CN108352560B - 锂二次电池 - Google Patents
锂二次电池 Download PDFInfo
- Publication number
- CN108352560B CN108352560B CN201780003672.XA CN201780003672A CN108352560B CN 108352560 B CN108352560 B CN 108352560B CN 201780003672 A CN201780003672 A CN 201780003672A CN 108352560 B CN108352560 B CN 108352560B
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- CN
- China
- Prior art keywords
- carbonate
- secondary battery
- electrolyte
- lithium secondary
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 49
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- 230000035699 permeability Effects 0.000 claims abstract description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- -1 polyethylene Polymers 0.000 claims description 29
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 22
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 7
- 229940017219 methyl propionate Drugs 0.000 claims description 7
- 229920000307 polymer substrate Polymers 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- 229920002530 polyetherether ketone Polymers 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 4
- 229930182556 Polyacetal Natural products 0.000 claims description 4
- 239000004693 Polybenzimidazole Substances 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920002480 polybenzimidazole Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 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
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 3
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 claims description 3
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 claims description 3
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- 229940093499 ethyl acetate Drugs 0.000 claims description 3
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002312 polyamide-imide Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229920006260 polyaryletherketone Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 claims description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000003411 electrode reaction Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000011301 petroleum pitch Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
- 229910018671 Lix(NiaCobMnc)O2 Inorganic materials 0.000 description 1
- 229910018642 Lix(NiaCobMnc)O4 Inorganic materials 0.000 description 1
- 229910018700 LixCo1-yMnyO2 Inorganic materials 0.000 description 1
- 229910018708 LixCo1−yMnyO2 Inorganic materials 0.000 description 1
- 229910001091 LixCoO2 Inorganic materials 0.000 description 1
- 229910016717 LixCoPO4 Inorganic materials 0.000 description 1
- 229910001246 LixFePO4 Inorganic materials 0.000 description 1
- 229910015237 LixMn2-zCozO4 Inorganic materials 0.000 description 1
- 229910015260 LixMn2-zNizO4 Inorganic materials 0.000 description 1
- 229910015329 LixMn2O4 Inorganic materials 0.000 description 1
- 229910015286 LixMn2−zCozO4 Inorganic materials 0.000 description 1
- 229910015257 LixMn2−zNizO4 Inorganic materials 0.000 description 1
- 229910003007 LixMnO2 Inorganic materials 0.000 description 1
- 229910014212 LixNi1-yCoyO2 Inorganic materials 0.000 description 1
- 229910014220 LixNi1-yMnyO2 Inorganic materials 0.000 description 1
- 229910014322 LixNi1−yCoyO2 Inorganic materials 0.000 description 1
- 229910014344 LixNi1−yMnyO2 Inorganic materials 0.000 description 1
- 229910014149 LixNiO2 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 229910006145 SO3Li Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PWRLWCQANJNXOR-UHFFFAOYSA-N dilithium chloro(dioxido)borane Chemical compound [Li+].[Li+].[O-]B([O-])Cl PWRLWCQANJNXOR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
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Abstract
本公开内容涉及一种锂二次电池,即便使用高负载电极时,该锂二次电池也可确保反应均匀性,并因此具有高的容量和改善的循环特性。所述锂二次电池包括:包括正极、负极和插置于正极和负极之间的隔板在内的电极组件;包括锂盐和有机溶剂在内的电解质;和容纳所述电极组件和所述电解质的电池壳体;其中正极具有3.5mAh/cm2以上的负载量,隔板具有200秒/100mL‑1200秒/100mL的透气率,并且电解质具有11mS/cm‑20mS/cm的锂离子电导率。
Description
技术领域
本发明涉及一种锂二次电池。更具体地,本发明涉及一种具有高容量特性的锂二次电池。
本申请要求在2016年2月26日在韩国提交的韩国专利申请第10-2016-0023442号的优先权,将上述专利申请的公开内容通过引用结合在此。
背景技术
近年来,能量储存技术已经受到越来越多的关注。随着能量储存技术的应用已经扩展到用于移动电话、便携式摄像机及笔记本电脑的能量乃至用于电动汽车的能量,对于电化学装置的研究和开发的努力已经越来越多地得以实现。在这种情况下,电化学装置一直是最受关注的。特别是,随着近来电子设备已小型化和轻量化,具有紧凑尺寸、轻质和高容量的可再充电二次电池的开发已成焦点。
关于电化学装置的持续研究已经开发出具有显著改善的性能(特别是输出特性)的电极活性材料。在市售的二次电池中,在20世纪90年代早期开发的锂二次电池备受关注,因为相较于诸如Ni-MH电池之类的传统电池,它们具有更高的驱动电压以及明显更高的能量密度。
这种锂二次电池包括正极、负极和电解质。在首次充电期间从正极活性材料中脱嵌的锂离子被嵌入到负极活性材料(例如碳粒子)中,然后在放电期间锂离子再次从中脱嵌出来。锂离子在两个电极之间的这种移动有助于传递能量并使得电池充电/放电。
随着技术发展和对移动仪器的需求增加,对于作为能源的二次电池的需求迅速地增加。在这样的二次电池中,具有高的能量密度和电压、长循环寿命和低放电率的锂二次电池已经商品化并广为使用。除此之外,随着对环境问题的关注增加,诸如电动车辆和混合动力车辆之类的使用高容量电池的系统的市场已经成长,所述电动车辆和混合动力车辆能够替代包括汽油车辆和柴油车辆在内的使用化石燃料的车辆,这是空气污染的主要原因之一。
在这些情况下,对于高容量电池的需求的基础已经扩大,需要设计一种用于制造作为上述系统用的电源且具有高能量密度、高输出和高放电电压的锂二次电池的高容量电极。
在电池市场中,基于正极3.5mAh/cm2以上的负载量被评估作为高负载电极的必要条件。由于出于高负载的目的,高负载电极包括了增量的活性材料,所以高负载电极通常具有较厚的厚度。然而,厚电极经受在其厚度方向上不均匀的反应,导致循环特性的劣化。
发明内容
技术问题
设计本公开内容以解决现有技术的问题,因此本公开内容是致力于提供一种高负载电极,通过导致均匀的电极反应,所述电极得以控制锂离子的移动以满足适当的范围,并因此提供一种具有优异循环特性的锂二次电池。
技术方案
设计本公开内容以解决根据现有技术的上述问题。在本公开内容的一个方面中,提供一种锂二次电池,所述锂二次电池包括:包括正极、负极以及插置于正极和负极之间的隔板在内的电极组件;包括锂盐和有机溶剂在内的电解质;和容纳所述电极组件和所述电解质的电池壳体,其中所述正极具有3.5mAh/cm2以上的负载量,所述隔板具有200秒/100mL-1200秒/100mL的透气率,所述电解质具有11mS/cm-20mS/cm的锂离子电导率。
优选地,所述隔板可具有250秒/100mL-1000秒/100mL的透气率,并且所述电解质可具有12mS/cm-19mS/cm的锂离子电导率。
更优选地,所述隔板可具有300秒/100mL-800秒/100mL的透气率,并且所述电解质可具有14mS/cm-18mS/cm的锂离子电导率。
优选地,所述隔板可具有2μm-50μm的厚度。
优选地,所述隔板可以是多孔聚合物基材。
优选地,所述多孔聚合物基材可包括选自由聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚酯、聚缩醛、聚酰胺、聚碳酸酯、聚酰胺、聚碳酸酯、聚酰亚胺、聚醚醚酮、聚芳醚酮、聚醚酰亚胺、聚酰胺酰亚胺、聚苯并咪唑、聚醚砜、聚苯醚、环烯烃共聚物、聚苯硫醚和聚乙烯萘组成的群组中的任一种聚合物、或其两种以上的组合。
优选地,所述电解质可以具有1.0cP-3.0cP的粘度。
优选地,所述电解质可进一步包括添加剂。
优选地,所述锂盐可以是选自由LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiN(C2F5SO2)2、LiN(CF3SO2)2、CF3SO3Li和LiC(CF3SO2)3组成的群组中的任一种、或其两种以上的组合。
优选地,所述有机溶剂可以是选自由碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸1,2-丁烯酯、碳酸2,3-丁烯酯、碳酸1,2-戊烯酯、碳酸2,3-戊烯酯、碳酸亚乙烯酯、碳酸乙烯基亚乙酯、氟代碳酸乙烯酯(FEC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸甲乙酯(EMC)、碳酸甲丙酯、碳酸乙丙酯、二甲醚、二乙醚、二丙醚、甲乙醚、甲丙醚、乙丙醚、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、γ-戊内酯、γ-己内酯、σ-戊内酯和ε-己内酯组成的群组中的任一种、或其两种以上的组合。
优选地,所述正极可具有50μm-200μm的厚度。
有益效果
根据本公开内容的锂二次电池即使使用高负载电极,也确保反应均匀性,并因此具有高的容量和改善的循环特性。
附图说明
附图图解说明了本公开内容的优选实施方式,并且与前述公开内容一起用于提供对本公开内容的技术精神的进一步理解,因此,本公开内容不被解释为受限于附图。
图1为示出实施例和比较例中所制备的各电池的容量测定结果的曲线图。
具体实施方式
应理解的是,在说明书和所附权利要求书中使用的术语不应解释为受限于一般意义和字典意义,而是应在以允许发明人对最佳解释适当地定义术语的原则的基础上根据对应于本公开内容的技术方面的意义和概念来解释。因此,本文中给出的描述仅仅是为了说明目的的优选实施例,并非旨在限制本公开内容的范围,因此应当理解,可在不背离本公开内容的范围的情况下对其进行其他等同替换和修改。
在传统的具有3.5mAh/cm2以上的正极负载量的高负载电极的情况下,由于电极的厚度增加,锂离子的移动可能会不好,使得在电极厚度方向上的电极反应不均匀,由此电池的循环特性可能会劣化。除此之外,仅当锂离子的移动增加时,锂离子不能扩散到电极活性材料中,因此锂离子滞留并积聚在电极表面上。
根据本公开内容,通过实验已经发现,当隔板的透气率和电解质的锂离子电导率被调控为在隔板和电解质中锂离子良好移动的期望范围时,锂离子能够很好地扩散到电极活性材料中以使得在电极中均匀反应,从而改善电池的循环特性。
与常规的锂二次电池一样,根据本公开内容的锂二次电池包括:包括正极、负极以及插置于正极和负极之间的隔板在内的电极组件;包括锂盐和有机溶剂在内的电解质;以及容纳所述电极组件和所述电解质的电池壳体。
根据本公开内容的锂二次电池是具有3.5mAh/cm2以上的正极负载量的高负载电池。为了设计高负载电极,正极可具有50μm-200μm的厚度。
除此之外,根据本公开内容,为了确保锂离子的移动满足适当的范围,隔板被调控为具有200秒/100mL-1200秒/100mL的透气率,以允许锂离子很好地扩散进入电极活性材料,并最终实现均匀的电极反应。当隔板具有小于200秒/100mL的透气率时,锂离子的移动增加,因此电池在安全性方面经受快速劣化,并且在电极中锂离子的移动速率不能跟上在隔板中锂离子的移动速率。当隔板具有大于1200秒/100mL的透气率时,在隔板中锂离子的移动减少,导致反复充电/放电过程后的效率和循环特性劣化。优选地,隔板可具有250秒/100mL-1000秒/100mL、更优选300秒/100mL-900秒/100mL的透气率。
在本公开内容中,用于测定隔板的透气率的方法并没有特别地限定,诸如根据日本工业标准(JIS)的Gurley法之类的本领域中的任何常规方法可以使用,以通过利用从Toyoseiki公司获得的Gurley型密度计(No.158)来测定透气率。换句话说,隔板的透气率可以通过测量于室温在0.05MPa的压力下100mL(或100cc)空气穿过1cm2的隔板所需的时间来测定。
根据本公开内容的隔板可具有5μm-20μm的厚度和30%-60%的孔隙率以获得以上定义的透气率。
除此之外,根据本公开内容,为了确保锂离子的移动满足适当的范围,电解质被调控为具有11mS/cm-20mS/cm的锂离子电导率,以允许锂离子很好地扩散进入电极活性材料,并最终实现均匀的电极反应。当电解质具有低于11mS/cm的锂离子电导率时,可能导致在电极中锂离子的移动减少,从而引起在电极表面的内部和表面上的不均匀的反应,由此电池可能经受充电/放电效率和循环特性的劣化。当电解质具有大于20mS/cm的锂离子电导率时,可能导致在隔板中的锂离子的移动相较于在正极中的锂离子的嵌入/脱嵌速率而减少,因此负极和锂离子可能积聚在电极和隔板之间的界面处,由此引起与电解质的副反应。优选地,电解质可以具有12mS/cm-19mS/cm、更优选14mS/cm-18mS/cm的锂离子电导率。通过调节在电解质和溶剂中的盐的浓度,电解质能够满足以上定义的锂离子电导率。此外,锂离子电导率可根据溶剂份额或测量仪器条件而变化。
在本公开内容中,用于测定锂离子电导率的方法并没有特别地限制,本领域的任何常规方法均可使用。例如,锂离子电导率可以通过使用电导率测量仪器(例如Inolab731)来测定。
正极包括正极集电器和在在正极集电器的至少一个表面上所形成的正极层。负极包括负极集电器和在负极集电器的至少一个表面上所形成的负极层。
通常,正极集电器可具有10μm-500μm的厚度。正极集电器并没有特别地限定,只要其具有高的导电性同时不在相应的电池中引起任何化学变化即可。例如,可以使用不锈钢、铝、镍、钛、焙烧碳、或经碳、镍、钛、银等表面处理过的铝或不锈钢。集电器可具有细微的表面不平整以增加正极活性材料对其的粘附,并且可具有诸如膜、片、箔、网、多孔体、泡沫和无纺布体之类的各种形状。
通常,负极集电器可具有10μm-500μm的厚度。负极集电器并没有特别地限定,只要其具有导电性同时不在相应电池中引起任何化学变化即可。例如,可以使用铜、不锈钢、铝、镍、钛、焙烧碳、或经碳、镍、钛、银等表面处理过的铜或不锈钢、铝-镉合金、或类似物。除此之外,与正极集电器相同,负极集电器可具有细微的表面不平整以增强负极的结合力,并且可具有诸如膜、片、箔、网、多孔体、泡沫、无纺布体、或类似物的各种形状。
正极活性材料可以是含锂氧化物,优选地是含锂过渡金属氧化物。含锂过渡金属氧化物的具体实例包括选自由LixCoO2(0.5<x<1.3)、LixNiO2(0.5<x<1.3)、LixMnO2(0.5<x<1.3)、LixMn2O4(0.5<x<1.3)、Lix(NiaCobMnc)O2(0.5<x<1.3,0<a<1,0<b<1,0<c<1,a+b+c=1)、LixNi1-yCoyO2(0.5<x<1.3,0<y<1)、LixCo1-yMnyO2(0.5<x<1.3,0≤y<1)、LixNi1-yMnyO2(0.5<x<1.3,O≤y<1)、Lix(NiaCobMnc)O4(0.5<x<1.3,0<a<2、0<b<2,0<c<2,a+b+c=2)、LixMn2-zNizO4(0.5<x<1.3,0<z<2)、LixMn2-zCozO4(0.5<x<1.3,0<z<2)、LixCoPO4(0.5<x<1.3)和LixFePO4(0.5<x<1.3)组成的群组中的任一种、或其两种以上的组合。含锂过渡金属氧化物可以涂覆有诸如铝(Al)之类的金属或金属氧化物。除了这样的含锂过渡金属氧化物之外,还可以使用含锂过渡金属的硫化物、硒化物和卤化物。
通常,负极活性材料是能够嵌入/脱嵌锂离子,并且可包括锂金属、碳质材料、金属化合物、或其组合。
碳质材料的具体实例可包括低结晶碳和高结晶碳。低结晶碳的代表性实例包括软碳(soft carbon)和硬碳(hard carbon)。高结晶碳的代表性实例包括高温焙烧碳,诸如如天然石墨、Kish石墨(Kish graphite)、热解碳(pyrolytic carbon)、中间相沥青基碳纤维(mesophase pitch based carbon fiber)、中位碳微球(meso-carbon microbeads)、中间相沥青(mesophase pitches),以及石油或煤焦油沥青衍生的焦炭(petroleum or coaltar pitch derived cokes)之类的高温焙烧碳。
金属化合物的具体实例包括含有至少一种诸如Si、Ge、Sn、Pb、P、Sb、Bi、Al、Ga、In、Ti、Mn、Fe、Co、Ni、Cu、Zn、Ag、Mg、Sr和Ba之类的金属元素的化合物。尽管这些金属化合物可以包括单质、合金、氧化物(TiO2、SnO2等)、氮化物、硫化物、硼化物以及与锂的合金在内的各种形式中的任一种来使用,但是单质、氧化物以及与锂的合金可具有高的容量。特别地,含有选自由Si、Ge和Sn中的至少一种元素(特别是Si和Sn)的金属化合物能够提供具有更高容量的电池。
隔板可以是多孔聚合物基材。除此之外,多孔聚合物基材的孔径和孔隙率并没有特别地限定,但可分别为约0.01μm-50μm和约10%-95%。
此外,多孔聚合物基材可包括在多孔聚合物基材的至少一个表面上、含有无机颗粒和聚合物粘合剂的多孔涂层,以提高机械强度并抑制在正极与负极之间的短路。
多孔聚合物基材的非限制性实例包括选自由聚乙烯(polyethylene)、聚丙烯(polypropylene)、聚对苯二甲酸乙二醇酯(polyethylene terephthalate)、聚对苯二甲酸丁二醇酯(polybutylene terephthalate)、聚酯(polyester)、聚缩醛(polyacetal)、聚酰胺(polyamide)、聚碳酸酯(polycarbonate)、聚酰胺(polyamide)、聚碳酸酯(polycarbonate)、聚酰亚胺(polyimide)、聚醚醚酮(polyetherether ketone)、聚芳醚酮(polyarylether ketone)、聚醚酰亚胺(polyether imide)、聚酰胺酰亚胺(polyamideimide)、聚苯并咪唑(polybenzimidazole)、聚醚砜(polyether sulfone)、聚苯醚(polyphenylene oxide)、环烯烃共聚物(cyclic olefin copolymer)、聚苯硫醚(polyphenylene sulfide)和聚乙烯萘(polyethylene naphthalene)组成的群组中的任一种、或其两种以上的组合。
电解质可具有在室温(25℃)1.0cP-4.0cP、优选1.0cP-3.0cP的粘度。电解质可进一步包括可能影响离子电导率、固体电解质界面相(SEI)在负极表面上的形成、粘度、或类似性能的添加剂。
锂盐可以是选自由LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼酸锂、低级脂族羧酸锂、和四苯硼酸锂组成的群组的任一种、或其两种以上的组合。根据本公开内容,这样的锂盐可以1.0M-1.5M、优选1.0M-1.3M的浓度来使用,以使电解质满足以上定义的锂离子电导率的范围。
有机溶剂可以是选自由碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸1,2-丁烯酯、碳酸2,3-丁烯酯、碳酸1,2-戊烯酯、碳酸2,3-戊烯酯、碳酸亚乙烯酯、碳酸乙烯基亚乙酯、氟代碳酸乙烯酯(FEC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸甲乙酯(EMC)、碳酸甲丙酯、碳酸乙丙酯、二甲醚、二乙醚、二丙醚、甲乙醚、甲丙醚、乙丙醚、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、γ-戊内酯、γ-己内酯、σ-戊内酯和ε-己内酯组成的群组中的任一种、或其两种以上的组合。在这些溶剂中,优选的是组合地使用诸如碳酸乙烯酯(EC)之类的环状碳酸酯与诸如碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、乙酸乙酯(EA)或丙酸甲酯(MP)之类的非环状碳酸酯。特别地,为了满足以上定义的电解质的锂离子电导率的范围,诸如碳酸乙烯酯(EC)之类的环状碳酸酯可以基于溶剂的总体积的10体积%-40体积%、优选20体积%-30体积%的量来使用,而诸如碳酸二甲酯(DMC)之类的非环状碳酸酯可以60体积%-90体积%、优选70体积%-80体积%的量来使用。特别地,为了确保锂离子电导率为14mS/cm以上,碳酸二甲酯(DMC)可以50体积%以上的量来使用,或者具有高离子电导率和低粘度的乙酸乙酯(EA)或丙酸甲酯(MP)可以30体积%以上的量来使用。
添加剂可以是选自由在环中具有碳-碳饱和键的磺内酯化合物、在环中具有碳-碳饱和键的硫酸酯化合物、含乙烯基环状碳酸酯化合物和卤素取代的环状草酸硼酸酯化合物组成的群组中的至少一种。添加剂的具体实例包括1,3-丙烷磺内酯(PS)、碳酸亚乙烯酯(VC)、硫酸乙烯酯(ESA)、或类似物。
实施方式
在下文中,将参照各实施例详细地解释本公开内容。然而,以下各实施例可以多种不同的形式来实施,并且不应被解释为受限于在此所阐述的示例性实施方式。相反,提供这些示例性实施方式以使得本公开内容是完全的和完整的,并且将本公开内容的范围充分地传达给本领域的技术人员。
实施例1
首先,将3重量%的炭黑、作为正极活性材料的95重量%的Li(Ni1/3Mn1/3Co1/3)O2和作为粘合剂的2重量%的聚偏二氟乙烯(PVdF)进行混合以形成正极浆料。接着,将该浆料以4.5mAh/cm2的负载量涂布在铝箔上,并于100℃在真空烘箱中干燥10小时以上。然后,藉由使用辊式压制机进行压制以提供具有100μm厚度的正极。
除此之外,将1重量%的炭黑、作为负极活性材料的96重量%的天然石墨、2重量%的丁苯橡胶(SBR)粘结剂和1重量%的羧甲基纤维素(CMC)进行混合以形成负极浆料。接着,将该浆料以5.4mAh/cm2的负载量涂布在铜箔上,并于100℃在真空烘箱中干燥10小时以上。然后,藉由使用辊式压制机进行压制以提供具有120μm厚度的负极。
使用如上所述而获得的负极和正极,将具有900秒/100mL透气率的聚烯烃隔板插置于负极和正极之间。然后,将含有1M LiPF6溶解于碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和碳酸甲乙酯(EMC)(以3:4:3的体积比混合)中的电解质,与包含3wt%碳酸亚乙烯酯(VC)、0.5重量%的1,3-丙烷磺内酯(PS)和1重量%的硫酸乙烯酯(ESA)的添加剂一起,组合地注入以获得基于正极具有16.5cm2尺寸的单电池。所述电解质具有13.5S/cm的锂离子电导率。
实施例2
首先,将3重量%的炭黑、作为正极活性材料的95重量%的Li(Ni1/3Mn1/3Co1/3)O2和作为粘合剂的2重量%的聚偏二氟乙烯(PVdF)进行混合以形成正极浆料。接着,将该浆料以4.5mAh/cm2的负载量涂布在铝箔上,并于100℃在真空烘箱中干燥10小时或以上。然后,藉由使用辊式压制机进行压制以提供具有100μm厚度的正极。
除此之外,将1重量%的炭黑、作为负极活性材料的96重量%的天然石墨、2重量%的SBR粘结剂和1重量%的CMC进行混合以形成负极浆料。接着,将该浆料以5.4mAh/cm2的负载量涂布在铜箔上,并于100℃在真空烘箱中干燥10小时以上。然后,藉由使用辊式压制机进行压制以提供具有120μm厚度的负极。
使用如上所述而获得的负极和正极,将具有900秒/100mL透气率的聚烯烃隔板插置于负极和正极之间。然后,将含有1M LiPF6溶解于碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和乙酸乙酯(EA)(以3:4:3的体积比混合)中的电解质,与包含3wt%碳酸亚乙烯酯(VC)、0.5重量%的1,3-丙烷磺内酯(PS)和1重量%的硫酸乙烯酯(ESA)的添加剂一起,组合地注入以获得基于正极具有16.5cm2尺寸的单电池。所述电解质具有14S/cm的锂离子电导率。
比较例1
以与在实施例1中所述的同样方式获得一个单电池,不同之处在于:通过组合地使用含有1M LiPF6溶解于碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和碳酸甲乙酯(EMC)(以3:3:4的体积比混合)中的电解质,与包含3wt%碳酸亚乙烯酯(VC)、0.5重量%的1,3-丙烷磺内酯(PS)和1重量%的硫酸乙烯酯(ESA)的添加剂,隔板具有100秒/100mL的透气率,以及锂离子电导率被调控为10.9mS/cm。
比较例2
以与在实施例1中所述的同样方式获得一个单电池,不同之处在于:通过组合地使用含有1M LiPF6溶解于碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和碳酸甲乙酯(EMC)(以3:3:4的体积比混合)中的电解质,与包含3wt%碳酸亚乙烯酯(VC)、0.5重量%的1,3-丙烷磺内酯(PS)和1重量%的硫酸乙烯酯(ESA)的添加剂,隔板具有900秒/100mL的透气率,以及锂离子电导率被调控为10.9mS/cm。
比较例3
以与在实施例1中所述的同样方式获得一个单电池,不同之处:通过组合地使用含有1M LiPF6溶解于碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和乙酸乙酯(EA)(以3:3:4的体积比混合)中的电解质,与包含3wt%碳酸亚乙烯酯(VC)、0.5重量%的1,3-丙烷磺内酯(PS)和1重量%的硫酸乙烯酯(ESA)的添加剂,隔板具有1400秒/100mL的透气率,以及锂离子电导率被调控为16.2mS/cm。
比较例4
以与在实施例1中所述的同样方式获得一个单电池,不同之处在于:通过组合地使用含有1M LiPF6溶解于碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和碳酸甲乙酯(EMC)(以3:3:4的体积比混合)中的电解质,与包含3wt%碳酸亚乙烯酯(VC)、0.5重量%的1,3-丙烷磺内酯(PS)和1重量%的硫酸亚乙酯(ESA)的添加剂,隔板具有1400秒/100mL的透气率,以及锂离子电导率被调控为10.9mS/cm。
寿命特性的测试
在1C充电、1C放电和25℃的条件下,根据实施例2和比较例1-4的每个单电池测定相较于初始容量的、在重复循环之后的容量。
参照图1,可以看出,相较于不满足以上定义的物理性质之一或两种的比较例1-4,实施例使用了具有200秒/100mL-1200秒/100mL的透气率的隔板以及具有11mS/cm-16mS/cm的锂离子电导率的电解质而提供了非常优异的循环特性。
Claims (10)
1.一种锂二次电池,所述锂二次电池包括:包括正极、负极以及插置于正极和负极之间的隔板在内的电极组件;包括锂盐和有机溶剂在内的电解质;和容纳所述电极组件和所述电解质的电池壳体,
其中,所述正极具有4.5mAh/cm2以上的负载量,所述隔板具有300秒/100mL-1200秒/100mL的透气率,所述电解质具有13.5mS/cm-20mS/cm的锂离子电导率和具有在25℃时1.0cP-4.0cP的粘度;
其中,所述透气率是通过测量于室温在0.05MPa的压力下100mL空气穿过1cm2的隔板所需的时间来测定,所述锂离子电导率是通过使用电导率测量仪器来测定。
2.根据权利要求1所述的锂二次电池,其中,所述隔板具有300秒/100mL-800秒/100mL的透气率,并且所述电解质具有14mS/cm-18mS/cm的锂离子电导率。
3.根据权利要求1所述的锂二次电池,其中,所述隔板具有2μm-50μm的厚度。
4.根据权利要求1所述的锂二次电池,其中,所述隔板是多孔聚合物基材。
5.根据权利要求4所述的锂二次电池,其中,所述多孔聚合物基材包括选自由聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚缩醛、聚酰胺、聚碳酸酯、聚酰亚胺、聚醚醚酮、聚芳醚酮、聚醚酰亚胺、聚酰胺酰亚胺、聚苯并咪唑、聚醚砜、聚苯醚、环烯烃共聚物、聚苯硫醚和聚乙烯萘组成的群组中的任一种聚合物、或其两种以上的组合。
6.根据权利要求1所述的锂二次电池,其中,所述电解质具有1.0cP-3.0cP的粘度。
7.根据权利要求1所述的锂二次电池,其中,所述电解质还包含添加剂。
8.根据权利要求1所述的锂二次电池,其中,所述锂盐是选自由LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiN(C2F5SO2)2、LiN(CF3SO2)2、LiCF3SO3和LiC(CF3SO2)3组成的群组中的任一种、或其两种以上的组合。
9.根据权利要求1所述的锂二次电池,其中,所述有机溶剂选自由碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸1,2-丁烯酯、碳酸2,3-丁烯酯、碳酸1,2-戊烯酯、碳酸2,3-戊烯酯、碳酸亚乙烯酯、碳酸乙烯基亚乙酯、氟代碳酸乙烯酯(FEC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸甲乙酯(EMC)、碳酸甲丙酯、碳酸乙丙酯、二甲醚、二乙醚、二丙醚、甲乙醚、甲丙醚、乙丙醚、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、γ-戊内酯、γ-己内酯、σ-戊内酯和ε-己内酯组成的群组中的任一种、或其两种以上的组合。
10.根据权利要求1所述的锂二次电池,其中,所述正极具有50μm-200μm的厚度。
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