TWI815251B - 電解質、以及包含其之鋰離子電池 - Google Patents
電解質、以及包含其之鋰離子電池 Download PDFInfo
- Publication number
- TWI815251B TWI815251B TW110148114A TW110148114A TWI815251B TW I815251 B TWI815251 B TW I815251B TW 110148114 A TW110148114 A TW 110148114A TW 110148114 A TW110148114 A TW 110148114A TW I815251 B TWI815251 B TW I815251B
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- Prior art keywords
- electrolyte
- fluorine
- lithium
- present disclosure
- monomer
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 116
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 239000011737 fluorine Substances 0.000 claims abstract description 70
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 70
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 150000002118 epoxides Chemical class 0.000 claims abstract 5
- -1 LiGaCl 4 Inorganic materials 0.000 claims description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000002955 isolation Methods 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 16
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229920001155 polypropylene 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
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229910012424 LiSO 3 Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- PEXNRZDEKZDXPZ-UHFFFAOYSA-N lithium selenidolithium Chemical compound [Li][Se][Li] PEXNRZDEKZDXPZ-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 229910013075 LiBF Inorganic materials 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- CHTMGMOOSROXRD-UHFFFAOYSA-N 1,2-diethoxyethane Chemical group CCOCCOCC.CCOCCOCC CHTMGMOOSROXRD-UHFFFAOYSA-N 0.000 claims description 2
- ZRHKKTWFXVZSLS-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC.CCCCOCCOCCCC ZRHKKTWFXVZSLS-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- VIETUFSZPCIVQL-UHFFFAOYSA-N 1-methyl-3h-pyrrol-2-one Chemical compound CN1C=CCC1=O VIETUFSZPCIVQL-UHFFFAOYSA-N 0.000 claims description 2
- JGZFZZXWCPJDRH-UHFFFAOYSA-N 2-methyloxolane Chemical compound CC1CCCO1.CC1CCCO1 JGZFZZXWCPJDRH-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 2
- 229910013398 LiN(SO2CF2CF3)2 Inorganic materials 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- UZZWBUYVTBPQIV-UHFFFAOYSA-N dme dimethoxyethane Chemical compound COCCOC.COCCOC UZZWBUYVTBPQIV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- GKWAQTFPHUTRMG-UHFFFAOYSA-N lithium telluride Chemical compound [Li][Te][Li] GKWAQTFPHUTRMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229910021332 silicide Inorganic materials 0.000 claims description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims 1
- 229910013131 LiN Inorganic materials 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 description 32
- 230000003647 oxidation Effects 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 22
- 230000014759 maintenance of location Effects 0.000 description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 20
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 17
- 241000285023 Formosa Species 0.000 description 16
- DSSYKIVIOFKYAU-UHFFFAOYSA-N camphor Chemical compound C1CC2(C)C(=O)CC1C2(C)C DSSYKIVIOFKYAU-UHFFFAOYSA-N 0.000 description 16
- 229920003023 plastic Polymers 0.000 description 16
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- 238000010438 heat treatment Methods 0.000 description 15
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- 238000000576 coating method Methods 0.000 description 12
- 239000002482 conductive additive Substances 0.000 description 12
- 238000005538 encapsulation Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- QERNPKXJOBLNFM-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentane Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(F)F QERNPKXJOBLNFM-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- ZLQGITSKRNWIOT-UHFFFAOYSA-N 5-(dimethylamino)furan-2-carbaldehyde Chemical compound CN(C)C1=CC=C(C=O)O1 ZLQGITSKRNWIOT-UHFFFAOYSA-N 0.000 description 6
- 239000006182 cathode active material Substances 0.000 description 6
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- HMXSIEIEXLGIET-UHFFFAOYSA-N 2-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 HMXSIEIEXLGIET-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MLBWTXHUVGBPNL-UHFFFAOYSA-N 1-pyridin-4-ylheptan-1-one Chemical compound CCCCCCC(=O)C1=CC=NC=C1 MLBWTXHUVGBPNL-UHFFFAOYSA-N 0.000 description 4
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 4
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 description 4
- RSVZYSKAPMBSMY-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)F RSVZYSKAPMBSMY-UHFFFAOYSA-N 0.000 description 4
- DFVPUWGVOPDJTC-UHFFFAOYSA-N 2,2,3,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)C(F)(F)F DFVPUWGVOPDJTC-UHFFFAOYSA-N 0.000 description 4
- LMVLEDTVXAGBJV-UHFFFAOYSA-N 2,2,3,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)C(F)C(F)(F)COC(=O)C=C LMVLEDTVXAGBJV-UHFFFAOYSA-N 0.000 description 4
- GYUPEJSTJSFVRR-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C GYUPEJSTJSFVRR-UHFFFAOYSA-N 0.000 description 4
- HBZFBSFGXQBQTB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HBZFBSFGXQBQTB-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 239000006245 Carbon black Super-P Substances 0.000 description 4
- 239000006257 cathode slurry Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- ZKRJCMKLCDWROR-ONEGZZNKSA-N ethyl (e)-4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)\C=C\C(F)(F)F ZKRJCMKLCDWROR-ONEGZZNKSA-N 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
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- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
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- ZSBBXERJYQIAAZ-UHFFFAOYSA-N [4,4-bis(dimethylamino)cyclohexa-1,5-dien-1-yl]-phenylmethanone Chemical compound CN(C1(CC=C(C(=O)C2=CC=CC=C2)C=C1)N(C)C)C.CN(C1(CC=C(C(=O)C2=CC=CC=C2)C=C1)N(C)C)C ZSBBXERJYQIAAZ-UHFFFAOYSA-N 0.000 description 1
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- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- YITAGJCAYNNEIP-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[Cr+3].[Mn++] Chemical compound [Li+].[O--].[O--].[O--].[Cr+3].[Mn++] YITAGJCAYNNEIP-UHFFFAOYSA-N 0.000 description 1
- PORYXSMWPCZBEK-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[V+5].[Co++] Chemical compound [Li+].[O--].[O--].[O--].[O--].[V+5].[Co++] PORYXSMWPCZBEK-UHFFFAOYSA-N 0.000 description 1
- MGBJUXYJNGMFMN-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[V+5].[Ni++] Chemical compound [Li+].[O--].[O--].[O--].[O--].[V+5].[Ni++] MGBJUXYJNGMFMN-UHFFFAOYSA-N 0.000 description 1
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 229910052787 antimony Inorganic materials 0.000 description 1
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- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000006001 difluoroethyl group Chemical group 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
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- GOPRFQYEQXSXNS-UHFFFAOYSA-N ethyl 2-[4-[4,6-bis(trichloromethyl)-1,3,5-triazin-2-yl]phenyl]sulfanylacetate Chemical compound C1=CC(SCC(=O)OCC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 GOPRFQYEQXSXNS-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BVPMZCWLVVIHKO-UHFFFAOYSA-N lithium cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Co+2].[Li+] BVPMZCWLVVIHKO-UHFFFAOYSA-N 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
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate 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
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BCVXHSPFUWZLGQ-UHFFFAOYSA-N mecn acetonitrile Chemical compound CC#N.CC#N BCVXHSPFUWZLGQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- ALIATVYMFGMEJC-UHFFFAOYSA-N phenyl-[2,4,6-tris(methylamino)phenyl]methanone Chemical compound CNC1=CC(NC)=CC(NC)=C1C(=O)C1=CC=CC=C1 ALIATVYMFGMEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WGFLSDNAKHGQFS-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1.CC(C)(C)OOC(=O)C1=CC=CC=C1 WGFLSDNAKHGQFS-UHFFFAOYSA-N 0.000 description 1
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
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Images
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Abstract
Description
本揭露關於一種聚合物、電解質、以及包含其之鋰離子電池。
鋰離子電池已成為商業化電池之主流,並朝向更輕薄短小、能量密度更高、壽命更長及更安全之方向努力。
現行液態鋰離子電池之重量能量密度偏低,循環壽命有限,導致單位蓄電成本居高不下。但是單方面提升電池之能量密度,容易加速誘發電化學電池一連串安全問題,其中包括漏液、膨罐、發熱、冒煙、燃燒、或爆炸等問題,嚴重限制使用性。
此外,當提昇鋰離子電池的操作電壓時,易使得電解質的氧化反應加速,導致電池在高電壓充電時的穩定性差。雖然,業界進一步提出加入聚合物作為電解質添加劑來改善穩定性,但傳統用於電解質的聚合物其於電解質系統中的界面阻抗仍然偏高,且亦無法有效抑制電解質的氧化反應。
因此,業界需要一種新穎的電解質,以應用於鋰離子電池中解決上述問題。
根據本揭露實施例,本揭露提供一種聚合物。該聚合物可為一組合物經一反應(例如聚合反應)之產物。根據本揭露實施例,該組合物可包含一第一單體以及一第二單體。該第一單體可具有式(I)所示結構。該第二單體可為含氟丙烯酸酯(fluorine-containing acrylate)、含氟烯(fluorine-containing alkene)、含氟環氧化合物(fluorine-containing epoxide)、或上述之組合。
式(I)
其中,n、m、以及l可獨立為1、2、3、4、5、或6, R
1、R
2、以及R
3可獨立為-OH、
、
或
,R
4、R
5、以及R
6可獨立為氫、或C
1-3烷基。
根據本揭露其他實施例,本揭露提供一種電解質,例如用於鋰離子電池的電解質。該電解質可包含一鋰鹽、一溶劑、以及上述聚合物(例如作為電解質添加劑)。根據本揭露實施例,該聚合物的含量可為2wt%至20 wt%,以該溶劑、鋰鹽以及聚合物的總重為基準。
根據本揭露其他實施例,本揭露提供一種鋰離子電池,例如鋰離子二次電池。該鋰離子電池可包括一正極、一負極、一隔離膜、以及上述電解質。其中,該隔離膜配置於該正極與該負極之間;以及,該電解質可設置於該正極與負極之間。
以下針對本揭露之聚合物、電解質、以及鋰離子電池作詳細說明。應了解的是,以下之敘述提供許多不同的實施例或例子,用以實施本揭露之不同樣態。以下所述特定的元件及排列方式僅為簡單描述本揭露。當然,這些僅用以舉例而非本揭露之限定。此外,在不同實施例中可能使用重複的標號或標示。這些重複僅為了簡單清楚地敘述本揭露,不代表所討論之不同實施例及/或結構之間具有任何關連性。本揭露中,用詞「約」係指所指定之量可增加或減少一本領域技藝人士可認知為一般且合理的大小的量。
必需了解的是,為特別描述或圖示之元件可以此技術人士所熟知之各種形式存在。此外,當某層在其它層或基板「上」時,有可能是指「直接」在其它層或基板上,或指某層在其它層或基板上,或指其它層或基板之間夾設某層。
且在圖式中,實施例之形狀或是厚度可擴大,並以簡化或是方便標示。再者,圖式中各元件之部分將以分別描述說明之,值得注意的是,圖中未繪示或描述之元件,為所屬技術領域中具有通常知識者所知的形式,此外,特定之實施例僅為揭示本揭露使用之特定方式,其並非用以限定本揭露。
本揭露提供一種聚合物。藉由具有三個反應官能基之異氰脲酸酯單體(即第一單體)與特定比例的含氟可反應性單體(即第二單體)反應,使得本揭露所述聚合物可具有較鬆散的立體網狀結構(three-dimensional network structure)以及較佳的熱穩定性。另一方面,本揭露所述聚合物係為含氟之聚合物,因此具有疏水的性質可降低水氣通過,避免電池效能降低。本揭露亦提供一種電解質(例如鋰離子電池之電解質)。該電解質可為類固態(quasi-solid state)電解質,可藉由添加包含第一單體及第二單體的組合物至一具有鋰鹽的溶液中並進行一加熱製程後所得。由於所導入的聚合物具有較鬆散的立體網狀結構,因此在本揭露所述電解質中,該聚合物可利用分子間作用力吸附鋰鹽及溶劑,可降低電解質的界面阻抗、提昇電解質的離子導電度(例如可具有近似液態電解質之離子導電度(1x10
-2S/cm ~9x10
-3S/cm))、並增加電解質的電化學視窗。此外,由於該聚合物導入了含氟可反應性單體,使得該電解質整體的阻燃性提昇,並可使電解質同時具有抑制高電壓氧化反應的效能。在該電解質中,聚合物係以特定的比例搭配鋰鹽以及溶劑,以確保所得電解質符合耐高電壓鋰離子電池之需求。根據本揭露實施例,本揭露亦提供一種鋰離子電池。該鋰離子電池係包括上述電解質。藉由本揭露所述電解質,可進一步改善鋰離子電池的倍率放電性能以及延長鋰離子電池的循環壽命。
根據本揭露實施例,本揭露提供一種聚合物。該聚合物可為一組合物經一反應(例如聚合反應)之產物。根據本揭露實施例,該組合物可包含一第一單體以及一第二單體。該第一單體可具有式(I)所示結構。該第二單體可為含氟丙烯酸酯(fluorine-containing acrylate)、含氟烯(fluorine-containing alkene)、含氟環氧化合物(fluorine-containing epoxide)、或上述之組合。
式(I)
其中,n、m、以及l可獨立為1、2、3、4、5、或6; R
1、R
2、以及R
3可獨立為-OH、
、
或
;R
4、R
5、以及R
6可獨立為氫、或C
1-3烷基。根據本揭露實施例,本揭露所述C
1-3烷基可為直鏈或分支(linear or branched)鏈的烷基。舉例來說,C
1-3烷基可為甲基(methyl)、乙基(ethyl)、丙基(propyl)、或其異構體(isomer)。
根據本揭露實施例,該第一單體可進行自聚合,或與該第二單體進行共聚合,使得該聚合物具有立體網狀結構(three-dimensional network structure)。根據本揭露實施例,該第一單體與該第二單體的重量比可為約5:1至1:2,例如4:1、3:1、2:1、1:1、或2:3。當第一單體與該第二單體的重量比過高時,所得之聚合物具有較為緻密的立體網狀結構,且使得聚合物之氟含量下降。如此一來,將使得後續包含該聚合物之電解質的界面阻抗增加、降低電解質離子導電度,並且使所得之電解質在高電壓操作下易發生氧化反應。此外,當第一單體與該第二單體的重量比過低時,將導致聚合物無法固化電解質,使電解質高電壓操作易產生氧化反應,增加不可逆容量損失與劣化電池循環壽命。
根據本揭露實施例,該第一單體可為
、
、
、
、或上述組合。其中,R
4、R
5、以及R
6係獨立為氫、或C
1-3烷基。
根據本揭露實施例,該第一單體可為1,3,5-三烯丙基異氰脲酸酯(1,3,5-triallyl isocyanurate,TAIC)、三甲基烯丙基異氰脲酸酯(1,3,5- trimethallyl isocyanurate,TMAIC)、1,3,5- 三(2-羥乙基)異氰脲酸酯(1,3,5-tris(2-hydroxyethyl)isocyanurate)、異氰脲酸三縮水甘油酯(triglycidyl isocyanurate)、三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、或上述之組合。
根據本揭露實施例,該第二單體可為含氟丙烯酸酯(fluorine-containing acrylate)。根據本揭露實施例,該第二單體可為具有丙烯酸酯基的含氟化合物。該第二單體可為具有一個丙烯酸酯基的含氟化合物、或具有二個丙烯酸酯基的含氟化合物。根據本揭露實施例,該含氟丙烯酸酯可具有式(II)所示結構
式(II)
,其中i係0、1、2、3、4、5、6、7、8、或9;R
7、R
8、R
9 、R
10、R
11 、以及R
12 係獨立為氫、氟、C
1-3烷基、或C
1-3氟烷基,且R
7、R
8 、R
9、R
10 、R
11 以及R
12 之至少一者為氟或C
1-3氟烷基。根據本揭露實施例,當i係2、3、4、5、6、7、8、或9時,R
10係獨立為氫、氟、C
1-3烷基、或C
1-3氟烷基、以及R
11 係獨立為氫、氟、C
1-3烷基、或C
1-3氟烷基。根據本揭露實施例,該含氟丙烯酸酯可具有式(III)所示結構
式(III)
j係1、2、3、4、5、或6;R
13、R
14、R
15、R
16、R
17 、R
18、R
19、以及R
20係獨立為氫、氟、C
1-3烷基、或C
1-3氟烷基,且R
13、R
14、R
15、R
16、R
17 、R
18、R
19、以及R
20之至少一者為氟或C
1-3氟烷基。根據本揭露實施例,當j係2、3、4、5、或6時,R
16係獨立為氫、氟、C
1-3烷基、或C
1-3氟烷基、以及R
17 係獨立為氫、氟、C
1-3烷基、或C
1-3氟烷基。本揭露所述C
1-3氟烷基係指碳上的氫全部或部份被氟取代的烷基,且可為直鏈(linear)或分支鍵(branched),例如氟甲基、氟乙基、氟丙基、或其異構體(isomer)。在此,本揭露所述氟甲基可為單氟甲基、二氟甲基、或全氟甲基;而氟乙基可為單氟乙基、二氟乙基、三氟乙基、四氟乙基、或全氟乙基。
根據本揭露實施例,該含氟丙烯酸酯可為2-氟丙烯酸甲酯(methyl 2-fluoroacrylate)、2-氟丙烯酸乙酯(ethyl 2-fluoroacrylate)、4,4,4-三氟巴豆酸乙酯(ethyl 4,4,4-trifluorocrotonate)、1,6-二(丙烯醯氧基)-2,2,3,3,4,4,5,5-八氟己烷(1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane)、全氟辛基乙基丙烯酸酯(1H,1H,2H,2H-heptadecafluorodecyl acrylate)、丙烯酸1H,1H,2H,2H-九氟己酯(1H,1H,2H,2H-nonafluorohexyl acrylate) 、丙烯酸1,1,1,3,3,3-六氟異丙酯(1,1,1,3,3,3-hexafluoroisopropyl acrylate)、丙烯酸1H, 1H,2H,2H-十七氟癸酯(1H,1H,2H,2H-heptadecafluorodecyl acrylate)、甲基丙烯酸1H,1H,2H,2H-十七氟癸酯(1H,1H,2H,2H-heptadecafluorodecyl methacrylate)、丙烯酸1H,1H,3H-六氟丁酯(1H,1H,3H-hexafluorobutyl acrylate)、甲基丙烯酸1H,1H,3H-六氟丁酯(1H,1H,3H-hexafluorobutyl methacrylate)、甲基丙烯酸1H,1H,3H-四氟丙酯(1H,1H,3H-tetrafluoropropyl methacrylate)、丙烯酸1H,1H,5H-八氟戊酯(1H,1H,5H-octafluoropentyl acrylate)、甲基丙烯酸1H,1H,5H-八氟戊酯(1H,1H,5H-octafluoropentyl methacrylate)、甲基丙烯酸1H, 1H,7H-十二氟庚酯(1H,1H,7H-dodecafluoroheptyl methacrylate)、丙烯酸1H,1H-七氟丁酯(1H,1H-heptafluorobutyl acrylate)、丙烯酸2,2,2-三氟乙酯(2,2,2-trifluoroethyl acrylate)、甲基丙烯酸2,2,2-三氟乙酯(2,2,2-trifluoroethyl methacrylate)、甲基丙烯酸六氟異丙酯(hexafluoro-iso-propyl methacrylate)、或上述之組合。
根據本揭露實施例,該第二單體可為含氟烯(fluorine-containing alkene)。根據本揭露實施例,該第二單體可為具有烯基的含氟化合物。根據本揭露實施例,該含氟烯可具有式(IV)所示結構
式(IV)
,其中k係1、2、3、4、5、6、7、8、或9;以及,R
21、R
22、以及R
23 係獨立為氫、或氟。根據本揭露實施例,R
21、R
22、以及R
23 之至少一者為氟。
根據本揭露實施例,該含氟烯可為全氟丙基乙烯(perfluoropropyl ethylene)、全氟丁基乙烯(perfluorobutyl ethylene)、全氟戊基乙烯(perfluoropentyl ethylene)、全氟己基乙烯(perfluorohexyl ethylene)、全氟庚基乙烯(perfluoroheptyl ethylene) 、全氟辛基乙烯(perfluorooctyl ethylene)、或上述之組合。
根據本揭露實施例,該第二單體可為含氟環氧化合物(fluorine-containing epoxide)。根據本揭露實施例,該第二單體可為具有環氧基的含氟化合物。該含氟環氧化合物可具有式(V)所示結構
式(V)
,其中p係1、2、3、4、5、6、7、8、或9;R
24 係氫、氟、或C
1-3烷基;以及,R
25、R
26、以及R
27 係獨立為氫、或氟。根據本揭露實施例,R
24 、R
25、R
26、以及R
27 之至少一者為氟。根據本揭露實施例,該含氟環氧化合物係3-(全氟正辛基)-1,2-環氧丙烷(3-perfluorooctyl-1,2-epoxypropane)。
根據本揭露實施例,該第二單體可為2-氟丙烯酸甲酯(methyl 2-fluoroacrylate)、2-氟丙烯酸乙酯(ethyl 2-fluoroacrylate)、4,4,4-三氟巴豆酸乙酯(ethyl 4,4,4-trifluorocrotonate)、1,6-二(丙烯醯氧基)-2,2,3,3,4,4,5,5-八氟己烷(1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane)、全氟辛基乙基丙烯酸酯(1H,1H,2H,2H-heptadecafluorodecyl acrylate)、丙烯酸1H,1H,2H,2H-九氟己酯(1H,1H,2H,2H-nonafluorohexyl acrylate) 、丙烯酸1,1,1,3,3,3-六氟異丙酯(1,1,1,3,3,3-hexafluoroisopropyl acrylate)、丙烯酸1H, 1H,2H,2H-十七氟癸酯(1H,1H,2H,2H-heptadecafluorodecyl acrylate)、甲基丙烯酸1H,1H,2H,2H-十七氟癸酯(1H,1H,2H,2H-heptadecafluorodecyl methacrylate)、丙烯酸1H,1H,3H-六氟丁酯(1H,1H,3H-hexafluorobutyl acrylate)、甲基丙烯酸1H,1H,3H-六氟丁酯(1H,1H,3H-hexafluorobutyl methacrylate)、甲基丙烯酸1H,1H,3H-四氟丙酯(1H,1H,3H-tetrafluoropropyl methacrylate)、丙烯酸1H,1H,5H-八氟戊酯(1H,1H,5H-octafluoropentyl acrylate)、甲基丙烯酸1H,1H,5H-八氟戊酯(1H,1H,5H-octafluoropentyl methacrylate)、甲基丙烯酸1H, 1H,7H-十二氟庚酯(1H,1H,7H-dodecafluoroheptyl methacrylate)、丙烯酸1H,1H-七氟丁酯(1H,1H-heptafluorobutyl acrylate)、丙烯酸2,2,2-三氟乙酯(2,2,2-trifluoroethyl acrylate)、甲基丙烯酸2,2,2-三氟乙酯(2,2,2-trifluoroethyl methacrylate)、甲基丙烯酸六氟異丙酯(hexafluoro-iso-propyl methacrylate)、全氟丙基乙烯(perfluoropropyl ethylene)、全氟丁基乙烯(perfluorobutyl ethylene)、全氟戊基乙烯(perfluoropentyl ethylene)、全氟己基乙烯(perfluorohexyl ethylene)、全氟庚基乙烯(perfluoroheptyl ethylene) 、全氟辛基乙烯(perfluorooctyl ethylene)、3-(全氟正辛基)-1,2-環氧丙烷(3-perfluorooctyl-1,2-epoxypropane)、或上述之組合。
根據本揭露實施例,當該第一單體為
時,該第二單體係含氟丙烯酸酯(fluorine-containing acrylate)、或含氟烯(fluorine-containing alkene)。
根據本揭露實施例,當該第一單體為
時,該第二單體係含氟丙烯酸酯(fluorine-containing acrylate)、或含氟烯(fluorine-containing alkene)。
根據本揭露實施例,其中當該第一單體為
時,該第二單體係含氟環氧化合物(fluorine-containing epoxide)。
根據本揭露實施例,當該第一單體係
時,該第二單體係含氟環氧化合物(fluorine-containing epoxide)。
根據本揭露實施例,用來形成該聚合物的組合物可更包含一起始劑。根據本揭露實施例,該起始劑的含量可為約0.01wt%至10wt%(例如:0.1wt%、0.5wt%、1wt%、2wt%、3wt%、4wt%、5wt%、6wt%、7wt%、8wt%、或9wt%),以該第一單體以及第二單體的總重為基準。根據本揭露實施例,該起始劑可為光起始劑、熱起始劑、電子束聚合起始劑、或上述之組合。
根據本揭露實施例,該起始劑可以為安息香系 (benzoin-based)化合物、苯乙酮系(acetophenone-based)化合物、噻噸酮系 (thioxanthone-based)化合物、縮酮 (ketal)化合物、苯甲酮系(benzophenone-based)化合物、α-氨基苯乙酮 (α-aminoacetophenone)化合物、醯基氧化膦 (acylphosphineoxide)化合物、二咪唑系(biimidazole-based)化合物、三嗪系 (triazine-based)化合物或上述之組合。安息香系化合物,例如安息香(benzoin)、安息香甲基醚(benzoin methyl ether)、或安息香二甲醚(benzyl dimethyl ketal);苯乙酮系化合物,例如對二甲胺苯乙酮(p-dimethylamino-acetophenone)、α,α’-二甲氧基氧化偶氮苯乙酮(α,α’-dimethoxyazoxy-acetophenone)、2,2’-二甲基-2-苯基苯乙酮(2,2’-dimethyl-2-phenyl-acetophenone)、對甲氧基苯乙酮(p-methoxy-acetophenone)、2-甲基-1-(4-甲基硫代苯基)-2-嗎啉代-1-丙酮(2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone)、2-苄基-2-氮,氮-二甲胺-1-(4-嗎啉代苯基)-1-丁酮(2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone);苯甲酮系化合物,例如二苯甲酮(benzophenone)、4,4-雙(二甲基氨基)二苯甲酮(4,4-bis(dimethylamino)benzophenone)、4,4-雙(二乙基氨基)二苯甲酮(4,4-bis(diethylamino)benzophenone)、2,4,6-三甲基氨基二苯甲酮醯(2,4,6-trimethylaminobenzophenone)、鄰苯甲醯苯甲酸甲酯(methyl-o-benzoyl benzoate)、3,3-二甲基-4-甲氧基二苯甲酮(3,3-dimethyl-4-methoxybenzophenone)、及3,3,4,4-四(叔丁基過氧化羰基)二苯甲酮(3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone);噻噸酮系化合物,例如噻噸酮(thioxanthone)、2,4-二乙基噻噸酮(2,4-diethyl-thioxanthanone)、噻噸酮-4-碸(thioxanthone-4-sulfone);二咪唑系化合物,例如2,2’-雙(鄰-氯苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(鄰-氟苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-fluorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(鄰-甲基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-methylphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(鄰-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(鄰-乙基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(o-ethylphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(對甲氧基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(p-methoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(2,2’,4,4’-四甲氧基苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(2,2’,4,4’-tetramethoxyphenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole]、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑[2,2’-bis(2,4-dichlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole];氧化膦系化合物,例如2,4,6-三甲基苯甲醯基二苯基氧化膦(2,4,6-trimethylbenzoyl diphenylphosphine oxide)及雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦(bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide);三嗪系化合物,例如為3-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸(3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid)、1,1,1,3,3,3-六氟異丙基-3-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸酯(1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionate)、乙基-2-{4-[2,4-雙(三氯甲基-s-三嗪-6-基]苯硫基}乙酸甲酯(ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate)、2-環氧乙基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯(2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate)、環己基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯(cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate)、芐基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯(benzyl-2-{4 -[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate)、3-{氯-4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸(3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid)、3-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙醯胺(3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionamide)、2,4-雙(三氯甲基)-6-對甲氧基苯乙烯基-S-三嗪(2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine)、2,4-雙(三氯甲基)-6-(1-對-二甲基氨基苯基)-1,3-丁二烯基-s-三嗪(2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3,-butadienyl-s-triazine)、或2-三氯甲基-4-氨基-6-對甲氧基苯乙烯基-s-三嗪(2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine)。
根據本揭露實施例,該起始劑可以為偶氮類(azo) 化合物、氰基戊酸系(cyanovaleric-acid-based)化合物、過氧化物(peroxide)或上述之組合。該偶氮類化合物,例如2,2’-偶氮雙(2,4-二甲基戊腈)(2,2’-azobis(2,4-dimethyl valeronitrile))、二甲基-2,2’-偶氮雙(2-丙酸甲酯)(dimethyl 2,2’-azobis(2-methylpropionate))、2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile,以下簡稱AIBN)、2,2-偶氮雙(2-甲 基異丁腈)(2,2-azobis(2-methylisobutyronitrile))、1,1’-偶氮雙(環己烷-1-腈)1,1’-azobis(cyclohexane-1-carbonitrile))、2,2’-偶氮雙[N-(2-丙烯基)-2-甲基丙醯胺](2,2’-azobis[N-(2-propenyl)-2-methylpropionamide])、1-[(氰基-1-甲基乙基)-偶氮基]甲醯胺(1-[(cyano-1-methylethyl)azo]formamide)、2,2’-偶氮雙(N-丁基-2-甲基丙醯胺)(2,2’-azobis(N-butyl-2-methylpropionamide))、或2,2’-偶氮雙(N-環己基-2-甲基丙醯胺)(2,2’-azobis(N-cyclohexyl-2-methylpropionamide));該過氧化物,例如苯甲醯基過氧化物(benzoyl peroxide)、1,1-雙(第三丁基過氧基)環己烷(1,1-bis(tert-butylperoxy)cyclohexane)、2,5-雙(第三丁基過氧基)-2,5-二甲基環己烷(2,5-bis(tert-butylperoxy)-2,5-dimethylcyclohexane)、2,5-雙(第三丁基過氧基)-2,5-二甲基-3-環己炔(2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-cyclohexyne)、雙(1-(第三丁基過氧基)-1-甲基乙基)苯(bis(1-(tert-butylpeorxy)-1-methy-ethyl)benzene)、第三丁基過氧化氫(tert-butyl hydroperoxide)、第三丁基過氧化物(tert-butyl peroxide)、過氧化苯甲酸第三丁基酯(tert-butyl peroxybenzoate)、茴香基過氧化氫(cumene hydroperoxide)、環己酮基過氧化物(cyclohexanone peroxide)、二茴香基過氧化物(dicumyl peroxide)、或月桂基過氧化物(lauroyl peroxide)。在一些實施例中,該起始劑可以為離子化合物,例如二氟草酸硼酸鋰(lithium difluoro(oxalato)borate,LiBF
2(C
2O
4))(LiDFOB)。
根據本揭露實施例,用來形成該聚合物的組合物由該第一單體、該第二單體、及該起始劑所組成。
根據本揭露實施例,該組合物可在50℃至150℃下反應60分鐘至600分鐘,以使該組合物進行一聚合反應,得到該聚合物。
根據本揭露實施例,本揭露所述該聚合物的重量平均分子量(Mw)可為約1,000至200,000,例如2,000至150,000、或3,000至100,000。舉例來說,本揭露所述聚合物之重量平均分子量(Mw)若低於約40,000時,可以凝膠滲透色層分析法(GPC)測得(以聚苯乙烯作為標準品製作檢量線)。
根據本揭露實施例,本揭露亦提供一種電解質,其中該電解質包含一鋰鹽、一溶劑、以及上述聚合物,其中該聚合物的含量為約2wt%至20 wt%(例如約2wt%、3wt%、4wt%、5wt%、6wt%、7wt%、8wt%、9wt%、10wt%、11wt%、12wt%、13wt%、14wt%、15wt%、16wt%、17wt%、18wt%、或19wt%),以該溶劑、鋰鹽以及聚合物的總重為基準。若該聚合物的含量過高,則所得電解質具有較低的離子導電度、及較高的界面阻抗。若該聚合物的含量過低,則所得電解質的阻燃性無法提昇,且不具有抑制高電壓氧化反應的效能。
根據本揭露實施例,該鋰鹽在該溶劑中的的濃度為約0.8M至1.6M,例如約0.9M、1.0M、1.1M、1.2M、1.3M、1.4M、或1.5M。
根據本揭露實施例,該電解質的製備方式包含以下步驟。首先,將一鋰鹽、一溶劑、以及一組合物混合,得到一混合物。接著,對該混合物進行一加熱製程(溫度可為50℃至150℃、以及時間可為60分鐘至600分鐘),得到本揭露所述電解質。根據本揭露實施例,該組合物包含該第一單體、以及該第二單體。根據本揭露實施例,該組合物包含該第一單體、該第二單體、以及該起始劑。根據本揭露實施例,該組合物由該第一單體、該第二單體、及該起始劑所組成。
根據本揭露實施例,該鋰鹽與該溶劑的重量比可為約1:19至7:13,例如約2:18、3:17、4:16、5:15、或6:14。根據本揭露實施例。該鋰鹽係六氟磷酸鋰(lithium hexafluorophosphate,LiPF
6)、過氯酸鋰(lithium perchlorate,LiClO
4)、雙氟磺醯亞胺鋰(bis(fluorosulfonyl)imide lithium,LiN(SO
2F)
2)(LiFSI) 、二氟草酸硼酸鋰(lithium difluoro(oxalato)borate,LiBF
2(C
2O
4))(LiDFOB)、四氟硼酸鋰(lithium tetrafluoroborate,LiBF
4)、 三氟甲磺酸鋰(lithium trifluoromethanesulfonate,LiSO
3CF
3)、雙(三氟甲磺醯基)醯亞胺鋰(bis(trifluoromethane)sulfonimide lithium,LiN(SO
2CF
3)
2)(LiTFSI)、雙(五氟乙基磺醯基)亞胺鋰(lithium bis perfluoroethanesulfonimide,LiN(SO
2CF
2CF
3)
2)、六氟砷酸鋰(LiAsF
6)、六氟銻酸鋰(LiSbF
6)、四氯鋁酸鋰(LiAlCl
4)、四氯鎵酸鋰(LiGaCl
4)、硝酸鋰(LiNO
3)、三(三氟甲基磺醯)甲基鋰(tris(trifluoromethanesulfonyl)methyllithium,LiC(SO
2CF
3)
3)、硫氰酸鋰水合物(lithium thiocyanate hydrate,LiSCN)、LiO
3SCF
2CF
3、LiC
6F
5SO
3、LiO
2CCF
3、氟磺酸鋰(lithiumfluorosulfonate,LiSO
3F)、四(五氟苯基)硼酸鋰(Lithium tetrakis(pentafluorophenyl)borate,LiB(C
6H
5)
4)、二草酸硼酸锂(lithium bis(oxalato)borate,LiB(C
2O
4)
2)(LiBOB)、或上述之組合。
根據本揭露實施例,該溶劑可為有機溶劑,例如酯類溶劑、酮類溶劑、碳酸酯類溶劑、醚類溶劑、烷類溶劑、醯胺類溶劑、或上述之組合。根據本揭露實施例,該溶劑可為1,2-二乙氧基乙烷(1,2-diethoxyethane)、1,2-二甲氧基乙烷(1,2-dimethoxyethane)、1,2-二丁氧基乙烷(1,2-dibutoxyethane) 、四氫呋喃(tetrahydrofuran)、2-甲基四氫呋喃(2-methyl tetrahydrofuran)、二甲基乙醯胺(dimethylacetamide,DMAc)、N-甲基吡咯酮 (N-methyl-2-pyrrolidone,NMP)、乙酸甲酯(methyl acetate)、乙酸乙酯(ethyl acetate)、丁酸甲酯(methyl butyrate)、丁酸乙酯(ethyl butyrate)、丙酸甲酯(methyl proionate)、丙酸乙酯(ethyl proionate)、乙酸丙酯(propyl acetate,PA)、丁基內酯(γ-butyrolactone,GBL)、碳酸乙烯酯(ethylene carbonate,EC)、碳酸丙烯酯(propylene carbonate,PC)、碳酸二乙酯(diethyl carbonate,DEC)、碳酸甲乙酯(ethylmethyl carbonate,EMC)、碳酸二甲酯(dimethyl carbonate,DMC)、碳酸乙烯基酯(vinylene carbonate)、碳酸丁烯酯(butylene carbonate)、1,3-丙磺酸內酯(1,3-propanesultone) 、碳酸二丙基酯(dipropyl carbonate)、或上述之組合。
根據本揭露實施例,本揭露亦提供一鋰離子電池,包括上述電解質。請參照第1圖,該鋰離子電池100包括一負極10、一正極20、以及一隔離膜30,其中該負極10係以該隔離膜30與該正極20相隔。根據本揭露實施例,該電池100可包括一電解質40,且該電解質40設置於該負極10與正極20之間。換言之,該負極10、隔離膜30與正極20的相互堆疊結構是浸泡於該電解質40中。根據本揭露實施例,電解質是散佈於整個電池100內。
根據本揭露實施例,該負極10包含一負極活性層,其中該負極活性層包含一負極活性材料。根據本揭露實施例,該負極活性材料可為鋰金屬、鋰合金、過渡金屬氧化物、穩相球狀碳(MCMB)、奈米碳管(CNT)、石墨烯、焦炭、石墨(例如人造石墨、天然石墨)、碳黑、碳纖維、中間相碳微球、玻璃質碳、含鋰化合物、含矽化合物、錫、含錫化合物、或上述之組合。根據本揭露實施例,該含鋰化合物可包含LiAl、LiMg、LiZn、Li
3Bi、Li
3Cd、Li
3Sb、Li
4Si、Li
4.4Pb、Li
4.4Sn、LiC
6、Li
3FeN
2、Li
2.6Co
0.4N、或Li
2.6Cu
0.4N。根據本揭露實施例,該含矽化合物可包含氧化矽、碳修飾之氧化矽、矽碳或純矽材料、或上述之組合。根據本揭露實施例,該含錫化合物可包含錫銻合金(SnSb)和錫氧化物(SnO)。根據本揭露實施例,該過渡金屬氧化物可包含Li
4Ti
5O
12、或TiNb
2O
7。根據本揭露實施例,該鋰合金可例如為含鋁鋰之合金(aluminum-lithium-containing alloy)、含鋰鎂之合金(lithium-magnesium-containing alloy)、含鋰鋅之合金(lithium-zinc-containing alloy)、含鋰鉛之合金(lithium-lead-containing alloy)、或含鋰錫之合金(lithium-tin-containing alloy)。
根據本揭露實施例,該負極活性層可更包含一導電添加劑,其中該導電添加劑可例如為碳黑、導電石墨、奈米碳管、碳纖維、或石墨烯。根據本揭露實施例,該負極活性層可更包含一黏著劑,其中該黏著劑可包含聚乙烯醇、聚四氟乙烯、羧甲基纖維素鈉、聚偏氟乙烯、聚苯乙烯丁二烯共聚物、氟化橡膠、聚氨脂、聚乙烯基吡咯烷酮、聚丙烯酸乙脂、聚氯乙烯、聚丙烯腈、聚丁二烯、聚丙烯酸、或上述的組合。
根據本揭露實施例,該負極10可更包含一負極集電層,而該負極活性材料配置於該負極集電層之上。根據本揭露實施例,該負極活性材料可配置於該隔離膜及該負極集電層之間。根據本揭露實施例,該負極集電層可為導電性碳基材、金屬箔、或具有多孔結構的金屬材料,例如碳布、碳氈、或碳紙、銅箔、鎳箔、鋁箔、鎳網、銅網、鉬網、發泡鎳、發泡銅、或發泡鉬。根據本揭露實施例,具有多孔結構的金屬材料可具有一孔隙率約為10%至99.9%(例如:約60%、或70%)。
根據本揭露實施例,該負極活性層可由一負極漿料所製備而得。根據本揭露實施例,該負極漿料可包含負極活性材料、導電添加劑、黏著劑、以及一溶劑,其中該負極活性材料、導電添加劑、黏著劑分散於該溶劑中,其中該負極漿料的固含量可為40wt%至80wt%。根據本揭露實施例,該負極的製備方式可包含以下步驟。首先,將負極漿料以一塗佈製程形成在該負極集電層的表面,形成一塗層。接著,對該塗層進行一乾燥製程(製程溫度可為50℃至180℃),得到具有負極活性層的負極。根據本揭露實施例,該溶劑可為N-甲基吡咯烷酮(NMP)、N, N-二甲基甲醯胺(DMF)、N, N-二甲基乙醯胺(DMAc)、吡咯烷酮(pyrrolidone)、N-月桂基吡咯烷酮(N-dodecylpyrrolidone)、γ-丁內酯(γ- butyrolactone)、水(water)、或上述之組合。根據本揭露實施例,該塗佈製程可為網印、旋轉塗佈法(spin coating)、棒狀塗佈法(bar coating)、刮刀塗佈法(blade coating)、滾筒塗佈法(roller coating)、溶劑澆鑄法(solvent casting)、或浸漬塗佈法(dip coating)。
根據本揭露實施例,在該負極活性層中,該負極活性材料可具有一重量百分比為約80wt%至99.8wt%、該導電添加劑可具有一重量百分比為約0.1wt%至10wt%、以及該黏著劑可具有一重量百分比為約0.1wt%至10wt%,以該負極材料、該導電添加劑、及該黏著劑之總重為基準。
根據本揭露實施例,該正極10包含一正極活性層,其中該正極活性層包含一正極活性材料。根據本揭露實施例,該正極活性材料可為硫、有機硫化物、硫碳複合物(sulfur-carbon composite)、含金屬之氧化鋰、含金屬之硫化鋰、含金屬之硒化鋰、含金屬之碲化鋰、含金屬之磷化鋰、含金屬之矽化鋰、含金屬之硼化鋰、或上述之組合,其中該金屬係擇自由鋁、釩、鈦、鉻、銅、鉬、鈮、鐵、鎳、鈷、及錳所組成的族群中之至少一者。根據本揭露實施例,該正極材料可為氧化鋰鈷(lithium cobalt oxide)、氧化鋰鎳(lithium nickle oxide)、氧化鋰錳(lithium manganese oxide)、氧化鋰鈷錳(lithium cobalt manganese oxide)、氧化鋰鎳鈷(lithium nickel cobalt oxide)、氧化鋰錳鎳(lithium nickle manganese oxide)、氧化鋰鎳錳鈷 (lithium nickle manganese cobalt oxide)、磷酸鋰鈷(lithium cobalt phosphate)、氧化鋰錳鉻(lithium-chromium-manganese oxide)、氧化鋰鎳釩(lithium-nickel-vanadium oxide)、氧化鋰錳鎳(lithium-manganese-nickel oxide)、氧化鋰鈷釩(lithium-cobalt-vanadium oxide)、氧化鋰鎳鈷鋁(lithium-nickle-cobalt-aluminum oxide)、磷酸鋰鐵(lithium iron phosphate)、磷酸鋰錳鐵(lithium manganese iron phosphate)、或上述之組合。
根據本揭露實施例,該正極活性層可更包含一導電添加劑,其中該導電添加劑可例如為碳黑、導電石墨、奈米碳管、碳纖維、或石墨烯。根據本揭露實施例,該正極活性層可更包含一黏著劑,其中該黏著劑可包含聚乙烯醇、聚四氟乙烯、羧甲基纖維素鈉、聚偏氟乙烯、聚苯乙烯丁二烯共聚物、氟化橡膠、聚氨脂、聚乙烯基吡咯烷酮、聚丙烯酸乙脂、聚氯乙烯、聚丙烯腈、聚丁二烯、聚丙烯酸、或上述的組合。
根據本揭露實施例,該正極可更包含一正極集電層,而該正極活性材料配置於該正極集電層之上。根據本揭露實施例,該正極活性材料可配置於該隔離膜及該正極集電層之間。根據本揭露實施例,該正極集電層可為導電性碳基材、金屬箔、或具有多孔結構的金屬材料,例如碳布、碳氈、或碳紙、銅箔、鎳箔、鋁箔、鎳網、銅網、鉬網、發泡鎳、發泡銅、或發泡鉬。根據本揭露實施例,具有多孔結構的金屬材料可具有一孔隙率約為10%至99.9%(例如:約60%、或70%)。
根據本揭露實施例,該正極活性層可由一正極漿料所製備而得。根據本揭露實施例,該正極漿料可包含正極活性材料、導電添加劑、黏著劑、以及一溶劑,其中該正極活性材料、導電添加劑、黏著劑分散於該溶劑中,其中該正極漿料的固含量可為40wt%至80wt%。根據本揭露實施例,該正極的製備方式可包含以下步驟。首先,將正極漿料以一塗佈製程形成在該正極集電層的表面,形成一塗層。接著,對該塗層進行一乾燥製程(製程溫度可為90℃至180℃),得到具有正極活性層的正極。根據本揭露實施例,該溶劑可為N-甲基吡咯烷酮(NMP)、N, N-二甲基甲醯胺(DMF)、N, N-二甲基乙醯胺(DMAc)、吡咯烷酮(pyrrolidone)、N-月桂基吡咯烷酮(N-dodecylpyrrolidone)、γ-丁酸內酯(γ- butyrolactone)、或上述之組合。根據本揭露實施例,該塗佈製程可為網印、旋轉塗佈法(spin coating)、棒狀塗佈法(bar coating)、刮刀塗佈法(blade coating)、滾筒塗佈法(roller coating)、溶劑澆鑄法(solvent casting)、或浸漬塗佈法(dip coating)。
根據本揭露實施例,在該正極活性層中,該正極活性材料可具有一重量百分比為約80wt%至99.8wt%、該導電添加劑可具有一重量百分比為約0.1wt%至10wt%、以及該黏著劑可具有一重量百分比為約0.1wt%至10wt%,以該正極材料、該導電添加劑、及該黏著劑之總重為基準。
根據本揭露實施例,該隔離膜30可為絕緣材料,例如聚乙烯(PE)、聚丙烯(polypropylene,PP)、聚四氟乙烯膜、聚醯胺膜、聚氯乙烯膜、聚二氟乙烯膜、聚苯胺膜、聚醯亞胺膜、聚對苯二甲二乙酯(polyethylene terephthalate)、聚苯乙烯(polystyrene,PS)、纖維素(cellulose)、或上述組合。舉例來說,該隔離膜可例如為PE/PP/PE多層複合結構。根據本揭露實施例,該隔離膜的厚度並無特別限制,所屬技術領域中具有通常知識者可視實際需要加以調整。根據本揭露實施例,舉例來說,該隔離膜30的厚度可約為1μm至1,000μm(例如約10μm、50μm、100μm、200μm、300μm、400μm、500μm、600μm、700μm、800μm、或900μm)。若隔離膜的厚度過高,則降低電池的能量密度。若隔離膜的厚度過低,則膜材機械強度不足增加正負極短路風險,同時增加電池自放電現象,且影響電池循環穩定性。
為了讓本揭露之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉數實施例及比較實施例,作詳細說明如下:
聚合物的製備
實施例1:
將50重量份的三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、50重量份的全氟丁基乙烯(perfluorobutyl ethylene)、以及0.5重量份的2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile,AIBN)溶於乙腈(acetonitrile)中,得到一溶液,其中該溶液之固含量為30wt%。接著,將該溶液加熱至70℃並反應2小時,得到聚合物。
接著,利用核磁共振光譜分析實施例1所述聚合物,所得之光譜資訊如下所示:
1H NMR (CDCl
3, 500 MHz) 4.32-4.37 (m), 3.42-3.47 (m), 2.24-2.30 (m), 1.66-1.70 (m), 1.60-1.64 (m), 1.27-1.32 (m), 1.12-1.17 (m)。
電解質
實施例2:
將89.95wt%標準電解液(購自台塑、商品編號為EED352,由20wt%碳酸二乙酯、4wt%碳酸丙烯酯、18wt%碳酸二甲酯、15wt%碳酸甲乙酯、22wt%碳酸乙烯酯、6wt%1,3-丙烷磺內酯、以及15wt%六氟磷酸鋰所組成)、5wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、5wt%全氟丁基乙烯(perfluorobutyl ethylene)、以及0.05wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile,AIBN)混合,得到一混合物。接著,將該混合物加熱至70℃並反應2小時,使得三(2-丙烯醯氧乙基)異氰脲酸酯與全氟丁基乙烯進行聚合,得到電解質。
接著,以點火槍分別嘗試將實施例2所得電解質與標準電解液(購自台塑、商品編號為EED352)點燃,可觀察到實施例2所得電解質無法被點燃,而標準電解液則可輕易被點燃並且持續燃燒。
鋰離子電池
實施例3:
將標準鋰離子電池正極漿料(包括97.3wt%NMC811(LiNi
iMn
jCo
kO
2;其中i:0.83~0.85;j:0.4~0.5;k:0.11~0.12)(商品編號為NMC811-S85E,由寧波容百新能源科技公司製造)、1 wt %Super-P(導電碳粉,購自Timcal)、1.4 wt%PVDF-5130、以及0.3 wt %奈米碳管(商品編號為TUBALL™ BATT,購自OCSiAl);其中,NMC811-S85E、Super-P、PVDF-5130、奈米碳管均勻分散於N-甲基砒喀烷酮(NMP)中)塗佈於一鋁箔(作為正極集電層)(購自安全企業,厚度為12微米)上。乾燥後,得到一正極。
接著,將標準負極漿料(包含96.3wt%的SiO/C(氧化矽與碳的混合物) (編號為KYX-2,購自凱金新能源)、0.3wt% Super-P(導電碳粉,購自Timcal)、1.5wt%丁苯橡胶(styrene butadiene rubber,SBR)(購自JSR)、1.3wt% 的羧甲基纖維素(CMC)(商品編號為CMC-2200,購自Daicel Chemical industries)、以及0.6wt%奈米碳管(商品編號為TUBALL™,購自OCSiAl) ;其中,SiO/C、Super-P、SBR、CMC、以及奈米碳管均勻混合分散於去離子水中),塗佈於一銅箔(商品編號BFR-F,購自長春公司)(厚度為12微米)上。乾燥後,得到一負極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。
接著,依照負極/隔離膜/正極的順序排列,並注入一混合物(包含89.95wt%標準電解液(購自台塑、商品編號為EED352,由20wt%碳酸二乙酯、4wt%碳酸丙烯酯、18wt%碳酸二甲酯、15wt%碳酸甲乙酯、22wt%碳酸乙烯酯、6wt%1,3-丙烷磺內酯、以及15wt%六氟磷酸鋰所組成)、5wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、5wt%全氟丁基乙烯(perfluorobutyl ethylene)、以及0.05wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile))。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表1所示。
高電壓氧化電流係以電化學線性掃瞄伏安法(Linear Sweep Voltammetry, LSV)對電池進行量測,量測條件如下:掃描速率為10mV/s、以及電壓範圍為3.0V至5.5V,並記錄在5.5V的電流數值。電流數值愈大則表示電解質在高電壓下的氧化反應活性越高、而穩定性越差。電容維持率係以0.5C/1C的充放電速率分別量測電池第1圈及第80圈的放電克電容量,並計算出第第80圈的電容量維持率(%)。
比較例1
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入標準電解液(購自台塑、商品編號為EED352),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表1所示。
比較例2
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入94.95wt%標準電解液(購自台塑、商品編號為EED352)、5wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、以及0.05wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile)。封裝並加熱至70℃反應2小時後,形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表1所示。
比較例3
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入95wt%標準電解液(購自台塑、商品編號為EED352)以及5wt%全氟丁基乙烯(perfluorobutyl ethylene)。封裝形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表1所示。
表1
標準電解液 (wt%) | 三(2-丙烯醯氧乙基)異氰脲酸酯(wt%) | 全氟丁基乙烯(wt%) | 起始劑(wt%) | 電容維持率 (%) (第80圈) | 氧化電流(mA) (5.5V) | |
比較例1 | 100 | 0 | 0 | 0 | ~70 | 0.060 |
比較例2 | 94.95 | 5 | 0 | 0.05 | ~74 | 0.022 |
比較例3 | 95 | 0 | 5 | 0 | ~14 | 0.170 |
實施例3 | 89.95 | 5 | 5 | 0.05 | ~82 | 0.010 |
由表1可知,與比較例1所述之電池相比(使用標準電解液),實施例3所述之電池(使用本揭露所述電解質)其氧化電流明顯降低,且電容維持率可達到80%以上。比較例2所述之電池其電解質雖然有進一步添加三(2-丙烯醯氧乙基)異氰脲酸酯及起始劑至標準電解液中,但由於比較例2的電解質沒有添加全氟丁基乙烯,因此比較例2所述電解質中的聚合物不具有氟原子,因此其具有較高的高電壓氧化電流,以及較差的電容維持率(與實施例3所述電池相比)。
實施例4:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入一混合物(包含91.96wt%標準電解液(購自台塑、商品編號為EED352)、4wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、4wt%全氟丁基乙烯、以及0.04wt% 2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile))。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,分別量測比較例1、比較例2、以及實施例4所得之電池在2C的放電電容量,結果如表2所示。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
表2
比較例1 | 比較例2 | 實施例4 | |
放電電容量 (mAh/g) | ~107 | ~97 | ~118 |
由表2可知,與比較例1所述之電池相比(使用標準電解液),實施例4所述之電池(使用本揭露所述電解質)具有較高的放電容量。這表示本揭露所述電解質確實可改善電池的高倍率放電性能。比較例2所述之電池其電解質雖然有進一步添加三(2-丙烯醯氧乙基)異氰脲酸酯及起始劑至標準電解液中,但由於比較例2的電解質沒有添加全氟丁基乙烯,因此比較例2所述電解質中的聚合物具有較緻密(或剛性)的網狀結構,不易吸附鋰鹽及溶液,反而導致標準電解液之離子傳導性降低。
實施例5:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入一混合物(包含93.96wt%標準電解液(購自台塑、商品編號為EED352)、4wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、2wt%全氟丁基乙烯、以及0.04wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile))。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
實施例6:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入一混合物(包含94.97wt%標準電解液(購自台塑、商品編號為EED352)、3wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、2wt%全氟丁基乙烯、以及0.03wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile))。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
實施例7:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入90.96wt%標準電解液(購自台塑、商品編號為EED352)、4wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、5wt%全氟丁基乙烯、以及0.04wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile)。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
實施例8:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入89.96wt%標準電解液(購自台塑、商品編號為EED352)、4wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、6wt%全氟丁基乙烯、以及0.04wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile)。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
實施例9:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入85.93wt%標準電解液(購自台塑、商品編號為EED352)、7wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、7wt%全氟丁基乙烯、以及0.07wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile)。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
實施例10:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入93.95wt%標準電解液(購自台塑、商品編號為EED352)、5wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、1wt%全氟丁基乙烯、以及0.05wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile)。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
實施例11:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入93.98wt%標準電解液(購自台塑、商品編號為EED352)、2wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、4wt%全氟丁基乙烯、以及0.02wt%2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile)。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
實施例12:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入約79wt%標準電解液(購自台塑、商品編號為EED352)、約10.45wt%三(2-丙烯醯氧乙基)異氰脲酸酯(tris[2-(acryloyloxy)ethyl]isocyanurate)、約10.45wt%全氟丁基乙烯、以及0.1wt% 2,2-偶氮雙異丁腈(2,2-azobisisobutyronitrile)。封裝並加熱至70℃反應2小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表3所示。
表3
標準電解液 (wt%) | 三(2-丙烯醯氧乙基)異氰脲酸酯(wt%) | 全氟丁基乙烯(wt%) | 起始劑(wt%) | 電容維持率(%) (第80圈) | 氧化電流(mA) (5.5V) | |
實施例4 | 91.96 | 4 | 4 | 0.04 | ~92 | 0.005 |
實施例5 | 93.96 | 4 | 2 | 0.04 | ~90 | 0.013 |
實施例6 | 94.97 | 3 | 2 | 0.03 | ~88 | 0.017 |
實施例7 | 90.96 | 4 | 5 | 0.04 | ~91 | 0.007 |
實施例8 | 89.96 | 4 | 6 | 0.04 | ~91 | 0.008 |
實施例9 | 85.93 | 7 | 7 | 0.07 | ~80 | 0.003 |
實施例10 | 93.95 | 5 | 1 | 0.05 | ~80 | 0.020 |
實施例11 | 93.98 | 2 | 4 | 0.02 | ~80 | 0.019 |
實施例12 | ~79.00 | ~10.45 | ~10.45 | 0.1 | ~75 | - |
實施例13:
依據實施例4所述電池的製備方法,除了將全氟丁基乙烯置換成丙烯酸1H,1H,5H-八氟戊酯(1H,1H,5H-octafluoropentyl acrylate),得到電池。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表4所示。
表4
標準電解液 (wt%) | 三(2-丙烯醯氧乙基)異氰脲酸酯(wt%) | 丙烯酸1H,1H,5H-八氟戊酯(wt%) | 起始劑(wt%) | 電容維持率 (%) (第80圈) | 氧化電流(mA) (5.5V) | |
比較例1 | 100 | 0 | 0 | 0 | ~70 | 0.060 |
實施例13 | 91.96 | 4 | 4 | 0.04 | ~80 | 0.009 |
由表4可知,與比較例1所述之電池相比(使用標準電解液),實施例13所述之電池(使用本揭露所述電解質)其氧化電流明顯降低,且電容維持率可達到80%。
實施例14:
提供實施例3所得之負極以及正極。接著,提供一隔離膜(型號為Celgard 2320,AsahiKasei)。接著,依照負極/隔離膜/正極的順序排列,並注入93wt%標準電解液(購自台塑、商品編號為EED352)、3wt%異氰脲酸三縮水甘油酯(triglycidyl isocyanurate)、2wt%3-(全氟正辛基)-1,2-環氧丙烷(3-perfluorooctyl-1,2-epoxypropane)、以及2wt%二氟草酸硼酸鋰(lithium difluoro(oxalato)borate,LiDFOB)。封裝並加熱至55℃反應10小時後(即將該混合物轉換成電解質),形成鈕扣型電池CR2032(尺寸為3.2mm (厚) x 20mm (寬)x 20mm(長))。接著,量測該電池之高電壓氧化電流(mA)以及電容維持率(%),結果如表5所示。
表5
標準電解液 (wt%) | 異氰脲酸三縮水甘油酯(wt%) | 3-(全氟正辛基)-1,2-環氧丙烷(wt%) | 二氟草酸硼酸鋰(wt%) | 電容維持率 (%) (第80圈) | 氧化電流(mA) (5.5V) | |
比較例1 | 100 | 0 | 0 | 0 | ~70 | 0.060 |
實施例14 | 93 | 3 | 2 | 2 | ~88 | 0.003 |
由表5可知,與比較例1所述之電池相比(使用標準電解液),實施例14所述之電池(使用本揭露所述電解質)其氧化電流明顯降低,且電容維持率可達到80%以上。
基於上述,本揭露所述具有特定組成的類固態電解質確實具有較佳的阻燃性,並具有可抑制高電壓氧化反應的效能。如此一來,可進一步改善鋰離子電池的高電壓操作、倍率性能與安全特性,以及延長鋰離子電池的循環壽命。
雖然本揭露已以數個實施例揭露如上,然其並非用以限定本揭露,任何本技術領域中具有通常知識者,在不脫離本揭露之精神和範圍內,當可作任意之更動與潤飾,因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。
10:負極
20:正極
30:隔離膜
40:電解質
100:鋰離子電池
第1圖為本揭露實施例所述鋰離子電池之示意圖。
10:負極
20:正極
30:隔離膜
40:電解質
100:鋰離子電池
Claims (17)
- 一種電解質,包含:一鋰鹽;一溶劑;以及一聚合物,其中該聚合物係一組合物經聚合反應之產物,其中該組合物包含一第一單體以及一第二單體,其中該第一單體具有式(I)所示結構、以及該第二單體係含氟丙烯酸酯(fluorine-containing acrylate)、含氟烯(fluorine-containing alkene)、含氟環氧化合物(fluorine-containing epoxide)、或上述之組合
- 如請求項1之電解質,其中該鋰鹽與該溶劑的重量比為1:19至7:13。
- 如請求項1之電解質,其中該鋰鹽係LiPF6、LiClO4、LiN(SO2F)2、LiBF2(C2O4)、LiBF4、LiSO3CF3、LiN(SO2CF3)2、LiN(SO2CF2CF3)2、LiAsF6、LiSbF6、LiAlCl4、LiGaCl4、LiNO3、LiC(SO2CF3)3、LiSCN、LiO3SCF2CF3、LiC6F5SO3、LiO2CCF3、LiSO3F、LiB(C6H5)4、LiB(C2O4)2、或上述之組合。
- 如請求項1之電解質,其中該溶劑係1,2-二乙氧基乙烷(1,2-diethoxyethane)、1,2-二甲氧基乙烷(1,2-dimethoxyethane)、1,2-二丁氧基乙烷(1,2-dibutoxyethane)、四氫呋喃(tetrahydrofuran)、2-甲基四氫呋喃(2-methyl tetrahydrofuran)、二甲基乙醯胺(dimethylacetamide,DMAc)、N-甲基吡咯酮(N-methyl-2-pyrrolidone,NMP)、乙酸甲酯(methyl acetate)、乙酸乙酯(ethyl acetate)、丁酸甲酯(methyl butyrate)、丁酸乙酯(ethyl butyrate)、丙酸甲酯(methyl proionate)、丙酸乙酯(ethyl proionate)、乙酸丙酯(propyl acetate,PA)、丁基內酯(γ-butyrolactone,GBL)、碳酸乙烯酯(ethylene carbonate,EC)、碳酸丙烯酯(propylene carbonate,PC)、碳酸二乙酯(diethyl carbonate,DEC)、碳酸甲乙酯(ethylmethyl carbonate,EMC)、碳酸二甲酯(dimethyl carbonate,DMC)、碳酸乙烯基酯(vinylene carbonate)、碳酸丁烯酯(butylene carbonate)、1,3-丙磺酸內酯(1,3-propanesultone)、碳酸二丙基酯(dipropyl carbonate)、或上述之組合。
- 如請求項1之電解質,其中該第一單體與該第二單體的重量比為5:1至1:2。
- 如請求項1之電解質,其中該含氟丙烯酸酯(fluorine-containing acrylate)具有式(II)或式(III)所示結構
- 如請求項1之電解質,其中該組合物更包含一起始劑,其中該起始劑的含量為0.01wt%至10wt%,以該第一單體以及第二單體的總重為基準。
- 一種鋰離子電池,包含:一正極;一負極;一隔離膜,其中該隔離膜配置於該正極與該負極之間;以及一電解質設置於該正極與負極之間,其中該電解質係請求項1所述之電解質。
- 如請求項14之鋰離子電池,其中該負極包含負極活性材料,且該負極活性材料係鋰金屬、鋰合金、過渡金屬氧化物、穩相球狀碳(MCMB)、奈米碳管(CNT)、石墨烯、焦炭、石墨、碳黑、碳纖維、中間相碳微球、玻璃質碳、含鋰化合物、含矽化合物、錫、含錫化合物、或上述之組合。
- 如請求項15之鋰離子電池,其中該正極包含正極活性材料,且該正極活性材料包括硫、有機硫化物、硫碳複合物(sulfur-carbon composite)、含金屬之氧化鋰、含金屬之硫化鋰、含金屬之硒化鋰、含金屬之碲化鋰、含金屬之磷化鋰、含金屬之矽化鋰、含金屬之硼化鋰、或上述之組合,其中該金屬係擇自由鋁、 釩、鈦、鉻、銅、鉬、鈮、鐵、鎳、鈷、及錳所組成的族群。
- 如請求項16之鋰離子電池,其中該隔離膜係聚乙烯(PE)、聚丙烯(polypropylene,PP)、聚四氟乙烯膜、聚醯胺膜、聚氯乙烯膜、聚二氟乙烯膜、聚苯胺膜、聚醯亞胺膜、聚對苯二甲二乙酯(polyethylene terephthalate)、聚苯乙烯(polystyrene,PS)、纖維素(cellulose)、或上述組合。
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TW202033368A (zh) * | 2018-10-26 | 2020-09-16 | 南韓商Lg化學股份有限公司 | 隔離膜以及包含其的電性或電子元件 |
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KR20040020631A (ko) * | 2002-08-31 | 2004-03-09 | 삼성에스디아이 주식회사 | 고분자 전해질 및 이를 채용한 리튬 전지 |
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KR101765191B1 (ko) * | 2013-04-10 | 2017-08-07 | 삼성에스디아이 주식회사 | 리튬 이차 전지 및 이의 제조 방법 |
CN107078352B (zh) * | 2014-09-30 | 2020-04-28 | 三菱化学株式会社 | 非水电解液及使用了该非水电解液的非水电解质二次电池 |
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CN105637041A (zh) * | 2013-10-11 | 2016-06-01 | 亨茨曼国际有限公司 | 基于多异氰酸酯的膨胀型涂料 |
TW202033368A (zh) * | 2018-10-26 | 2020-09-16 | 南韓商Lg化學股份有限公司 | 隔離膜以及包含其的電性或電子元件 |
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