WO2006106657A1 - 電解液 - Google Patents
電解液 Download PDFInfo
- Publication number
- WO2006106657A1 WO2006106657A1 PCT/JP2006/306249 JP2006306249W WO2006106657A1 WO 2006106657 A1 WO2006106657 A1 WO 2006106657A1 JP 2006306249 W JP2006306249 W JP 2006306249W WO 2006106657 A1 WO2006106657 A1 WO 2006106657A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- group
- carbonate
- electrolyte
- formula
- Prior art date
Links
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 124
- 239000011737 fluorine Substances 0.000 claims abstract description 113
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 101
- 150000003839 salts Chemical class 0.000 claims abstract description 72
- 239000003792 electrolyte Substances 0.000 claims abstract description 58
- 125000001033 ether group Chemical group 0.000 claims abstract description 48
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 150000005678 chain carbonates Chemical class 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 18
- -1 hexafluoroisopropyl groups Chemical group 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical class [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000007423 decrease Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910013872 LiPF Inorganic materials 0.000 description 8
- 101150058243 Lipf gene Proteins 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 4
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 229910013075 LiBF Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002221 fluorine Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- NZSICTQUKULOSA-UHFFFAOYSA-N 5-azoniaspiro[4.4]nonane Chemical class C1CCC[N+]21CCCC2 NZSICTQUKULOSA-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910015013 LiAsF Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910020808 NaBF Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- MXLZUALXSYVAIV-UHFFFAOYSA-N 1,2-dimethyl-3-propylimidazol-1-ium Chemical compound CCCN1C=C[N+](C)=C1C MXLZUALXSYVAIV-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000009840 oxygen flask method Methods 0.000 description 1
- 238000005191 phase separation 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQKDTTWZXHEGAQ-UHFFFAOYSA-N propyl carbonochloridate Chemical compound CCCOC(Cl)=O QQKDTTWZXHEGAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- 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
- H01G11/64—Liquid electrolytes characterised by additives
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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 to a chain containing at least one fluorine-containing ether group having a CF at the terminal.
- the present invention relates to an electrolytic solution containing a carbonate and an electrolyte salt.
- Carbonates such as ethylene carbonate, propylene carbonate, and dimethyl carbonate are used as solvents for electrolyte salts of lithium secondary batteries, solar batteries, radical batteries, and capacitors.
- carbonates such as ethylene carbonate, propylene carbonate, and dimethyl carbonate are used as solvents for electrolyte salts of lithium secondary batteries, solar batteries, radical batteries, and capacitors.
- overcharge 'ignition explosion due to overheating', and when the output decreases due to low viscosity and low conductivity at low temperatures, is there.
- a fluorinated chain carbonate obtained by fluorinating a chain carbonate For example, a carbonate comprising one fluorine-containing alkyl group and the other comprising a hydrocarbon alkyl group (Japanese Patent Laid-Open No. 6-219992), dicarbonate having ethylene at the center and CF (CF) (CH) — at both ends (special feature) Kaihei 10-149840
- the fluorine-containing ether compound is low in viscosity at low temperatures compared to the force-containing boronate alkyl group terminal, but the solubility of the lithium salt as an electrolyte salt is low.
- it is necessary to improve the flame retardancy with a relatively low flash point. It has become.
- the present invention is intended to solve the problems associated with the prior art as described above, and is excellent in low temperature characteristics and withstand voltage, improved in flame retardancy, and soluble in electrolyte salts.
- the purpose is to provide an electrolyte solution that is highly compatible with hydrocarbon solvents, which are high in chemistry!
- the present inventors have maintained the excellent low-temperature characteristics and withstand voltage of the fluorine-containing ether group-containing chain carbonate, while maintaining the effect based on the fluorine-containing ether group, which is the disadvantage of the solubility of the electrolyte salt.
- the disadvantages of lowering the compatibility with hydrocarbon solvents and insufficient flame retardancy are that CF is arranged at the end of at least one fluorine-containing ether group.
- Rf 1 is a fluorine-containing ether group having a CF terminal (la);
- Rf 2 is a fluorine-containing ether
- CF-terminal fluorine-containing ether group fluorine-containing alkyl group
- the present invention relates to an electrolytic solution containing a chain carbonate (I) and an electrolyte salt (II) represented by BEST MODE FOR CARRYING OUT THE INVENTION
- the electrolytic solution of the present invention is a specific CF-terminal fluorinated ether that is a solvent for dissolving an electrolyte salt.
- Rf 1 is a fluorine-containing ether group having a CF at its terminal (la), preferably 2 to 16 carbon atoms.
- Rf 2 is a fluorine-containing ether group, preferably CF or CH terminated
- a fluorine-containing ether group having 2 to 16 carbon atoms or a fluorine-containing alkyl group, preferably a fluorine-containing alkyl group having 1 to 16 carbon atoms having CF or CH at the terminal).
- a further decrease in viscosity and an increase in flash point can be expected.
- the number of carbon atoms of the fluorine-containing alkyl group Rf 2 are carbon atoms 2 to 16 were Sigma preferred fluorine-containing ether group of Rf 1 and Rf 2 are 1 to 16 is preferred.
- the carbon number exceeds 16
- the viscosity of the chain carbonate (I) increases, and the fluorine-containing group increases, so that the solubility of the electrolyte salt decreases due to a decrease in the dielectric constant, and other solvents.
- the compatibility may be reduced.
- the number of carbon atoms of Rf 1 and Rf 2 is preferably 2 to 10 for a fluorine-containing ether group, more preferably 1 to 10 for a fluorine-containing alkyl group, particularly preferably 1 to 7 for a fluorine-containing alkyl group.
- the fluorine content of Rf 1 and Rf 2 is preferably 10% by mass or less, the effect of improving the viscosity at low temperatures and the effect of improving the flash point cannot be obtained sufficiently.
- This aspect forces R f 1 and the fluorine content of Rf 2 is 20 mass% or more is not more preferable preferably fixture least 30% by weight. The upper limit is usually 76% by mass.
- the fluorine content of Rf 1 and Rf 2 is calculated from the compositional power of the constituent atoms.
- the fluorine content of the entire fluorine-containing cyclic carbonate (I) is 10% by mass or more, preferably 20% by mass or more, and the upper limit is usually 76% by mass.
- the method for measuring the fluorine content of the entire fluorine-containing cyclic carbonate is based on the combustion method described later.
- Rf 1 is a fluorine-containing ether group
- the alkylene group constituting the ether portion is a straight-chain or branched alkylene group.
- Such straight-chain or branched alkylene groups An example of the minimum structural unit is shown below.
- the alkylene group may be any one of these minimum structural units, alone or in a straight chain (0 to each other, branched chain type)
- the unit is composed of a constituent unit that does not contain C1 because it does not cause de-HC1 reaction by a base and is more stable.
- Rf 1 is the formula (la-1):
- R 1 and R 2 have the same force or different, and both have an alkylene group which may have a fluorine atom, preferably a fluorine atom having 14 carbon atoms! /, /, Alkylene group; n 1 is 0 or 1; n2 is an integer of 1 3)
- R 1 and R 2 include the above-described alkylene groups, and these may be configured by appropriately combining them.
- nl When nl is 0, the case is CF—, and as a specific example when nl is 1, R 1 is linear.
- CF CH can be exemplified, and as a branched chain
- a mold is more preferred.
- R 2 is the same but different! / Take it! /.
- R 2 Preferable specific examples of R 2 include the following linear or branched types.
- F can be exemplified, and as a branched chain type, [0039] [8]
- Etc. can be exemplified.
- Rf 2 which is the other fluorine-containing organic group of the chain carbonate (I) has (1) CF as a terminal.
- Fluorinated ether group (2) fluorinated ether group terminated with CH, or (3)
- CF terminal fluorine-containing ether group is preferred, and can be exemplified with specific examples.
- the fluorine-containing ether group having a CH at the end of (2) includes the CF powder described in Rf 1 above.
- Examples include those in which the terminal CF of the 3-terminal fluorinated ether group is substituted with CH.
- the fluorine-containing ether group (2) having 3 2 2 3 3 3 3 3 2 2 3 2 2 at the terminal is preferable.
- the fluorine-containing alkyl group (3) preferably has 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms.
- R 3 may have a fluorine atom, an alkylene group, preferably a fluorine atom having 1 to 9 carbon atoms) /, May! /, An alkylene group; n4 is 0 or 1; provided that when X 1 , X 2 and X 3 are all H, R 3 has a fluorine atom! /, Can be exemplified.
- the linear minimum structural unit (i) and the branched minimum structural unit (ii) described above for Rf 1 can be used alone or in combination with an example. However, among the examples, it is preferable to be composed of a structural unit that does not contain C1, since de-HC1 reaction due to a salt group does not occur and it is more stable.
- Rf 2 is specifically HCF-, HCF-, CHCFCH-, HCFCHCH-, CH
- the number is small, (1) or zero is more preferred! /.
- X 1 and X 2 are the same or different, both H or F; n is an integer from 0 to 10; m is an integer from 0 to 5; provided that ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ is not 0) and is a fluorine-containing alkyl group having a hydrogen atom at the terminal end.
- n is an integer of 0 to 4, the dielectric constant is high, the solubility of the electrolyte salt is improved, and the compatibility with other solvents is also excellent.
- m is an integer of 0 to 2 and is excellent in flame retardancy and withstand voltage improvement effect, and is also excellent in low viscosity (low temperature characteristics).
- n and m is 0 or more and 15 or less, preferably 6 or less. If it exceeds 15, the effect of improving the solubility of the electrolyte salt and the compatibility with other solvents will decrease.
- n is an integer of 0 to 0, preferably an integer of 0 to 4, particularly preferably an integer of 0 to 2), [0060] [Chemical Formula 14] HCH 2 ⁇ CF 2 h,
- n is an integer of 1 to 10, preferably an integer of 1 to 4, particularly preferably 1 or 2.].
- Rf 2 is also CF-, CF C in which the terminal CH—, HCF, and H CF are changed to CF— in the above examples.
- CF CF CF CH CH, etc. can be displayed in the f column.
- the terminal may be CF or a group having a hydrogen atom, but in terms of improving the withstand voltage,
- Fluorine-containing alkyl group having a hydrogen atom at the end is desirable
- Rf 1 and Rf 2 constitutes the chain carbonate (I).
- the combination of Rf 1 and Rf 2 is
- CF containing a CF-terminal fluorine-containing ether group is particularly preferred.
- R 4 and R 5 are the same or different and are reacted with an alkyl group, preferably a methyl group or an ethyl group), and a by-product alcohol (methanol or ethanol) is distilled off. Let the reaction proceed.
- an alkyl group preferably a methyl group or an ethyl group
- a by-product alcohol methanol or ethanol
- R 6 and R 7 are the same or different and are aryl groups, preferably phenyl groups).
- R 8 is an alkyl group, preferably a methyl group or an ethyl group
- the reaction proceeds while distilling off by-produced alcohol (methanol or ethanol).
- each compound is synthesized in two steps, each of which is reacted with another type of fluorinated alcohol.
- Rf 1 and Rf 2 are different types, they may be synthesized in two stages using the methods (4) and (5) above. [0084] [Chemical 21] oo
- the solvent for dissolving the electrolyte salt has a CF-terminal fluorinated ether group.
- chain carbonate (I) In addition to the chain carbonate (I) to be used, other electrolyte salt dissolving solvents ( ⁇ ) may be used alone or in combination.
- electrolyte salt-dissolving solvents (III) include hydrocarbon-based carbonate solvents, nitrile-based solvents, Radon-based solvents, ester-based solvents, and other non-fluorinated solvents, and further fluorine-containing chain carbonates. Fluorine-containing solvents other than (I) may be used.
- non-fluorinated solvent examples include ethylene carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolatathone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3 dioxolane, 4-methyl 1,3 dioxolan.
- Methyl formate methyl acetate, methyl propionate, dimethyl carbonate, ethylmethyl carbonate, jetyl carbonate, acetonitrile, propio-tolyl, succino-tolyl, butyronitrile, isobutyronitrile, benzonitrile, glutaronitrile, dimethylsulfoxide, methyl Pyrrolidone, etc., especially ethylene carbonate, propylene carbonate, jetyl carbonate, ⁇ -butyrolacta from the viewpoint of improving dielectric constant, oxidation resistance, and electrochemical stability.
- 1,2 dimethoxyethane, 1,3 dioxolane, acetonitrylpropionitrile, succinonitrile, butyronitrile, isobutyronitrile, benzo Nitril and glutarto-tolyl are preferred.
- fluorine-containing solvent other than the fluorine-containing chain carbonate (I) examples include, for example, JP-A-6-219992, JP-A-10-149840, JP-A-2001-256983, JP-A-2000-.
- fluorine-containing ethers are useful because they have excellent nonflammability-improving effects.
- Non-fluorine electrolytes have a low compatibility with non-fluorine electrolyte salt dissolving solvents, especially hydrocarbon carbonates such as ethylene carbonate and diethylene carbonate.
- hydrocarbon carbonates such as ethylene carbonate and diethylene carbonate.
- fluorine-containing chain carbonate (I) acts as a compatibilizing agent for compatibilizing the fluorine-containing ether and the solvent for dissolving the non-fluorinated electrolyte salt.
- a uniform electrolyte solution containing (I), electrolyte salt (II), solvent for dissolving non-fluorine electrolyte salt, and fluorine-containing ether further improvement in nonflammability can be expected.
- the amount of the other electrolyte salt dissolving solvent (III) to be mixed is 1% by mass or more, preferably 10% by mass or more, particularly 20% by mass or more of the total electrolyte salt dissolving solvent.
- the upper limit of preferable solubility is 98% by mass, preferably 90% by mass, particularly 80% by mass in terms of flame retardancy, low temperature characteristics and withstand voltage.
- a capacitor can cope with a large current density. Therefore, it is desirable that the electrolyte salt concentration of the electrolytic solution be high. From this point of view, it is preferable to use a hydrocarbon solvent excellent in solubility of the electrolyte salt, in particular, propylene carbonate, ⁇ -butyrolatatone, acetonitrile, 1,3-dioxolan, and the like.
- electrolyte salt ( ⁇ ) examples include conventionally known metal salts, liquid salts (ionic liquids), inorganic polymer salts, organic polymer salts, and the like.
- electrolyte salts include particularly suitable compounds depending on the intended use of the electrolytic solution.
- suitable electrolyte salts are exemplified for each application, but are not limited to the illustrated specific examples. In other applications, the following exemplified electrolyte salts can be used as appropriate.
- metal salts of lithium secondary batteries various organic metal salts such as boron-on type, oxygen-on type, nitrogen-on type, carbon-on type, and phosphorus-on type are available. It is preferable to use oxygen-on type or nitrogen-on type.
- oxygen-on type specifically, CF SO Li, C F SO Li, C F SO Li, CH
- Nitrogen-on types include (CF SO) NLi (TFSl), (C F SO) NLi (BETI), (C
- LiPF LiPF, LiBF, LiAsF, LiCIO, etc.
- LiPF LiPF, LiBF, LiAsF, LiCIO, etc.
- LiPF or LiBF LiPF or LiBF
- a quaternary ammonium salt in which two alkyl groups are ethers.
- N, N-jetyl-N-methyl-N- (2-methoxyethyl) ammonium salt is preferred because of its low viscosity.
- a spirobipyrrolidinium salt or a salt obtained by substituting a part of hydrogen atoms of spirobiviridinium with a fluorine atom is also preferred because of its low viscosity and excellent low temperature characteristics.
- Tetraalkyl quaternary ammonia Among the humic salts, those in which the alkyl group is one or more fluorine-containing alkyl groups or fluorine-containing ether groups are preferred from the viewpoints of improving acid resistance and decreasing the viscosity. Furthermore, an imidazolium salt containing a fluorine atom, a fluorine-containing alkyl group, or a fluorine-containing ether group is also preferred from the viewpoint of improving acid resistance and lowering viscosity. BF-, PF-, AsF- and SbF-, which are excellent in oxidation resistance, are preferred as the salt ion species.
- Inorganic metal salts include LiPF, LiBF, LiAsF, LiCIO, NaPF, NaBF, NaAsF
- NaCIO, KPF, KBF, KAsF, KCIO etc. can be used, especially LiPF, L
- R 9 R 1Q R U R 12 NI (R 9 to R 12 are the same force or different, alkyl group having 1 to 3 carbon atoms), Lil, Nal, KI,
- a liquid salt is used as the electrolyte salt (II)
- organic and inorganic cation and polyalkyl imidazolium cations for lithium secondary batteries, capacitors, and dye-sensitized solar cells Alkyl pyridinium cations, tetraalkyl ammonium cations, tetraalkyl ammonium cations containing ether chains, tetraalkyl phosphoric cations, salts with spirobipyrrolidinium cations, especially 1,3-dialkylimidazolium salts, spirobipyrrolidinium And alkyl ammonium salts containing an ether chain are preferred.
- a salt in which a part of the cation of the above salt is substituted with fluorine is desirable from the viewpoint of viscosity reduction and oxidation resistance improvement.
- Polyalkylimidazolium cations include 1,3-dialkylimidazolium cations such as 1-ethyl-3-methylimidazolium cation ( ⁇ +) and 1-butyl-3-methylimidazolium cation ( ⁇ +); Trialkyl imidazolium cations such as 1,2 dimethyl 3 propyl imidazolium cation (DMPI +) are preferred. Further, those in which some of these hydrogen atoms are substituted with fluorine atoms are more preferable.
- Examples of preferable inorganic ions include A1C1-, BF-, PF-, AsF-, and ⁇ .
- EMIA1C1 EMIBF, EMIPF, EMIAsF, EMII, EMICH C
- MI CF SO
- BMI C F SO
- DMPIAICI DMPIBF
- DMPIPF DMPIAICI
- PIAsF PIAsF
- DMPII DMPII
- DMPICH COO DMPICF COO
- DMPIC F COO DMPIC
- F SO examples include F SO, DMPIC F SO, DMPI (CF SO) N, DMPI (C F SO) N
- Iodides such as cocoons, cocoons, and DMPII are particularly suitable for dye-sensitized solar cells.
- the amount of electrolyte salt ( ⁇ ) blended varies depending on the required current density, application, type of electrolyte salt, etc., but the amount of CF carbonate-containing chain carbonate (I) is 100 parts by weight.
- it is preferably 1 part by mass or more, more preferably 1 part by mass or more, especially 5 parts by mass or more, 200 parts by mass or less, further 100 parts by mass or less, particularly 50 parts by mass or less.
- the electrolytic solution of the present invention comprises an electrolyte salt ( ⁇ ) containing a CF-containing fluorine-containing ether group-containing chain carbon
- the electrolytic solution of the present invention may be used as a gel (plasticized) gel electrolytic solution in combination with a polymer material that dissolves or swells in the solvent used in the electrolytic solution of the present invention.
- Examples of such a polymer material include conventionally known polyethylene oxide polypropylene oxide, and modified products thereof (Japanese Patent Laid-Open Nos. 8-222270 and 2002-100405); a polyacrylate polymer; Fluororesin, such as polyacrylonitrile, poly (vinylidene fluoride), poly (vinylidene fluoride) hexafluoropropylene copolymer (Japanese National Publication No. 4 506726, Japanese National Publication No. 8-507407, Japanese (Kaihei 10-294131); Composites of these fluorinated resins and hydrocarbon-based resins (JP-A-11-35765, JP-A-11-86630) Gazette).
- This ionic conductive compound is represented by the formula (1):
- Rf is crosslinkable functional group which may have a fluorine-containing ether group
- R 13 is Rf and the main chain of the group or a bond that binds
- FAE is the formula (2b):
- Rfa represents a hydrogen atom, which may have a crosslinkable functional group-containing fluorinated alkyl group;
- R 14 is a group or a bond that binds the Rf a main chain) in the side chain represented by Ether units having a fluorine-containing alkyl group;
- R 16 represents a hydrogen atom, an alkyl group optionally having a crosslinkable functional group, a crosslinkable functional group] /, May have! /, Have an aliphatic cyclic hydrocarbon group or a crosslinkable functional group! /, May have an aromatic hydrocarbon group;
- Y represents the formula (2d-l) to (2d-3):
- a unit comprising at least one of [0131];
- ⁇ and ⁇ are the same force or different and contain hydrogen atoms, fluorine atoms and Z or crosslinkable functional groups !, but contain alkyl groups, fluorine atoms and Z or crosslinkable functional groups
- a phenol group, —COOH group, —OR 17 R 17 is a hydrogen atom or a fluorine atom and an alkyl group which may contain Z or a crosslinkable functional group), an ester group or a carbonate group ( However, when the terminal of D is an oxygen atom, it is not a —COOH group, —OR 17 , an ester group or a carbonate group)], and an amorphous fluorine-containing polyether compound having a fluorine
- the electrolyte solution of the present invention may contain other additives as necessary. Examples of other additives include metal oxides and glass.
- the electrolytic solution of the present invention does not freeze at a low temperature (for example, 0 ° C or 20 ° C), or does not precipitate an electrolyte salt.
- the viscosity at 0 ° C. is preferably 10 mPa ′ seconds or less, more preferably 30 mPa ′ seconds or less, and particularly preferably 15 mPa ′ seconds or less. More specifically, the viscosity at 20 ° C. is preferably 10 mPa ′ seconds or less, more preferably 40 mPa ′ seconds or less, and even more preferably 15 mPa ′ seconds or less.
- the electrolytic solution of the present invention can simultaneously improve the flame retardancy, low-temperature characteristics, withstand voltage, solubility of electrolyte salts, and compatibility with hydrocarbon solvents. It is particularly useful as an electrolyte, a capacitor electrolyte, a radical battery electrolyte, and a solar cell (particularly dye-sensitized solar cell) electrolyte. In addition, it can also be used as electrolytes for various sensors, electrolytes for electoric chromic elements, electrolytes for electrochemical switching elements, aluminum electrolytic capacitors, electrolytes for tantalum electrolytic capacitors, and ionic conductors for antistatic coating materials. I'll do it.
- NMR AC-300 manufactured by BRUKER is used.
- the reaction was conducted.
- the fluorine content of this fluorine-containing ether carbonate was 65.2% by mass.
- Synthesis Example 2 Synthesis of carbonate having both terminal CF fluorine-containing ether groups
- the fluorine-containing ether alcohol used in Synthesis Example 1 was added to the reaction apparatus:
- the fluorine content of this fluorine-containing ether carbonate is 63.5 mass 0 /. Met.
- This fluorine-containing ether carbonate has a fluorine content of 60.1 mass 0 /. Met.
- Ethylene carbonate and diethylene carbonate were mixed 1: 1 by weight to obtain a uniform mixed solution.
- V withstand voltage
- hydrocarbon solvent added to the solution until it reaches 50% by volume at room temperature, stir well, and visually observe the solubility.
- the hydrocarbon solvents used are propylene carbonate (PC) and diethylene carbonate (DEC).
- a coin-type lithium secondary battery was produced by the following method.
- LiCoO (85% by mass), carbon black (6% by mass) and poly
- Vinylidene fluoride (trade name KF-1000, manufactured by Kureha Chemical Co., Ltd.) (9% by mass) was added and mixed, and dispersed in N-methyl-2-pyrrolidone to form a slurry. Uniformly apply onto an aluminum foil with a thickness of 20 / zm, which is a conductor, and after drying, a disk shape with a diameter of 12.5mm The positive electrode was punched out.
- the positive electrode is housed in a stainless steel can body that also serves as a positive electrode current collector, and the negative electrode is placed thereon via a polyethylene separator impregnated with various electrolytic solutions shown below.
- the sealing plate that also serves as the negative electrode current collector was sealed with an insulating gasket to produce a coin-type lithium secondary battery.
- the secondary battery was charged and discharged at a current density of 0.3 mA / cm 2 after applying a DC voltage (3.5 V) for 48 hours. 100 cycles of charge / discharge were taken as one cycle, and the rate of decrease from the initial capacity was determined.
- the rate of capacity decrease after 100 cycles was 8%.
- the capacity reduction rate after 100 cycles was 6%.
- the rate of capacity decrease after 100 cycles was 8%.
- This disc-shaped electrode was bonded to the inside of the positive electrode side and the negative electrode side of a stainless steel case serving as a current collector and nosing member of a coin-type cell using a graphite-based adhesive.
- this stainless steel case is heat-treated at 200 ° C under reduced pressure to remove moisture.
- Tetramethylammonium 'BF is added as an electrolyte salt to the compound synthesized in Synthesis Example 1.
- An electrolytic solution was prepared by dissolving to a concentration of 1M, and this electrolytic solution was impregnated into a disk-shaped electrode.
- a polypropylene fiber nonwoven fabric separator (thickness 160 ⁇ m, porosity 70%) is sandwiched between both electrodes, and the stainless steel case is caulked and sealed through an insulating gasket, and the diameter is 18.4 mm, thick. 2.
- An Omm coin-type electric double layer capacitor was fabricated.
- the initial capacity was 132FZg
- the capacity after 2000 charge / discharge cycles was 119FZg
- the capacity reduction rate was 9.8%.
- an electrolytic solution capable of improving the flame retardancy, the low temperature characteristics, the withstand voltage, the solubility of the electrolyte salt, and the compatibility with the hydrocarbon solvent in a well-balanced manner.
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Abstract
Description
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010013739A1 (ja) | 2008-07-30 | 2010-02-04 | ダイキン工業株式会社 | リチウム二次電池の電解質塩溶解用溶媒 |
US20110216477A1 (en) * | 2008-11-14 | 2011-09-08 | Daikin Industries, Ltd. | Electrical double layer capacitor |
US8435679B2 (en) | 2006-12-20 | 2013-05-07 | 3M Innovative Properties Counsel | Fluorinated compounds for use in lithium battery electrolytes |
JP2015528434A (ja) * | 2012-08-13 | 2015-09-28 | エイチエスシー コーポレーション | トリフルオロメチル含有直鎖炭酸エステルの製造方法 |
JP2017224496A (ja) * | 2016-06-15 | 2017-12-21 | 株式会社東芝 | 非水電解質電池、電池モジュール及び車両 |
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CN101156215B (zh) | 2005-03-30 | 2012-04-18 | 大金工业株式会社 | 电解液 |
US20110304950A1 (en) * | 2009-02-25 | 2011-12-15 | Daikin Industries, Ltd. | Electric double layer capacitor |
CN102082296B (zh) * | 2010-12-30 | 2012-12-26 | 东莞市杉杉电池材料有限公司 | 一种阻燃型锂离子电池的电解液 |
WO2013110741A1 (en) * | 2012-01-25 | 2013-08-01 | Solvay Sa | Fluorinated carbonates in hybrid supercapacitors |
EP2909886A4 (en) | 2012-10-19 | 2016-06-15 | Univ North Carolina | IONIC CONDUCTIVE POLYMERS AND MIXTURES OF POLYMERS FOR ALKALINOMETALLIC-ION BATTERIES |
US9755273B2 (en) | 2013-04-01 | 2017-09-05 | The University Of North Carolina At Chapel Hill | Ion conducting fluoropolymer carbonates for alkali metal ion batteries |
US10077231B2 (en) | 2015-02-03 | 2018-09-18 | Blue Current, Inc. | Functionalized fluoropolymers and electrolyte compositions |
WO2020073189A1 (zh) * | 2018-10-09 | 2020-04-16 | 丰宾电子(深圳)有限公司 | 混合型铝电解电容器及其制造方法 |
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- 2006-03-28 US US11/887,540 patent/US8007679B2/en not_active Expired - Fee Related
- 2006-03-28 KR KR1020077024957A patent/KR100907773B1/ko not_active IP Right Cessation
- 2006-03-28 JP JP2007512737A patent/JP4710902B2/ja not_active Expired - Fee Related
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8435679B2 (en) | 2006-12-20 | 2013-05-07 | 3M Innovative Properties Counsel | Fluorinated compounds for use in lithium battery electrolytes |
US9406977B2 (en) | 2006-12-20 | 2016-08-02 | 3M Innovative Properties Company | Fluorinated compounds for use in lithium battery electrolytes |
WO2010013739A1 (ja) | 2008-07-30 | 2010-02-04 | ダイキン工業株式会社 | リチウム二次電池の電解質塩溶解用溶媒 |
US20110216477A1 (en) * | 2008-11-14 | 2011-09-08 | Daikin Industries, Ltd. | Electrical double layer capacitor |
US8668838B2 (en) * | 2008-11-14 | 2014-03-11 | Daikin Industries, Ltd. | Electrical double layer capacitor |
JP2015528434A (ja) * | 2012-08-13 | 2015-09-28 | エイチエスシー コーポレーション | トリフルオロメチル含有直鎖炭酸エステルの製造方法 |
JP2017224496A (ja) * | 2016-06-15 | 2017-12-21 | 株式会社東芝 | 非水電解質電池、電池モジュール及び車両 |
Also Published As
Publication number | Publication date |
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JP4710902B2 (ja) | 2011-06-29 |
US8007679B2 (en) | 2011-08-30 |
US20090134353A1 (en) | 2009-05-28 |
CN101156217A (zh) | 2008-04-02 |
KR20070116668A (ko) | 2007-12-10 |
CN101156217B (zh) | 2012-04-18 |
JPWO2006106657A1 (ja) | 2008-09-11 |
KR100907773B1 (ko) | 2009-07-15 |
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