JP2009170279A - リチウムイオン二次電池用電解液及びリチウムイオン二次電池 - Google Patents
リチウムイオン二次電池用電解液及びリチウムイオン二次電池 Download PDFInfo
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- JP2009170279A JP2009170279A JP2008007632A JP2008007632A JP2009170279A JP 2009170279 A JP2009170279 A JP 2009170279A JP 2008007632 A JP2008007632 A JP 2008007632A JP 2008007632 A JP2008007632 A JP 2008007632A JP 2009170279 A JP2009170279 A JP 2009170279A
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- lithium
- secondary battery
- ion secondary
- imide
- ionic liquid
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 239000003792 electrolyte Substances 0.000 title claims abstract description 9
- 239000002608 ionic liquid Substances 0.000 claims abstract description 47
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- -1 tetrafluoroborate Chemical compound 0.000 claims description 61
- 150000001450 anions Chemical class 0.000 claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 8
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- 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 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 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 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052744 lithium Inorganic materials 0.000 abstract description 26
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000003115 supporting electrolyte Substances 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- MOBFBESVVHOHDW-UHFFFAOYSA-N 1,3,5-trimethyl-2-propylpyrazol-1-ium Chemical compound CCC[N+]1=C(C)C=C(C)N1C MOBFBESVVHOHDW-UHFFFAOYSA-N 0.000 description 3
- GXNZJXAATBWYOL-UHFFFAOYSA-N 1-butyl-2,3,5-trimethylpyrazol-2-ium Chemical compound CCCC[N+]1=C(C)C=C(C)N1C GXNZJXAATBWYOL-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical group C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- HLNRRPIYRBBHSQ-UHFFFAOYSA-N 1-propylpyrrolidine Chemical compound CCCN1CCCC1 HLNRRPIYRBBHSQ-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XJBALIUUDWYQES-UHFFFAOYSA-N 1-ethyl-2,3,5-trimethylpyrazol-2-ium Chemical compound CC[N+]1=C(C)C=C(C)N1C XJBALIUUDWYQES-UHFFFAOYSA-N 0.000 description 1
- OGLIVJFAKNJZRE-UHFFFAOYSA-N 1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1 OGLIVJFAKNJZRE-UHFFFAOYSA-N 0.000 description 1
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018087 Al-Cd Inorganic materials 0.000 description 1
- 229910018188 Al—Cd Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910017326 LixMn Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BXHHZLMBMOBPEH-UHFFFAOYSA-N diethyl-(2-methoxyethyl)-methylazanium Chemical compound CC[N+](C)(CC)CCOC BXHHZLMBMOBPEH-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- XTPRURKTXNFVQT-UHFFFAOYSA-N hexyl(trimethyl)azanium Chemical compound CCCCCC[N+](C)(C)C XTPRURKTXNFVQT-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- PPPHYGCRGMTZNA-UHFFFAOYSA-M trifluoromethyl sulfate Chemical compound [O-]S(=O)(=O)OC(F)(F)F PPPHYGCRGMTZNA-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
Description
現在実用化されているリチウムイオン二次電池としては、例えば、正極活物質としてリチウムと遷移金属との複合酸化物を用い、負極活物質として黒鉛などのリチウムをドープ・脱ドープ可能な材料を用いたものが挙げられる。
これらの中でも、1位が炭素数1〜4のアルキル基で置換され、その他の2、3及び5位がメチル基で置換されてなる、1−エチル−2,3,5−トリメチルピラゾリウムイオン、1−プロピル−2,3,5−トリメチルピラゾリウムイオン及び1−ブチル−2,3,5−トリメチルピラゾリウムイオンからなる群から選ばれるものが低粘性及び高安定性の面で特に好ましい。
・導電剤、アセチレンブラック:電気化学工業(株)、デンカブラック
・負極活物質、MCMB:大阪ガスケミカル(株)、MCMB 25−28
・バインダー、PVDF:(株)クレハ、KFバインダー
正極活物質であるLiMn2O4100gと導電剤としてのアセチレンブラック5g,バインダーとしてPVDF6g、分散媒としてN−メチル−2−ピロリドン(NMP)97.5gを遊星型ミキサーで混合し、固形分(NMPを除く成分)53.2%の正極塗工液を調製した。この塗工液を塗工機で厚み20μmのアルミニウム箔上にコーティングを行い、130℃で乾燥後ロールプレス処理を行い、正極活物質重量16mg/cm2の電極を得た。
負極活物質であるMCMB100gと導電剤としてアセチレンブラック10g、バインダーとしてPVDF5g、分散媒としてNMP107.5gを遊星型ミキサーで混合し、固形分(NMPを除く成分)50%の負極塗工液を調製した。この塗工液を塗工機で厚み10μmの銅箔上にコーティングを行い、130℃で乾燥後ロールプレス処理を行い、負極活物質重量7mg/cm2の電極を得た。
得られた正極、負極とポリプロピレン製セパレータを用いて、正極面積4cm2、負極面積4.41cm2のリチウム二次電池を作製した。そこに、1−エチル−2,3,5−トリメチルピラゾリウムビス(トリフルオロメタンスルホニル)イミドに0.8モルのリチウムビス(トリフルオロメタンスルホニル)イミドを溶解した電解液を注入した後、注入口を密封し電池を作製した。
イオン液体のカチオンに1−プロピル−2,3,5−トリメチルピラゾリウムを用いた以外は実施例1と同様にして電池を作製した。
イオン液体のカチオンに1−ブチル−2,3,5−トリメチルピラゾリウムを用いた以外は実施例1と同様にして電池を作製した。
イオン液体のアニオンにヘキサフルオロホスフェートを用い、リチウム系支持電解質にリチウムヘキサフルオロホスフェートを用いた以外は実施例1と同様にして電池を作製した。
イオン液体のカチオンに1−プロピル−2,3,5−トリメチルピラゾリウムを用いた以外は実施例4と同様にして電池を作製した。
イオン液体のカチオンに1−ブチル−2,3,5−トリメチルピラゾリウムを用いた以外は実施例4と同様にして電池を作製した。
イオン液体のアニオンにテトラフルオロボレートを用い、リチウム系支持電解質にリチウムテトラフルオロボレートを用いた以外は実施例1と同様にして電池を作製した。
イオン液体のカチオンに1−プロピル−2,3,5−トリメチルピラゾリウムを用いた以外は実施例7と同様にして電池を作製した。
イオン液体のカチオンに1−ブチル−2,3,5−トリメチルピラゾリウムを用いた以外は実施例7と同様にして電池を作製した。
イオン液体のカチオンに1−エチル−3−メチルイミダゾリウムを用いた以外は実施例1と同様にして電池を作製した。
イオン液体のアニオンにヘキサフルオロホスフェートを用いたところ、25℃で固体となり、電池を作製することができなかった。
イオン液体のアニオンにテトラフルオロボレートを用い、リチウム系支持電解質にリチウムテトラフルオロボレートを用いた以外は比較例1と同様にして電池を作製した。
イオン液体のカチオンに1−ブチルピリジニウムを用いた以外は実施例1と同様にして電池を作製した。
イオン液体のアニオンにヘキサフルオロホスフェートを用い、リチウム系支持電解質にリチウムヘキサフルオロホスフェートを用いた以外は比較例5と同様にして電池を作製した。
イオン液体のアニオンにテトラフルオロボレートを用い、リチウム系支持電解質にリチウムテトラフルオロボレートを用いた以外は比較例5と同様にして電池を作製した。
イオン液体のカチオンにジエチルメチル(2−メトキシエチル)アンモニウムを用いた以外は実施例1と同様にして電池を作製した。
イオン液体のアニオンにヘキサフルオロホスフェートを用いたところ、25℃で固体となり、電池を作製することができなかった。
イオン液体のアニオンにテトラフルオロボレートを用い、リチウム系支持電解質としてリチウムテトラフルオロボレートを用いた以外は比較例7と同様にして電池を作製した。
充放電試験装置を用いて、充電を0.5時間率、放電を1時間率の条件で、電池性能及び放電平均電圧を確認した。さらに、充電及び放電を1時間率の条件で500サイクルのサイクル特性試験を行い、サイクル試験初回の放電容量に対して容量が80%に低下するサイクル数を確認した。表2に示すサイクル試験結果は、初回の正極活物質当たりの放電容量を基準とした。
Claims (4)
- 対アニオンAが、テトラフルオロボレート、ヘキサフルオロホスフェート、トリフルオロメタンスルフォネート、ビス(トリフルオロメタンスルフォニル)イミド、ビス(ペンタフルオロエタンスルフォニル)イミド、ビス(フルオロスルフォニル)イミドからなる群から選ばれる少なくとも1種であることを特徴とする請求項1に記載のリチウムイオン二次電池用電解液。
- リチウム塩が、リチウムテトラフルオロボレート、リチウムヘキサフルオロホスフェート、リチウムトリフルオロメタンスルフォネート、リチウムビス(トリフルオロメタンスルフォニル)イミド、リチウムビス(ペンタフルオロエタンスルフォニル)イミド、リチウムビス(フルオロスルフォニル)イミドからなる群から選ばれる少なくとも1種であることを特徴とする請求項1又は2に記載のリチウムイオン二次電池用電解液。
- 請求項1〜3のいずれかに記載の電解液を用いたリチウムイオン二次電池。
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