US20040222401A1 - Electrochemically stable onium salts and electrolytes containing such for electrochemical capacitors - Google Patents
Electrochemically stable onium salts and electrolytes containing such for electrochemical capacitors Download PDFInfo
- Publication number
- US20040222401A1 US20040222401A1 US10/855,646 US85564604A US2004222401A1 US 20040222401 A1 US20040222401 A1 US 20040222401A1 US 85564604 A US85564604 A US 85564604A US 2004222401 A1 US2004222401 A1 US 2004222401A1
- Authority
- US
- United States
- Prior art keywords
- salt
- onium
- onium salt
- salt comprises
- methylammonium
- 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.)
- Abandoned
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 177
- 239000003792 electrolyte Substances 0.000 title abstract description 37
- 239000003990 capacitor Substances 0.000 title abstract description 26
- 150000001768 cations Chemical class 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- -1 heterocyclic organic bases Chemical class 0.000 claims description 65
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 15
- 125000004429 atom Chemical group 0.000 claims description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- XKFPGUWSSPXXMF-UHFFFAOYSA-N tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC XKFPGUWSSPXXMF-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000007527 lewis bases Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 150000002891 organic anions Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- MEOSJQYRVZIIOI-UHFFFAOYSA-M triethyl(methyl)azanium;trifluoromethanesulfonate Chemical compound CC[N+](C)(CC)CC.[O-]S(=O)(=O)C(F)(F)F MEOSJQYRVZIIOI-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
- 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 2
- DOYSIZKQWJYULQ-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n-(1,1,2,2,2-pentafluoroethylsulfonyl)ethanesulfonamide Chemical compound FC(F)(F)C(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)C(F)(F)F DOYSIZKQWJYULQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000001540 azides Chemical class 0.000 claims description 2
- LXSPHLDBQNKODC-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide ethyl-methyl-di(propan-2-yl)azanium Chemical compound [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C(C)[N+](C(C)C)(C(C)C)C LXSPHLDBQNKODC-UHFFFAOYSA-N 0.000 claims description 2
- YWQNGJZYCSFDSO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide triethyl(methyl)azanium Chemical compound C(C)[N+](C)(CC)CC.[N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F YWQNGJZYCSFDSO-UHFFFAOYSA-N 0.000 claims description 2
- UQWLFOMXECTXNQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F UQWLFOMXECTXNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- HJXBKLNSRLFQOU-UHFFFAOYSA-M ethyl-methyl-di(propan-2-yl)azanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC[N+](C)(C(C)C)C(C)C HJXBKLNSRLFQOU-UHFFFAOYSA-M 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims 2
- VUZHZBFVQSUQDP-UHFFFAOYSA-N 4,4,5,5-tetrafluoro-1,3-dioxolan-2-one Chemical compound FC1(F)OC(=O)OC1(F)F VUZHZBFVQSUQDP-UHFFFAOYSA-N 0.000 claims 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims 2
- AETJTBDBQRMLLQ-UHFFFAOYSA-N 4-chloro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1Cl AETJTBDBQRMLLQ-UHFFFAOYSA-N 0.000 claims 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims 2
- RCIJMMSZBQEWKW-UHFFFAOYSA-N methyl propan-2-yl carbonate Chemical compound COC(=O)OC(C)C RCIJMMSZBQEWKW-UHFFFAOYSA-N 0.000 claims 2
- TXQPIYKVIOKFAB-UHFFFAOYSA-N 4,4,5,5-tetrachloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)OC(=O)OC1(Cl)Cl TXQPIYKVIOKFAB-UHFFFAOYSA-N 0.000 claims 1
- QXNWAXFYVUWULZ-UHFFFAOYSA-N 4,4,5-trichloro-5-(trichloromethyl)-1,3-dioxolan-2-one Chemical compound ClC(Cl)(Cl)C1(Cl)OC(=O)OC1(Cl)Cl QXNWAXFYVUWULZ-UHFFFAOYSA-N 0.000 claims 1
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 claims 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims 1
- CJPPXWNKPQCNIU-UHFFFAOYSA-N FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.C[P+](CC)(CC)CC Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.C[P+](CC)(CC)CC CJPPXWNKPQCNIU-UHFFFAOYSA-N 0.000 claims 1
- XALVHDZWUBSWES-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XALVHDZWUBSWES-UHFFFAOYSA-N 0.000 claims 1
- YJPDLBMZLGTDRZ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YJPDLBMZLGTDRZ-UHFFFAOYSA-N 0.000 claims 1
- QEQDASPBFKPHEH-UHFFFAOYSA-M ethyl(dimethyl)sulfanium;trifluoromethanesulfonate Chemical compound CC[S+](C)C.[O-]S(=O)(=O)C(F)(F)F QEQDASPBFKPHEH-UHFFFAOYSA-M 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- AFDNEAAQDGUENW-UHFFFAOYSA-M methyl(tripropyl)azanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCC[N+](C)(CCC)CCC AFDNEAAQDGUENW-UHFFFAOYSA-M 0.000 claims 1
- NVZMNWQGDZWQIK-UHFFFAOYSA-M methyl-tris(2-methylpropyl)azanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC(C)C[N+](C)(CC(C)C)CC(C)C NVZMNWQGDZWQIK-UHFFFAOYSA-M 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- QJYWKNDUJQVUJU-UHFFFAOYSA-M tributyl(methyl)azanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](C)(CCCC)CCCC QJYWKNDUJQVUJU-UHFFFAOYSA-M 0.000 claims 1
- BOJSGWOJLRZTJR-UHFFFAOYSA-M triethyl(methyl)phosphanium;trifluoromethanesulfonate Chemical compound CC[P+](C)(CC)CC.[O-]S(=O)(=O)C(F)(F)F BOJSGWOJLRZTJR-UHFFFAOYSA-M 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 11
- 230000008018 melting Effects 0.000 abstract description 11
- 239000003125 aqueous solvent Substances 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 7
- 238000006467 substitution reaction Methods 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 29
- 238000003786 synthesis reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 239000013078 crystal Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 238000005349 anion exchange Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229940021013 electrolyte solution Drugs 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910004713 HPF6 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 229910019785 NBF4 Inorganic materials 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 0 [1*]C.[2*]C([3*])[4*].[5*]C([6*])([7*])[8*] Chemical compound [1*]C.[2*]C([3*])[4*].[5*]C([6*])([7*])[8*] 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 3
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- SKTBLRVARGMUJY-UHFFFAOYSA-M 1-methylpyridin-1-ium;hydroxide Chemical compound [OH-].C[N+]1=CC=CC=C1 SKTBLRVARGMUJY-UHFFFAOYSA-M 0.000 description 1
- HLNJFEXZDGURGZ-UHFFFAOYSA-M 1-methylpyridin-1-ium;iodide Chemical compound [I-].C[N+]1=CC=CC=C1 HLNJFEXZDGURGZ-UHFFFAOYSA-M 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BXWAQMLUTGMYRC-UHFFFAOYSA-M ethyl(dimethyl)sulfanium;iodide Chemical compound [I-].CC[S+](C)C BXWAQMLUTGMYRC-UHFFFAOYSA-M 0.000 description 1
- AJJWIZPIIXYCGG-UHFFFAOYSA-M ethyl-methyl-di(propan-2-yl)azanium;methyl carbonate Chemical compound COC([O-])=O.CC[N+](C)(C(C)C)C(C)C AJJWIZPIIXYCGG-UHFFFAOYSA-M 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 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 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- IOPLHGOSNCJOOO-UHFFFAOYSA-N methyl 3,4-diaminobenzoate Chemical compound COC(=O)C1=CC=C(N)C(N)=C1 IOPLHGOSNCJOOO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JDXQQVMPAZDGSI-UHFFFAOYSA-M methyl-tri(propan-2-yl)azanium;bromide Chemical compound [Br-].CC(C)[N+](C)(C(C)C)C(C)C JDXQQVMPAZDGSI-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- ZERULLAPCVRMCO-UHFFFAOYSA-N sulfure de di n-propyle Natural products CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates generally to onium salts and to methods of producing the same. These salts, obtained by the methods provided herein, are useful components in a wide spectrum of fields, such as phase transfer catalysis, electrolyte solutes for aqueous or non-aqueous electrochemical devices, various additives, and medicaments, etc. More particularly, the present invention provides a new family of asymmetric onium cations, which when combined with an appropriate anion, result in salts having high electrochemical stability and high solubility in non-aqueous polar solvents. Most particularly, the present invention relates to the formulation of a non-aqueous electrochemically stable electrolyte solution comprising these onium salts and an appropriate solvent or solvent mixture. Finally, the present invention relates to improved electrochemical capacitors utilizing these novel electrolyte solutions and thereby having improved energy density and power capabilities.
- Electrochemical capacitors are energy storage devices that are able to store and release energy by the means of ion adsorption/desorption on high surface area electrodes. These capacitors typically consist of two porous electrodes that are isolated from electrical contact with each other by a separator. Both the separator and the electrodes are impregnated with an electrolytic solution, i.e., a salt or mixture of salts dissolved in appropriate solvent or mixture of solvents.
- an electrolytic solution i.e., a salt or mixture of salts dissolved in appropriate solvent or mixture of solvents.
- E is the storable energy at a potential difference ⁇ V between the electrodes and C is the storage capacitance of the electrodes (B. E. Conway, J. Electrochem. Soc., 1991, 138, 1539).
- ⁇ V the storage capacitance of the electrodes
- the stability limit is usually imposed by the decomposition of the salts, especially at the negative potential extreme, where the cation usually determines the cathodic stability limit of the electrolyte alone, independent of the anion and the solvent it is in.
- the salt should have a cation which is stable against reduction at the negative electrode, and an anion which is stable against oxidation at positive electrode, and their stability should be higher or at least as high as that of the solvent.
- any improvement in electrochemical stability will increase operating potential ( ⁇ V) and have an impact on energy output by the magnitude squared as shown by Equation (1).
- energy density can be affected by the number of ions available in the electrolytic solution (J. P. Zheng, J. Huang, T. R. Jow, J. Electrochem. Soc., 1997, 144, 2026).
- limited solubility of most salts in aprotic, non-aqueous solvents often limits the energy density at high operating voltages.
- the number of ions available in the electrolytic solution also limits the power output, i.e., where high demand for ions lowers the ion concentration in the solution thus increasing the resistance and limiting the power output. It is therefore also highly desirable to find a salt having higher solubility in aprotic, non-aqueous solvents.
- the electrolyte used in state-of-the-art electrochemical capacitors contains tetraethylammonium tetrafluoroborate (Et 4 NBF 4 ) in propylene carbonate (PC) solvent as described in U.S. Pat. No. 5,150,283, A Yoshida and K. Imoto, “Electric Double Layer Capacitor and Method for Producing the Same”; or the same salt in acetonitrile (AN) solvent as described in U.S. Pat. No. 5,621,607, C. J. Farahmandi and J. M. Dispennette, “High Performance Double Layer Capacitors Including Aluminum Carbon Composite Electrodes”.
- these electrolytes have serious shortcomings.
- the electrolyte solution of Et 4 NBF 4 in PC exhibits low salt solubility, having a saturated concentration of 0.86 M at room temperature, and low conductivity of 8.8 mS/cm at 0.65 M at room temperature.
- This electrolyte is suitable for low power applications such as memory protection but not for high power applications.
- the electrolyte solution of Et 4 NBF 4 in AN has high conductivity, about 50 mS/cm at 1.4 M at room temperature, and the saturated salt concentration is about 1.68 M at room temperatures.
- the operating voltages of the capacitor using this electrolyte is about 0.5 V lower than that using the electrolyte of Et 4 NBF 4 in PC.
- the high vapor pressures of AN makes it unsuitable for applications at elevated temperatures.
- the state-of-the-art solutes comprising symmetrical quaternary ammonium salts such as tetraethyl ammonium salt are inadequate.
- the present invention fulfills these needs by providing asymmetrical onium salts or mixtures of such salts in aprotic, non-aqueous solvents or mixtures of such solvents. These novel electrolytes are able to perform at a high rate of charge/discharge, at low operating temperatures, and within a wide range of operating voltage due to the high solubility, low melting temperature, and the improved reduction stability of the new onium cations, respectively.
- It is yet another object of the present invention to provide an electrolyte formulation comprising an electrochemically stable onium salt or mixture of such salts dissolved in an aprotic, non-aqueous solvent or mixture of such solvents.
- the present invention provides a novel family of onium salts which, in appropriate solvents, will form electrolyte solutions having these desirable properties.
- FIG. 1 shows the correlation of melting point and solubility (in 50:50 EC:DMC) with weight as well as symmetry for some of the onium cations described in the present invention.
- Commercially available salt tetraethylammonium hexafluorophosphate (Et 4 N + PF 6 ⁇ ) is used as a control.
- FIG. 2 shows the temperature dependence of conductivity of electrolytes comprising some of the onium salts described in the present invention.
- Commercially available salt Et 4 N + PF 6 ⁇ is used as a control.
- the solvent is a mixture of EC:DMC in a 1:1 weight ratio.
- FIG. 3 shows the concentration dependence of conductivity of electrolytes based on one of the onium salts described in the present invention.
- Commercially available salt Et 4 N + PF 6 ⁇ is used as a control.
- the solvent is a mixture of EC:DMC in a 1:1 weight ratio.
- FIG. 4 shows the electrochemical stability window of the electrolyte comprising novel onium salts described in this invention, and commercially available salt Et 4 N + PF 6 ⁇ is used as a control.
- FIG. 5 shows the voltage profile for galvanostatic charging/discharging of a capacitor comprising novel electrolytes described in this invention.
- onium cation is used to indicate a positively charged atom group, which is formed because the central Lewis basic atom increases its valency by donating a lone pair of electrons;
- substituted is used to indicate the group of atoms which are covalently bonded to the central atom of the onium cation
- normal alkyl refers to unbranched, saturated hydrocarbon groups, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl and the like, with preferred normal alkyl groups are unbranched alkyl group containing 1 to 10 carbon atoms;
- branched alkyl refers to the group of saturated hydrocarbons which contain at least one secondary or tertiary carbon atom which are designated as “branch points”, such as iso-propyl, sec-butyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl and the like.
- Preferred branched alkyl groups are branched alkyl groups with a branch point close to the central atom of the onium cation, and with 3 to 8 carbon atoms;
- alkenyl refers to a branched or unbranched hydrocarbon chain typically containing from 2 to 10 carbon atoms and at least one double bond
- aryl refers to a monocyclic or multiple-cyclic aromatic moiety, and is typically phenyl
- aromatic refers to moieties containing both alkyls and aromatic moieties as defined above, typically containing less than 10 carbon atoms;
- halogen refers to fluoro- (hereafter designated as F), chloro- (hereafter designated as Cl), bromo- (hereafter designated as Br) or iodo- (hereafter designated as I), and usually relates to substitution for a hydrogen atom in an organic compound, this substitution is optionally a full substitution for the hydrogen;
- sulfone refers to the class of compounds which are dioxides of the corresponding sulfide
- ether linkage refers to oligomeric collection of the units containing alkylene oxygen linkages, such as (CH 2 OCH 2 ) n or (CH 2 O) n where n ranges from 2 to 50;
- carbonic diester refers to compounds having the structure R—O—C(O)—O—R;
- asymmetry and asymmetrical refers to the substituents on the onium cation, where at least one of the substituents is different from the rest;
- the new salts are constructed on the basis of onium cations having the structure as shown in formulas (I), (II) and (III):
- X, Y and Z are central atoms bearing the charge, and are either elements selected from Groups 14, 15, 16 or 17 of The Periodic Table of the Elements or any inorganic/organic Lewis base groups, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are substituents independently selected from the groups consisting of (a) C 1 ⁇ C 10 normal alkyl, (b) C 3 ⁇ C 10 branched alkyl, (c) C 6 ⁇ C 12 aryl, (d) C 7 ⁇ C 15 aralkyl, and (e) C 1 ⁇ C 10 normal or branched alkyl containing functional groups, such as, but not limited to, (i) 0 ⁇ 2n+1 halogens, wherein n is the number of carbon atoms in the substituent, (ii) sulfone, (iii) ether linkage, and (iv) carbonic diester.
- That the central atom group X is selected from the following organic or inorganic compounds of Lewis base nature: heterocyclic bases such as pyridine; nitrile (R′—CN); nitroso (R′—NO); nitro (R′—NO); carbon oxide (CO); and azide (R′N 3 ); where R′ is selected from the categories (a) through (e) for substituents as defined above;
- That the central atom Y is preferentially, but not limited to, Oxygen, or Sulfur;
- That the central atom Z is preferentially, but not limited to, Nitrogen or Phosphorus;
- alkyl substituents and the functionalized alkyl substituents as defined above are preferentially branched;
- alkyl substituents and the functionalized alkyl substituents as defined above are preferentially branched; and more preferentially that the branching point be closer to the central atom of the cation as opposed to further away from the central atom;
- the new salts based on the above-defined cations and anions are dissolved in an aprotic, non-aqueous solvent or the mixture of such solvents known to those skilled in the art, among which are, but not limited to, cyclic carbonates including ethylene carbonates (hereafter designated as EC), propylene carbonates (PC) etc, linear carbonates including dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) etc, and sulfones including ethylmethylsulfone (EMSF), sulfolane, dimethylsulfone etc., thereby forming improved electrolyte solutions.
- cyclic carbonates including ethylene carbonates (hereafter designated as EC), propylene carbonates (PC) etc
- linear carbonates including dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) etc
- sulfones including ethylmethyls
- Impedance spectroscopy was employed to determine the solution bulk resistance and conductivity was then derived from the cell geometry, which comprised a pair of parallel platinum electrodes. The cell was placed in a temperature-controlled environment and computers were used to control the heating/cooling as well as impedance measurement.
- Electrochemical stability window was measured by cyclic voltammetry using EG&G 273 Potentiostat/Galvanostat.
- a three-electrode configuration cell was employed, with glassy carbon as the working electrode, Li as the reference electrode and Pt or Ti as the counter electrode.
- a scan rate was 5 mV/s and 100 ⁇ A/cm 2 was used as cutoff current density for stability window limit.
- the assembled cell was subjected to charge/discharge test on an EG&G 273 Potentiostat/Galvanostat. Typically a charge/discharge rate of 1.0 mA/cm 2 was used.
- EtMeiPr 2 NMeCO 3 was dissolved in distilled water, and 60% hexafluorophosphoric acid (HPF 6 ) was added to this solution with precaution. After neutralization, the solution was subject to evaporation under reduced pressure to remove water. Resultant crystal was repeatedly recrystallized from hot methanol solution, and the final product EtMeiPr 2 NPF 6 was fine needle.
- Triflic acid aqueous solution was prepared in a procedure similar to that described in Example 2, except that lithium triflate (96% Aldrich) was used in the place of lithium imide, and it was then used to neutralize the solution of EtMeiPr 2 NMeCO 3 . After the neutralization the solution was subject to evaporation under reduced pressure to remove water. Resultant solid was repeatedly re-crystallized from hot methanol solution, and the final product EtMeiPr 2 N + Tf ⁇ obtained is fine crystal.
- Tetrafluoroboric acid (Aldrich, 48% aqueous solution) was used to neutralize Pr 3 MeN + MeCO 3 ⁇ , the preparation of which has been described in Example 6. The subsequent re-crystallization procedure was described in example 3.
- This example describes the preparation and characterization of novel electrolytic solutions comprising the electrochemically stable onium salts whose synthesis has been disclosed in Examples 1 through 12 and appropriate solvents.
- the novel electrolyte was prepared to have the following composition: one onium salt or mixtures of two or more of the onium salts as described in Examples 1 through 12, and a 50:50 mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC).
- the amount of onium salt or mixture of onium salts were such that the total concentration was between 0.5 ⁇ 2.5 M, with the preferred concentration between 0.7 ⁇ 1.5 M.
- FIG. 1 shows the correlation of melting point and solubility in 50:50 EC:DMC with cationic weight as well as the effect of cationic symmetry for some of the onium cations described in the present invention.
- Commercially available salt Et 4 NPF 6 is used as control.
- FIG. 2 shows the temperature dependence of conductivity of electrolytes comprising some of the onium salts in 50:50 EC:DMC solvent described in the present invention.
- Commercially available salt Et 4 NPF 6 is used as control. It can be seen that most of the asymmetrical onium salts described herein can yield conductivity higher than 10 mS/cm at room temperature.
- FIG. 3 shows the comparison of concentration dependencies between one of the onium salts in 50:50 EC:DMC as described in the present invention and the commercially available salt Et 4 NPF 6 in 50:50 EC:DMC.
- asymmetrical onium salts have maximum conductivity at higher concentration. Since high concentration minimizes the concentration polarization during charging, the novel onium salts described herein provides capacitors containing them with an advantage of working at higher rates.
- FIG. 4 shows the electrochemical stability window of the electrolyte comprising novel onium salts in 50:50 EC:DMC as described herein, and commercially available salt Et 4 NPF 6 in 50:50 EC:DMC used as a control.
- the asymmetrical onium cations with bulky, branched alkyl substituents tend to be reduced at much lower potential.
- This shielding effect of the substituents extends the electrochemical stability window by as much as 0.5 V in the case of Pr 3 MeN + PF 6 ⁇ and iBu 3 MeN + PF 6 ⁇ .
- the operating voltage of the capacitor containing these novel salts described herein can be increased from 2.3 ⁇ 2.5 V to 2.8 ⁇ 3.0 V, which translates into an increase of 44% in energy density.
- This example describes the preparation of a capacitor comprising two activated carbon-based electrodes, a separator, and an electrolyte containing the novel onium salts as described in Examples 1 through 13.
- the carbon electrode was prepared from 95 parts of activated carbon of various brands and 5 parts of Teflon® as binder. The resultant mixture was dispersed thoroughly in an appropriate solvent. Then the solution was either evaporated to make an activated carbon-based paste, or directly coated onto an Aluminum substrate by spraying. Typically the electrodes were cut into an area of ca. 100 cm 2 , with loading of ca. 2.8 mg/cm 2 . The prepared electrodes were thoroughly dried under vacuum.
- FIG. 5 shows the voltage profile for galvanostatic charging/discharging such a capacitor including the novel electrolyte described herein.
- the charge/discharge were carried at different operating voltages, and eventually the voltage was deliberately brought over the decomposition potential of the electrolytes. While commercial capacitor (GoldCap®) burst the safety valve at ca. 4.0 V charging, the electrolytes used in this invention operate well at 4.0 V, and only failed but did not burst even at 5.0 V in a cell with the same safety valve.
- GoldCap® commercial capacitor
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Abstract
Based on the discovery that the melting point and solubility of onium salts are affected by the asymmetry of the substitution on cation, and that the branched substituents effectively shield onium cations from electrochemical reduction, new onium salts are synthesized and high performance electrolytes based on these salts for electrochemical capacitor are provided. The composition of the new electrolyte comprises an onium salt or mixture of such onium salts dissolved in aprotic, non-aqueous solvents or mixture of such solvents. The electrolyte is able to perform at high rate of charge/discharge, at low ambient temperatures, and within wide operating voltage, due to the high solubility, low melting temperature, and the improved reduction stability of the new onium cations, respectively.
Description
- [0001] The invention described herein may be manufactured, used, and/or licensed by or for the United States Government.
- 1. Field of the Invention
- The present invention relates generally to onium salts and to methods of producing the same. These salts, obtained by the methods provided herein, are useful components in a wide spectrum of fields, such as phase transfer catalysis, electrolyte solutes for aqueous or non-aqueous electrochemical devices, various additives, and medicaments, etc. More particularly, the present invention provides a new family of asymmetric onium cations, which when combined with an appropriate anion, result in salts having high electrochemical stability and high solubility in non-aqueous polar solvents. Most particularly, the present invention relates to the formulation of a non-aqueous electrochemically stable electrolyte solution comprising these onium salts and an appropriate solvent or solvent mixture. Finally, the present invention relates to improved electrochemical capacitors utilizing these novel electrolyte solutions and thereby having improved energy density and power capabilities.
- 2. Description of the Related Art
- Electrochemical capacitors are energy storage devices that are able to store and release energy by the means of ion adsorption/desorption on high surface area electrodes. These capacitors typically consist of two porous electrodes that are isolated from electrical contact with each other by a separator. Both the separator and the electrodes are impregnated with an electrolytic solution, i.e., a salt or mixture of salts dissolved in appropriate solvent or mixture of solvents.
- When electric potential is applied across the two electrodes during charge, ionic current flows within the capacitor due to the attraction of anions by the positive electrode and cations by the negative electrode. Upon reaching the surface of their respective electrodes, equal amounts of anions and cations are absorbed in the electrode/electrolyte interphase and are held in the region by the opposite charges in the solid electrode.
- The above state of charge-separation tends to go back to the ground level of lower energy where no charge is separated. Thus, when the two electrodes are no longer held at separate potential and are connected via a load, these absorbed cations and anions desorb from the electrode/electrolyte interphase and migrate back to the bulk of the electrolyte. During this process the current produced within the capacitor drives the load as the capacitor is discharged. The above process can be repeated tens of thousands of times.
- The rate at which energy can be stored/released in such capacitors is extremely high, on the order of 500˜3000 W/Kg, which is higher than most electrochemical energy devices including the state-of-the-art Li-ion batteries (50˜300 W/Kg). However, a disadvantage for capacitors is their low to moderate energy densities, 5˜10 Wh/Kg compared to 40˜200 Wh/Kg for Li-ion batteries.
-
- Where E is the storable energy at a potential difference ΔV between the electrodes and C is the storage capacitance of the electrodes (B. E. Conway,J. Electrochem. Soc., 1991, 138, 1539). For a given electrode material with a certain C, it is desirable to increase the operating potential ΔV in order to obtain high energy density output. However, this operating potential is always restricted by the stability limit of the solvent and salt.
- For aqueous or any protic solvents, the stability limit imposed by the reduction of proton and/or oxidation of hydroxyl ion is ca. 1.2˜2.0 V. Earlier efforts aimed at increased operating potential led to the use of non-aqueous aprotic solvents. See, for example, Boos et al., U.S. Pat. No. 3,536,963, and Yoshida et al., U.S. Pat. No. 5,150,283, describing electrolytes of non-aqueous solvents and ammonium salts, among others, which usually can support up to 3.0 V potential difference.
- For these electrolyte solutions the stability limit is usually imposed by the decomposition of the salts, especially at the negative potential extreme, where the cation usually determines the cathodic stability limit of the electrolyte alone, independent of the anion and the solvent it is in.
- Therefore it is highly desirable to find a new electrochemically stable salt, which, when dissolved in non-aqueous aprotic solvents, can provide high resistance toward oxidation and reduction. More specifically, the salt should have a cation which is stable against reduction at the negative electrode, and an anion which is stable against oxidation at positive electrode, and their stability should be higher or at least as high as that of the solvent. Thus, any improvement in electrochemical stability will increase operating potential (ΔV) and have an impact on energy output by the magnitude squared as shown by Equation (1).
- Furthermore, energy density can be affected by the number of ions available in the electrolytic solution (J. P. Zheng, J. Huang, T. R. Jow,J. Electrochem. Soc., 1997, 144, 2026). In other words, limited solubility of most salts in aprotic, non-aqueous solvents often limits the energy density at high operating voltages. At high rate discharge/charge operations, the number of ions available in the electrolytic solution also limits the power output, i.e., where high demand for ions lowers the ion concentration in the solution thus increasing the resistance and limiting the power output. It is therefore also highly desirable to find a salt having higher solubility in aprotic, non-aqueous solvents.
- The electrolyte used in state-of-the-art electrochemical capacitors contains tetraethylammonium tetrafluoroborate (Et4NBF4) in propylene carbonate (PC) solvent as described in U.S. Pat. No. 5,150,283, A Yoshida and K. Imoto, “Electric Double Layer Capacitor and Method for Producing the Same”; or the same salt in acetonitrile (AN) solvent as described in U.S. Pat. No. 5,621,607, C. J. Farahmandi and J. M. Dispennette, “High Performance Double Layer Capacitors Including Aluminum Carbon Composite Electrodes”. However, these electrolytes have serious shortcomings.
- For example, the electrolyte solution of Et4NBF4 in PC exhibits low salt solubility, having a saturated concentration of 0.86 M at room temperature, and low conductivity of 8.8 mS/cm at 0.65 M at room temperature. This electrolyte is suitable for low power applications such as memory protection but not for high power applications.
- In contrast, the electrolyte solution of Et4NBF4 in AN has high conductivity, about 50 mS/cm at 1.4 M at room temperature, and the saturated salt concentration is about 1.68 M at room temperatures. However, the operating voltages of the capacitor using this electrolyte is about 0.5 V lower than that using the electrolyte of Et4NBF4 in PC. Furthermore, the high vapor pressures of AN makes it unsuitable for applications at elevated temperatures.
- Where both high salt solubility and high operational voltage are desired for an electrolyte, the state-of-the-art solutes comprising symmetrical quaternary ammonium salts such as tetraethyl ammonium salt are inadequate. The present invention fulfills these needs by providing asymmetrical onium salts or mixtures of such salts in aprotic, non-aqueous solvents or mixtures of such solvents. These novel electrolytes are able to perform at a high rate of charge/discharge, at low operating temperatures, and within a wide range of operating voltage due to the high solubility, low melting temperature, and the improved reduction stability of the new onium cations, respectively.
- Accordingly, it is a primary object of the present invention to provide an electrochemically stable salt.
- It is another object of the present invention to provide an electrochemically stable salt having electrochemically stable cations against reduction at the negative electrode, and electrochemically stable anions against oxidation at the positive electrode.
- It is still another object of the present invention to provide a salt which comprises electrochemically stable onium cations, and electrochemically stable inorganic or organic anions.
- It is still another object of the present invention to provide an electrochemically stable salt which also has high solubility in an aprotic, non-aqueous solvent or mixtures of such solvents.
- It is still another object of the present invention to provide an electrochemically stable salt having a low melting temperature.
- It is yet another object of the present invention to provide an electrolyte formulation comprising an electrochemically stable onium salt or mixture of such salts dissolved in an aprotic, non-aqueous solvent or mixture of such solvents.
- It is a still further object of the present invention to provide an electrolyte capable of performing at a high rate of charge/discharge, at low ambient temperatures, and within a wide range of operating voltages.
- It is a still further object of the present invention to provide an electrochemical capacitor comprising two porous electrodes, a separator, and the aforementioned electrolyte having an electrochemically stable salt solute.
- In satisfaction of the foregoing objects and advantages, the present invention provides a novel family of onium salts which, in appropriate solvents, will form electrolyte solutions having these desirable properties.
- The foregoing and other objects and advantages of the present invention will hereafter become more fully apparent from the following detailed description. In the description, reference is made to examples and drawings which form a part hereof, and in which is shown by way of illustration, and not limitation, preferred embodiments. Such description does not represent the full extent of the invention, but rather, the invention may be employed according to the full scope and spirit of the invention as defined in the appended claims.
- FIG. 1 shows the correlation of melting point and solubility (in 50:50 EC:DMC) with weight as well as symmetry for some of the onium cations described in the present invention. Commercially available salt tetraethylammonium hexafluorophosphate (Et4N+PF6 −) is used as a control.
- FIG. 2 shows the temperature dependence of conductivity of electrolytes comprising some of the onium salts described in the present invention. Commercially available salt Et4N+PF6 − is used as a control. The solvent is a mixture of EC:DMC in a 1:1 weight ratio.
- FIG. 3 shows the concentration dependence of conductivity of electrolytes based on one of the onium salts described in the present invention. Commercially available salt Et4N+PF6 − is used as a control. The solvent is a mixture of EC:DMC in a 1:1 weight ratio.
- FIG. 4 shows the electrochemical stability window of the electrolyte comprising novel onium salts described in this invention, and commercially available salt Et4N+PF6 − is used as a control.
- FIG. 5 shows the voltage profile for galvanostatic charging/discharging of a capacitor comprising novel electrolytes described in this invention.
- The practice of the present invention will employ, unless otherwise indicated, conventional techniques of synthetic chemistry, electrochemistry and battery/capacitor engineering that are within the skill of the art. Such techniques are explained fully in the literature. See, for example, March'sAdvanced Organic Chemistry, House's Modern Synthetic Chemistry, Houben-Weyl's Methoden der organischen Chemie, Hiers' text Organic Synthesis, U.S. Pat. No. 4,892,944 to Mori et al., and Lindens' Handbook of Batteries.
- Definitions:
- Before describing the present invention in detail, it is to be understood that this invention is not limited to the particular cations or salts, methods of synthesis, solvents or the like, which are described in the preferred embodiments, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
- In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:
- The term “onium cation” is used to indicate a positively charged atom group, which is formed because the central Lewis basic atom increases its valency by donating a lone pair of electrons;
- The term “substituents” is used to indicate the group of atoms which are covalently bonded to the central atom of the onium cation;
- The term “normal alkyl” as used herein refers to unbranched, saturated hydrocarbon groups, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl and the like, with preferred normal alkyl groups are unbranched alkyl group containing 1 to 10 carbon atoms;
- The term “branched alkyl” as used herein refers to the group of saturated hydrocarbons which contain at least one secondary or tertiary carbon atom which are designated as “branch points”, such as iso-propyl, sec-butyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl and the like. Preferred branched alkyl groups are branched alkyl groups with a branch point close to the central atom of the onium cation, and with 3 to 8 carbon atoms;
- The term “alkenyl” as used herein refers to a branched or unbranched hydrocarbon chain typically containing from 2 to 10 carbon atoms and at least one double bond;
- The term “aryl” as used herein refers to a monocyclic or multiple-cyclic aromatic moiety, and is typically phenyl;
- The term “arakyl” as used herein refers to moieties containing both alkyls and aromatic moieties as defined above, typically containing less than 10 carbon atoms;
- The term “halogen” as used herein refers to fluoro- (hereafter designated as F), chloro- (hereafter designated as Cl), bromo- (hereafter designated as Br) or iodo- (hereafter designated as I), and usually relates to substitution for a hydrogen atom in an organic compound, this substitution is optionally a full substitution for the hydrogen;
- The term “sulfone” as used herein refers to the class of compounds which are dioxides of the corresponding sulfide;
- The term “ether linkage” as used herein refers to oligomeric collection of the units containing alkylene oxygen linkages, such as (CH2OCH2)n or (CH2O)n where n ranges from 2 to 50;
- The term “carbonic diester” as used herein refers to compounds having the structure R—O—C(O)—O—R;
- The terms “asymmetry” and “asymmetrical” refers to the substituents on the onium cation, where at least one of the substituents is different from the rest;
- “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, and that the description includes instances in which the said circumstance occurs and instances in which it does not.
-
- wherein X, Y and Z are central atoms bearing the charge, and are either elements selected from
Groups 14, 15, 16 or 17 of The Periodic Table of the Elements or any inorganic/organic Lewis base groups, and R1, R2, R3, R4, R5, R6, R7 and R8 are substituents independently selected from the groups consisting of (a) C1˜C10 normal alkyl, (b) C3˜C10 branched alkyl, (c) C6˜C12 aryl, (d) C7˜C15 aralkyl, and (e) C1˜C10 normal or branched alkyl containing functional groups, such as, but not limited to, (i) 0˜2n+1 halogens, wherein n is the number of carbon atoms in the substituent, (ii) sulfone, (iii) ether linkage, and (iv) carbonic diester. Optionally, within a structure any two substituents Ri (i=1˜8) as defined above may link together and form a cyclic bridge. - More preferentially but not intending to be limiting, the following specifications apply to the above structures (I), (II) and (III):
- That the central atom group X is selected from the following organic or inorganic compounds of Lewis base nature: heterocyclic bases such as pyridine; nitrile (R′—CN); nitroso (R′—NO); nitro (R′—NO); carbon oxide (CO); and azide (R′N3); where R′ is selected from the categories (a) through (e) for substituents as defined above;
- That the central atom Y is preferentially, but not limited to, Oxygen, or Sulfur;
- That the central atom Z is preferentially, but not limited to, Nitrogen or Phosphorus;
- That R1 is different in structure from the X atom group;
- That at least one of the 3 substituents Ri (i=2˜4) in structure (II) is different from the other substituents;
- That at least one of the 4 substituents Ri (i=5˜8) in structure (III) is different from the other substituents;
- That the alkyl substituents and the functionalized alkyl substituents as defined above are preferentially branched;
- That the alkyl substituents and the functionalized alkyl substituents as defined above are preferentially branched; and more preferentially that the branching point be closer to the central atom of the cation as opposed to further away from the central atom;
- In still further aspects of the invention, the anions of the salt are selected from the organic or inorganic anions known to those skilled in the art, among which are, but not limited to, triflate (CF3SO3 −; hereafter designated as Tf−); bis(trifluoromethane sulfonyl)imide ((CF3SO2)2N−, hereafter designated as Im−); tetrafluoroborate (hereafter designated as BF4 −); perchlorate (hereafter designated as ClO4 −); tris(trifluoromethanesulfonyl)methide ((CF3SO2)3C−, hereafter designated as Me−); polyhaloaluminate (AlX4 −, X=F, Cl, Br and I); bis(penta fluoroethane sulfonyl)imide ((C2F5SO2)2N−); hexafluoroarsenate (hereafter designated as AsF6 −); and hexafluorophosphate (hereafter designated as PF6 −); and the mixture thereof;
- In yet further aspects of the invention the new salts based on the above-defined cations and anions are dissolved in an aprotic, non-aqueous solvent or the mixture of such solvents known to those skilled in the art, among which are, but not limited to, cyclic carbonates including ethylene carbonates (hereafter designated as EC), propylene carbonates (PC) etc, linear carbonates including dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) etc, and sulfones including ethylmethylsulfone (EMSF), sulfolane, dimethylsulfone etc., thereby forming improved electrolyte solutions.
- Experimental
- Materials
- All chemicals used in the synthesis were used as received. All solvents used in the fabrication of electrolytes were dried and re-distilled. Activated carbon (M series) was from Osaka Gas and used without further treatment. Procedures handling the electrolytes and subsequent measurement were all conducted in a Vacuum Atmosphere Glove Box under Ar atmosphere with O2 level <5 ppm and the H2O level <2 ppm.
- Melting Point
- Differential Scanning Calorimetry was employed to determine the melting point of the salts. Typically the experiment was conducted under a helium atmosphere at a heating rate of 5° C. The onset point of the melting process was taken as the melting point.
- Electrical Conductivity
- Impedance spectroscopy was employed to determine the solution bulk resistance and conductivity was then derived from the cell geometry, which comprised a pair of parallel platinum electrodes. The cell was placed in a temperature-controlled environment and computers were used to control the heating/cooling as well as impedance measurement.
- Cyclic Voltammetry
- Electrochemical stability window was measured by cyclic voltammetry using EG&G 273 Potentiostat/Galvanostat. A three-electrode configuration cell was employed, with glassy carbon as the working electrode, Li as the reference electrode and Pt or Ti as the counter electrode. Typically a scan rate was 5 mV/s and 100 μA/cm2 was used as cutoff current density for stability window limit.
- Cell Testing
- The assembled cell was subjected to charge/discharge test on an EG&G 273 Potentiostat/Galvanostat. Typically a charge/discharge rate of 1.0 mA/cm2 was used.
- The following examples are intended to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the novel new electrochemically stable salts in a new electrolyte formulation, and are not intended to be limiting in any way. Efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperatures, etc), but some deviation should be allowed for. Unless otherwise indicated, parts are by weight, and temperatures are in degrees centigrade, and pressure is near atmospheric. All chemicals, reagents and the like, are commercially available or are otherwise readily synthesized using conventional techniques well known in the art.
- In a 500 mL flask equipped with an addition funnel, a refluxing condenser, and a stirrer, were filled 25.6 g of formic acid (0.5 mol, Aldrich, 95%) and 30.4 g di(iso-propyl)amine (0.30 mol, Aldrich, 99.5%). Under cooling and stirring was slowly added 13.0 g acetaldehyde solution (ca. 0.30 mol, Aldrich, 99%). After the solution became cleared, the reaction mixture was brought to ca. 90˜110° C. in an oil bath. A vigorous evolution of CO2 began after 2˜3 min., during which time the flask was removed from the bath from time to time until the evolution subsided. After 30 min. the reaction mixture stabilized and was kept in the oil bath at 100° C. for 8 hrs.
- After the solution cooled, 80 mL of 4.0 N HCl was added and the solution is evaporated to dryness under reduced pressure. The remaining residue was dissolved in water and the organic phase was liberated by the addition of 50 mL 9.0 N NaOH solution. The organic phase was separated and dried with anhydrous K2CO3. Distillation yielded ca. 32.0 g Ethyldi(iso-propyl)amine.
- The above amine was mixed with 22.5 g dimethylcarbonate (0.25 mol, Aldrich, 99%) in 100 mL methanol. The mixture was then added to a Parr mini-reactor and the temperature was brought up to 130° C. for 5 hrs. under vehement stirring. After the reaction the product was transferred into a flask and evaporated under reduced pressure. The brownish residue, ethylmethyldi(iso-propyl)ammonium methylcarbonate (EtMeiPr2NMeCO3) weighed ca. 50.0 g.
- EtMeiPr2NMeCO3 was dissolved in distilled water, and 60% hexafluorophosphoric acid (HPF6) was added to this solution with precaution. After neutralization, the solution was subject to evaporation under reduced pressure to remove water. Resultant crystal was repeatedly recrystallized from hot methanol solution, and the final product EtMeiPr2NPF6 was fine needle.
- 40 g Lithium bis(trifluoromethane sulfonyl)imide (0.14 mol, 99%, 3M was dissolved in 200 mL distilled water and was passed through a pre-protonated cation exchange column of 4.5 eq. Capacity. The collected acid solution was once again passed through the regenerated cation exchange column to ensure quantitative conversion. The resultant aqueous solution of bis(trifluoromethane sulfonyl)imidic acid was condensed to ca. 2.0 M by evaporating excess water.
- The aqueous solution of bis(trifluoromethane sulfonyl)imidic acid was added to solution of EtMeiPr2NMeCO3. After the neutralization the solution was subject to evaporation under reduced pressure to remove water. Resultant solid was repeatedly recrystallized from hot methanol solution, and the final product EtMeiPr2N+Im− is fine needle crystal.
- Triflic acid aqueous solution was prepared in a procedure similar to that described in Example 2, except that lithium triflate (96% Aldrich) was used in the place of lithium imide, and it was then used to neutralize the solution of EtMeiPr2NMeCO3. After the neutralization the solution was subject to evaporation under reduced pressure to remove water. Resultant solid was repeatedly re-crystallized from hot methanol solution, and the final product EtMeiPr2N+Tf− obtained is fine crystal.
- 40.0 g Tri(iso-butyl)amine (0.21 mol, Aldrich, 98%) and 30.0 g methyliodide (0.21 mol, Aldrich, 99%) in 200 mL alcohol were charged into a Parr mini-reactor. The reaction temperature was kept at 60° C. for 5 hrs. before the reactor was opened. With the solvent evaporated under reduced pressure, the remaining solid residue was dissolved in water and passed through a strong base (in OH− form) anion exchange column with 4.0 eq. capacity. The resultant basic solution was passed through the regenerated column again to ensure complete conversion.
- After condensation, the basic solution was neutralized with HPF6 and then the solution was subject to evaporation under reduced pressure to remove water. Resultant solid was repeatedly re-crystallized from hot methanol solution, and the final product iBu3MeN+PF6 − obtained is fine crystal.
- 40 g di(isopropyl)amine (0.40 mol, Aldrich, 99.5%) in 100 mL of methanol was mixed with 51.2 g of formic acid (1.0 mol, Aldrich, 95%) in a 500 mL flask. Then under cooling and stirring was slowly added 33 g formaldehyde solution (ca. 0.40 mol, Aldrich, 37%). After the solution became cleared, the reaction mixture was brought to ca. 90˜110° C. in an oil bath. A vigorous evolution of CO2 began after 2˜3 min., during which time the flask was removed from the bath from time to time until the evolution subsided. After 30 min. the reaction mixture stabilized and was kept in the oil bath at 100° C. for 8 hrs.
- After the solution cooled, 100 mL of 4.0 N HCl was added and the solution is evaporated to dryness under reduced pressure. The remaining residue was dissolved in water and the organic phase was liberated by the addition of 80 mL 9.0 N NaOH solution. The organic phase was separated and dried with anhydrous K2CO3. Distillation yielded ca. 34.0 g methyldi(iso-propyl)amine.
- 37.0 g 2-Bromopropane (0.30 mol, Aldrich, 99%) was added slowly to methyldi(iso-propyl)amine as obtained above. The reaction mixture was kept at room temperature overnight under stirring. The crystal that formed was filtered and washed by methanol. The procedures for converting the crystal, which is methyltri(iso-propyl)ammonium bromide, into the corresponding hydroxide by anion exchange column, the subsequent neutralization with HPF6 and re-crystallization in methanol were described in Example 4. The resultant iPr3MeNPF6 is fine crystal.
- In a Parr mini-reactor were charged 28.6 g tripropylamine (0.2 mol, Aldrich, 99%) and 18.0 g dimethylcarbonate (0.2 mol, Aldrich, 99%) in 200 mL methanol. The reaction mixture was kept at 120° C. overnight, and the solvent and unreacted carbonate or amine were removed through evaporation under reduced pressure.
- The brownish residue, Pr3MeN+MeCO3 − was dissolved in distilled water, and neutralization was carried out with HPF6. The subsequent re-crystallization procedure was described in Example 3.
- Tetrafluoroboric acid (Aldrich, 48% aqueous solution) was used to neutralize Pr3MeN+MeCO3 −, the preparation of which has been described in Example 6. The subsequent re-crystallization procedure was described in example 3.
- 15 g Ethylmethyl sulfide (0.20 mol, Aldrich, 99%) was slowly added to 100 mL methyliodide solution in t-butyl methyl ether (0.20 mol, Aldrich, 2.0 M), and the reactants were kept at room temperature overnight. The crystalline precipitate was collected by filtration, washed by diethylether, and then dissolved in distilled water.
- The procedures for converting the crystal, which is ethyldimethylsulfonium iodide, into the corresponding hydroxide by anion exchange column, the subsequent neutralization with HPF6 and re-crystallization in methanol were described in Example 4. The resultant EtMe2SPF6 is fine white crystal.
- The synthesis of Et3MeN+MeCO3 − and its conversion into Et3MeN+PF6 − by means of anion exchange were conducted in a manner similar to that described in Example 6, except that an appropriate amount of triethylamine was used in place of tripropylamine. The resultant Et3MeN+PF6 − is fine crystal.
- Using 2.0 M aqueous solution of bis(trifluoromethane sulfonyl)imidic acid, whose preparation was described in Example 2, aqueous solution of Et3MeN+MeCO3 − was neutralized. After the neutralization the solution was subject to evaporation under reduced pressure to remove water. Resultant solid was repeatedly recrystallized from hot methanol solution, and the final product Et3MeN+Im− is fine flake crystal.
- Using 2.0 M aqueous solution of triflic acid, whose preparation was described in Example 3, an aqueous solution of Et3MeN+MeCO3 − was neutralized. After the neutralization the solution was subject to evaporation under reduced pressure to remove water. Resultant solid was repeatedly recrystallized from hot methanol solution, and the final product Et3MeN+Tf− is fine needle crystal.
- The synthesis of Et3MeP+MeCO3 − and its conversion into Et3MeP+PF6 − by means of anion exchange were conducted in a manner similar to that described in Example 6, except that an appropriate amount of triethylphosphine was used in place of tripropylamine. The resultant Et3MeP+PF6 − is fine crystal.
- The synthesis of Bu3MeP+MeCO3 − and its conversion into Bu3MeP+PF6 − by means of anion exchange were conducted in a manner similar to that described in Example 6, except that an appropriate amount of tributylphosphine was used in place of tripropylamine. The resultant Et3MeP+PF6 − is fine crystal.
- Equimolar pyridine and methyliodide are reacted at room temperature for two hours. The precipitate (1-methylpyridinium iodide, C6H8N+I−) was filtered, and an anion exchange column was used to convert it into 1-methylpyridinium hydroxide (C6H8N+OH−). Neutralization with HPF6, as described in Example 4, converts the salt into pyridinium hexafluorophosphate (C6H8N+PF6 −), and recrystallization was conducted in hot methanol three times. The final product is a white needle-like crystal.
- This example describes the preparation and characterization of novel electrolytic solutions comprising the electrochemically stable onium salts whose synthesis has been disclosed in Examples 1 through 12 and appropriate solvents.
- The novel electrolyte was prepared to have the following composition: one onium salt or mixtures of two or more of the onium salts as described in Examples 1 through 12, and a 50:50 mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC). The amount of onium salt or mixture of onium salts were such that the total concentration was between 0.5˜2.5 M, with the preferred concentration between 0.7˜1.5 M.
- FIG. 1 shows the correlation of melting point and solubility in 50:50 EC:DMC with cationic weight as well as the effect of cationic symmetry for some of the onium cations described in the present invention. Commercially available salt Et4NPF6 is used as control. These results confirmed that the “asymmetry” of the substitution on cation plays a decisive role in determining the melting point as well as the solubility of the salts. These asymmetrical salts described herein are much lower melting and more soluble in the aprotic solvent mixture than the symmetrical Et4NPF6. That provides the capacitors containing these asymmetrical salts with improved low temperature performance and also better high rate performance.
- FIG. 2 shows the temperature dependence of conductivity of electrolytes comprising some of the onium salts in 50:50 EC:DMC solvent described in the present invention. Commercially available salt Et4NPF6 is used as control. It can be seen that most of the asymmetrical onium salts described herein can yield conductivity higher than 10 mS/cm at room temperature.
- FIG. 3 shows the comparison of concentration dependencies between one of the onium salts in 50:50 EC:DMC as described in the present invention and the commercially available salt Et4NPF6 in 50:50 EC:DMC. Obviously, asymmetrical onium salts have maximum conductivity at higher concentration. Since high concentration minimizes the concentration polarization during charging, the novel onium salts described herein provides capacitors containing them with an advantage of working at higher rates.
- FIG. 4 shows the electrochemical stability window of the electrolyte comprising novel onium salts in 50:50 EC:DMC as described herein, and commercially available salt Et4NPF6 in 50:50 EC:DMC used as a control. Obviously, the asymmetrical onium cations with bulky, branched alkyl substituents tend to be reduced at much lower potential. This shielding effect of the substituents extends the electrochemical stability window by as much as 0.5 V in the case of Pr3MeN+PF6 − and iBu3MeN+PF6 −. As a result, the operating voltage of the capacitor containing these novel salts described herein can be increased from 2.3˜2.5 V to 2.8˜3.0 V, which translates into an increase of 44% in energy density.
- This example describes the preparation of a capacitor comprising two activated carbon-based electrodes, a separator, and an electrolyte containing the novel onium salts as described in Examples 1 through 13.
- The carbon electrode was prepared from 95 parts of activated carbon of various brands and 5 parts of Teflon® as binder. The resultant mixture was dispersed thoroughly in an appropriate solvent. Then the solution was either evaporated to make an activated carbon-based paste, or directly coated onto an Aluminum substrate by spraying. Typically the electrodes were cut into an area of ca. 100 cm2, with loading of ca. 2.8 mg/cm2. The prepared electrodes were thoroughly dried under vacuum.
- Different commercial separators including Celgard® series films were used as separator.
- After vigorous drying at 120° C. under vacuum the electrodes and the separator were vacuum-soaked with an electrolyte as prepared in Example 13, and were assembled as an experimental capacitor cell.
- FIG. 5 shows the voltage profile for galvanostatic charging/discharging such a capacitor including the novel electrolyte described herein. The charge/discharge were carried at different operating voltages, and eventually the voltage was deliberately brought over the decomposition potential of the electrolytes. While commercial capacitor (GoldCap®) burst the safety valve at ca. 4.0 V charging, the electrolytes used in this invention operate well at 4.0 V, and only failed but did not burst even at 5.0 V in a cell with the same safety valve.
- While the invention has been described in detail and with reference to specific embodiments thereof it will be apparent to one skilled in the art that various changes, alterations, and modifications can be made without departing from the spirit and scope of the invention and its equivalents as defined in the appended claims.
Claims (58)
1-14. (Cancelled)
15. An Asymmetric onium salt comprising an onium cation and an anion, and wherein said onium cation is selected from the group consisting of onium cations having the structure (I):
wherein the central atom group X is selected from the following compounds of Lewis base nature: heterocyclic organic bases; nitrile (R′—CN); nitroso (R′—NO); nitro (R′—NO2); carbon oxide (CO); azide (R′N3); and R′ and R1 are different and are substituents independently selected from the groups consisting of (a) C1˜C10 normal alkyl, (b) C3˜C10 branched alkyl, (c) C6˜C12 aryl, (d) C7˜C15 aralkyl, and (e) C1˜C10 normal or branched alkyls having functional groups selected from the group consisting of (i) 0˜2n+1 halogens, wherein n is the number of carbon atoms in the substituent, (ii) sulfone, (iii) ether linkage, and (iv) carbonic diester; an onium cation having the structure (II):
wherein Y is the central atom bearing the charge, and is an element selected from Groups 15 or 16 of The Periodic Table of the Elements, and R2, R3, and R4 are selected from categories (a) through (e) as defined above and at least one of R2, R3 and R4 is different from the rest; and an onium cation having the structure (III):
wherein Z is the central atom bearing the charge, and is an element selected from Group 15 of the Periodic Table of the Elements, and R5, R6, R7 and R8 are selected from categories of (a) through (e) as defined above and at least one of R5, R6, R7 and R8 is different from the rest; and wherein said anion comprises an organic or inorganic anion which is selected from the group consisting of polyhaloaluminate (AlX4 −, X=F, Cl, Br and I), triflate (CF3SO3 −, Tf−), bis(trifluoromethane sulfonyl)imide ((CF3 SO2)2N−, Im−), bis(pentafluoroethane sulfonyl)imide ((C2F5SO2)2N−), perchlorate (ClO4 −), tetrafluoroborate (BF4 −), tris(trifluoromethanesulfonyl)methide ((CF3SO2)3C−, Me−), hexafluoroarsenate (AsF6 −), hexafluorophosphate (PF6 −), and mixtures thereof.
16. The onium salt of claim 15 , wherein said salt comprises methyltripropylammonium hexafluorophosphate.
17. The onium salt of claim 15 , wherein said salt comprises methyltripropylammonium tetrafluoroborate.
18. The onium salt of claim 15 , wherein said salt comprises tri (isopropyl)methylammonium hexafluorophosphate.
19. The onium salt of claim 15 , wherein said salt comprises tri(n-butyl)methylammonium hexafluorophosphate.
20. The onium salt of claim 15 , wherein said salt comprises tri(iso-butyl)methylammonium hexafluorophosphate.
21. The onium salt of claim 15 , wherein said salt comprises ethylmethyldi(iso-propyl)ammonium hexafluorophosphate.
22. The onium salt of claim 15 , wherein said salt comprises ethylmethyldi(iso-propyl)ammonium bis(trifluoromethane sulfonyl)imide.
23. The onium salt of claim 15 , wherein said salt comprises ethylmethyldi(iso-propyl)ammonium triflate.
24. The onium salt of claim 15 , wherein said salt comprises ethyldimethylsulfonium hexafluorophosphate.
25. The onium salt of claim 15 , wherein said salt comprises triethylmethylphosphonium hexafluorophosphate.
26. The onium salt of claim 15 , wherein said salt comprises tributylmethylphosphonium hexafluorophosphate.
27. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium hexafluorophosphate.
28. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium bis(trifluoromethanesulfonyl)imide.
29. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium triflate.
30. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium tetrafluoroborate.
31. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium hexafluoroarsenate.
32. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium hexafluoroantimonate.
33. The onium salt of claim 15 , wherein said salt comprises methyltripropylammonium bis(trifluoromethanesulfonyl)imide.
34. The onium salt of claim 15 , wherein said salt comprises methyltripropylammonium triflate.
35. The onium salt of claim 15 , wherein said salt comprises methyltripropylammonium hexafluoroarsenate.
36. The onium salt of claim 15 , wherein said salt comprises methyltripropylammonium hexafluoroantimonate.
37. The onium salt of claim 15 , wherein said salt comprises tri(iso-propyl)methylammonium bis(trifluoromethanesulfonyl)imide.
38. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium triflate.
39. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium tetrafluoroborate.
40. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium hexafluoroarsenate.
41. The onium salt of claim 15 , wherein said salt comprises triethylmethylammonium hexafluoroantimonate.
42. The onium salt of claim 15 , wherein said salt comprises tri(n-butyl)methylammonium bis(trifluoromethanesulfonyl)imide.
43. The onium salt of claim 15 , wherein said salt comprises tri(n-butyl)methylammonium triflate.
44. The onium salt of claim 15 , wherein said salt comprises tri(n-butyl)methylammonium tetrafluoroborate.
45. The onium salt of claim 15 , wherein said salt comprises tri(n-butyl)methylammonium hexafluoroarsenate.
46. The onium salt of claim 15 , wherein said salt comprises tri(n-butyl)methylammonium hexafluoroantimonate.
47. The onium salt of claim 15 , wherein said salt comprises tri(iso-butyl)methylammonium bis(trifluoromethanesulfonyl)imide.
48. The onium salt of claim 15 , wherein said salt comprises tri(iso-butyl)methylammonium triflate.
49. The onium salt of claim 15 , wherein said salt comprises tri(iso-butyl)methylammonium tetrafluoroborate.
50. The onium salt of claim 15 , wherein said salt comprises tri(iso-butyl)methylammonium hexafluoroarsenate.
51. The onium salt of claim 15 , wherein said salt comprises tri(iso-butyl)methylammonium hexafluoroantimonate.
52. The onium salt of claim 15 , wherein said salt comprises ethylmethyldi(iso-propyl)ammonium tetrafluoroborate.
53. The onium salt of claim 15 , wherein said salt comprises ethylmethyldi(isopropyl)ammonium hexafluoroarsenate.
54. The onium salt of claim 15 , wherein said salt comprises ethylmethyldi(isopropyl)ammonium hexafluoroantimonate.
55. The onium salt of claim 15 , wherein said salt comprises ethyldimethylsulfonium bis(trifluoromethanesulfonyl)imide.
56. The onium salt of claim 15 , wherein said salt comprises ethyldimethylsulfonium triflate.
57. The onium salt of claim 15 , wherein said salt comprises ethyldimethylsulfonium tetrafluoroborate.
58. The onium salt of claim 15 , wherein said salt comprises ethyldimethylsulfonium hexafluoroarsenate.
59. The onium salt of claim 15 , wherein said salt comprises ethyldimethylsulfonium hexafluoroantimonate.
60. The onium salt of claim 15 , wherein said salt comprises triethylmethylphosphonium bis(trifluoromethanesulfonyl)imide.
61. The onium salt of claim 15 , wherein said salt comprises triethylmethylphosphonium triflate.
62. The onium salt of claim 15 , wherein said salt comprises triethylmethylphosphonium tetrafluoroborate.
63. The onium salt of claim 15 , wherein said salt comprises triethylmethylphosphonium hexafluoroarsenate.
64. The onium salt of claim 15 , wherein said salt comprises triethylmethylphosphonium hexafluoroantimonate.
65. The onium salt of claim 15 , wherein said salt comprises tributylmethylphosphonium bis(trifluoromethanesulfonyl)imide.
66. The onium salt of claim 15 , wherein said salt comprises tributylmethylphosphonium triflate.
67. The onium salt of claim 15 , wherein said salt comprises tributylmethylphosphonium tetrafluoroborate.
68. The onium salt of claim 15 , wherein said salt comprises tributylmethylphosphonium hexafluoroarsenate.
69. The onium salt of claim 15 , wherein said salt comprises tributylmethylphosphonium hexafluoroantimonate.
70. An electrolyte solution comprising the onium salt of claim 15 dissolved in a non-aqueous, aprotic solvent.
71. The electrolyte solution of claim 70 , wherein said solvent is selected from or is a mixture of the group consisting of: acetonitrile (AN), adipontrile (ADN), butylene carbonate (BC), γ-butyrolactone (γBL), diethylcarbonate (DEC), dimethylcarbonate (DMC), ethyl methylcarbonate (EMC), methyl-iso-propylcarbonate (MiPC), ethylene carbonate (EC), propylene carbonate (PC), chloroethylene carbonate (ClEC), fluoroethylene carbonate (FEC), dichloroethylene carbonate (Cl2EC), difluoroethylene carbonate (F2EC), perchloroethylene carbonate (Cl4EC), perfluoroethylene carbonate (F4EC), chloropropylene carbonate (ClPC), fluoropropylene carbonate (FPC), perchloropropylene carbonate (Cl3PC), perfluoroethylene carbonate (F4EC), dialkylsulfoxide (R—SO—R′), dialkylsulfone (R—SO2—R′), sulfolane, alkylsulfite (R—S(O)—OR′), α-disulfones (R—S2O4—R′), trialkylphosphate, phosphite, and aldehyde.
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US10/855,646 US20040222401A1 (en) | 1999-05-10 | 2004-05-28 | Electrochemically stable onium salts and electrolytes containing such for electrochemical capacitors |
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US09/309,393 US6743947B1 (en) | 1999-05-10 | 1999-05-10 | Electrochemically stable onium salts and electrolytes containing such for electrochemical capacitors |
US10/855,646 US20040222401A1 (en) | 1999-05-10 | 2004-05-28 | Electrochemically stable onium salts and electrolytes containing such for electrochemical capacitors |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4892944A (en) * | 1987-05-13 | 1990-01-09 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
US5527640A (en) * | 1992-11-25 | 1996-06-18 | The Regents Of The University Of California, Office Of Technology Transfer | Electrochemical supercapacitors |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3536963A (en) | 1968-05-29 | 1970-10-27 | Standard Oil Co | Electrolytic capacitor having carbon paste electrodes |
EP0449145B1 (en) | 1990-03-29 | 1998-01-28 | Matsushita Electric Industrial Co., Ltd. | Electric double layer capacitor and method for producing the same |
US5429893A (en) | 1994-02-04 | 1995-07-04 | Motorola, Inc. | Electrochemical capacitors having dissimilar electrodes |
US5629829A (en) * | 1994-09-14 | 1997-05-13 | Kabushiki Kaisha Toshiba | Electrolytic solution for electrolytic capacitor and electrolytic capacitor |
US5621607A (en) | 1994-10-07 | 1997-04-15 | Maxwell Laboratories, Inc. | High performance double layer capacitors including aluminum carbon composite electrodes |
US5568353A (en) | 1995-04-03 | 1996-10-22 | Motorola, Inc. | Electrochemical capacitor and method of making same |
-
1999
- 1999-05-10 US US09/309,393 patent/US6743947B1/en not_active Expired - Fee Related
-
2004
- 2004-05-28 US US10/855,646 patent/US20040222401A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4892944A (en) * | 1987-05-13 | 1990-01-09 | Mitsubishi Petrochemical Co., Ltd. | Process for producing quaternary salts |
US5527640A (en) * | 1992-11-25 | 1996-06-18 | The Regents Of The University Of California, Office Of Technology Transfer | Electrochemical supercapacitors |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100833041B1 (en) | 2005-05-03 | 2008-05-27 | 주식회사 엘지화학 | Nonaqueous electrolyte for improving performance and lithium secondary battery comprising the same |
KR20170037450A (en) * | 2015-09-25 | 2017-04-04 | 삼성전자주식회사 | Electrolyte for lithium air battery and lithium air battery including the same |
US10270114B2 (en) * | 2015-09-25 | 2019-04-23 | Samsung Electronics Co., Ltd. | Electrolyte for lithium air battery and lithium air battery including the same |
KR102501474B1 (en) * | 2015-09-25 | 2023-02-22 | 삼성전자주식회사 | Electrolyte for lithium air battery and lithium air battery including the same |
CN112778170A (en) * | 2020-12-30 | 2021-05-11 | 中船重工(邯郸)派瑞特种气体有限公司 | Method and device for preparing lithium trifluoromethanesulfonate |
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