CN111799433B - 制造包括基于含氟聚合物的固体电解质界面层电极的方法 - Google Patents
制造包括基于含氟聚合物的固体电解质界面层电极的方法 Download PDFInfo
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- CN111799433B CN111799433B CN201910502820.3A CN201910502820A CN111799433B CN 111799433 B CN111799433 B CN 111799433B CN 201910502820 A CN201910502820 A CN 201910502820A CN 111799433 B CN111799433 B CN 111799433B
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- lithium
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- fluoropolymers
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- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 93
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 93
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 87
- 239000000463 material Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 14
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims abstract description 12
- 229920009441 perflouroethylene propylene Polymers 0.000 claims abstract description 12
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 claims abstract description 11
- -1 hexafluoropropylene, tetrafluoroethylene, ethylene-tetrafluoroethylene Chemical group 0.000 claims abstract description 11
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 claims abstract description 11
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 5
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006115 defluorination reaction Methods 0.000 claims description 18
- 238000002161 passivation Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 9
- 239000011244 liquid electrolyte Substances 0.000 claims description 8
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims 2
- 210000004027 cell Anatomy 0.000 description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 30
- 229910001416 lithium ion Inorganic materials 0.000 description 30
- 239000011149 active material Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000002134 carbon nanofiber Substances 0.000 description 6
- 229910052798 chalcogen Inorganic materials 0.000 description 6
- 150000001787 chalcogens Chemical class 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 5
- 229910018091 Li 2 S Inorganic materials 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 5
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229910004499 Li(Ni1/3Mn1/3Co1/3)O2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910013391 LizN Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229910018077 Li 15 Si 4 Inorganic materials 0.000 description 1
- 229910004041 Li(Ni0.5Mn1.5)O2 Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910013210 LiNiMnCoO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012506 LiSi Inorganic materials 0.000 description 1
- 229910012381 LiSn Inorganic materials 0.000 description 1
- 229910015868 MSiO Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910017093 Ni0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 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 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000000541 cathodic arc deposition Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- YFKPABFAJKUPTN-UHFFFAOYSA-N germanium lithium Chemical compound [Li].[Ge] YFKPABFAJKUPTN-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FGSXRUYPQWMIRU-UHFFFAOYSA-L lithium fluoro-dioxido-oxo-lambda5-phosphane iron(2+) Chemical compound P(=O)([O-])([O-])F.[Fe+2].[Li+] FGSXRUYPQWMIRU-UHFFFAOYSA-L 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011834 metal-based active material Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
一种制造电极的方法包括将含氟聚合物膜施加到锂基主体材料上,通过加热使含氟聚合物膜脱氟以产生具有固体电解质界面(SEI)层的锂电极,所述固体电解质界面(SEI)层包括脱氟含氟聚合物和至少约5重量%的LiF。含氟聚合物可包括氟化乙烯丙烯、全氟烷氧基烷烃、偏二氟乙烯和全氟甲基乙烯基醚与四氟乙烯的共聚物中的一种或多种。含氟聚合物可包括一种或多种氟化单体,包括六氟丙烯、四氟乙烯、乙烯‑四氟乙烯、全氟醚和偏二氟乙烯。脱氟含氟聚合物的‑CF3官能团可占SEI层的约3重量%至约10重量%。SEI层可包括约30重量%至约50重量%的LiF。所述方法可以包括通过在阴极和电极之间设置电池隔板,并将电池隔板、阴极和电极设置在电解质中来组装电池单元。
Description
引言
锂离子电池描述了一类可充电电池,其中锂离子在负电极(即阳极)和正电极(即阴极)之间移动。液体、固体和聚合物电解质可以促进锂离子在阳极和阴极之间的移动。锂离子电池由于其高能量密度和经历连续充电和放电循环的能力而在国防、汽车和航空航天应用中日益普及。Li金属电极的大体积变化和高反应性会导致“苔藓”锂结构和/或锂枝晶生长,这会降低这种锂离子电池的循环效率和应用。
发明内容
提供了制造电极的方法。所述方法包括提供包括集电器和施加到其上的锂基主体材料的电极,将包括一种或多种含氟聚合物的含氟聚合物膜施加到锂基主体材料的暴露表面,并通过加热使含氟聚合物膜脱氟以产生具有固体电解质界面(SEI)层的锂电极,其包括脱氟含氟聚合物和至少约5重量%的LiF。一种或多种含氟聚合物可包括氟化乙烯丙烯(FEP)、全氟烷氧基烷烃(PFA)、偏二氟乙烯(THV)和全氟甲基乙烯基醚与四氟乙烯(MFA)的共聚物中的一种或多种。含氟聚合物膜可包括选自由氟化乙烯丙烯(FEP)、全氟烷氧基烷烃(PFA)、偏二氟乙烯(THV)和全氟甲基乙烯基醚与四氟乙烯(MFA)的共聚物构成的群组的一种或多种含氟聚合物。一种或多种含氟聚合物可包括一种或多种氟化单体,其中氟化单体包括六氟丙烯、四氟乙烯、乙烯-四氟乙烯、全氟醚和偏二氟乙烯。一种或多种含氟聚合物的-CF3官能团可以是施加于锂基主体材料的含氟聚合物膜的至少约10重量%。一种或多种脱氟含氟聚合物的-CF3官能团可占SEI层的约3重量%至约10重量%。SEI层可包括约30重量%至约50重量%的LiF。锂基主体材料可包括至少约50重量%的锂。加热可以在低于锂基主体材料的熔点下发生。所述方法还可以包括从随后施加含氟聚合物膜的锂基主体材料的暴露表面去除天然钝化层。
还提供了制造电池单元的方法。所述方法包括提供包括集电器和施加到其上的锂基主体材料的阳极,将包括一种或多种含氟聚合物的含氟聚合物膜施加到锂基主体材料的多个暴露表面,通过加热使含氟聚合物膜脱氟以产生具有固体电解质界面(SEI)层的锂阳极,所述固体电解质界面(SEI)层包括脱氟含氟聚合物和至少约5重量%的LiF,并随后组装电池单元。可以通过在阴极和锂阳极之间设置电池隔板,并将电池隔板、阴极和锂阳极设置在电解质中来组装电池单元。电解质可以是液体电解质。施加可以在真空和/或惰性气氛中进行。可以通过基于等离子体的工艺将一种或多种含氟聚合物施加到锂基主体材料的多个暴露表面,并且可以在施加期间至少部分地发生加热。所述方法还可以包括在施加之前从锂基主体材料中去除天然钝化层,其中在施加期间发生的加热实现含氟聚合物膜的合适程度的脱氟。所述方法还可包括在脱氟之前在非惰性环境中施加、运输和/或储存锂阳极。可以通过热蒸发或电子束蒸发将一种或多种含氟聚合物施加到锂基主体材料的多个暴露表面上。锂基主体材料的多个暴露表面均可包括钝化层,并且在施加之前不去除多个钝化层。一种或多种含氟聚合物的-CF3官能团可以是施加于锂基主体材料的含氟聚合物膜的至少约10重量%。SEI层可包括约30重量%至约50重量%的LiF。
根据示例性实施例的以下详细描述和附图,示例性实施例的其他目的、优点和新颖特征将变得更加清楚。
附图说明
图1示出了根据一个或多个实施例的锂电池单元;
图2示出了根据一个或多个实施例的混合动力电动车辆的示意图;
图3示出了根据一个或多个实施例的用于形成电极和附属电池单元的方法的示意图;并且
图4示出了根据一个或多个实施例的两个纽扣电池的放电容量与放电循环次数的关系图。
具体实施方式
本文描述了本公开的实施例。然而,应该理解,所公开的实施例仅仅是示例,并且其他实施例可以采用各种和替代形式。这些附图不一定按比例;某些功能可能会被夸大或最小化,以显示特定部件的详细信息。因此,本文公开的具体结构和功能细节不应被解释为限制,而仅仅作为用于教导本领域技术人员以各种方式使用本发明的代表性基础。如本领域普通技术人员将理解的,参考任何一个附图示出和描述的各种特征可以与一个或多个其他附图中示出的特征组合以产生未明确示出或描述的实施例。所示特征的组合提供了典型应用的代表性实施例。然而,对于特定应用或实现,可能需要与本公开的教导一致的特征的各种组合和修改。
本文提供了形成包括固体电解质界面(SEI)层的锂阳极的方法。本文所述的SEI层在电池循环期间抑制或防止Li枝晶和/或“苔藓”结构的生长,并且表现出柔性特性,其为锂阳极和附属电池单元结构提供机械保护。此外,用于形成SEI层的方法产生疏水性电极中间产物,其允许在制造步骤之间的非惰性环境中运输和/或存储疏水性电极中间产物。本文所述的SEI层及其形成方法通常包括将一种或多种含氟聚合物施加到锂基主体材料上,并利用含氟聚合物和锂基主体材料之间的直接接触,并加热,以实现所述含氟聚合物的脱氟。
图1示出了锂电池单元10,其包括负电极(即,阳极)11、正电极(即,阴极)14、可操作地设置在阳极11和阴极14之间的电解质17、以及隔板18。阳极11、阴极14和电解质17可以封装在容器19中,容器19可以是例如硬(例如金属)壳或软(例如聚合物)袋。阳极11和阴极14位于隔板18的相对侧,隔板18可包括微孔聚合物或能够传导锂离子和任选的电解质的其他合适材料(即液体电解质)。电解质17是包括溶解在非水溶剂中的一种或多种锂盐的液体电解质。阳极11通常包括集电器12和施加于其上的锂嵌入主体材料13。阴极14通常包括集电器15和施加于其上的活性材料16。例如,电池单元10可以包括硫属元素活性材料16或锂金属氧化物活性材料16等,如下所述。例如,活性材料16可以以比嵌入的主体材料13更高的电势存储锂离子。与两个电极相关联的集电器12和15通过可中断的外部电路连接,该外部电路允许电流在电极之间通过以电平衡锂离子的相关迁移。尽管为了清楚起见,图1示意性地示出了主体材料13和活性材料16,但是主体材料13和活性材料16可以分别包括阳极11和阴极14之间的专用界面,以及电解质17。
电池单元10可用于任何数量的应用中。例如,图2示出了包括电池组20和相关部件的混合动力电动或电动车辆1的示意图。诸如电池组20的电池组可以包括多个电池单元10。例如,多个电池单元10可以并联连接以形成组,并且多个组可以串联连接。本领域技术人员将理解,利用本文公开的电池单元架构,任何数量的电池单元连接配置都是可行的,并且将进一步认识到车辆应用不限于所描述的车辆架构。电池组20可以向牵引逆变器2提供能量,牵引逆变器2将直流(DC)电池电压转换成三相交流电(AC)信号,该信号由驱动马达3用于经由一个或多个车轮推进车辆1(未示出)。可选的发动机5可用于驱动发电机4,发电机4又可提供能量以通过逆变器2对电池组20再充电。在一些实施例中,驱动马达3和发电机4包括单个设备(即,马达/发电机)。外部(例如,电网)电力也可用于通过附加电路(未示出)对电池组20再充电。例如,发动机5可包括汽油或柴油发动机。
电池单元10通常通过在阳极11和阴极14之间可逆地传递锂离子来操作。在充电时锂离子从阴极14移动到阳极11,并且在放电时锂离子从阳极11移动到阴极14。在放电开始时,阳极11含有高浓度的嵌入/合金锂离子,而阴极14相对耗尽,并且在这种情况下在阳极11和阴极14之间建立闭合的外部电路导致从阳极11提取嵌入/合金化锂离子。提取的锂原子在电极-电解质界面处离开嵌入/合金化主体时分裂成锂离子和电子。锂离子通过离子导电电解质17从隔板18的微孔通过离子导电电解质17传送到阴极14,同时电子通过外部电路从阳极11传输到阴极14以平衡整个电化学单元。可以利用这种通过外部电路的电子流并将其馈送到负载设备,直到负电极中嵌入/合金化锂子的水平降至可操作水平以下或停止电力需求为止。
电池单元10可在其可用容量的部分或完全放电之后再充电。为了给锂离子电池单元充电或重新供电,外部电源(未示出)连接到正电极和负电极,以驱动电池放电电化学反应的逆转。也就是说,在充电期间,外部电源提取阴极14中存在的锂离子以产生锂离子和电子。锂离子通过电解质溶液被带回隔板,并且电子通过外部电路被驱回,两者都朝向阳极11。锂离子和电子最终在负电极处重新组合,从而用嵌入/合金锂子对其进行补充,用于将来的电池放电。
锂离子电池单元10,或包括串联和/或并联连接的多个电池单元10的电池模块或电池组可用于可逆地向相关联的负载设备供应电力和能量。锂离子电池还可以用于各种消费电子设备(例如,膝上型计算机、照相机和蜂窝/智能电话)、军用电子设备(例如,无线电、探雷器和热武器)、飞机和卫星等。锂离子电池、模块和组可以结合在诸如混合动力电动车辆(HEV)、电池电动车辆(BEV)、插入式HEV或增程式电动车辆(EREV)的车辆中以产生足够的功率和能量来操作车辆的一个或多个系统。例如,电池单元、模块和组可以与汽油或柴油内燃机组合使用以推进车辆(例如在混合动力电动车辆中),或者可以单独使用以推进车辆(例如在电池供电的车辆)。
返回图1,电解质17在阳极11和阴极14之间传导锂离子,例如在电池单元10的充电或放电期间。电解质17包括一种或多种溶剂,并且一种或多种锂盐溶解在一种或多种溶剂中。合适的溶剂可包括环状碳酸酯(碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯)、非环碳酸酯(碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯)、脂族羧酸酯(甲酸甲酯、乙酸甲酯、丙酸甲酯)、γ-内酯(γ-丁内酯、γ-戊内酯)、链结构醚(1,3-二甲氧基丙烷、1,2-二甲氧基乙烷(DME)、1-2-二乙氧基乙烷、乙氧基甲氧基乙烷)、环醚(四氢呋喃、2-甲基四氢呋喃、1,3-二氧戊环)及其组合。可以溶解在有机溶剂中以形成非水液体电解质溶液的锂盐的非限制性列表包括LiClO4、LiAlCl4、LiI、LiBr、LiSCN、LiBF4、LiB(C6H5)4LiAsF6、LiCF3SO3、LiN(CF3SO2)2、LiN(FSO2)2、LiPF6及其混合物。
活性材料16可包括能够充分进行锂嵌入和脱嵌的任何锂基活性材料,同时用作电池单元10的正极端子。活性材料16还可包括聚合物粘合剂材料以在结构上将锂基活性材料保持在一起。活性材料16可包括锂过渡金属氧化物(例如,层状锂过渡金属氧化物)或硫属元素材料,以及本文所述或本领域已知的其他合适材料。阴极集电器15可包括铝或本领域技术人员已知的任何其它合适的导电材料,并且可形成为箔或栅格形状。阴极集电器15可以用高导电材料处理(例如,涂覆),包括导电炭黑、石墨、碳纳米管、碳纳米纤维、石墨烯和气相生长碳纤维(VGCF)等中的一种或多种。可以另外地或替代地将相同的高导电材料分散在主体材料13内。
适合用作活性材料16的锂过渡金属氧化物可包括尖晶石锂锰氧化物(LiMn2O4),锂钴氧化物(LiCoO2),镍-锰氧化物尖晶石(Li(Ni0.5Mn1.5)O2)、层状镍锰钴氧化物(具有通式xLi2MnO3·(1-x)LiMO2,其中M由Ni、Mn和/或Co的任何比例组成)中的一种或多种。层状镍-锰氧化物尖晶石的具体示例是xLi2MnO3·(1-x)Li(Ni1/3Mn1/3Co1/3)O2。其他合适的锂基活性材料包括Li(Ni1/3Mn1/3Co1/3)O2)、LiNiO2、Lix+yMn2-yO4(LMO,0<x<1and 0<y<0.1),或锂铁聚阴离子氧化物,例如磷酸铁锂(LiFePO4)或氟磷酸锂铁(Li2FePO4F)。也可以使用其他锂基活性材料,例如LiNixM1-xO2(M由Al、Co和/或Mg的任何比例组成)、LiNi1-xCo1-yMnx+yO2或LiMn1.5- xNi0.5-yMx+yO4(M由Al、Ti、Cr和/或Mg的任何比例组成)、稳定的锂锰氧化物尖晶石(LixMn2- yMyO4,其中M由Al、Ti、Cr和/或Mg的任何比例组成)、锂镍钴铝氧化物(例如LiNi0.8Co0.15Al0.05O2或NCA)、铝稳定锂锰氧化物尖晶石(LixMn2-xAlyO4)、锂钒氧化物(LiV2O5),Li2MSiO4(M由任何比例的Co、Fe和/或Mn组成),以及任何其他高效镍-锰-钴材料(HE-NMC、NMC或LiNiMnCoO2)。“任何比例”是指任何元素可以以任何量存在。因此,例如,M可以是Al,有或没有Co和/或Mg,或所列元素的任何其他组合。在另一个示例中,阴离子取代可以在锂过渡金属基活性材料的任何示例的晶格中进行,以稳定晶体结构。例如,任何O原子可以被F原子取代。
例如,基于硫属元素的活性材料16可包括一种或多种硫和/或一种或多种硒材料。适合用作活性材料16的硫材料可包括硫碳复合材料,S8、Li2S8、Li2S6、Li2S4、Li2S2、Li2S、SnS2及其组合。硫基活性材料的另一个示例包括硫-碳复合材料。适合用作活性材料16的硒材料可包括元素硒、Li2Se、硫化硒合金、SeS2、SnSexSy(例如,SnSe0.5S0.5)及其组合。正电极22'的基于硫属元素的活性材料可以与聚合物粘合剂和导电填料混合。合适的粘合剂包括聚偏二氟乙烯(PVDF)、聚环氧乙烷(PEO)、乙烯丙烯二烯单体(EPDM)橡胶、羧甲基纤维素(CMC)、苯乙烯-丁二烯橡胶(SBR)、苯乙烯-丁二烯橡胶羧甲基纤维素(SBR-CMC)、聚丙烯酸(PAA)、交联聚丙烯酸-聚乙烯亚胺、聚酰亚胺或本领域技术人员已知的任何其它合适的粘合剂材料。其他合适的粘合剂包括聚乙烯醇(PVA)、海藻酸钠或其他水溶性粘合剂。聚合物粘合剂在结构上将硫属元素基活性材料和导电填料保持在一起。导电填料的示例是高表面积碳,例如乙炔黑或活性炭。导电填料确保正侧集电器26和基于硫属元素的活性材料之间的电子传导。在一个示例中,正电极活性材料和聚合物粘合剂可以用碳封装。在一个示例中,正电极22'中S和/或Se与C的重量比在1:9至9:1的范围内。
阳极集电器12可包括铜、铝、不锈钢或本领域技术人员已知的任何其他合适的导电材料。阳极集电器12可以用高导电材料处理(例如,涂覆),包括导电炭黑、石墨、碳纳米管、碳纳米纤维、石墨烯和气相生长碳纤维(VGCF)中的一种或多种。施加到阳极集电器12的主体材料13可以包括能够充分进行锂离子嵌入、脱嵌和合金化的任何锂主体材料,同时用作锂离子电池10的负极端子。此外,主体材料13包括足够量的锂可以实现阳极11SEI层的适当脱氟,如下所述。例如,在一些实施例中,主体材料13包括至少50重量%的锂。在一些实施例中,主体材料13包括纯锂(例如,>99.9重量%的锂)。在一些实施例中,主体材料13包括例如锂-铝合金(例如,LiAl、Al2Li3、Al4Li9),锂-硅合金(例如,Li22Si5、Li15Si4、Li13Si4、Li7Si3、Li12Si17、LiSi),锂-锡合金(例如,Li22Sn5、Li15Sn4、Li13Sn4、Li7Sn3、Li12Sn17、LiSn、Li2Sn5),锂-锌合金(例如,LiZn、Li2Zn3、LiZn2、Li2Zn5、LiZn4)或锂-锗(例如,GeLi3、Ge5Li22)。
硅具有最高的已知锂理论充电容量,使其成为可充电锂离子电池最有前途的阳极主体材料13之一。在两个通用实施例中,硅主体材料13可包括Si颗粒或SiOx颗粒。SiOx颗粒,其中通常为x≤2,可以在组成上变化。在一些实施例中,对于一些SiOx颗粒,x≈1。例如,x可为约0.9至约1.1,或约0.99至约1.01。在SiOx颗粒体内,可以进一步存在SiOx和/或Si域。包括Si颗粒或SiOx颗粒的硅主体材料13可包括约20nm至约20μm的平均粒径,以及其他可能的尺寸。
图3示出了用于形成电极(例如,阳极11)和附属电池单元的方法100,其具有在阳极11主体材料13上形成的SEI层。方法100包括提供(101)包括集电器12的阳极11,并且将锂基主体材料13施加到其上,将一种或多种含氟聚合物膜111施加(110)到锂基主体材料13上,并使一种或多种含氟聚合物膜111脱氟(120),以产生具有一个或多个SEI层121的锂阳极150。
所提供(101)的阳极11包括具有一个或多个面(例如,第一集电器面12A和第二集电器面12B)的集电器12,并且锂基主体材料13可以施加于一个或多个集电器面。锂基主体材料13可以具有一个或多个暴露表面13*,并且含氟聚合物膜111可以施加(110)到锂基主体材料13的一个、多个或全部暴露表面13*。在一些实施例中,一个或多个暴露表面13*包括外钝化层(例如,厚度最多5nm),包括例如锂氧化物、氢氧化锂、氮化锂和/或碳酸锂。因为锂是非常活泼的,所以如果在施加(110)之前阳极11没有保持在惰性环境或真空中,则可能在一个或多个暴露表面13*上形成钝化层。方法100可可选地包括在施加(110)之前从锂基主体材料13去除(105)一个或多个钝化层。例如,可以机械地(例如,通过刷子或刀片)移除(105)一个或多个钝化层。然而,通过方法100形成SEI层121有利地消除了去除一个或多个钝化层的需要。
向锂基主体材料13施加(110)的含氟聚合物膜111包括一种或多种含氟聚合物。含氟聚合物可包括一种或多种均聚物和/或一种或多种具有氟化单体的共聚物,其中氟化单体可包括六氟丙烯(C3F6),四氟乙烯(C2F4),乙烯-四氟乙烯(C4F8),全氟醚(C2F3OR,其中R是全氟化的组)和偏二氟乙烯(C2H2F2)。合适的共聚物可包括,例如,氟化乙烯丙烯(FEP)-六氟丙烯和四氟乙烯的共聚物,全氟烷氧基烷烃(PFA)-四氟乙烯和全氟醚的共聚物,四氟乙烯、六氟丙烯和偏二氟乙烯(THV)的三元共聚物,以及全氟甲基乙烯基醚(C2F3OR,其中R是全氟化CF3基团)和四氟乙烯(MFA)的共聚物等。例如,FEP可具有约241000至约575000的分子量。例如,PFA可具有约200000至约450000的分子量。例如,THV可具有约150000至约500000的分子量。例如,MFA可具有约200000至约475000的分子量。
合适的均聚物可包括聚四氟乙烯(PTFE)-四氟乙烯的均聚物,聚偏二氟乙烯(PVDF)-偏二氟乙烯的均聚物,和聚六氟丙烯(PHFP)-六氟丙烯的均聚物。在一些实施例中,为了实现含氟聚合物膜111的合适的脱氟,含氟聚合物膜111的-CF3官能团必须包括至少约7.5重量%,至少约10重量%、或约10重量%至约30重量%的含氟聚合物膜111。因此,在其中含氟聚合物膜包括一种或多种上述均聚物的一些情况下,必须包括其它含氟聚合物,必须包括其他含氟聚合物,使得在含氟聚合物膜111中实现一种或多种含氟聚合物的合适量的-CF3官能团。例如,含氟聚合物膜111可包括一种或多种含氟聚合物,并且一种或多种含氟聚合物的-CF3官能团包括如施加于锂基主体材料13中的含氟聚合物膜111的至少10重量%。在一些实施例中,施加于锂基主体材料13的含氟聚合物膜111包括FEP、PFA、THV和MFA中的一种或多种。在一些实施例中,施加于锂基主体材料13的含氟聚合物膜111包括一种或多种选自由FEP、PFA、THV和MFA构成的群组的含氟聚合物。
含氟聚合物膜111可以通过各种工艺施加(110),并且通常在真空和/或惰性气氛中施加,以避免在锂基主体材料13暴露的表面13*上形成不期望的化合物。惰性气氛是不与锂基主体材料13反应的气氛,并且通常基本上不含N2、O2、H2O、H2S、CO和CO2。例如,惰性气氛可包括例如He和/或Ar。含氟聚合物膜可以通过热蒸发(例如,在惰性环境中或在真空中)、电子束蒸发(例如,在真空中)或通过基于等离子体的工艺施加(110)。基于等离子体的工艺可以包括磁控溅射(例如,在真空中),阴极电弧沉积(例如,在真空中),以及离子束物理气相沉积(例如,在真空中)等。
然后将施加(110)的含氟聚合物膜111脱氟(120),例如通过加热,以形成包括嵌有LiF的聚合物基质的一个或多个SEI层121。加热通常促使锂迁移到邻接的含氟聚合物膜111(并且可选地通过钝化层,如果存在的话)和对一种或多种含氟聚合物脱氟(120)以形成LiF。加热可以在低于锂基主体材料的熔点下发生(例如,对于包括纯锂的主体材料13,低于约180℃)。例如,加热可以在约100℃至约180℃的温度下进行。可调节加热温度和/或持续时间以实现如本文所述的期望的SEI层121性质。如果通过基于等离子体的工艺施加(110)含氟聚合物膜111,则由于基于等离子体的工艺产生的热量,在施加(110)期间可以至少部分地发生含氟聚合物膜111的脱氟(120)。在一些实施例中,特别是如果在施加(110)之前移除任何钝化层105,则在施加(110)期间,通过基于等离子体的工艺可以完全实现含氟聚合物膜111的合适程度的脱氟(120)。
在脱氟(120)之前,含氟聚合物膜111提供致密的疏水涂层,其保护锂基主体材料13免受非惰性物质的影响。因此,施加有含氟聚合物膜111的电极(例如,阳极11)可以在脱氟(120)之前可选地在各种非惰性环境(例如,潮湿、露天)中运输和/或储存(115),有利地为制造工艺提供灵活性。在施加有含氟聚合物膜111的电极(例如,阳极11)在脱氟(120)之前在各种非惰性环境中运输和/或储存(115)的方法100的实施例中,在施加(110)之前不从锂基主体材料13去除钝化层可能是有利的,以便在运输和/或储存(115)之前防止或最小化含氟聚合物膜111的脱氟(120)(并因此降低疏水性)。
如前所述,脱氟(120)形成包括嵌有LiF的聚合物基质的一个或多个SEI层121。SEI层121中LiF的存在有利地钝化锂基主体材料13的表面,并进一步抑制或防止电解质17的分解。通常,脱氟(120)包括部分地氟化含氟聚合物膜111的一种或多种含氟聚合物,使得所得到的SEI层121的聚合物基质包括至少约5重量%的LiF,或约5重量%至75重量%的LiF。SEI层121聚合物基质中较高浓度的LiF降低了其柔韧性(即,有益的机械性能)和其离子导电性,因此在一些实施例中,SEI层121聚合物基质包括约30重量%至约50重量%LiF,约35重量%至约45重量%的LiF,或约40重量%的LiF。LiF可以作为纳米晶体存在于聚合物基质内。LiF纳米晶体可具有约5nm至约500nm,或至多约400nm的平均直径。在一些实施例中,LiF纳米晶体可具有约10nm至约30nm,或约20nm的平均直径。
SEI层121的聚合物基质还包括具有-CF3官能团的含氟聚合物。在一些实施例中,一种或多种脱氟含氟聚合物的-CF3官能团占SEI层的至少约3重量%、或约3重量%至约10重量%。通常,SEI层的一种或多种脱氟含氟聚合物中-CF3官能团的重量%将相对于施加于锂基主体材料13(即,在脱氟(120)之前)的含氟聚合物的-CF3官能团的重量%降低。因此,在一些实施例中,一种或多种含氟聚合物的-CF3官能团包括施加于锂基主体材料13的含氟聚合物膜111的至少约7.5重量%,至少约10重量%,或至少约12.5重量%。
在脱氟(120)之后,方法100还可以包括组装(130)电池单元(例如,电池单元10)。组装(130)可包括将隔板(例如,隔板18)设置在阴极(例如,阴极14)和锂阳极150之间,并将电池隔板、阴极和锂阳极150设置在电解质(例如,电解质17)中。如上所述,电解质可以是液体电解质。例如,电动车辆1可以使用包括阳极150的电池单元10。在一些锂离子电池中,液体电解质可含有氟代碳酸亚乙酯(FEC),使得在初始电池循环期间消耗FEC以在阳极上形成SEI层。因为FEC的消耗可以在电池单元内产生气态物质,所以本文所述的电池单元10可以有利地使用不含FEC的电解质17。
随着SEI层121的厚度T增加,SEI层121的离子电导率和电池单元的体积能量密度降低,并且电池的机械强度(例如,抗冲击性)增加。因此,SEI层121的厚度T可以调节到电池单元的容量(以mAh/cm2为单位)。例如,对于具有高达约4mAh/cm2的锂基主体材料的容量的电池单元(例如,在电动车辆应用中),SEI层121可具有约200nm至约5μm的厚度。在另一个示例中,对于具有高达约2mAh/cm2的锂基主体材料的容量的电池单元(例如,在便携式电子设备中),SEI层121可具有约100nm至约500nm的厚度。在另一个示例中,对于具有高达约1mmAh/cm2的锂基主体材料(例如,在生物医学设备中)的容量的电池单元,SEI层121可具有约50nm至约100nm的厚度。
示例1:
通过将20um纯锂施加到10μm厚的铜箔集电器来制备阳极。将阳极置于热蒸发器腔室中。将氟化聚乙烯(FPE)切成约2mm×1cm×1cm的片,并装入热蒸发器室中的钽坩埚中。将腔室从10托下压至3托,并将坩埚加热至300℃,然后用FPE涂覆锂至约1μm的厚度。随后对阳极进行加热处理。
在Ar填充的手套箱中组装两个纽扣电池:使用如上制造的13.5mm阳极的第一纽扣电池和使用没有FPE涂层的相同阳极的第二纽扣电池。第一和第二纽扣电池各自使用13mm直径的Ni0.6Mn0.2Co0.2O2阴极和20μL包括碳酸甲乙酯和1M LiPF6的电解质。将在充满氩气的手套箱中组装电池单元,并使用Arbin电池循环仪(BT2000)在室温下循环,电压窗口为3V至4.3V。纽扣电池首先经历两个C/10形成循环,电池单元电流密度为约0.42mA/cm2,然后进行C/3充电/放电循环以进行寿命试验,电池单元电流密度为约1.3mA/cm2。图4示出了第一纽扣电池和第二纽扣电池的放电容量与放电循环次数的关系图。可以看出,利用涂有FPE的阳极(“保护的Li”)的第一纽扣电池比使用未涂覆的阳极的第二电池(“基线”)保持更高的放电容量,并且基本上没有放电容量的减小。
虽然以上描述了示例性实施例,但并不意味着这些实施例描述了权利要求所包括的所有可能形式。说明书中使用的词语是描述性词语而不是限制性词语,并且应当理解,在不脱离本公开的精神和范围的情况下,可以进行各种改变。如前所述,各种实施例的特征可以组合以形成可能未明确描述或说明的本发明的其他实施例。虽然各种实施例可以被描述为相对于一个或多个期望特性提供优于或优于其他实施例或现有技术实现,但是本领域普通技术人员认识到可以取决于具体的应用程序和实现牺牲一个或多个特征或特性以实现期望的整体系统属性。这些属性可以包括但不限于成本、强度、耐久性、生命周期成本、可销售性、外观、包装、尺寸、可维护性、重量、可制造性、易于组装等。因此,被描述为与其他实施例或关于一个或多个特征的现有技术实现不太理想的实施例不在本公开的范围之外,并且对于特定应用可能是期望的。
Claims (18)
1.一种制造电极的方法,所述方法包括:
提供包括集电器和施加于其上的锂基主体材料的电极;
将包括一种或多种含氟聚合物的含氟聚合物膜施加到所述锂基主体材料的暴露表面上,其中所述一种或多种含氟聚合物的-CF3官能团占施加于所述锂基主体材料的含氟聚合物膜的至少10重量%;以及
通过加热使所述含氟聚合物膜脱氟以产生具有固体电解质界面层的锂电极,所述固体电解质界面层包括脱氟的含氟聚合物和至少5重量%的LiF。
2.根据权利要求1所述的方法,其中所述一种或多种含氟聚合物包括氟化乙烯丙烯、全氟烷氧基烷烃、偏二氟乙烯和全氟甲基乙烯基醚与四氟乙烯的共聚物中的一种或多种。
3.根据权利要求1所述的方法,其中所述含氟聚合物膜包括选自由氟化乙烯丙烯、全氟烷氧基烷烃、偏二氟乙烯和全氟甲基乙烯基醚与四氟乙烯的共聚物构成的群组的一种或多种含氟聚合物。
4.根据权利要求1所述的方法,其中所述一种或多种含氟聚合物包括一种或多种氟化单体,其中所述氟化单体包括六氟丙烯、四氟乙烯、乙烯-四氟乙烯、全氟醚和偏二氟乙烯。
5.根据权利要求1所述的方法,其中一种或多种脱氟含氟聚合物的-CF3官能团占固体电解质界面层的3重量%至10重量%。
6.根据权利要求1所述的方法,其中所述固体电解质界面层包括30重量%至50重量%的LiF。
7.根据权利要求1所述的方法,其中所述锂基主体材料包括至少50重量%的锂。
8.根据权利要求1所述的方法,其中所述加热发生在低于所述锂基主体材料的熔点以下。
9.根据权利要求1所述的方法,还包括从随后施加含氟聚合物膜的锂基主体材料的暴露表面去除天然钝化层。
10.一种制造电池单元的方法,所述方法包括:
提供包括集电器和施加于其上的锂基主体材料的阳极;
将包括一种或多种含氟聚合物的含氟聚合物膜施加到所述锂基主体材料的多个暴露表面上,其中所述一种或多种含氟聚合物的-CF3官能团占施加于锂基主体材料的含氟聚合物膜的至少10重量%;
通过加热使含氟聚合物薄膜脱氟以产生具有固体电解质界面层的锂阳极,所述固体电解质界面层包括脱氟含氟聚合物和至少5重量%的LiF;以及
随后通过以下方式组装电池:
在阴极和锂阳极之间设置电池隔板,以及
将所述电池隔板、所述阴极和所述锂阳极设置在电解质中。
11.根据权利要求10所述的方法,其中所述电解质包括液体电解质。
12.根据权利要求10所述的方法,其中所述施加在真空和/或惰性气氛中进行。
13.根据权利要求10所述的方法,其中通过基于等离子体的工艺将所述一种或多种含氟聚合物施加到锂基主体材料的多个暴露表面,并且在所述施加期间至少部分地发生所述加热。
14.根据权利要求10所述的方法,还包括在施加之前从锂基主体材料中去除天然钝化层,其中在施加期间发生的加热实现含氟聚合物膜的合适程度的脱氟。
15.根据权利要求10所述的方法,还包括在脱氟之前,在非惰性环境中施加、运输和/或储存锂阳极。
16.根据权利要求15所述的方法,其中通过热蒸发或电子束蒸发将所述一种或多种含氟聚合物施加到锂基主体材料的多个暴露表面上。
17.根据权利要求15所述的方法,其中锂基主体材料的多个暴露表面均包括钝化层,并且在施加之前不去除多个钝化层。
18.根据权利要求10所述的方法,其中所述固体电解质界面层包括30重量%至50重量%的LiF。
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