JP7300393B2 - アノード保護ポリマー層を含有するリチウム金属二次バッテリー及び製造方法 - Google Patents
アノード保護ポリマー層を含有するリチウム金属二次バッテリー及び製造方法 Download PDFInfo
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- JP7300393B2 JP7300393B2 JP2019555187A JP2019555187A JP7300393B2 JP 7300393 B2 JP7300393 B2 JP 7300393B2 JP 2019555187 A JP2019555187 A JP 2019555187A JP 2019555187 A JP2019555187 A JP 2019555187A JP 7300393 B2 JP7300393 B2 JP 7300393B2
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- Prior art keywords
- lithium
- secondary battery
- lithium secondary
- polymer
- metal
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- 229910052744 lithium Inorganic materials 0.000 title claims description 196
- 229920000642 polymer Polymers 0.000 title claims description 160
- 238000004519 manufacturing process Methods 0.000 title description 12
- 230000001681 protective effect Effects 0.000 title description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 156
- -1 poly(methyl methacrylate) Polymers 0.000 claims description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 90
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 47
- 229910001416 lithium ion Inorganic materials 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 45
- 229910021389 graphene Inorganic materials 0.000 claims description 42
- 239000006182 cathode active material Substances 0.000 claims description 41
- 239000011888 foil Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 29
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 27
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 229910010272 inorganic material Inorganic materials 0.000 claims description 25
- 239000011147 inorganic material Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 20
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- 229920001451 polypropylene glycol Polymers 0.000 claims description 18
- 239000002482 conductive additive Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 150000003624 transition metals Chemical class 0.000 claims description 17
- 239000004020 conductor Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 150000003568 thioethers Chemical class 0.000 claims description 15
- 229920001940 conductive polymer Polymers 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000733 Li alloy Inorganic materials 0.000 claims description 11
- 239000002134 carbon nanofiber Substances 0.000 claims description 11
- 239000006183 anode active material Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000001989 lithium alloy Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- FQVOWPCGHLYSLB-UHFFFAOYSA-N pyrene-4,5,9,10-tetrone Chemical compound C12=C(C(C3=O)=O)C=CC=C2C(=O)C(=O)C2=C1C3=CC=C2 FQVOWPCGHLYSLB-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011368 organic material Substances 0.000 claims description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 7
- MDCIYXHEPARHMN-UHFFFAOYSA-N 3,5,6,7,8,30-hexazaheptacyclo[20.8.0.02,11.04,9.012,21.014,19.024,29]triaconta-1(30),2,4(9),5,7,10,12,14,16,18,20,22,24,26,28-pentadecaene Chemical group N1=NN=C2C=C3C4=CC5=CC=CC=C5C=C4C4=CC5=CC=CC=C5N=C4C3=NC2=N1 MDCIYXHEPARHMN-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- OXQYGVSMUGQPDF-UHFFFAOYSA-N 5-amino-1,4-dihydroxyanthracene-9,10-dione Chemical compound O=C1C2=C(O)C=CC(O)=C2C(=O)C2=C1C=CC=C2N OXQYGVSMUGQPDF-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 6
- 150000003346 selenoethers Chemical class 0.000 claims description 6
- 229910021332 silicide Inorganic materials 0.000 claims description 6
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims description 6
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 5
- 239000002127 nanobelt Substances 0.000 claims description 5
- 239000005077 polysulfide Substances 0.000 claims description 5
- 229920001021 polysulfide Polymers 0.000 claims description 5
- 150000008117 polysulfides Polymers 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 4
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 229910013075 LiBF Inorganic materials 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 4
- 229910013872 LiPF Inorganic materials 0.000 claims description 4
- 101150058243 Lipf gene Proteins 0.000 claims description 4
- 229910001194 LixV2O5 Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910003092 TiS2 Inorganic materials 0.000 claims description 4
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229920005566 bicyclic polymer Polymers 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- BGSFCOHRQUBESL-UHFFFAOYSA-N ethyl prop-2-enyl carbonate Chemical compound CCOC(=O)OCC=C BGSFCOHRQUBESL-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 claims description 4
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 4
- 229910052961 molybdenite Inorganic materials 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
- 239000002107 nanodisc Substances 0.000 claims description 4
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- 239000002074 nanoribbon Substances 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 239000002071 nanotube Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 229920000414 polyfuran Polymers 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- UDTSPKADQGPZFS-SOFGYWHQSA-N (5e)-5-benzylideneimidazolidine-2,4-dione Chemical compound N1C(=O)NC(=O)\C1=C/C1=CC=CC=C1 UDTSPKADQGPZFS-SOFGYWHQSA-N 0.000 claims description 3
- RXFDPQXLULKAFY-UHFFFAOYSA-N 1,2,4,5-tetrakis(propylsulfanyl)benzene Chemical compound CCCSc1cc(SCCC)c(SCCC)cc1SCCC RXFDPQXLULKAFY-UHFFFAOYSA-N 0.000 claims description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 3
- YALAUFUASBIEEA-UHFFFAOYSA-N 1,4-diphenylpiperazine-2,3,5,6-tetrone Chemical compound O=C1C(=O)N(C=2C=CC=CC=2)C(=O)C(=O)N1C1=CC=CC=C1 YALAUFUASBIEEA-UHFFFAOYSA-N 0.000 claims description 3
- DXCZBBFNFURETH-UHFFFAOYSA-N 1,4-dipropylpiperazine-2,3,5,6-tetrone Chemical compound CCCN1C(=O)C(=O)N(CCC)C(=O)C1=O DXCZBBFNFURETH-UHFFFAOYSA-N 0.000 claims description 3
- UDTSPKADQGPZFS-UHFFFAOYSA-N 1/7/3775 Natural products N1C(=O)NC(=O)C1=CC1=CC=CC=C1 UDTSPKADQGPZFS-UHFFFAOYSA-N 0.000 claims description 3
- YTDHEFNWWHSXSU-UHFFFAOYSA-N 2,3,5,6-tetrachloroaniline Chemical compound NC1=C(Cl)C(Cl)=CC(Cl)=C1Cl YTDHEFNWWHSXSU-UHFFFAOYSA-N 0.000 claims description 3
- TXROZCSFVVIBFI-UHFFFAOYSA-N 2,3,6,7,10,11-hexamethoxytriphenylene Chemical group C12=CC(OC)=C(OC)C=C2C2=CC(OC)=C(OC)C=C2C2=C1C=C(OC)C(OC)=C2 TXROZCSFVVIBFI-UHFFFAOYSA-N 0.000 claims description 3
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 3
- YFCSASDLEBELEU-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene-11,12,15,16,17,18-hexacarbonitrile Chemical compound N#CC1=C(C#N)C(C#N)=C2C3=C(C#N)C(C#N)=NN=C3C3=NN=NN=C3C2=C1C#N YFCSASDLEBELEU-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052582 BN Inorganic materials 0.000 claims description 3
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- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 3
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
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- PMOWGTZPOVDCDO-UHFFFAOYSA-N NC1=C2C(C3=C(CCC(=C3C(C2=CC=C1)=O)O)O)=O Chemical compound NC1=C2C(C3=C(CCC(=C3C(C2=CC=C1)=O)O)O)=O PMOWGTZPOVDCDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910020050 NbSe3 Inorganic materials 0.000 claims description 3
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021608 Silver(I) fluoride Inorganic materials 0.000 claims description 3
- 229910004211 TaS2 Inorganic materials 0.000 claims description 3
- 229910010348 TiF3 Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 3
- FMLZGWFPVTXRBT-UHFFFAOYSA-N [Li].[C]=O Chemical compound [Li].[C]=O FMLZGWFPVTXRBT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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Description
本出願は、2017年4月10日に出願された米国特許出願第15/483348号(その内容を参照によって本願明細書に組み入れる)に対する優先権を主張する。
0%より高く、さらにより好ましくは50%より高く、なおより好ましくは100%より高い。
カソード活物質層は、それぞれ、V2O5粒子及びグラフェン包含V2O5粒子から調製した。V2O5粒子は商業的に入手可能であった。グラフェン包含V2O5粒子は企業内で調製した。典型的な実験において、LiCl水溶液中でのV2O5の混合によって五酸化バナジウムゲルが得られた。LiCl溶液による相互作用によって得られたLi+交換ゲル(Li:Vモル比は1:1に保持された)をGO懸濁液と混合し、次いでTeflonラインステンレス鋼35mlオートクレーブ中に配置し、密封し、そして12時間、180℃まで加熱した。そのような水熱処理後、緑色の固体を回収し、これを徹底的に洗浄し、2分間超音波処理し、そして70℃で12時間乾燥後、別の水中0.1%GOと混合し、超音波処理してナノベルトサイズまで分解し、次いで、200℃において噴霧乾燥させ、グラフェン包含V2O5複合物粒状物を得た。次いで、V2O5粒子及びグラフェン包含V2O5粒子の選択された量でそれぞれカソード層を製造し、続いて、周知のスラリーコーティングプロセスを行った。
Li-LiCoO2セルにおけるアノード層保護のための高弾性ポリマーは、超高分子量ポリアクリロニトリル(UHMW PAN)をベースとするものであった。UHMW PAN(0.3g)を5mlのジメチルホルムアミド(DMF)中に溶解し、溶液を形成した。次いで、いくらかのLiPF6塩(5重量%)及びいくらかのCNT(2重量%)を溶液中に分散させ、スラリーを形成した。次いで、スラリーを別々にキャストし、乾燥させ、ポリマー膜を形成した。
リチウムアノードの保護のために、実施例1に記載の手順と同様の手順を使用することによって、UHMW PPOポリマーを保護薄層として導入した。CoF3、MnF3、FeF3、VF3、VOF3、TiF3及びBiF3の商業的に入手可能な粉末に高強度ボールミル粉砕を受けさせ、粒径を約0.5~2.3μmまで低下させた。次いで、これらの金属フッ化物粒子のそれぞれの種類を、グラフェンシート(導電性添加剤として)と一緒にNMP及びPVDF結合剤懸濁液中に添加し、複数成分スラリーを形成した。次いで、スラリーをAl箔上にスラリーコーティングし、カソード層を形成した。
ミル粉砕チャンバー中で30分間、FePc及びRGOの混合物をボールミル粉砕することによって、組み合わせたFePcの粒子/グラフェンシートが得られた。得られたFePc/RGO混合物粒子は、ポテト様形状であった。パンコーティング手順を使用して、これらの混合物粒子のいくつかを高弾性UHMW PANポリマーによって封入した。それぞれ、Li箔アノード、多孔性分離体及びFePc/RGO粒子(封入又は未封入)のカソード層を含有する2つのリチウムセルを調製した。
硫黄を導電性材料(例えば、炭素/黒鉛粒子)と組み合わせる1つの方法は、溶液又は溶融混合プロセスを使用することである。高度に多孔性の活性炭粒子、化学エッチングされたメソカーボンミクロボール(活性化MCMB)、及び剥離黒鉛ワームを10~60分間、117~120℃(Sの融点、115.2℃よりわずかに高い温度)において硫黄溶融体と混合し、硫黄含浸炭素粒子を得た。
カソード調製手順には、元素硫黄の蒸気を生じさせ、単層又は数層のグラフェンシートの表面上でのS蒸気の堆積を可能にさせることが含まれる。第1のステップとして、液体培地中に懸濁されたグラフェンシート(例えば、水中のグラフェンオキシド又はNMP中のグラフェン)を基板(例えばガラス表面)上に噴霧し、グラフェンシートの薄層を形成した。次いで、このようなグラフェンの薄層を昇華によって生じる物理的蒸着に曝露した。固体硫黄の昇華は40℃より高い温度で生じるが、有意であり、且つ実際に有用な昇華レートは温度が100℃超になるまで典型的に生じない。我々は、グラフェン表面上に硫黄の薄膜(約1nm~10nmの厚さの硫黄)を堆積させるために、典型的に10~120分の蒸着時間で117~160℃を使用した。次いで、硫黄の薄膜がその上に堆積されたグラフェンのこの薄層は、エアジェットミルを使用して、容易にSコーティングのグラフェンシートの破片へ粉砕された。これらのSコーティンググラフェンシートから(例えば、噴霧乾燥によって)直径約5~15μmの二次粒子を作成し、次いで、これを高弾性UHMW PANポリマーによって封入した。従来のスラリーコーティング手順を使用して、これらの封入粒状物からカソード電極を作成した。
種々のリチウムイオン導電性添加剤をいくつかの異なるポリマーマトリックス材料に添加し、アノード保護層を調製した。得られるポリマー/塩複合材料のリチウムイオン導電率値を表1に要約する。我々は、室温におけるそれらのリチウムイオン導電率が10-6S/cm以上である場合、これらのポリマー複合材料が適切なアノード保護層材料であることを発見した。これらの材料によって、リチウムイオンは、1μm以下の厚さを有する保護層を通して容易に拡散することが可能であるように思われる。より厚いポリマー膜(例えば10μm)に関しては、10-4S/cm以上のこれらのUHMWポリマーの室温におけるリチウムイオン導電率が必要とされるであろう。
Claims (36)
- カソードと、アノードと、前記カソードと前記アノードとの間に配置される電解質又は分離体-電解質アセンブリとを含んでなるリチウム二次バッテリーにおいて、前記アノードが、
a)アノード活物質としてのリチウム又はリチウム合金の箔又はコーティングと、
b)5%以上の回復可能な引張歪み、室温において10-6S/cm以上のリチウムイオン導電率及び1nm~10μmの厚さを有する高弾性ポリマーの薄層と
を含んでなり、前記高弾性ポリマーが、0.5×106~9×106グラム/モルの分子量を有する超高分子量ポリマーを含有し、且つ前記リチウム又はリチウム合金と前記電解質又は分離体-電解質アセンブリとの間に配置されていることを特徴とするリチウム二次バッテリー。 - 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、ポリアクリロニトリル、ポリエチレンオキシド、ポリプロピレンオキシド、ポリエチレングリコール、ポリビニルアルコール、ポリアクリルアミド、ポリ(メチルメタクリレート)、ポリ(メチルエーテルアクリレート)、そのコポリマー、そのスルホン化誘導体、その化学的誘導体、及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、0.5×106~5×106グラム/モル未満の分子量を有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、1×106~3×106グラム/モル未満の分子量を有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、前記超高分子量ポリマーの連鎖間に分散されたリチウム塩及び/又は液体溶媒を含有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、その中に分散された電気導電性材料を含有することを特徴とするリチウム二次バッテリー。
- 請求項6に記載のリチウム二次バッテリーにおいて、前記電気導電性材料が、電子導電性ポリマー、金属粒子若しくはワイヤー、グラフェンシート、カーボン繊維、黒鉛繊維、カーボンナノ繊維、黒鉛ナノ繊維、カーボンナノチューブ、黒鉛粒子、膨張黒鉛フレーク、アセチレンブラック粒子、及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項7に記載のリチウム二次バッテリーにおいて、前記電気導電性材料が100nm未満の厚さ又は直径を有することを特徴とするリチウム二次バッテリー。
- 請求項5に記載のリチウム二次バッテリーにおいて、前記液体溶媒が、1,3-ジオキソラン(DOL)、1,2-ジメトキシエタン(DME)、テトラエチレングリコールジメチルエーテル(TEGDME)、ポリ(エチレングリコール)ジメチルエーテル(PEGDME)、ジエチレングリコールジブチルエーテル(DEGDBE)、2-エトキシエチルエーテル(EEE)、スルホン、スルホラン、炭酸エチレン(EC)、炭酸プロピレン(PC)、炭酸ジメチル(DMC)、炭酸メチルエチル(MEC)、炭酸ジエチル(DEC)、プロピオン酸エチル、プロピオン酸メチル、ガンマ-ブチロラクトン(γ-BL)、アセトニトリル(AN)、酢酸エチル(EA)、ギ酸プロピル(PF)、ギ酸メチル(MF)、トルエン、キシレン、酢酸メチル(MA)、フルオロエチレンカーボネート(FEC)、ビニレンカーボネート(VC)、アリルエチルカーボネート(AEC)、ヒドロフルオロエーテル、イオン液体溶媒、及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項5に記載のリチウム二次バッテリーにおいて、前記リチウム塩が、過塩素酸リチウム、LiClO4、ヘキサフルオロリン酸リチウム、LiPF6、ホウフッ化リチウム、LiBF4、ヘキサフルオロヒ化リチウム、LiAsF6、トリフルオロメタスルホン酸リチウム、LiCF3SO3、ビス-トリフルオロメチルスルホニルイミドリチウム、LiN(CF3SO2)2、ビス(オキサラト)ホウ酸リチウム、LiBOB、オキサリルジフルオロホウ酸リチウム、LiBF2C2O4、硝酸リチウム、LiNO3、Li-フルオロアルキル-リン酸塩、LiPF3(CF2CF3)3、リチウムビスペルフルオロ-エチスルホニルイミド、LiBETI、リチウムビス(トリフルオロメタンスルホニル)イミド、リチウムビス(フルオロスルホニル)イミド、リチウムトリフルオロメタンスルホンイミド、LiTFSI、イオン性液体ベースのリチウム塩、又はそれらの組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記高弾性ポリマーの薄層が、1nm~1μmの厚さを有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記高弾性ポリマーの薄層が、100nm未満の厚さを有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記高弾性ポリマーの薄層が、10nm未満の厚さを有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記高弾性ポリマーが、1×10-4S/cm~10-2S/cmのリチウムイオン導電率を有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記カソードの活物質が、無機材料、有機材料、ポリマー材料又はその組合せから選択され、且つ前記無機材料が、硫黄又はアルカリ金属ポリスルフィドを含まないことを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記無機材料が、金属酸化物、金属リン酸塩、金属ケイ化物、金属セレン化物、遷移金属硫化物及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記無機材料が、酸化リチウムコバルト、酸化リチウムニッケル、酸化リチウムマンガン、酸化リチウムバナジウム、リチウム-混合金属酸化物、リン酸リチウム鉄、リン酸リチウムマンガン、リン酸リチウムバナジウム、リチウム-混合金属リン酸塩、リチウム金属ケイ化物及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記無機材料が、CoF3、MnF3、FeF3、VF3、VOF3、TiF3、BiF3、NiF2、FeF2、CuF2、CuF、SnF2、AgF、CuCl2、FeCl3、MnCl2及びその組合せからなる群を含む金属フッ化物又は金属塩化物から選択されることを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記無機材料が、M及びMaが、Fe、Mn、Co、Ni、V又はVOから選択され、Mbが、Fe、Mn、Co、Ni、V、Ti、Al、B、Sn又はBiから選択され;且つx+y≦1である、Li2MSiO4又はLi2MaxMbySiO4として示されるリチウム遷移金属ケイ酸塩から選択されることを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記無機材料が、遷移金属ジカルコゲン化物、遷移金属トリカルコゲン化物及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記無機材料が、TiS2、TaS2、MoS2、NbSe3、MnO2、CoO2、酸化鉄、酸化バナジウム及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項16に記載のリチウム二次バッテリーにおいて、前記金属酸化物が、VO2、LixVO2、V2O5、LixV2O5、V3O8、LixV3O8、LixV3O7、V4O9、LixV4O9、V6O13、LixV6O13(式中、0.1<x<5)、それらのドープされた変種、それらの誘導体及びその組合せからなる群から選択される酸化バナジウムを含有することを特徴とするリチウム二次バッテリー。
- 請求項16に記載のリチウム二次バッテリーにおいて、前記金属酸化物又は金属リン酸塩が、層状化合物LiMO2、スピネル化合物LiM2O4、カンラン石(olivine)化合物LiMPO4、ケイ酸塩化合物Li2MSiO4、タボライト(Tavorite)化合物LiMPO4F、ホウ酸塩化合物LiMBO3又はその組合せ(式中、Mは遷移金属又は複数の遷移金属の混合物である)から選択されることを特徴とするリチウム二次バッテリー。
- 請求項16に記載のリチウム二次バッテリーにおいて、前記無機材料が、(a)セレン化ビスマス又はテルル化ビスマス、(b)遷移金属ジカルコゲン化物又はトリカルコゲン化物、(c)ニオブ、ジルコニウム、モリブデン、ハフニウム、タンタル、タングステン、チタン、コバルト、マンガン、鉄、ニッケル又は遷移金属の硫化物、セレン化物又はテルル化物;(d)窒化ホウ素、及び(e)その組合せからなる群から選択されることを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記有機材料又はポリマー材料が、ポリ(硫化アントラキノニル)(PAQS)、リチウムオキソ炭素、3,4,9,10-ペリレンテトラカルボン酸二無水物(PTCDA)、ポリ(硫化アントラキノニル)、ピレン-4,5,9,10-テトラオン(PYT)、ポリマー結合PYT、キノ(トリアゼン)、酸化還元活性有機材料、テトラシアノキノジメタン(TCNQ)、テトラシアノエチレン(TCNE)、2,3,6,7,10,11-ヘキサメトキシトリフェニレン(HMTP)、ポリ(5-アミノ-1,4-ジヒドロキシアントラキノン)(PADAQ)、二硫化ホスファゼンポリマー([(NPS2)3]n)、リチウム化1,4,5,8-ナフタレンテトラオールホルムアルデヒドポリマー、ヘキサアザトリナフチレン(HATN)、ヘキサアザトリフェニレンヘキサカルボニトリル(HAT(CN)6)、5-ベンジリデンヒダントイン、イサチンリチウム塩、ピロメリット酸ジイミドリチウム塩、テトラヒドロキシ-p-ベンゾキノン誘導体(THQLi4)、N,N’-ジフェニル-2,3,5,6-テトラケトピペラジン(PHP)、N,N’-ジアリル-2,3,5,6-テトラケトピペラジン(AP)、N,N’-ジプロピル-2,3,5,6-テトラケトピペラジン(PRP)、チオエーテルポリマー、キノン化合物、1,4-ベンゾキノン、5,7,12,14-ペンタセンテトロン(PT)、5-アミノ-2,3-ジヒドロ-1,4-ジヒドロキシアントラキノン(ADDAQ)、5-アミノ-1,4-ジヒドロキシアントラキノン(ADAQ)、カリックスキノン、Li4C6O6、Li2C6O6、Li6C6O6及びその組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項25に記載のリチウム二次バッテリーにおいて、前記チオエーテルポリマーが、ポリ[メタンテトリル-テトラ(チオメチレン)](PMTTM)、ポリ(2,4-ジチオペンタニレン)(PDTP)、主鎖チオエーテルポリマーとしてポリ(エテン-1,1,2,2-テトラチオール)(PETT)を含有するポリマー、共役芳香族部分からなる主鎖を有し、且つペンダントとしてチオエーテル側鎖を有する側鎖チオエーテルポリマー、ポリ(2-フェニル-1,3-ジチオラン)(PPDT)、ポリ(1,4-ジ(1,3-ジチオラン-2-イル)ベンゼン)(PDDTB)、ポリ(テトラヒドロベンゾジチオフェン)(PTHBDT)、ポリ[1,2,4,5-テトラキス(プロピルチオ)ベンゼン](PTKPTB)又はポリ[3,4(エチレンジチオ)チオフェン](PEDTT)から選択されることを特徴とするリチウム二次バッテリー。
- 請求項15に記載のリチウム二次バッテリーにおいて、前記有機材料が、銅フタロシアニン、亜鉛フタロシアニン、スズフタロシアニン、鉄フタロシアニン、鉛フタロシアニン、ニッケルフタロシアニン、バナジルフタロシアニン、フルオロクロムフタロシアニン、マグネシウムフタロシアニン、マンガンフタロシアニン、ジリチウムフタロシアニン、アルミニウムフタロシアニンクロリド、カドミウムフタロシアニン、クロロガリウムフタロシアニン、コバルトフタロシアニン、銀フタロシアニン、無金属フタロシアニン、その化学誘導体及びその組合せから選択されるフタロシアニン化合物を含有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記カソードの活物質が、0.5nm~100nmの厚さ又は直径を有するナノ粒子、ナノワイヤー、ナノ繊維、ナノチューブ、ナノシート、ナノベルト、ナノリボン、ナノディスク、ナノプレートリット、又はナノホーンの形態であることを特徴とするリチウム二次バッテリー。
- 請求項28に記載のリチウム二次バッテリーにおいて、前記ナノ粒子、ナノワイヤー、ナノ繊維、ナノチューブ、ナノシート、ナノベルト、ナノリボン、ナノディスク、ナノプレートリット、又はナノホーンが、カーボン材料、グラフェン、電子導電性ポリマー、導電性金属酸化物、又は導電性金属コーティングから選択される導電性保護コーティングでコートされるか、又は包含されることを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記高弾性ポリマーが、その中に分散された添加剤又は充填剤を有さないニートポリマーであることを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、その中に分散されたリチウムイオン導電性添加剤0.1重量%~50重量%を含有するか、或いは0.1重量%~10重量%のカーボンナノチューブ、カーボンナノ繊維、グラフェン及びそれらの組合せから選択される強化材ナノフィラメントを含有することを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーがリチウムイオン導電性添加剤と混合されて、複合物が形成され、前記リチウムイオン導電性添加剤が、前記高弾性ポリマー中に分散され、且つLi2CO3、Li2O、Li2C2O4、LiOH、LiX、ROCO2Li、HCOLi、ROLi、(ROCO2Li)2、(CH2OCO2Li)2、Li2S、LixSOy及びそれらの組合せ(式中、X=F、Cl、I又はBr、R=炭化水素基、x=0~1、y=1~4である)から選択されることを特徴とするリチウム二次バッテリー。
- 請求項1に記載のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、ポリアニリン、ポリピロール、ポリチオフェン、ポリフラン、二環式ポリマー、そのスルホン化誘導体又はその組合せから選択される電子導電性ポリマーと混合されて、ブレンド、コポリマー又は半相互侵入ネットワークが形成されることを特徴とするリチウム二次バッテリー。
- 請求項1のリチウム二次バッテリーにおいて、前記超高分子量ポリマーが、0.5×106g/モル未満の分子量を有するリチウムイオン導電性ポリマーとの混合物、ブレンド、コポリマー、又は半相互侵入ネットワークを形成し、且つポリ(エチレンオキシド)(PEO)、ポリプロピレンオキシド(PPO)、ポリ(アクリロニトリル)(PAN)、ポリ(メチルメタクリレート)(PMMA)、ポリ(ビニリデンフルオリド)(PVdF)、ポリビス-メトキシエトキシエトキシド-ホスファゼンエクス(phosphazenex)、ポリビニルクロリド、ポリジメチルシロキサン、ポリ(ビニリデンフルオリド)-ヘキサフルオロプロピレン(PVDF-HFP)、それらのスルホン化誘導体、及びそれらの組合せから選択されることを特徴とするリチウム二次バッテリー。
- 請求項1のリチウム二次バッテリーにおいて、前記カソードが、硫黄、硫黄含有分子、硫黄含有化合物、金属硫化物、硫黄-炭素ポリマー、リチウム多硫化物、硫黄/炭素ハイブリッド又は複合材料、硫黄/黒鉛ハイブリッド又は複合材料、硫黄/グラフェンハイブリッド又は複合材料、硫黄-ポリマー化合物、及びその組合せを含んでなるリチウム-硫黄バッテリーであることを特徴とするリチウム二次バッテリー。
- 請求項1のリチウムバッテリーにおいて、リチウム金属バッテリー、リチウム-硫黄バッテリー、リチウム-セレンバッテリー、又はリチウム-エアバッテリーであることを特徴とするリチウムバッテリー。
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CN110710023A (zh) | 2020-01-17 |
JP2020517054A (ja) | 2020-06-11 |
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KR20190130170A (ko) | 2019-11-21 |
US10770721B2 (en) | 2020-09-08 |
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CN110710023B (zh) | 2023-11-03 |
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