change, rate, cyclability, cost, etc. that are still far from commercial application.
In the 80's last century, lithium metal cathodes produced by Moli company were commercialized for the first time, but safety accidents occurred soon after, and the company carried out failure analysis on batteries and found that lithium dendrites could pierce through a separator to cause short circuit, and thermal runaway behavior of the batteries occurred. However, the safety of the lithium metal is not only reflected in the internal short circuit caused by lithium dendrite, but also in the gas and heat generated by the continuous side reaction of the lithium powder or 'dead lithium' generated after multiple cycles and the electrolyte. Therefore, in order to use metallic lithium as a negative electrode material of a lithium ion battery, it is necessary to solve both problems of lithium dendrite growth and interface stability. The first difficulty, due to the uneven deposition of metallic lithium during battery cycling, is that metallic lithium continues to grow at the tip in the form of lithium dendrites,eventually, the solid electrolyte membrane (SEI film) is easily punctured; the second challenge, whether commercialized today as LiPF6The stability of the interface between the electrolyte, gel electrolyte or future solid electrolyte with wide prospect and metal lithium is relatively poor, and the battery is easy to lose efficacy in the circulation process due to side reaction at the interface. Also, for a solid-state battery, since the interface between the electrolyte and the electrode is a solid-solid contact interface, the contact wettability is poor, lithium dendrites more easily start to grow from the interface, penetrating the electrolyte to reach the positive electrode to form a short circuit. Therefore, it is necessary to develop an interfacial layer capable of suppressing the growth of lithium dendrites and facilitating stable deposition.
Disclosure of Invention
In order to solve the problems of lithium dendrite growth between the conventional solid electrolyte and a metal lithium negative electrode and the like, the invention provides an interface layer between the solid electrolyte and the metal lithium negative electrode and a lithium ion battery comprising the interface layer.
In order to achieve the purpose, the invention adopts the technical scheme that:
an interfacial layer comprising a lithium halide and metal particles.
According to an embodiment of the present invention, the molar ratio of the lithium halide to the metal particles is n:1, where n is the valence state of the metal, illustratively the molar ratio of the lithium halide to the metal particles is 1:1, 2:1, or 3: 1. That is, when the metal is a 1-valent metal, the molar ratio of the lithium halide to the metal particles is 1: 1; when the metal is a 2-valent metal, the molar ratio of the lithium halide to the metal particles is 2: 1; when the metal is a 3-valent metal, the molar ratio of the lithium halide to the metal particles is 3: 1.
According to an embodiment of the invention, the lithium halide and the metal particles are obtained by reacting raw materials comprising lithium metal and a metal halide. Wherein the lithium metal is derived from a lithium metal negative electrode.
According to an embodiment of the invention, the interface layer is arranged between the solid-state electrolyte and the metallic lithium negative electrode.
According to an embodiment of the present invention, the metal halide is selected from at least one of copper fluoride, copper chloride, copper bromide, copper iodide, silver fluoride, silver chloride, silver bromide, silver iodide, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, iron fluoride, iron chloride, iron bromide, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, indium fluoride, indium chloride, indium bromide, indium iodide, aluminum fluoride, aluminum chloride, aluminum bromide, and aluminum iodide.
According to an embodiment of the present invention, the lithium halide is selected from at least one of lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
According to an embodiment of the present invention, the metal particles are selected from at least one of Cu, Ag, Ni, Fe, Zn, In, Al.
According to an embodiment of the present invention, the interface layer is a mixture layer including lithium halide and metal particles generated after a metal halide reacts with metal lithium. Specifically, a metal halide reacts with lithium metal at the interface of the solid electrolyte and the lithium metal negative electrode to generate lithium halide and metal particles; lithium halide generated by in-situ reaction at the interface can increase interface contact and can provide a rapid ion diffusion path, compared to directly coating a mixed layer including lithium halide and metal particles; metal particles generated by in-situ reaction at the interface can guide an electric field to be uniformly distributed and regulate and control the uniform deposition of metal lithium; in addition, the thickness of the interface layer generated in situ is controllable, and the problems of difficulty increase of shuttling and deposition of lithium ions and the like are avoided.
According to an embodiment of the invention, the thickness of the interface layer is 10nm to 10 μm, for example 10nm, 20nm, 30nm, 50nm, 60nm, 80nm, 90nm, 100nm, 120nm, 150nm, 180nm, 200nm, 250nm, 300nm, 320nm, 350nm, 380nm, 400nm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
The invention also provides a lithium ion battery, which comprises a negative electrode, a solid electrolyte and the interface layer, wherein the interface layer is positioned between the negative electrode and the solid electrolyte, and the negative electrode is a lithium metal negative electrode.
According to an embodiment of the invention, the lithium ion battery further comprises a positive electrode, wherein the solid state electrolyte is located between the positive electrode and the negative electrode, the interface layer is located between the negative electrode and the solid state electrolyte, and the negative electrode is a lithium metal negative electrode.
According to an embodiment of the present invention, the solid electrolyte is selected from inorganic solid electrolytes, which may be oxide solid electrolytes or sulfide solid electrolytes.
According to an embodiment of the present invention, the oxide solid electrolyte is selected from one or more of a perovskite type electrolyte, an anti-perovskite type electrolyte, a Garnet (Garnet) type electrolyte, a NASICON type electrolyte and a LISICON type electrolyte.
Wherein the perovskite electrolyte is Li3xLa2/3-xTiO3Wherein, 0.04<x<0.17。
Wherein the anti-perovskite electrolyte is Li3-n(OHn) Cl (n is more than or equal to 0.83 and less than or equal to 2) and Li3-n(OHn) One or two of Br (n is more than or equal to 1 and less than or equal to 2).
Wherein the garnet-type electrolyte is selected from doped or undoped lithium lanthanum zirconium oxide electrolyte, wherein the doped element is selected from at least one of Al, Ga, Fe, Ge, Ca, Ba, Sr, Y, Nb, Ta, W and Sb; preferably, the garnet-type electrolyte is selected from Li7-nLa3Zr2-nTanO12(0≤n≤0.6)、Li7-nLa3Zr2-nNbnO12(n is 0. ltoreq. n.ltoreq.0.6) and Li6.4- xLa3Zr2-xTaxAl0.2O12(0.2. ltoreq. x. ltoreq.0.5).
Wherein the NASICON type electrolyte is selected from Li1+xTi2-xMx(PO4)3、Li1+xGe2-xMx(PO4)3(M ═ Al, Cr, Ga, Fe, Sc, In, Lu, Y, La), and more preferably Li1+xTi2-xAlx(PO4)3(LATP) where x is 0.2. ltoreq. x.ltoreq.0.5, or Li1+ xGe2-xAlx(PO4)3(LAGP), wherein x is more than or equal to 0.4 and less than or equal to 0.5.
Wherein the LISICON type electrolyte is Li4-xGe1-xPxS4(x ═ 0.4 or 0.6).
According to an embodiment of the invention, the sulfide solid state electrolyte is selected from Li2S-SiS2、Li2S-P2S5、Li2S-P2S5-GeS2、Li7P3S11、Li6PS5One or more of X (X ═ Cl, Br, I).
According to an embodiment of the present invention, the positive electrode includes a positive electrode current collector and a positive electrode active material layer coated on one or both surfaces of the positive electrode current collector.
According to an embodiment of the present invention, the positive electrode active material layer includes a positive electrode active material, a conductive agent, and a binder.
Wherein the positive electrode active material is selected from lithium iron phosphate (LiFePO)4) Lithium cobaltate (LiCoO)2) Lithium nickel cobalt manganese oxide (Li)zNixCoyMn1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，x+y<1) Lithium manganate (LiMnO)2) Lithium nickel cobalt aluminate (Li)zNixCoyAl1-x-yO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，0.8≤x+y<1) Lithium nickel cobalt manganese aluminate (Li)zNixCoyMnwAl1-x-y-wO2Wherein z is more than or equal to 0.95 and less than or equal to 1.05, x>0，y>0，w>0，0.8≤x+y+w<1) Nickel cobalt aluminum tungsten material, lithium-rich manganese-based solid solution positive electrode material, lithium nickel cobalt oxide (LiNi)xCoyO2Wherein x is>0，y>0, x + y ═ 1), lithium nickel titanium magnesium oxide (LiNi)xTiyMgzO2Wherein x is>0，y>0，z>0, x + y + z ═ 1), lithium nickelate (Li)2NiO2) Spinel lithium manganate (LiMn)2O4) And one or more of nickel, cobalt and tungsten.
The conductive agent is selected from one or more of conductive carbon black (SP), Ketjen black, acetylene black, Carbon Nanotubes (CNT), graphene and flake graphite.
Wherein the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene.
According to an embodiment of the present invention, the positive electrode active material layer further includes a solid electrolyte, the solid electrolyte being defined as described above.
According to an embodiment of the present invention, the lithium ion battery may be a button battery, a mold battery, or a pouch battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) lithium halide generated by in-situ reaction at the interface of the solid electrolyte and the metallic lithium negative electrode in the invention can optimize interface contact and interface wettability and provide a rapid ion diffusion path.
(2) The metal particles generated by the in-situ reaction at the interface of the solid electrolyte and the lithium metal cathode can guide the electric field to be uniformly distributed, regulate and control the uniform deposition of the lithium metal in the circulation process, and inhibit the formation and growth of lithium dendrites.
(3) The lithium ion battery can effectively stabilize the interface between the electrode and the electrolyte, reduce the chemical reaction activity of the metal lithium cathode, and avoid the occurrence of side reactions at the interface, and the lithium ion battery shows higher cycle stability and coulombic efficiency in continuous charge-discharge cycles.
Drawings
FIG. 1 is a schematic diagram of the structure of a lithium metal negative electrode containing a Cu current collector according to the present invention, wherein (r) is a solid electrolyte; interface layer; ③ is the anode; and the fourth is a metallic lithium negative electrode.
Fig. 2 is an ac impedance spectrum of the all-solid batteries of example 2 and comparative example 2.
FIG. 3 is a cycle stability test of the Li/SE/Li lithium symmetric cell of example 3.
Detailed Description
< first method for producing interface layer >
As mentioned above, the present invention provides an interfacial layer, and also provides a method for preparing the interfacial layer, the method comprising the steps of:
1) dissolving metal halide in a solvent to prepare a precursor solution;
2) coating the precursor solution on one side surface of the solid electrolyte, and performing vacuum drying;
3) and attaching a metal lithium negative electrode to one side surface of the solid electrolyte coated with the precursor solution, and reacting to prepare the interface layer.
According to an embodiment of the present invention, in step 1), the solvent is at least one selected from the group consisting of deionized water, methanol, ethanol, diethyl ether, acetone, ammonia, hydrofluoric acid, tetrahydrofuran, dimethyl sulfoxide, chloroform, benzene, toluene, and xylene.
According to an embodiment of the invention, in step 1), the metal halide is as defined above.
According to the embodiment of the invention, in the step 1), the mass fraction of the precursor liquid is 1-20 wt%.
According to an embodiment of the present invention, in step 1), it is preferable to perform a stirring process during the preparation of the precursor solution, wherein the stirring speed is 100 to 1000rpm, and the stirring time is 1 to 24 hours.
According to an embodiment of the present invention, in step 2), the solid electrolyte is prepared by:
a) drying to remove trace moisture in the solid electrolyte powder;
b) and cold-pressing the solid electrolyte powder into a sheet, sintering, and cooling for later use.
Further, in the step b), the pressure of cold pressing for sheeting is 1-10 MPa.
Further, in the step b), the sintering temperature is 200-1300 ℃.
Further, in the step b), the sintering time is 3-24 hours.
Further, in step b), the cooling method of the sintered solid electrolyte may be air cooling or furnace cooling.
According to an embodiment of the present invention, in step 2), the solid electrolyte may be a sintered solid electrolyte sheet directly purchased commercially.
According to an embodiment of the present invention, in step 2), the coating may be knife coating, spin coating, or dip coating.
According to an embodiment of the invention, in the step 2), the temperature of the vacuum drying is 20-180 ℃;
according to the embodiment of the invention, in the step 2), the vacuum drying time is 1-48 h.
According to an embodiment of the present invention, step 3) specifically includes the following steps:
attaching a metallic lithium negative electrode to one side surface of the solid electrolyte coated with the precursor solution, and performing physical rolling to prepare the interface layer, or,
and heating the metallic lithium to 180-250 ℃ to enable the metallic lithium to be molten, coating the molten metallic lithium on the surface of one side of the solid electrolyte coated with the precursor solution, and reacting to obtain the interface layer.
The physical rolling means that the metallic lithium negative electrode is tightly attached to the surface of the electrolyte by pressure in a flat pressing or rolling mode, and in the physical rolling process, the precursor solution reacts with the metallic lithium to prepare the interface layer.
Wherein the precursor solution reacts with molten lithium metal to prepare the interface layer.
According to an embodiment of the present invention, an interfacial layer is formed between the solid state electrolyte and the metallic lithium negative electrode.
< second method for producing interface layer >
As mentioned above, the present invention provides an interfacial layer, and also provides a method for preparing the interfacial layer, the method comprising the steps of:
i) coating metal halide on one side surface of the solid electrolyte by adopting a physical vapor deposition technology;
ii) attaching a metallic lithium negative electrode to one side surface of the solid electrolyte coated with the precursor solution, and reacting to prepare the interface layer.
According to an embodiment of the present invention, in step i), the physical vapor deposition technique may be at least one of vacuum evaporation, sputter coating, and ion coating.
According to an embodiment of the present invention, step ii) specifically includes the following steps:
attaching a metallic lithium negative electrode to one side surface of the solid electrolyte coated with the precursor solution, and performing physical rolling to prepare the interface layer, or,
and heating the metallic lithium to 180-250 ℃ to enable the metallic lithium to be molten, coating the molten metallic lithium on the surface of one side of the solid electrolyte coated with the precursor solution, and reacting to obtain the interface layer.
The physical rolling means that the metallic lithium negative electrode is tightly attached to the surface of the electrolyte by pressure in a flat pressing or rolling mode, and in the physical rolling process, the precursor solution reacts with the metallic lithium to prepare the interface layer.
Wherein the precursor solution reacts with molten lithium metal to prepare the interface layer.
According to an embodiment of the present invention, an interfacial layer is formed between the solid state electrolyte and the metallic lithium negative electrode.
< first production method of lithium ion Battery >
As mentioned above, the present invention provides a lithium ion battery, and herein also provides a method for preparing the above lithium ion battery, the method comprising the steps of:
1) dissolving metal halide in a solvent to prepare a precursor solution;
2) coating the precursor solution on one side surface of the solid electrolyte, and performing vacuum drying;
3) assembling the metallic lithium negative electrode, the positive electrode and the solid electrolyte in the step 2) into a lithium ion battery, wherein the metallic lithium negative electrode is attached to one side surface of the solid electrolyte coated with the precursor liquid.
According to an embodiment of the present invention, in step 1), the solvent is at least one selected from the group consisting of deionized water, methanol, ethanol, diethyl ether, acetone, ammonia, hydrofluoric acid, tetrahydrofuran, dimethyl sulfoxide, chloroform, benzene, toluene, and xylene.
According to an embodiment of the invention, in step 1), the metal halide is as defined above.
According to the embodiment of the invention, in the step 1), the mass fraction of the precursor liquid is 1-20 wt%.
According to an embodiment of the present invention, in step 1), it is preferable to perform a stirring process during the preparation of the precursor solution, wherein the stirring speed is 100 to 1000rpm, and the stirring time is 1 to 24 hours.
According to an embodiment of the present invention, in step 2), the solid electrolyte is prepared by:
a) drying to remove trace moisture in the solid electrolyte powder;
b) and cold-pressing the solid electrolyte powder into a sheet, sintering, and cooling for later use.
Further, in the step b), the pressure of cold pressing for sheeting is 1-10 MPa.
Further, in the step b), the sintering temperature is 200-1300 ℃.
Further, in the step b), the sintering time is 3-24 hours.
Further, in step b), the cooling method of the sintered solid electrolyte may be air cooling or furnace cooling.
According to an embodiment of the present invention, in step 2), the solid electrolyte may be a sintered solid electrolyte sheet directly purchased commercially.
According to an embodiment of the present invention, in step 2), the coating may be knife coating, spin coating, or dip coating.
According to an embodiment of the invention, in the step 2), the temperature of the vacuum drying is 20-180 ℃;
according to the embodiment of the invention, in the step 2), the vacuum drying time is 1-48 h.
According to an embodiment of the present invention, step 3) specifically includes the following steps:
attaching a metal lithium cathode to one side surface of the solid electrolyte coated with the precursor solution, performing physical calendering, and then assembling the metal lithium cathode and the anode into a lithium ion battery, or,
heating the metal lithium to 180-250 ℃ to enable the metal lithium to be molten, coating the molten metal lithium on the surface of one side of the solid electrolyte coated with the precursor solution, and assembling the lithium ion battery with the anode.
The physical rolling means that the metallic lithium negative electrode is tightly attached to the surface of the electrolyte by pressure in a flat pressing or rolling mode, and in the physical rolling process, the precursor solution reacts with the metallic lithium to prepare the interface layer.
Wherein the precursor solution reacts with molten lithium metal to prepare the interface layer.
According to an embodiment of the present invention, an interfacial layer is formed between the solid state electrolyte and the metallic lithium negative electrode.
< second production method of lithium ion Battery >
As mentioned above, the present invention provides a lithium ion battery, and herein also provides a method for preparing the above lithium ion battery, the method comprising the steps of:
i) coating metal halide on one side surface of the solid electrolyte by adopting a physical vapor deposition technology;
ii) assembling the metallic lithium negative electrode, the positive electrode and the solid electrolyte of step i) into a lithium ion battery, wherein the metallic lithium negative electrode is attached to one side surface of the solid electrolyte coated with the precursor liquid.
According to an embodiment of the present invention, in step i), the physical vapor deposition technique may be at least one of vacuum evaporation, sputter coating, and ion coating.
According to an embodiment of the present invention, step ii) specifically includes the following steps:
attaching a metal lithium cathode to one side surface of the solid electrolyte coated with the precursor solution, performing physical calendering, and then assembling the metal lithium cathode and the anode into a lithium ion battery, or,
heating the metal lithium to 180-250 ℃ to enable the metal lithium to be molten, coating the molten metal lithium on the surface of one side of the solid electrolyte coated with the precursor solution, and assembling the lithium ion battery with the anode.
The physical rolling means that the metallic lithium negative electrode is tightly attached to the surface of the electrolyte by pressure in a flat pressing or rolling mode, and in the physical rolling process, the precursor solution reacts with the metallic lithium to prepare the interface layer.
Wherein the precursor solution reacts with molten lithium metal to prepare the interface layer.
According to an embodiment of the present invention, an interfacial layer is formed between the solid state electrolyte and the metallic lithium negative electrode.
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The test methods for the following examples and comparative examples are as follows:
1. AC impedance test at room temperature
Testing the prepared lithium ion battery by adopting a Shanghai Hua CHI600E electrochemical workstation, and setting parameters: the amplitude was 10mV, the frequency ranged from 0.1Hz to 3MHz, and the test results are shown in Table 1.
2. Lithium symmetric battery cycling test
The test instrument is Wuhan blue battery test equipment;
and (3) testing conditions are as follows: to be provided with0.2mA/cm2The current density of the battery is measured by performing a constant current charge and discharge test on the Li/interface layer/solid electrolyte/interface layer/Li symmetrical battery, and the test result is shown in FIG. 3.
3. All-solid-state battery cycling test
The test instrument is Wuhan blue battery test equipment;
and (3) testing conditions are as follows: under the condition that the initial capacities are basically consistent, the exertion of the specific capacity, the capacity retention rate after 500 cycles and the first-cycle coulombic efficiency of the all-solid-state battery are measured under the conditions of 25 ℃ and 0.2C/0.2C, and the test results are shown in table 1.
Example 1
S1: mixing Li6.6La3Zr1.6Ta0.4O12Fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li6.6La3Zr1.6Ta0.4O12Cold-pressing the solid electrolyte powder into a sheet at 5MPa, then sintering the sheet at 1000 ℃ for 5h, and cooling the sheet to room temperature along with the furnace;
s3: adding cupric chloride CuCl2Dissolving in acetone to prepare a precursor solution with the proportion of 20 wt%, and fully stirring at the speed of 500rpm for 10h to obtain a homogeneous solution;
s4: then adding CuCl in S32The precursor liquid is evenly coated on Li6.6La3Zr1.6Ta0.4O12Fully vacuum-drying the upper surface of the solid electrolyte sheet for 12 hours at 30 ℃ to form a film layer;
s5: metallic lithium was heated to 190 ℃ to be in a molten state, and then uniformly coated on the Li treated in S46.6La3Zr1.6Ta0.4O12On the upper surface of the solid electrolyte sheet, in-situ reaction is carried out at the interface, copper chloride is converted into lithium chloride, Cu particles are distributed in the interface layer, and the thickness of the interface layer is 200 nm;
s6: placing the positive electrode on the lower surface of the solid electrolyte in S5, and sequentially forming a lithium metal negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprisesAn Al current collector and a positive electrode active material layer coated on the surface of the Al current collector, wherein the surface density of the positive electrode active material layer is 10mg/cm2The composition comprised 95 wt% lithium cobaltate, 2.5 wt% acetylene black and 2.5 wt% PVDF.
Comparative example 1
S1: mixing Li6.6La3Zr1.6Ta0.4O12Fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li6.6La3Zr1.6Ta0.4O12Cold-pressing the solid electrolyte powder into a sheet at 5MPa, then sintering the sheet at 1000 ℃ for 5h, and cooling the sheet to room temperature along with the furnace;
s3: metallic lithium was heated to 190 ℃ to be in a molten state, and then Li was uniformly coated in S26.6La3Zr1.6Ta0.4O12An upper surface of the solid electrolyte sheet;
s4: placing the positive electrode on the lower surface of the solid electrolyte in S3 to form an all-solid-state battery of a metallic lithium negative electrode, the solid electrolyte and the positive electrode in sequence, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 10mg/cm2The composition comprised 95 wt% lithium cobaltate, 2.5 wt% acetylene black and 2.5 wt% PVDF.
Example 2
S1: mixing Li1.5Al0.5Ti1.5(PO4)3Fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li1.5Al0.5Ti1.5(PO4)3Cold-pressing the solid electrolyte powder into a sheet at 4MPa, then sintering the sheet at 850 ℃ for 8h, and cooling the sheet to room temperature along with the furnace;
s3: nickel bromide NiBr2Dissolving in methanol to prepare a precursor solution with the proportion of 8 wt%, and fully stirring for 6h at the speed of 700rpm to obtain a homogeneous solution;
s4: then NiBr in S32Precursor ofLiquid-uniform spin coating on Li1.5Al0.5Ti1.5(PO4)3The spin coating speed of the upper surface of the solid electrolyte sheet is 1000rpm, and the upper surface is fully dried in vacuum for 10 hours at 50 ℃ after the spin coating is finished to form a thin film layer;
s5: metallic lithium was heated to 200 ℃ to be in a molten state, and then uniformly coated on the Li treated in S41.5Al0.5Ti1.5(PO4)3On the upper surface of the solid electrolyte sheet, nickel bromide is converted into lithium bromide and Ni particles distributed in an interface layer through in-situ reaction at the interface, and the thickness of the interface layer is 90 nm;
s6: placing the positive electrode on the lower surface of the solid electrolyte in S5, and sequentially forming an all-solid-state battery of a metallic lithium negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 18mg/cm2The composition comprises 80 wt% of lithium iron phosphate, 6 wt% of CNT, 4 wt% of PVDF and 10 wt% of Li1.5Al0.5Ti1.5(PO4)3A solid electrolyte.
Comparative example 2
S1: mixing Li1.5Al0.5Ti1.5(PO4)3Fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li1.5Al0.5Ti1.5(PO4)3Cold-pressing the solid electrolyte powder into a sheet at 4MPa, then sintering the sheet at 850 ℃ for 8h, and cooling the sheet to room temperature along with the furnace;
s3: metallic lithium was heated to 200 ℃ to be in a molten state, and then Li was uniformly coated in S21.5Al0.5Ti1.5(PO4)3An upper surface of the solid electrolyte sheet;
s4: placing the positive electrode on the lower surface of the solid electrolyte in S3 to form the all-solid-state battery of the metallic lithium negative electrode, the solid electrolyte and the positive electrode in sequence, wherein the positive electrode comprises an Al current collector and an Al current collector coated on the surface of the Al current collectorA positive electrode active material layer having an area density of 18mg/cm2The composition comprises 80 wt% of lithium iron phosphate, 6 wt% of CNT, 4 wt% of PVDF and 10 wt% of Li1.5Al0.5Ti1.5(PO4)3A solid electrolyte.
As shown in fig. 2, in example 2, compared with comparative example 2, the ac impedance at room temperature is smaller, which indicates that the introduction of the interface layer makes the ion transport smoother and the overall performance of the battery is more excellent.
Example 3
S1: mixing Li6.4La3Zr1.4Nb0.6O12Fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li6.4La3Zr1.4Nb0.6O12Cold-pressing the solid electrolyte powder into sheets at 10MPa, then sintering at 1200 ℃ for 4h, and cooling to room temperature along with the furnace;
s3: dissolving silver fluoride AgF in dimethyl sulfoxide to prepare precursor solution with the proportion of 5 wt%, and fully stirring at 900rpm for 10h to obtain homogeneous solution;
s4: then the silver fluoride AgF precursor solution in S3 is evenly dipped and coated on Li6.4La3Zr1.4Nb0.6O12Fully vacuum-drying the upper surface of the solid electrolyte sheet for 24 hours at 160 ℃ after dip-coating is finished to form a film layer;
s5: metallic lithium was heated to 220 ℃ to be in a molten state, and then uniformly coated on the Li treated in S46.4La3Zr1.4Nb0.6O12On the upper surface of the solid electrolyte sheet, in-situ reaction is carried out at the interface, silver fluoride is converted into lithium fluoride and Ag particles are distributed in the interface layer, and the thickness of the interface layer is 480 nm;
s6: placing the positive electrode on the lower surface of the solid electrolyte in S5, and sequentially forming an all-solid-state battery of a metallic lithium negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the positive electrode active substance layerHas an areal density of 12mg/cm2The composition comprises 94 wt% of LiNi0.5Co0.3Mn0.2O22.9 wt% of Super-P and 3.1 wt% of PVDF-HFP;
s7: uniformly dip-coating the silver fluoride AgF precursor solution in S3 in Li6.4La3Zr1.4Nb0.6O12The upper surface and the lower surface of the solid electrolyte sheet are fully dried in vacuum for 24 hours at 160 ℃ after the dip coating is finished to form Li6.4La3Zr1.4Nb0.6O12A solid electrolyte thin film layer; heating metal lithium to 220 deg.C to melt, and uniformly coating the above Li6.4La3Zr1.4Nb0.6O12On the surface of the solid electrolyte film layer, in-situ reaction is carried out at the interface, silver fluoride is converted into lithium fluoride and Ag particles are distributed in the interface layer, and the thickness of the interface layer is 480 nm; the assembly layer Li/interface layer/solid electrolyte/interface layer/Li symmetrical battery was subjected to constant current charge and discharge tests, and the test results are shown in FIG. 3.
As can be seen from fig. 3, the voltage platform of the lithium symmetric battery in example 3 shows excellent stability, and the voltage platform is smaller, which indicates that the interface layer in the invention can play a role in stabilizing the interface, and can well regulate and control the uniform deposition of metal lithium.
Comparative example 3
S1: mixing Li6.4La3Zr1.4Nb0.6O12Fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li6.4La3Zr1.4Nb0.6O12Cold-pressing the solid electrolyte powder into sheets at 10MPa, then sintering at 1200 ℃ for 4h, and cooling to room temperature along with the furnace;
s3: metallic lithium was heated to 220 ℃ to be in a molten state, and then Li was uniformly coated in S26.4La3Zr1.4Nb0.6O12An upper surface of the solid electrolyte sheet;
s4: solid electrolyte with positive electrode placed in S3The cathode comprises an Al current collector and a cathode active substance layer coated on the surface of the Al current collector, and the surface density of the cathode active substance layer is 12mg/cm2The composition comprises 94 wt% of LiNi0.5Co0.3Mn0.2O22.9 wt% of Super-P and 3.1 wt% of PVDF-HFP.
Example 4
S1: mixing Li7P3S11Fully drying the solid electrolyte powder, removing the influence of trace moisture, and placing the solid electrolyte powder in an argon atmosphere;
s2: mixing Li7P3S11Cold-pressing the solid electrolyte powder into a sheet at 4MPa, then sintering the sheet for 12 hours at 600 ℃ under the condition of argon, and cooling the sheet to room temperature along with a furnace;
s3: adding indium chloride InCl3Vacuum evaporation equipment is adopted to uniformly deposit Li6.4La3Zr1.4Nb0.6O12Coating the upper surface of the electrolyte thin sheet;
s4: metallic lithium was heated to 185 ℃ to be in a molten state, and then uniformly coated on the Li treated in S37P3S11On the upper surface of the solid electrolyte sheet, lithium chloride and In particles are converted at the interface through In-situ reaction and distributed In the interface layer, and the thickness of the interface layer is 1 μm;
s5: placing the positive electrode on the lower surface of the solid electrolyte in S4, and sequentially forming an all-solid-state battery of a metallic lithium negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 6mg/cm2The composition comprises 70 wt% of LiNi0.8Co0.15Al0.05O25 wt% of Ketjen black, 20 wt% of Li7P3S11Solid electrolyte, 5 wt% PVDF binder.
Comparative example 4
S1: mixing Li7P3S11Fully drying the solid electrolyte powder, removing the influence of trace moisture, and placing the solid electrolyte powder in an argon atmosphere;
s2: mixing Li7P3S11Cold-pressing the solid electrolyte powder into a sheet at 4MPa, then sintering the sheet for 12 hours at 600 ℃ under the condition of argon, and cooling the sheet to room temperature along with a furnace;
s3: metallic lithium was heated to 185 ℃ to be in a molten state, and then Li was uniformly coated in S27P3S11An upper surface of the solid electrolyte sheet;
s4: placing the positive electrode on the lower surface of the solid electrolyte in S3 to form an all-solid-state battery of a metallic lithium negative electrode, the solid electrolyte and the positive electrode in sequence, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 6mg/cm2The composition comprises 70 wt% of LiNi0.8Co0.15Al0.05O25 wt% of Ketjen black, 20 wt% of Li7P3S11Solid electrolyte, 5 wt% PVDF binder.
Example 5
S1: mixing Li3xLa2/3-xTiO3(x is 0.11) fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li3xLa2/3-xTiO3(x ═ 0.11) solid electrolyte powder was cold-pressed into sheets at 5MPa, then sintered at 800 ℃ for 3 hours, furnace-cooled to room temperature;
s3: zinc iodide ZnI2Dissolving in tetrahydrofuran to prepare precursor solution with the proportion of 6 wt%, and fully stirring at the speed of 400rpm for 7h to obtain homogeneous solution;
s4: then zinc iodide ZnI in S32The precursor solution is uniformly coated on Li in a spinning mode3xLa2/3-xTiO3(x is 0.11) the upper surface of the solid electrolyte sheet, the spin coating rotating speed is 1500rpm, and after the spin coating is finished, the vacuum drying is fully carried out for 8 hours at the temperature of 45 ℃ to form a thin film layer;
s5: heating metallic lithium to 200 deg.C to make it into molten state, and homogenizingCoating of treated Li in S43xLa2/3-xTiO3(x ═ 0.11) the upper surface of the solid electrolyte sheet, the interface where the zinc iodide was converted to lithium iodide by in-situ reaction and Zn particles distributed in the interface layer, the thickness of the interface layer was 120 nm;
s6: placing the positive electrode on the lower surface of the solid electrolyte in S5, and sequentially forming an all-solid-state battery of a metallic lithium negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 13mg/cm2The composition comprises 95 wt% LiCoO 23 wt% of Ketjen black and 2 wt% of polytetrafluoroethylene.
Example 6
S1: mixing Li3Fully drying the OCl solid electrolyte sheet to remove the influence of trace moisture;
s2: adding FeCl into iron chloride3Dissolving in acetone to prepare a precursor solution with the proportion of 8 wt%, and fully stirring at the speed of 800rpm for 3 hours to obtain a homogeneous solution;
s3: then FeCl is added to the ferric chloride in S33The precursor liquid is evenly coated on Li3Fully vacuum-drying the upper surface of the OCl solid electrolyte thin sheet for 20 hours at 40 ℃ after the spin coating is finished to form a thin film layer;
s4: metallic lithium was heated to 210 ℃ to be in a molten state, and then uniformly coated on the Li treated in S33The interface of the upper surface of the OCl solid electrolyte sheet is subjected to in-situ reaction, ferric chloride is converted into lithium chloride and Fe particles which are distributed in the interface layer, and the thickness of the interface layer is 120 nm;
s5: placing the positive electrode on the lower surface of the solid electrolyte in S4, and sequentially forming an all-solid-state battery of a metallic lithium negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 5mg/cm2The composition comprises 90 wt% of LiNi0.6Co0.2Mn0.2O26% by weight of conductive carbon black and 4% by weight of PVDF.
Example 7
S1: mixing Li1.5Al0.5Ge1.5(PO4)3Fully drying the solid electrolyte powder to remove the influence of trace moisture;
s2: mixing Li1.5Al0.5Ge1.5(PO4)3Cold-pressing the solid electrolyte powder into a sheet at 2MPa, sintering at 880 ℃ for 4h, and cooling to room temperature along with the furnace;
s3: adding cupric bromide CuBr2Dissolving in ethanol to prepare a precursor solution with the proportion of 10 wt%, and fully stirring at the speed of 500rpm for 12h to obtain a homogeneous solution;
s4: then adding copper bromide CuBr in S32The precursor liquid is evenly dipped and coated in Li1.5Al0.5Ge1.5(PO4)3Fully vacuum-drying the upper surface of the electrolyte thin sheet for 3 hours at 25 ℃ after the spin coating is finished to form a thin film layer;
s5: metallic lithium was heated to 195 ℃ to be in a molten state and then uniformly coated on the Li treated in S41.5Al0.5Ge1.5(PO4)3On the upper surface of the solid electrolyte sheet, in-situ reaction is carried out at the interface, copper bromide is converted into lithium bromide and Cu particles are distributed in the interface layer, and the thickness of the interface layer is 3 microns;
s6: placing the positive electrode on the lower surface of the solid electrolyte in S5, and sequentially forming an all-solid-state battery of a metallic lithium negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 20mg/cm2The composition comprises 85 wt% LiFePO 43 wt% CNT, 5 wt% PVDF-HFP and 7 wt% Li1.5Al0.5Ge1.5(PO4)3A solid electrolyte.
Example 8
S1: mixing Li6La3Zr1.6Ta0.4Al0.2O12Drying and removing the solid electrolyte powderThe effect of trace moisture;
s2: mixing Li6La3Zr1.6Ta0.4Al0.2O12Cold-pressing the solid electrolyte powder into sheets at 6MPa, then sintering at 1050 ℃ for 6h, and cooling to room temperature along with the furnace;
s3: nickel fluoride NiF2Dissolving in deionized water to prepare a precursor solution with the proportion of 2 wt%, and fully stirring at the speed of 800rpm for 9 hours to obtain a homogeneous solution;
s4: then the nickel fluoride NiF in S32The precursor solution is uniformly coated on Li in a spinning mode6La3Zr1.6Ta0.4Al0.2O12Fully vacuum-drying the upper surface of the electrolyte thin sheet for 40h at 110 ℃ after the spin coating is finished to form a thin film layer;
s5: metallic lithium was heated to 220 ℃ to be in a molten state, and then uniformly coated on the Li treated in S46La3Zr1.6Ta0.4Al0.2O12On the upper surface of the solid electrolyte sheet, in-situ reaction is carried out on the interface, nickel fluoride is converted into lithium fluoride and Ni particles are distributed in the interface layer, and the thickness of the interface layer is 200 nm;
s6: placing the positive electrode on the lower surface of the solid electrolyte in S5, and sequentially forming an all-solid-state battery of a metallic lithium negative electrode, an interface layer, the solid electrolyte and the positive electrode, wherein the positive electrode comprises an Al current collector and a positive electrode active substance layer coated on the surface of the Al current collector, and the surface density of the positive electrode active substance layer is 20mg/cm2The composition comprises 85 wt% LiFePO 43 wt% CNT, 5 wt% PVDF-HFP and Li6La3Zr1.6Ta0.4Al0.2O12A solid electrolyte.
The structures of the lithium ion batteries of examples 1 to 8 and comparative examples 1 to 4, that is, the structures of all-solid batteries in which the metallic lithium negative electrode, the interface layer, the solid electrolyte and the positive electrode are sequentially formed are shown in fig. 1, that is, the positive electrode and the metallic lithium negative electrode are on two sides, and the solid electrolyte and the interface layer are in the middle, specifically, the solid electrolyte is located between the positive electrode and the negative electrode, and the interface layer is located between the negative electrode and the solid electrolyte.
Table 1 shows the results of the performance tests of the lithium ion batteries of examples 1 to 8 and comparative examples 1 to 4 of the present invention on the specific capacity exertion ratio, the ac impedance, the cycle capacity retention ratio, and the coulombic efficiency at room temperature.
TABLE 1 results of the Performance test of the lithium ion batteries of examples 1 to 8 and comparative examples 1 to 4
As shown in table 1, it can be seen from comparing each example with the comparative example that the lithium ion battery of the present invention exhibits higher specific capacity exertion, smaller ac impedance, and more excellent cycle capacity retention rate and coulombic efficiency, and it is demonstrated that the use of the interface layer can improve the interfacial wettability between the solid electrolyte and the metallic lithium negative electrode, and can improve the interfacial stability between the solid electrolyte and the metallic lithium negative electrode, and can rapidly conduct lithium ions and stably regulate and control the uniform deposition of the metallic lithium, so that the lithium ion battery including the interface layer has good electrochemical performance and cycle stability.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An interfacial layer, wherein the interfacial layer comprises lithium halide and metal particles.
2. The interfacial layer of claim 1, wherein the molar ratio of the lithium halide to the metal particles is n:1, where n is the valence state of the metal.
3. An interfacial layer according to claim 1 or 2, wherein the lithium halide and the metal particles are obtained from a reaction of raw materials comprising metallic lithium and a metal halide; wherein the lithium metal is derived from a lithium metal negative electrode.
4. The interfacial layer of claim 3, wherein the metal halide is selected from at least one of copper fluoride, copper chloride, copper bromide, copper iodide, silver fluoride, silver chloride, silver bromide, silver iodide, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, iron fluoride, iron chloride, iron bromide, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, indium fluoride, indium chloride, indium bromide, indium iodide, aluminum fluoride, aluminum chloride, aluminum bromide, and aluminum iodide.
5. The interfacial layer according to any one of claims 1 to 4, wherein the lithium halide is selected from at least one of lithium fluoride, lithium chloride, lithium bromide and lithium iodide; and/or the metal particles are selected from at least one of Cu, Ag, Ni, Fe, Zn, In and Al.
6. An interfacial layer according to any one of claims 1 to 5, wherein the thickness of the interfacial layer is 10nm to 10 μm.
7. A lithium ion battery comprising a negative electrode, a solid state electrolyte, and the interface layer of any one of claims 1-6, the interface layer being between the negative electrode and the solid state electrolyte, the negative electrode being a lithium metal negative electrode.
8. The lithium ion battery of claim 7, further comprising a positive electrode, wherein the solid state electrolyte is between the positive electrode and a negative electrode, wherein the interface layer is between the negative electrode and the solid state electrolyte, and wherein the negative electrode is a lithium metal negative electrode.
9. The lithium ion battery of claim 7 or 8, wherein the solid state electrolyte is selected from inorganic solid state electrolytes that are oxide solid electrolytes or sulfide solid electrolytes.
10. The lithium ion battery of any of claims 7-9, wherein the lithium ion battery is a button cell, a die cell, or a pouch cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110741435.1A CN113451580A (en) | 2021-06-30 | 2021-06-30 | Interface layer and lithium ion battery comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110741435.1A CN113451580A (en) | 2021-06-30 | 2021-06-30 | Interface layer and lithium ion battery comprising same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113451580A true CN113451580A (en) | 2021-09-28 |
Family
ID=77814538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110741435.1A Pending CN113451580A (en) | 2021-06-30 | 2021-06-30 | Interface layer and lithium ion battery comprising same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113451580A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113937352A (en) * | 2021-12-17 | 2022-01-14 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Composite solid electrolyte, preparation method thereof and battery |
| CN114300767A (en) * | 2021-12-29 | 2022-04-08 | 华中科技大学 | Alkali metal solid-state battery interface modification method based on low-temperature molten salt and application |
| CN114388895A (en) * | 2021-12-29 | 2022-04-22 | 深圳大学 | Preparation method of interface modification layer between lithium metal and garnet type solid electrolyte and solid lithium metal battery |
| CN114421029A (en) * | 2021-12-29 | 2022-04-29 | 华中科技大学 | Construction method and application of in-situ alloy-SEI layer on surface of metal lithium |
| CN115483502A (en) * | 2022-07-22 | 2022-12-16 | 四川新能源汽车创新中心有限公司 | Protective film for improving interface stability of solid electrolyte and negative electrode, preparation method of protective film and solid battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784629A (en) * | 2017-01-19 | 2017-05-31 | 武汉大学 | A kind of lithium metal battery cathode interface method of modifying |
| CN106803580A (en) * | 2017-01-19 | 2017-06-06 | 浙江大学 | A kind of negative material for lithium metal battery |
| CN108565398A (en) * | 2018-06-01 | 2018-09-21 | 哈尔滨工业大学 | Cathode of lithium and preparation method thereof with inorganic protective coating |
| CN207909974U (en) * | 2017-12-19 | 2018-09-25 | 成都亦道科技合伙企业（有限合伙） | A kind of solid state lithium battery composite negative pole |
| CN109328413A (en) * | 2016-06-21 | 2019-02-12 | 应用材料公司 | The boundary layer that lithium metal for improvement recycles |
| CN109728249A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | A kind of interface protection structure, preparation method and the battery comprising the structure |
| CN109950476A (en) * | 2019-04-18 | 2019-06-28 | 电子科技大学 | A kind of lithium anode material and its preparation method and application |
| CN110429281A (en) * | 2019-08-01 | 2019-11-08 | 浙江锋锂新能源科技有限公司 | A kind of high-energy density all-solid-state battery based on sulfide solid electrolyte |
| CN111987278A (en) * | 2020-07-30 | 2020-11-24 | 中国科学院化学研究所 | Composite diaphragm for lithium metal secondary battery and preparation method and application thereof |
| CN112210098A (en) * | 2020-09-30 | 2021-01-12 | 蜂巢能源科技有限公司 | Interface protection film, preparation method thereof and application in lithium battery |
| CN112750982A (en) * | 2020-12-30 | 2021-05-04 | 复旦大学 | Laminated lithium metal battery negative electrode material, preparation method thereof and lithium metal secondary battery |
-
2021
- 2021-06-30 CN CN202110741435.1A patent/CN113451580A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109328413A (en) * | 2016-06-21 | 2019-02-12 | 应用材料公司 | The boundary layer that lithium metal for improvement recycles |
| CN106784629A (en) * | 2017-01-19 | 2017-05-31 | 武汉大学 | A kind of lithium metal battery cathode interface method of modifying |
| CN106803580A (en) * | 2017-01-19 | 2017-06-06 | 浙江大学 | A kind of negative material for lithium metal battery |
| CN109728249A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | A kind of interface protection structure, preparation method and the battery comprising the structure |
| CN207909974U (en) * | 2017-12-19 | 2018-09-25 | 成都亦道科技合伙企业（有限合伙） | A kind of solid state lithium battery composite negative pole |
| CN108565398A (en) * | 2018-06-01 | 2018-09-21 | 哈尔滨工业大学 | Cathode of lithium and preparation method thereof with inorganic protective coating |
| CN109950476A (en) * | 2019-04-18 | 2019-06-28 | 电子科技大学 | A kind of lithium anode material and its preparation method and application |
| CN110429281A (en) * | 2019-08-01 | 2019-11-08 | 浙江锋锂新能源科技有限公司 | A kind of high-energy density all-solid-state battery based on sulfide solid electrolyte |
| CN111987278A (en) * | 2020-07-30 | 2020-11-24 | 中国科学院化学研究所 | Composite diaphragm for lithium metal secondary battery and preparation method and application thereof |
| CN112210098A (en) * | 2020-09-30 | 2021-01-12 | 蜂巢能源科技有限公司 | Interface protection film, preparation method thereof and application in lithium battery |
| CN112750982A (en) * | 2020-12-30 | 2021-05-04 | 复旦大学 | Laminated lithium metal battery negative electrode material, preparation method thereof and lithium metal secondary battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113937352A (en) * | 2021-12-17 | 2022-01-14 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Composite solid electrolyte, preparation method thereof and battery |
| CN114300767A (en) * | 2021-12-29 | 2022-04-08 | 华中科技大学 | Alkali metal solid-state battery interface modification method based on low-temperature molten salt and application |
| CN114388895A (en) * | 2021-12-29 | 2022-04-22 | 深圳大学 | Preparation method of interface modification layer between lithium metal and garnet type solid electrolyte and solid lithium metal battery |
| CN114421029A (en) * | 2021-12-29 | 2022-04-29 | 华中科技大学 | Construction method and application of in-situ alloy-SEI layer on surface of metal lithium |
| CN114300767B (en) * | 2021-12-29 | 2023-08-25 | 华中科技大学 | Low-temperature molten salt-based alkali metal solid-state battery interface modification method and application |
| CN114421029B (en) * | 2021-12-29 | 2023-09-01 | 华中科技大学 | Construction method and application of in-situ alloy-SEI layer on surface of metallic lithium |
| CN115483502A (en) * | 2022-07-22 | 2022-12-16 | 四川新能源汽车创新中心有限公司 | Protective film for improving interface stability of solid electrolyte and negative electrode, preparation method of protective film and solid battery |
| CN115483502B (en) * | 2022-07-22 | 2023-12-05 | 四川新能源汽车创新中心有限公司 | Protective film for improving interface stability of solid electrolyte and negative electrode, preparation method of protective film and solid battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3588628B1 (en) | Lithium ion battery | |
| CN110010903B (en) | Positive pole piece and battery | |
| US6878487B2 (en) | Active material for battery and method of preparing same | |
| WO2020134780A1 (en) | Positive electrode material, preparation method therefor, and use thereof | |
| CN112397762B (en) | Solid-state battery | |
| CN113451580A (en) | Interface layer and lithium ion battery comprising same | |
| CN111834662B (en) | Interface functional layer, preparation method thereof and lithium ion battery | |
| WO2020073915A1 (en) | Lithium ion battery negative electrode material and non-aqueous electrolyte battery | |
| CN111725561B (en) | Solid electrolyte, preparation method thereof and all-solid-state battery | |
| CN112599850A (en) | Solid electrolyte composite layer and lithium ion battery | |
| Yuan et al. | Surfactant-assisted hydrothermal synthesis of V2O5 coated LiNi1/3Co1/3Mn1/3O2 with ideal electrochemical performance | |
| CN113782708B (en) | Positive electrode and electrochemical device comprising same | |
| CN113140731B (en) | All-solid-state lithium battery and preparation method thereof | |
| CN111834620A (en) | Lithium metal battery positive electrode, lithium metal battery and preparation method thereof | |
| CN111883765A (en) | Lithium battery positive active material, preparation method thereof and lithium battery | |
| KR20150083382A (en) | Negative electrode and rechargeable lithium battery including same | |
| CN111816842B (en) | Lithium electrode containing passivation protective film, preparation method thereof and lithium ion battery | |
| CN114050271A (en) | Positive active material with core-shell structure, preparation method thereof and all-solid-state lithium battery containing positive active material | |
| CN112420977A (en) | Lithium battery and preparation method thereof | |
| CN113285117B (en) | Composite solid electrolyte and lithium ion battery comprising same | |
| CN113451547B (en) | Composite metal lithium cathode and lithium ion battery comprising same | |
| CN113764615B (en) | Positive electrode and electrochemical device comprising same | |
| CN113603141B (en) | Composite positive electrode material, preparation method and application thereof | |
| CN112701347B (en) | Electrochemical device and electronic equipment | |
| JP2009104974A (en) | Cathode material for nonaqueous secondary battery, its manufacturing method, and nonaqueous secondary battery using it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |