US20060188788A1 - Solvents and novel electrolytic compositions having a large range of stability and high conductivity - Google Patents
Solvents and novel electrolytic compositions having a large range of stability and high conductivity Download PDFInfo
- Publication number
- US20060188788A1 US20060188788A1 US11/406,279 US40627906A US2006188788A1 US 20060188788 A1 US20060188788 A1 US 20060188788A1 US 40627906 A US40627906 A US 40627906A US 2006188788 A1 US2006188788 A1 US 2006188788A1
- Authority
- US
- United States
- Prior art keywords
- electrolytic composition
- alkyl
- oxaalkyl
- composition according
- polymer
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000002904 solvent Substances 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- -1 epifluorohydrine Chemical compound 0.000 claims description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006184 cosolvent Substances 0.000 claims description 9
- 229910003844 NSO2 Inorganic materials 0.000 claims description 8
- 229910005143 FSO2 Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 7
- 230000002687 intercalation Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 150000001983 dialkylethers Chemical class 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- JUXHETNKWVWTBW-UHFFFAOYSA-N 1,2,3,4,5-pentakis(trifluoromethyl)cyclopenta-1,3-diene Chemical compound FC(F)(F)C1C(C(F)(F)F)=C(C(F)(F)F)C(C(F)(F)F)=C1C(F)(F)F JUXHETNKWVWTBW-UHFFFAOYSA-N 0.000 claims description 2
- AQZRARFZZMGLHL-UHFFFAOYSA-N 2-(trifluoromethyl)oxirane Chemical compound FC(F)(F)C1CO1 AQZRARFZZMGLHL-UHFFFAOYSA-N 0.000 claims description 2
- FHDREPHXTFSCHT-UHFFFAOYSA-N 3,4-bis(sulfanyl)cyclobut-3-ene-1,2-dione Chemical compound SC1=C(S)C(=O)C1=O FHDREPHXTFSCHT-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- HFWIMJHBCIGYFH-UHFFFAOYSA-N cyanoform Chemical compound N#CC(C#N)C#N HFWIMJHBCIGYFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 claims description 2
- SZRONZXSOSCLOK-UHFFFAOYSA-N pentacyanocyclopentadiene Chemical compound N#CC1C(C#N)=C(C#N)C(C#N)=C1C#N SZRONZXSOSCLOK-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- WCJLIWFWHPOTAC-UHFFFAOYSA-N rhodizonic acid Chemical compound OC1=C(O)C(=O)C(=O)C(=O)C1=O WCJLIWFWHPOTAC-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 2
- IPBSAENIOZDPPM-UHFFFAOYSA-N 1,3,4-oxadiazolidine-2,5-dithione Chemical compound SC1=NN=C(S)O1 IPBSAENIOZDPPM-UHFFFAOYSA-N 0.000 claims 1
- YTQQIHUQLOZOJI-UHFFFAOYSA-N 2,3-dihydro-1,2-thiazole Chemical compound C1NSC=C1 YTQQIHUQLOZOJI-UHFFFAOYSA-N 0.000 claims 1
- 229910000733 Li alloy Inorganic materials 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 239000001989 lithium alloy Substances 0.000 claims 1
- 229940006487 lithium cation Drugs 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000002006 petroleum coke Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 abstract description 7
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052566 spinel group Inorganic materials 0.000 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 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical compound CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- JFCHSQDLLFJHOA-UHFFFAOYSA-N n,n-dimethylsulfamoyl chloride Chemical compound CN(C)S(Cl)(=O)=O JFCHSQDLLFJHOA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 229910018926 (FSO2)2NLi Inorganic materials 0.000 description 1
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- IVANFNGOSJTZFM-UHFFFAOYSA-N 2h-triazole-4,5-dicarbonitrile Chemical compound N#CC1=NNN=C1C#N IVANFNGOSJTZFM-UHFFFAOYSA-N 0.000 description 1
- YCPWROQUVWUCJM-UHFFFAOYSA-N CCN(C)S(=O)(=NC#N)N(C)CC Chemical compound CCN(C)S(=O)(=NC#N)N(C)CC YCPWROQUVWUCJM-UHFFFAOYSA-N 0.000 description 1
- LODQKBXAHBXMNA-UHFFFAOYSA-N CCN(CC)S(=O)(=NS(=O)(=O)N(C)C)N(C)C Chemical compound CCN(CC)S(=O)(=NS(=O)(=O)N(C)C)N(C)C LODQKBXAHBXMNA-UHFFFAOYSA-N 0.000 description 1
- RBCWKBGDPGZTID-UHFFFAOYSA-N CN(C)S(N(C)C)(=NC#N)=O Chemical compound CN(C)S(N(C)C)(=NC#N)=O RBCWKBGDPGZTID-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910016955 Fe1-xMnx Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910008172 Li3-xCoxN Inorganic materials 0.000 description 1
- 229910012621 Li3FeN2 Inorganic materials 0.000 description 1
- 229910012130 Li3−xCoxN Inorganic materials 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910011141 Li7MnN4 Inorganic materials 0.000 description 1
- 229910012970 LiV3O8 Inorganic materials 0.000 description 1
- 229910006074 SO2NH2 Inorganic materials 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052963 cobaltite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- GEHLEADVHVVTET-UHFFFAOYSA-N ethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[NH2+]C GEHLEADVHVVTET-UHFFFAOYSA-N 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- SXLDJBWDCDALLM-UHFFFAOYSA-N hexane-1,2,6-tricarbonitrile Chemical compound N#CCCCCC(C#N)CC#N SXLDJBWDCDALLM-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZSWXMTQLPYVTLZ-UHFFFAOYSA-N n-ethyl-n-methylsulfamoyl chloride Chemical compound CCN(C)S(Cl)(=O)=O ZSWXMTQLPYVTLZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical class NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-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
- H01M10/0568—Liquid materials characterised by the solutes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/10—Compounds containing sulfur atoms doubly-bound to nitrogen atoms
-
- 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
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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
-
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- 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
-
- 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
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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 invention concerns new polar solvents and new electrolytic compositions comprising the same, and having a large range of stability, as required for applications in the field of electrochemistry.
- Polar aprotic solvents such as cyclic or linear carbonates, or ethers used alone or in mixtures, are known in various electrolytic compositions.
- Products of the amide type, whether linear or cyclic, such as dimethylformamide or N-methylpyrrolidinone possess excellent properties as solvents, but are oxidized at potentials that are still lower, in the order of 3.7 V with respect to Li + /Li°.
- U.S. Pat. Nos. 4,851,307 and 5,063,124 describe electrolytes comprising a salt, a solvating polymer and an aprotic sulfamide of the general formula R 1 R 2 NSO 2 R 3 R 4 wherein R 1 , R 2 , R 3 and R 4 , the same or different, are independently selected from C 1-10 alkyl or C 1-10 oxaalkyl.
- These materials have increased stability towards reducing or basic agents present and having potentials near those of alkaline metals. However, they are oxidized at potentials between 3.8 and 4V with respect to Li + /Li°.
- EP 0 339 284 discloses dielectric and insulating compounds like perfluoro-acylamides or perfluoro-sulfonamides R F CONA 1 A 2 and R F SO 2 NA 1 A 2 , wherein A 1 and A 2 are alkyl groups.
- the proposed use of these products in capacitors implies that the materials are not conductive and that the impurities and inevitable contaminants, particularly ionic products, are not inducing significant conductivity.
- novel polar solvents and novel electrolytic compositions comprising the same and having a high degree of stability, as required for applications in the field of electrochemistry.
- essentially fluorinated means that the degree of fluorination in the chain is sufficient to provide properties similar to those obtained with a chain entirely perfluorated, such as a hydrophobic character and properties of attracting electrons.
- at least half of the hydrogen atoms of the chain are replaced by fluorine atoms.
- partially chlorinated means that within the essentially fluorinated products, the hydrogen atoms remaining are at least partially replaced with chlorine atoms.
- materials with a highly polar amide function are used for preparing electrolytic compositions useful for electrochemical applications. It has unexpectedly been found that groups strongly attracting electrons, when combined with the amide function, allow the maintenance of solubilizing power towards ionic products, particularly those having a highly delocalized anionic charge, and thus inducing high ionic conductivities.
- a polar polymer By adding a polar polymer to these compositions, there is obtained electrolytes with mechanical properties allowing the fabrication of films for use in electrochemical devices, and increasing the security when in operation.
- the consistency thereof can be adjusted to a gel or a plasticized polymer. Further, the polymers can be reticulated to improve mechanical properties.
- the electrolytic compositions of the present invention have higher stability when compared to materials of the prior art, particularly at very anodic potentials, especially those exceeding 4 V with respect to Li + /Li°.
- Preferred low energy reticular salts that are soluble in the polar solvents of the present invention to form conductive solutions comprise those having a delocalized charge, such as I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , R F SO 3 ⁇ , XSO 2 NSO 2 X′ ⁇ , (XSO 2 )(X′SO 2 )(Y)C ⁇ and mixtures thereof, wherein
- X and X′ is R F , R F CH 2 O—, (R F ) 2 CHO—, (R F CH 2 ) 2 N—, R 8 , R 9 R 10 N—, with the proviso that at least one X or X′ is R F , R F CH 2 O—, (R F ) 2 CHO—, (R F CH 2 ) 2 N—;
- Y R F , R F SO 2 or CN
- R F is as defined above.
- R 8 to R 10 are the same or different, and are C 1-18 alkyl or —C 1-18 oxaalkyl.
- R F and R 8 -R 10 can be part of a molecular chain. Also preferred are anions derived from 4,5-dicyano-1,2,3-triazole, 3,5-bis(RF)-1,2,4-triazole, tricyanomethane, pentacyanocyclopentadiene and pentakis(trifluoromethyl)cyclopentadiene and anions derived from cyanamide and malononitrile, i.e., R F SO 2 NCN ⁇ , C(CN) 3 ⁇ , R F SO 2 C(CN) 2 ⁇ .
- Preferred cations comprise those derived from alkaline metals, more preferably lithium, alkaline earth metals, and organic cations of the “onium” type, such as ammonium, imidazolium, sulphonium, phosphonium and oxonium.
- the electrolytic compositions of the present invention include those containing at least one polar solvent as defined above in combination with one or more polar molecules acting as a co-solvent.
- Such other polar molecules include solvents capable of forming compatible mixtures, such as dialkyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols preferably having a mass of from 400 to 2000; or esters, preferably carbonic acid esters, whether linear or cyclic, such as dimethylcarbonate, methylethylcarbonate, diethylcarbonate, ethylene carbonate, propylene carbonate, or esters such as ⁇ -butyrolactone, nitriles such as glutaronitrile, or 1,2,6-tricyanohexane.
- These other polar molecules, or co-solvent can be added alone or in mixtures to the solvent of the present invention.
- An example of the preferred mixture is ethylene carbonate with a dialkyl ether.
- the present invention further includes solid electrolytes obtained by the addiiton of the polymer to a solvent or solvent-co-solvent mixture containing at least one salt as defined above in solution.
- the amount of polymer can be selected so that the solvent acts as a plasticizing agent of the polymer, i.e. in concentration of 3 to 30% by weight, preferably between 10 and 25% by weight.
- Preferred polymers for such compositions are those with monomer units containing solvating units, such as those derived from ethylene oxide, propylene oxide, epichlorohydrine, epifluorohydrine, trifluoroepoxypropane, etc.
- the amount of solvent and salt in the composition should be between 30 and 95% by weight, preferably between 40 and 70%.
- those containing units derived from acrylonitrile, methylmethacrylate, vinylidene fluoride, N-vinylpyrolidinone are also preferred, and can be either homo- or copolymers, such as vinylidene fluoride and hexafluoropropene copolymers.
- a copolymer containing from 5 to 30% molar of hexafluoropropene is particularly preferred.
- the polymers are polyelectrolytes incorporating anions with a delocalized charge in the macromolecular woof. In such conditions, negative charges are immobilized and only positive counter-charges participate in the ionic conduction process.
- the present electrolytic compositions can be used wherever a high stability is required, particularly when oxidation or highly positive potentials are present.
- a good example is an electrochemical generator wherein it is advantageous to have a high electromotive force, particularly in generators containing lithium ions.
- the negative electrode comprises metallic lithium, one of its alloys, a carbon derivative, preferably petrolium coke or graphite, an oxide with a low potential of intercalation such as titanium spinels Li 2x+1+3y Ti x+5 O 12 (x ⁇ 0 and y ⁇ 1), a double nitride of a transition metal and lithium such as Li 3 ⁇ x Co x N, or having an antifluorite type structure such as Li 3 FeN 2 or Li 7 MnN 4 .
- the materials for the positive electrode comprise intercalation compounds, polydisulfides or oxocarbones.
- Oxocarbones electrode materials are preferably rhodizonic acid salts; polydisulfides including derivatives resulting from the oxidation of dimercaptoethane, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-oxaadiazole, and 1,2-dimercaptocyclobutene-3,4-dione.
- Electrochemical generators using the present electrolytic compositions preferably contain solid electrolytes, either plasticized or gelled.
- at least one of the electrodes is a composite comprising the electrode materials in a mixture with the electrolytic composition and carbon such as Shawinigan® black, Ketjenblack®, or graphite.
- the two electrodes are symmetrically built with carbon having high surface area, and this material is mixed with the electrolyte to form a composite.
- the electrode material containing at least one polymer having conjugated double bonds may have three degrees of oxidation, obtained by reduction (“n” doping) concomitant to an injection of electrons and cations, or by oxidation (“p” doping) concomitant to an electron extraction and anion injections, from the neutral form.
- Polymers comprising phenyl-3-thiophene, and particularly poly(4-fluorophenyl-3-thiophene) are preferred.
- Trifluoroethanol (18.2 mL, 25 mml) dissolved in 100 mL of ether are added to 7 g of sodium hydride. When no more hydrogen gas evolves, the solution is centrifuged and the supernatant clear liquid is added at 0° C. to 35 ⁇ g (25 mml) of dimethysulfamoyl chloride dissolved in 100 mL of dry ether under stirring. A white precipitate of NaCl forms and the reaction is completed in two hours. The slurry is filtered and the ether stripped in a rotary evaporator. The residue is diluted with 50 ml of dichloromethane and washed with 10% HCl in water.
- the range of electrochemical stability is measured by cyclic voltametry on a platinum microelectrode (15 ⁇ m diameter) for anodic potentials, and nickel for cathodic potentials.
- the stability range is from 0 to 5.2 V vs. Li+/Li°.
- the variation of conductivity with respect to the temperature is found is Table 2 for a concentration of 0.898 mol ⁇ kg ⁇ 1 .
- TABLE 2 T (° C.) ⁇ sp (S ⁇ cm ⁇ 1 ) T (° C.) ⁇ sp (S ⁇ cm ⁇ 1 ) 14.90 0.753 30.29 1.203 14.92 0.7550 35.39 1.415 19.93 0.882 40.81 1.657 25.11 1.030
- the residue is placed in 20 mL of dichloromethane and washed with an aqueous solution of 10% hydrochloric acid.
- the organic phase is separated and dried with anhydrous magnesium sulphate.
- the hexafluoropropyle N,N-dimethylsulfamate is obtained by evaporating the dichloromethane and distilled under reduced pressure.
- the compound has a dielectric constant greater than 20, and the conductivity of solutions of salts of bis(trifluoromethanesulfonimide) (NC 2 H 5 ) 4 (CF 3 SO 2 ) 2 N in this solvent are between 5 ⁇ 10 ⁇ 4 and 2 ⁇ 10 ⁇ 3 Scm ⁇ 1 at 25° C. in concentrations varying from 0.2 to 1 mole ⁇ kg ⁇ 1 .
- cyanamide and 11.22 g of diazabicyclo 2,2,2-octane are added to 15.76 g of ethylmethylsulfamoyl chloride dissolved in 100 mL of tetrahydrofuran. After agitating the mixture at room temperature for 8 hours, 13 g of oxalyl chloride dissolved in 40 mL of anhydrous tetrahydrofuran are added dropwise. After gas emissions have stopped (CO and CO 2 ), the DABCO chlorohydrate is filtered and remaining THF is evaporated under reduced pressure.
- DABCO diazabicyclo 2,2,2-octane
- the solid is then placed in 50 mL of acetonitrile to which is added 12.2 g of ethylmethylamine at 0° C.
- the ethylmethylammonium chloride thus obtained is separated and the solvent is evaporated under reduced pressure.
- the polar product The polar product is solubilized in dichloromethane, and washed with water containing 2% hydrochloric acid, and subsequently 5% sodium bicarbonate. Following removal of dichloromethane, the compound is distilled under reduced pressure. This product can be used as a solvent for delocalized anions salts, particularly perfluorinated imides.
- An electrochemical generator comprising a negative electrode of lithium of 25 ⁇ m on a nickel support of 10 ⁇ m, a positive electrode composite containing 78% by weight of vanadium oxide V 2 O 5 , 8% of carbon black (Ketjenblack®) and 14% of a vinylidene fluoride-hexafluoropropene copolymer on a nickel collector (10 ⁇ m) has been prepared.
- the positive electrode capacity thus obtained by spreading from a cyclohexanone suspension, is 2.8 mAh/cm 2 .
- the electrolyte comprises a solution of 0.15 M ⁇ kg ⁇ 1 of Li(CF 3 SO 2 ) 2 N in the polar compound of Example 1 in a polypropylene porous separator of the Celgard® type.
- the generator was cycled over 150 cycles between 1.6 et 3.4V at C/3.7 while maintaining a ratio of charge and discharges capacities equal to 1 and a use rate of >75% over 30 cycles.
- the ohmic drop remained between 20 and 120 mV.
- An electrochemical generator of the “rocking chair” type was prepared with 2 composite electrodes similar to those of Example 6. Lithium and titanium spinel Li 4 Ti 5 O 12 was used as the negative electrode, to give a surface capacity of 2.6 mAh ⁇ cm ⁇ 2 . Lithium cobaltite was used for the positive electrode, to give a surface capacity of 2.4 MAh ⁇ cm ⁇ 2 .
- the electrolyte was prepared in a manner similar to that of Example 6 with a solution of 0.15 M ⁇ kg ⁇ 1 of Li(CF 3 SO 2 ) 2 N in the polar compound of Example 1 in a polypropylene porous separator of the Celgard® type. The generator was cycled over 500 cycles between 1.5 et 3.3 V a C/4 while maintaining a ratio of charge and discharges capacities equal to 1 and a use rate of 80%.
- An electrochemical generator of the supercapacitor type is prepared with 2 symetrical composite electrodes of high surface area carbon (680 m 2 ⁇ g ⁇ 1 ) and nickel fibres on a nickel support, and bound by a vinylidene fluoride-hexafluoropropene copolymer.
- the electrolyte comprises 75% by wieght of a gel of a molar solution of tetraethylammonium fluorosulfonimide (C 2 H 5 ) 4 N[(CF 3 SO 2 ) 2 N] in the same polymer.
- the system capacity is 1.2 F ⁇ g ⁇ 1 over 12 000 cycles performed between 0 and 2.5 V.
- a polymer electrolyte is prepared by plasticizing an ethylene oxide-allylglycidyl ether copolymer containing the lithium salt of dimethylaminosulfonyl-trifluoromethane-sulfonimide Li[(CH 3 ) 2 SO 2 NSO 2 CF 3 ] with a ratio oxygen from the ether functions of the polymer to lithium of 14:1 with the polar compound of Example 5 with a weight ratio 65:35.
- This electrolyte has a conductivity of 10 ⁇ 4 Scm ⁇ 1 at 25° C. and an electrochemical stability range of 0 to 4V vs. Li + /Li°.
- This electrolyte can be reticulated by a free radical source to give elastomers with good mechanical properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention is concerned with novel polar solvents and novel electrolytic compositions comprising such solvents, and having a high range of stability, as required for applications in the field of electrochemistry. The present solvents have a highly polar amide function, and preferably combine with a salt soluble in the solvent and having an anion with a delocalized charge, and at least one polymer, to form an electrolytic composition.
Description
- The invention concerns new polar solvents and new electrolytic compositions comprising the same, and having a large range of stability, as required for applications in the field of electrochemistry.
- Polar aprotic solvents such as cyclic or linear carbonates, or ethers used alone or in mixtures, are known in various electrolytic compositions. The stability of these products towards highly negative potentials, close to those of alkaline metals, or highly positive (≧4V with respect to Li+/Li°), are not satisfactory, and lithium batteries containing electrolytes obtained from the dissolution of a lithium salt in these solvents create serious safety problems. Products of the amide type, whether linear or cyclic, such as dimethylformamide or N-methylpyrrolidinone, possess excellent properties as solvents, but are oxidized at potentials that are still lower, in the order of 3.7 V with respect to Li+/Li°.
- Numerous materials of positive electrodes, such as mixed oxides of transition metals and lithium work under potentials near 4 V with respect to Li+/Li°and therefore require electrolyte stabilities significantly higher than that value. For example, products like Li1−yCo1−x−zNixAlyO2 wherein x+y≦1 and z≦0.3); manganese spinels Li1−αMn2−xMxO4.Li1−αCo1−x−yNixAly wherein 0≦x+y≦1; 0≦y≦0.3; 0≦α≦1 and M=Li, Mg, Al, Cr, Ni, Co, Cu, Ni, Fe.
- U.S. Pat. Nos. 4,851,307 and 5,063,124 describe electrolytes comprising a salt, a solvating polymer and an aprotic sulfamide of the general formula
R1R2NSO2R3R4
wherein R1, R2, R3 and R4, the same or different, are independently selected from C1-10alkyl or C1-10oxaalkyl. An example of the product of that group is the tetraethylfulfamide (R1=R2=R3=R4=C2H5). These materials have increased stability towards reducing or basic agents present and having potentials near those of alkaline metals. However, they are oxidized at potentials between 3.8 and 4V with respect to Li+/Li°. - EP 0 339 284 discloses dielectric and insulating compounds like perfluoro-acylamides or perfluoro-sulfonamides RFCONA1A2 and RFSO2NA1A2, wherein A1 and A2 are alkyl groups. The proposed use of these products in capacitors implies that the materials are not conductive and that the impurities and inevitable contaminants, particularly ionic products, are not inducing significant conductivity.
- The publication of Sartori et al. in an abstract of a meeting of the Electrochemical Society, Volume 97-1, May 1997, describes certain sulfonamides that could be used as electrolytes in a battery or in an energy storage system.
- In accordance with the present invention, there is provided novel polar solvents and novel electrolytic compositions comprising the same and having a high degree of stability, as required for applications in the field of electrochemistry. More specifically, the solvents of the present invention are of the general formula
R1R2NX(Z)R7
wherein
X=C or SO;
Z=O, NSO2NR3R4 or NCN;
R1 et R2 are the same or different and are C1-18alkyl, C1-18 oxaalkyl, C1-18 alkylene or C1-18oxaalkylene;
R3 a R6 are the same or different and are C1-18alkyl or C1-18 oxaalkyl;
R7 is RF, RFCH2O—, (RF)2 2CHO—, (RFCH2)2N— or NR5R6;
RF is fluorine, C1-4alkyl, C1-4oxaalkyl or C1-4azaalkyl wherein the alkyl chain is preferably essentially fluorinated and partly chlorinated,
with the provisos that:
1) if Z=O, then RF is not C1-4alkyl; and
2) if Z=O and X=SO, then R5 or R6 is not C1-4alkyl or C1-4oxaalkyl. - The expression “essentially fluorinated” means that the degree of fluorination in the chain is sufficient to provide properties similar to those obtained with a chain entirely perfluorated, such as a hydrophobic character and properties of attracting electrons. Preferably, at least half of the hydrogen atoms of the chain are replaced by fluorine atoms. The expression “partially chlorinated” means that within the essentially fluorinated products, the hydrogen atoms remaining are at least partially replaced with chlorine atoms.
- In the present invention, materials with a highly polar amide function are used for preparing electrolytic compositions useful for electrochemical applications. It has unexpectedly been found that groups strongly attracting electrons, when combined with the amide function, allow the maintenance of solubilizing power towards ionic products, particularly those having a highly delocalized anionic charge, and thus inducing high ionic conductivities. By adding a polar polymer to these compositions, there is obtained electrolytes with mechanical properties allowing the fabrication of films for use in electrochemical devices, and increasing the security when in operation. Depending on the amount of polar solvent and polymer in the electrolytic compositions, the consistency thereof can be adjusted to a gel or a plasticized polymer. Further, the polymers can be reticulated to improve mechanical properties.
- The electrolytic compositions of the present invention have higher stability when compared to materials of the prior art, particularly at very anodic potentials, especially those exceeding 4 V with respect to Li+/Li°.
- Preferred low energy reticular salts that are soluble in the polar solvents of the present invention to form conductive solutions comprise those having a delocalized charge, such as I−, ClO4 −, BF4 −, PF6 −, AsF6 −, SbF6 −, RFSO3 −, XSO2NSO2X′−, (XSO2)(X′SO2)(Y)C− and mixtures thereof, wherein
- X and X′ is RF, RFCH2O—, (RF)2CHO—, (RFCH2)2N—, R8, R9R10N—, with the proviso that at least one X or X′ is RF, RFCH2O—, (RF)2CHO—, (RFCH2)2N—;
- Y=RF, RFSO2 or CN;
- RF is as defined above; and
- R8 to R10 are the same or different, and are C1-18alkyl or —C1-18 oxaalkyl.
- RF and R8-R10 can be part of a molecular chain. Also preferred are anions derived from 4,5-dicyano-1,2,3-triazole, 3,5-bis(RF)-1,2,4-triazole, tricyanomethane, pentacyanocyclopentadiene and pentakis(trifluoromethyl)cyclopentadiene and anions derived from cyanamide and malononitrile, i.e., RFSO2NCN−, C(CN)3 −, RFSO2C(CN)2 −. Preferred cations comprise those derived from alkaline metals, more preferably lithium, alkaline earth metals, and organic cations of the “onium” type, such as ammonium, imidazolium, sulphonium, phosphonium and oxonium.
- With respect to the electrolytic compositions of the present invention, they include those containing at least one polar solvent as defined above in combination with one or more polar molecules acting as a co-solvent. Such other polar molecules include solvents capable of forming compatible mixtures, such as dialkyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols preferably having a mass of from 400 to 2000; or esters, preferably carbonic acid esters, whether linear or cyclic, such as dimethylcarbonate, methylethylcarbonate, diethylcarbonate, ethylene carbonate, propylene carbonate, or esters such as γ-butyrolactone, nitriles such as glutaronitrile, or 1,2,6-tricyanohexane. These other polar molecules, or co-solvent, can be added alone or in mixtures to the solvent of the present invention. An example of the preferred mixture is ethylene carbonate with a dialkyl ether.
- The present invention further includes solid electrolytes obtained by the addiiton of the polymer to a solvent or solvent-co-solvent mixture containing at least one salt as defined above in solution. The amount of polymer can be selected so that the solvent acts as a plasticizing agent of the polymer, i.e. in concentration of 3 to 30% by weight, preferably between 10 and 25% by weight. Preferred polymers for such compositions are those with monomer units containing solvating units, such as those derived from ethylene oxide, propylene oxide, epichlorohydrine, epifluorohydrine, trifluoroepoxypropane, etc. To obtain a gel, the amount of solvent and salt in the composition should be between 30 and 95% by weight, preferably between 40 and 70%. In addition to the polymers listed above, those containing units derived from acrylonitrile, methylmethacrylate, vinylidene fluoride, N-vinylpyrolidinone are also preferred, and can be either homo- or copolymers, such as vinylidene fluoride and hexafluoropropene copolymers. A copolymer containing from 5 to 30% molar of hexafluoropropene is particularly preferred. In a variation, the polymers are polyelectrolytes incorporating anions with a delocalized charge in the macromolecular woof. In such conditions, negative charges are immobilized and only positive counter-charges participate in the ionic conduction process.
- The present electrolytic compositions can be used wherever a high stability is required, particularly when oxidation or highly positive potentials are present. A good example is an electrochemical generator wherein it is advantageous to have a high electromotive force, particularly in generators containing lithium ions. In such systems, the negative electrode comprises metallic lithium, one of its alloys, a carbon derivative, preferably petrolium coke or graphite, an oxide with a low potential of intercalation such as titanium spinels Li2x+1+3yTix+5O12 (x≧0 and y≦1), a double nitride of a transition metal and lithium such as Li3−xCoxN, or having an antifluorite type structure such as Li3FeN2 or Li7MnN4.
- The materials for the positive electrode comprise intercalation compounds, polydisulfides or oxocarbones. Intercalation compounds include vanadium oxide, and preferably those with the formula VOx wherein 2≦x≦2.5; LiV3O8; cobalt and lithium mixed oxides of the general formula Li1−αCo1−x−yNixAly wherein 0≦x+y≦1; 0≦y≦0.3; 0≦α≦1; partly substituted manganese spinels of the general formula Li1−αMn2−zMzO4 wherein 0≦z≦1 and M=Li, Mg, Al, Cr, Ni, Co, Cu, Ni, Fe; and double phosphates of the olivine or Nasicon structure such as Li1−αFe1−xMnxPO4, Li1−α+2xFe2P1−xSxO4′ wherein x≧0 and α≦1. Oxocarbones electrode materials are preferably rhodizonic acid salts; polydisulfides including derivatives resulting from the oxidation of dimercaptoethane, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-oxaadiazole, and 1,2-dimercaptocyclobutene-3,4-dione.
- Electrochemical generators using the present electrolytic compositions preferably contain solid electrolytes, either plasticized or gelled. In a preferred embodiment of the invention, at least one of the electrodes is a composite comprising the electrode materials in a mixture with the electrolytic composition and carbon such as Shawinigan® black, Ketjenblack®, or graphite.
- Another application of the invention is that of supercapacitors wherein at least one electrode comprises high surface area carbon, and the electrical energy is stored as a result of the capacity of the double layer between the carbonated material and the electrolyte. In a preferred embodiment, the two electrodes are symmetrically built with carbon having high surface area, and this material is mixed with the electrolyte to form a composite. Another possibility is to use the electrode material containing at least one polymer having conjugated double bonds. In a preferred embodiment, the conjugated polymer may have three degrees of oxidation, obtained by reduction (“n” doping) concomitant to an injection of electrons and cations, or by oxidation (“p” doping) concomitant to an electron extraction and anion injections, from the neutral form. Polymers comprising phenyl-3-thiophene, and particularly poly(4-fluorophenyl-3-thiophene) are preferred.
- The following examples are provided to illustrate the preferred embodiments of the present invention, and should not be construed as limiting its scope.
- Trifluoroethanol (18.2 mL, 25 mml) dissolved in 100 mL of ether are added to 7 g of sodium hydride. When no more hydrogen gas evolves, the solution is centrifuged and the supernatant clear liquid is added at 0° C. to 35 μg (25 mml) of dimethysulfamoyl chloride dissolved in 100 mL of dry ether under stirring. A white precipitate of NaCl forms and the reaction is completed in two hours. The slurry is filtered and the ether stripped in a rotary evaporator. The residue is diluted with 50 ml of dichloromethane and washed with 10% HCl in water. The organic layer is separated, dried with anhydrous magnesium sulfate. The corresponding trifluoethyl-N,N dimethylsulfamate is distilled under reduced pressure. RMN: 19F: triplet δ=74.7 ppm, JHF=8.1 Hz; 1H: quartet δ=4.66 (2H), singlet δ=3.6 (6H). The conductivity of the lithium salts of the bis(trifluoromethanesulfonimide) (CF3SO2)2NLi in solution in this solvent is provided in Table 1 with respect to several concentrations.
TABLE 1 molality (mol · kg−1) conductivity κsp (S · cm−1) 0.265 0.634 0.506 0.922 0.898 1.025 1.160 0.796 - The range of electrochemical stability is measured by cyclic voltametry on a platinum microelectrode (15 μm diameter) for anodic potentials, and nickel for cathodic potentials. The stability range is from 0 to 5.2 V vs. Li+/Li°. The variation of conductivity with respect to the temperature is found is Table 2 for a concentration of 0.898 mol·kg−1.
TABLE 2 T (° C.) κsp (S · cm−1) T (° C.) κsp (S · cm−1) 14.90 0.753 30.29 1.203 14.92 0.7550 35.39 1.415 19.93 0.882 40.81 1.657 25.11 1.030 - 107.4 mL of dimethylsulfamoyl chloride are heated under reflux and nitrogen atmosphere with 70 g of potassium fluoride and 10 mL of water. The mixture is cooled and extracted with dichloromethane, dried with magnesium sulphate, and distilled. The compound obtained, (CH3)2NSO2F, has a dielectric constant greater than 30. The range of stability, as determined by cyclic voltametry, is 5 V vs. Li+/Li°. The lithium salt of the fluorosulfonimide, (FSO2)2NLi is soluble in this medium, and its conductivity at 25° C. is greater than 1 mScm−1 for concentrations between 0.5 and 1 mole·kg−1.
- 1.6 g of sodium hydride are added to 6.3 mL of 1,1,1,-3,3,3,-hexafluoropropanol dissolved in 25 ml of anhydrous ether. When no more hydrogen gas evolves, the solution is centrifuged, and 8.6 μg (60 mml) of dimethylsulfamoyl chloride dissolved in 25 mL of dry ether are added to the supernatant liquid under agitation at a temperature of 0° C. A white precipitate of sodium chloride is then formed et the reaction is completed after 2 hours. The slurry is filtered and the ether is evaporated with a rotary evaporator. The residue is placed in 20 mL of dichloromethane and washed with an aqueous solution of 10% hydrochloric acid. The organic phase is separated and dried with anhydrous magnesium sulphate. The hexafluoropropyle N,N-dimethylsulfamate is obtained by evaporating the dichloromethane and distilled under reduced pressure. The compound has a dielectric constant greater than 20, and the conductivity of solutions of salts of bis(trifluoromethanesulfonimide) (NC2H5)4(CF3SO2)2N in this solvent are between 5×10−4 and 2×10−3 Scm−1 at 25° C. in concentrations varying from 0.2 to 1 mole·kg−1.
- 4.2 g of cyanamide and 11.22 g of diazabicyclo 2,2,2-octane (DABCO) are added to 15.76 g of ethylmethylsulfamoyl chloride dissolved in 100 mL of tetrahydrofuran. After agitating the mixture at room temperature for 8 hours, 13 g of oxalyl chloride dissolved in 40 mL of anhydrous tetrahydrofuran are added dropwise. After gas emissions have stopped (CO and CO2), the DABCO chlorohydrate is filtered and remaining THF is evaporated under reduced pressure. The solid is then placed in 50 mL of acetonitrile to which is added 12.2 g of ethylmethylamine at 0° C. The ethylmethylammonium chloride thus obtained is separated and the solvent is evaporated under reduced pressure. The polar product
The polar product is solubilized in dichloromethane, and washed with water containing 2% hydrochloric acid, and subsequently 5% sodium bicarbonate. Following removal of dichloromethane, the compound is distilled under reduced pressure. This product can be used as a solvent for delocalized anions salts, particularly perfluorinated imides. - 33 g of 1,1-dimethylsulfamide (CH3)2SO2NH2 and 6 g of caustic soda in 200 mL of water are heated to reflux for 2 hours. The reaction product, the sodium salt of bis(dimethylaminosulfonimide), i.e., Na[N(SO2N(CH3)2)], is obtained by evaporation of the water and recristallisation in ethanol. 25 g of this salt suspended in 100 mL of anhydrous are reacted with 9 mL of oxalyl chloride. At then end of the reaction, i.e., no more gas emissions, the slurry is cooled to 0° C. and 20.7 mL of diethylamine dissolved in 50 mL of acetonitrile are added. The mixture is then agitated for 4 hours at room temperature, and subsequently filtered. Any remaining acetonitrile is removed under reduced pressure. The liquid obtained is solubilized in dichloromethane and washed with water containing 2% hydrochloric acid, and subsequently 5% of sodium bicarbonate. The solution is passed through an alumina column and the dichloromethane is evaporated under reduced pressure. The polar solvent
is kept anhydrous by adding lithium hydride. - An electrochemical generator comprising a negative electrode of lithium of 25 μm on a nickel support of 10 μm, a positive electrode composite containing 78% by weight of vanadium oxide V2O5, 8% of carbon black (Ketjenblack®) and 14% of a vinylidene fluoride-hexafluoropropene copolymer on a nickel collector (10 μm) has been prepared. The positive electrode capacity thus obtained by spreading from a cyclohexanone suspension, is 2.8 mAh/cm2. The electrolyte comprises a solution of 0.15 M·kg−1 of Li(CF3SO2)2N in the polar compound of Example 1 in a polypropylene porous separator of the Celgard® type. The generator was cycled over 150 cycles between 1.6 et 3.4V at C/3.7 while maintaining a ratio of charge and discharges capacities equal to 1 and a use rate of >75% over 30 cycles. The ohmic drop remained between 20 and 120 mV.
- An electrochemical generator of the “rocking chair” type was prepared with 2 composite electrodes similar to those of Example 6. Lithium and titanium spinel Li4Ti5O12 was used as the negative electrode, to give a surface capacity of 2.6 mAh·cm−2. Lithium cobaltite was used for the positive electrode, to give a surface capacity of 2.4 MAh·cm−2. The electrolyte was prepared in a manner similar to that of Example 6 with a solution of 0.15 M·kg−1 of Li(CF3SO2)2N in the polar compound of Example 1 in a polypropylene porous separator of the Celgard® type. The generator was cycled over 500 cycles between 1.5 et 3.3 V a C/4 while maintaining a ratio of charge and discharges capacities equal to 1 and a use rate of 80%.
- An electrochemical generator of the supercapacitor type is prepared with 2 symetrical composite electrodes of high surface area carbon (680 m2·g−1) and nickel fibres on a nickel support, and bound by a vinylidene fluoride-hexafluoropropene copolymer. The electrolyte comprises 75% by wieght of a gel of a molar solution of tetraethylammonium fluorosulfonimide (C2H5)4N[(CF3SO2)2N] in the same polymer. The system capacity is 1.2 F·g−1 over 12 000 cycles performed between 0 and 2.5 V.
- A polymer electrolyte is prepared by plasticizing an ethylene oxide-allylglycidyl ether copolymer containing the lithium salt of dimethylaminosulfonyl-trifluoromethane-sulfonimide Li[(CH3)2SO2NSO2CF3] with a ratio oxygen from the ether functions of the polymer to lithium of 14:1 with the polar compound of Example 5 with a weight ratio 65:35. This electrolyte has a conductivity of 10−4 Scm−1 at 25° C. and an electrochemical stability range of 0 to 4V vs. Li+/Li°. This electrolyte can be reticulated by a free radical source to give elastomers with good mechanical properties.
- While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses or adaptations of the invention following, in general, the principles of the invention and including such departures from the present description as come within known or customary practice within the art to which the invention pertains, and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims.
Claims (20)
1. An aprotic polar compound having solvent properties and having the formula:
R1R2NX(Z)R7
wherein
X=C or SO;
Z=O, NSO2NR3R4 or NCN;
R1 and R2 are the same or different and are C1-18 alkyl, C1-18 oxaalkyl, C1-18 alkylene, C1-18 oxaalkylene;
R7 is RF, RFCH2O—, (RF)2CHO—, or (RFCH2)2N— or R5R6N—;
R3 to R6 are the same or different and are C1-18 alkyl or C1-18 oxaalkyl;
RF is C1-4 alkyl, C1-4 oxaalkyl, C1-4 azaalkyl, wherein C1-4 alkyl, C1-4 oxaalkyl, C1-4 azaalkyl are each perfluorinated,
with the proviso that if Z=O then R7 is not NR5R6.
2. An electrolytic composition, comprising:
R1R2NX(Z)R7
at least one aprotic polar compound having solvent properties and having the formula:
R1R2NX(Z)R7
wherein
X=C or SO;
Z=O, NSO2NR3R4 or NCN;
R1 and R2 are the same or different and are C1-18 alkyl, C1-18 oxaalkyl, C1-18 alkylene, C1-18 oxaalkylene;
R7 is RF, RFCH2O—, (RF)2CHO—, or (RFCH2)2N— or NR5R6;
R3 to R6 are the same or different and are C1-18 alkyl or C1-18 oxaalkyl;
RF is a fluorine atom, C1-4 alkyl, C1-4 oxaalkyl, or C1-4 azaalkyl, wherein C1-4 alkyl, C1-4 oxaalkyl, C1-4 azaalkyl are each perfluorinated,
with the proviso that if Z=O then R is not NR5R6,
and a salt soluble in said polar compound having an anion with a delocalized charge.
3. The electrolytic composition according to claim 2 , wherein the salt comprises at least one selected from the group consisting of I−, ClO4 −, BF4 −, AsF6 −, SbF6 −, PF6 −, RFSO3 −, XSO2NSO2X′−, (XSO2)(X′SO2)(Y)C−, anionic derivative of 4,5-dicyano-1,2,3-triazole, 3,5-bis(RF)-1,2,4-triazole, tricyanomethane, pentacyanocyclopentadiene, pentakis(trifluoromethyl)cyclopentadiene, RFSO2NCN−, C(CN)3 −, RFSO2C(CN)2 −, and mixtures thereof, wherein
X and X′ comprise at least one selected from the group consisting of RF, RFCH2O—, (RF)2CHO—, or (RFCH2)2N—, and R8, R9R10N—, with the proviso that at least one X or X′ is RF, RFCH2O—, (RF)2CHO—, or (RFCH2)2N—;
Y=RF, RFSO2 or CN;
RF is a fluorine atom, C1-4 alkyl, C1-4 oxaalkyl, or C1-4 azaalkyl, wherein C1-4 alkyl, C1-4 oxaalkyl, C1-4 azaalkyl are each perfluorinated and can be part of a macromolecular chain; and
R8 to R10 are the same or different, and are C1-18 alkyl or C1-18 oxaalkyl.
4. The electrolytic composition according to claim 3 , further comprising at least one cation selected from the group consisting of alkaline metal, alkaline earth metal, organic onium cation, ammonium, imidazolium, sulfonium, phosphonium, oxonium, and mixtures thereof.
5. The electrolytic composition according to claim 3 , further comprising at least one lithium cation.
6. The electrolytic composition according to claim 2 , further comprsing a co-solvent.
7. The electrolytic composition according to claim 2 , further comprising at least one aprotic, polar co-solvent selected from the group consisting of dialkylethers of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol; carbonic acid ester; γ-butyrolactone; nitrile; tricyanohexane; dimethylformamide; N-methylpyrrolidinone; and mixtures thereof.
8. The electrolytic composition according to claim 2 , further comprising at least one polyethylene glycol co-solvent having a mass ranging from 400 to 2000 g/mol.
9. The electrolytic composition according to claim 2 , which comprises at least one polymer.
10. The electrolytic composition according to claim 2 , which comprises at least one polymer, wherein the polymer is a polyelectrolyte comprising a macromolecular chain and having a delocalized anionic charge.
11. The electrolytic composition according to claim 2 , which comprises at least one polymer, wherein the polymer is a homopolymer or copolymer comprising polymerized monomer units selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrine, epifluorohydrine, trifluoroepoxypropane, acrylonitrile, methylmethacrylate, vinylidene fluoride, N-vinylpyrolidinone, hexafluoropropene, and mixtures thereof.
12. The electrolytic composition according to claim 2 , which comprises at least one polymer, wherein the composition is plasticized or in the form of a gel.
13. An electrochemical generator, comprising at least one negative electrode, at least one positive electrode, and the electrolytic composition according to claim 2 .
14. The electrochemical generator according to claim 13 , wherein the electrolytic composition comprises at least one co-solvent.
15. The electrochemical generator according to claim 13 , wherein the electrolytic composition comprises at least one polymer.
16. The electrochemical generator according to claim 13 , wherein the negative electrode comprises at least one selected from the group consisting of lithium metal, lithium alloy, carbon intercalation compound, oxide having a low potential of intercalation, double nitride of a transition metal and lithium, and mixtures thereof.
17. The electrochemical generator according to claim 16 , wherein the carbon intercalation compound is petroleum coke or graphite, and wherein the oxide having a low potential of intercalation is a titanium spinel.
18. The electrochemical generator according to claim 13 , wherein the positive electrode comprises at least one selected from the group consisting of vanadium oxide, mixed oxide of lithium and vanadium, oxide of cobalt and lithium, manganese spinel, double phosphate of the olivine or Nasicon structure, salt of rhodizonic acid, polydisulfide derived from the oxidation of 2,5-dimercapto-1,3,4-thiazole, 2,5-dimercapto-1,3,4-oxadiazole, 1,2-dimercaptocyclobutene-3,4-dione, and mixtures thereof.
19. An supercapacitor-type energy storage system, comprising as an electrolyte the electrolytic composition according to claim 13 , at least one polymer, and optionally a co-solvent.
20. An electrochemical device, comprising as an electrolyte the electrolytic composition according to claim 2 , and optionally a co-solvent, impregnated in one or more porous membranes.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/406,279 US20060188788A1 (en) | 1997-09-11 | 2006-04-19 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US12/428,701 US20090206299A1 (en) | 1997-09-11 | 2009-04-23 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US12/650,135 US20100112455A1 (en) | 1997-09-11 | 2009-12-30 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US13/022,175 US8737039B2 (en) | 1997-09-11 | 2011-02-07 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002215849A CA2215849A1 (en) | 1997-09-11 | 1997-09-11 | New solvent and electrolytic composition with high conductivity and wide stability range |
CA2,215,849 | 1997-09-11 | ||
US09/151,599 US6296973B1 (en) | 1997-09-11 | 1998-09-11 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US09/824,103 US20010012591A1 (en) | 1997-09-11 | 2001-04-03 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US10/317,222 US20030162096A1 (en) | 1997-09-11 | 2002-12-12 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US11/406,279 US20060188788A1 (en) | 1997-09-11 | 2006-04-19 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/317,222 Continuation US20030162096A1 (en) | 1997-09-11 | 2002-12-12 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/428,701 Continuation US20090206299A1 (en) | 1997-09-11 | 2009-04-23 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060188788A1 true US20060188788A1 (en) | 2006-08-24 |
Family
ID=4161490
Family Applications (7)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/151,599 Expired - Lifetime US6296973B1 (en) | 1997-09-11 | 1998-09-11 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US09/824,103 Abandoned US20010012591A1 (en) | 1997-09-11 | 2001-04-03 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US10/317,222 Abandoned US20030162096A1 (en) | 1997-09-11 | 2002-12-12 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US11/406,279 Abandoned US20060188788A1 (en) | 1997-09-11 | 2006-04-19 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US12/428,701 Abandoned US20090206299A1 (en) | 1997-09-11 | 2009-04-23 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US12/650,135 Abandoned US20100112455A1 (en) | 1997-09-11 | 2009-12-30 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US13/022,175 Expired - Fee Related US8737039B2 (en) | 1997-09-11 | 2011-02-07 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/151,599 Expired - Lifetime US6296973B1 (en) | 1997-09-11 | 1998-09-11 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US09/824,103 Abandoned US20010012591A1 (en) | 1997-09-11 | 2001-04-03 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US10/317,222 Abandoned US20030162096A1 (en) | 1997-09-11 | 2002-12-12 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/428,701 Abandoned US20090206299A1 (en) | 1997-09-11 | 2009-04-23 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US12/650,135 Abandoned US20100112455A1 (en) | 1997-09-11 | 2009-12-30 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
US13/022,175 Expired - Fee Related US8737039B2 (en) | 1997-09-11 | 2011-02-07 | Solvents and novel electrolytic compositions having a large range of stability and high conductivity |
Country Status (5)
Country | Link |
---|---|
US (7) | US6296973B1 (en) |
EP (2) | EP0902492B1 (en) |
JP (1) | JP4699579B2 (en) |
CA (1) | CA2215849A1 (en) |
DE (1) | DE69838702T2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008040698A1 (en) * | 2006-10-02 | 2008-04-10 | Basf Se | Electrolyte for lithium ion batteries |
FR2925181A1 (en) * | 2007-12-12 | 2009-06-19 | Hydro Quebec | ELECTROCHROME OPTICAL LENS |
US20130018257A1 (en) * | 2010-03-23 | 2013-01-17 | Henri Mehier | Device For Administering Heat To A Human Or Animal Tissue, Vessel Or Cavity |
Families Citing this family (67)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69827239T2 (en) * | 1997-07-25 | 2005-12-01 | Acep Inc., Montreal | Membranes derived from ionic perfluorovinyl compounds |
EP0928287B1 (en) * | 1997-07-25 | 2003-10-01 | Acep Inc. | Ionic compounds with delocalized anionic charge, their use as components of ionic conductors or catalyst |
CA2215849A1 (en) * | 1997-09-11 | 1999-03-11 | Christophe Michot | New solvent and electrolytic composition with high conductivity and wide stability range |
EP0968181B1 (en) * | 1997-12-01 | 2005-04-27 | Acep Inc. | Perfluorynated sulphone salts, and their uses as ionic conduction materials |
US6063522A (en) * | 1998-03-24 | 2000-05-16 | 3M Innovative Properties Company | Electrolytes containing mixed fluorochemical/hydrocarbon imide and methide salts |
US6405070B1 (en) * | 1998-06-16 | 2002-06-11 | Bhaskar Banerjee | Detection of cancer using cellular autofluorescence |
US6859799B1 (en) | 1998-11-30 | 2005-02-22 | Gemstar Development Corporation | Search engine for video and graphics |
DE19858925A1 (en) | 1998-12-19 | 2000-06-21 | Aventis Res & Tech Gmbh & Co | Improving the safety of lithium batteries for use in electronic devices by using an electrolyte containing a partly-fluorinated amide |
DE19942021A1 (en) * | 1999-09-03 | 2001-03-08 | Solvay Fluor & Derivate | Mixtures with LiPF¶6¶ |
JP3991566B2 (en) * | 1999-09-16 | 2007-10-17 | 松下電器産業株式会社 | Electrochemical capacitor |
EP1088814A1 (en) * | 1999-09-29 | 2001-04-04 | MERCK PATENT GmbH | Fluorinated sulfonamides as highly flame-resistant solvents for use in electrochemical cells |
JP4517440B2 (en) | 2000-03-10 | 2010-08-04 | ソニー株式会社 | Lithium ion solid electrolyte secondary battery |
US7103906B1 (en) | 2000-09-29 | 2006-09-05 | International Business Machines Corporation | User controlled multi-device media-on-demand system |
KR20170128620A (en) * | 2000-10-11 | 2017-11-22 | 로비 가이드스, 인크. | Systems and methods for delivering media content |
JP2003203674A (en) * | 2001-10-29 | 2003-07-18 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary cell |
US20030162099A1 (en) | 2002-02-28 | 2003-08-28 | Bowden William L. | Non-aqueous electrochemical cell |
AUPS119502A0 (en) * | 2002-03-19 | 2002-04-18 | Energy Storage Systems Pty Ltd | An electrolyte for an energy storage device |
US7482097B2 (en) * | 2002-04-03 | 2009-01-27 | Valence Technology, Inc. | Alkali-transition metal phosphates having a +3 valence non-transition element and related electrode active materials |
US7422823B2 (en) * | 2002-04-03 | 2008-09-09 | Valence Technology, Inc. | Alkali-iron-cobalt phosphates and related electrode active materials |
US20030190527A1 (en) * | 2002-04-03 | 2003-10-09 | James Pugh | Batteries comprising alkali-transition metal phosphates and preferred electrolytes |
US7709157B2 (en) * | 2002-10-23 | 2010-05-04 | Panasonic Corporation | Non-aqueous electrolyte secondary battery and electrolyte for the same |
US7493646B2 (en) | 2003-01-30 | 2009-02-17 | United Video Properties, Inc. | Interactive television systems with digital video recording and adjustable reminders |
US7450294B2 (en) * | 2004-03-12 | 2008-11-11 | Boeing Co | Multi-color electrochromic apparatus and methods |
US8988757B2 (en) * | 2004-03-12 | 2015-03-24 | The Boeing Company | Low vapor pressure solvent for electrochromic devices |
US8064120B2 (en) * | 2004-03-12 | 2011-11-22 | The Boeing Company | Aircraft cabin services system including zone controllers for lighting control modules and dimmable windows |
JP4591847B2 (en) * | 2004-03-23 | 2010-12-01 | 三菱マテリアル電子化成株式会社 | Layered double hydroxide and composition containing the same |
WO2005109562A1 (en) * | 2004-05-10 | 2005-11-17 | Nippon Shokubai Co., Ltd. | Material for electrolytic solution, ionic material-containing composition and use thereof |
US7285356B2 (en) | 2004-07-23 | 2007-10-23 | The Gillette Company | Non-aqueous electrochemical cells |
US7776475B2 (en) * | 2004-08-03 | 2010-08-17 | Samsung Sdi Co., Ltd. | Lithium rechargeable battery and lithium rechargeable battery pack |
US8086575B2 (en) | 2004-09-23 | 2011-12-27 | Rovi Solutions Corporation | Methods and apparatus for integrating disparate media formats in a networked media system |
WO2006098213A1 (en) * | 2005-03-17 | 2006-09-21 | Kaneka Corporation | Electrochemical device |
US7479348B2 (en) | 2005-04-08 | 2009-01-20 | The Gillette Company | Non-aqueous electrochemical cells |
JP2007158203A (en) * | 2005-12-08 | 2007-06-21 | Nichicon Corp | Electrolytic capacitor |
US7355161B2 (en) * | 2005-12-15 | 2008-04-08 | The Boeing Company | Systems and methods for controlling windows with variable light transmission |
US20070157240A1 (en) * | 2005-12-29 | 2007-07-05 | United Video Properties, Inc. | Interactive media guidance system having multiple devices |
US20070157260A1 (en) * | 2005-12-29 | 2007-07-05 | United Video Properties, Inc. | Interactive media guidance system having multiple devices |
US9681105B2 (en) | 2005-12-29 | 2017-06-13 | Rovi Guides, Inc. | Interactive media guidance system having multiple devices |
US20070156521A1 (en) | 2005-12-29 | 2007-07-05 | United Video Properties, Inc. | Systems and methods for commerce in media program related merchandise |
US7840977B2 (en) * | 2005-12-29 | 2010-11-23 | United Video Properties, Inc. | Interactive media guidance system having multiple devices |
US20070156539A1 (en) * | 2005-12-29 | 2007-07-05 | United Video Properties, Inc. | Systems and methods for commerce in media program related merchandise |
US8607287B2 (en) | 2005-12-29 | 2013-12-10 | United Video Properties, Inc. | Interactive media guidance system having multiple devices |
JP4705476B2 (en) * | 2006-01-10 | 2011-06-22 | 第一工業製薬株式会社 | Method for producing fluorine compound |
JP2007250994A (en) * | 2006-03-17 | 2007-09-27 | Kaneka Corp | Conductive polymer redox type electrochemical element used as polar device |
WO2008039808A2 (en) | 2006-09-25 | 2008-04-03 | Board Of Regents, The University Of Texas System | Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries |
US20080240480A1 (en) * | 2007-03-26 | 2008-10-02 | Pinnell Leslie J | Secondary Batteries for Hearing Aids |
US20080241645A1 (en) * | 2007-03-26 | 2008-10-02 | Pinnell Leslie J | Lithium ion secondary batteries |
US20080248375A1 (en) * | 2007-03-26 | 2008-10-09 | Cintra George M | Lithium secondary batteries |
US20090019492A1 (en) | 2007-07-11 | 2009-01-15 | United Video Properties, Inc. | Systems and methods for mirroring and transcoding media content |
CN101420021B (en) * | 2007-10-26 | 2011-07-27 | 清华大学 | Positive pole of lithium ion cell and preparation method thereof |
US20090165049A1 (en) | 2007-12-19 | 2009-06-25 | United Video Properties, Inc. | Methods and devices for presenting and interactive media guidance application |
US8601526B2 (en) | 2008-06-13 | 2013-12-03 | United Video Properties, Inc. | Systems and methods for displaying media content and media guidance information |
US9014546B2 (en) | 2009-09-23 | 2015-04-21 | Rovi Guides, Inc. | Systems and methods for automatically detecting users within detection regions of media devices |
US10476100B2 (en) * | 2010-10-04 | 2019-11-12 | Ford Global Technologies, Llc | Lithium-containing electrode material for electrochemical cell systems |
DE102011055028A1 (en) * | 2011-11-04 | 2013-05-08 | Jacobs University Bremen Ggmbh | Electrolyte additive for lithium-based energy storage |
US8805418B2 (en) | 2011-12-23 | 2014-08-12 | United Video Properties, Inc. | Methods and systems for performing actions based on location-based rules |
US8956769B2 (en) * | 2011-12-27 | 2015-02-17 | Lg Chem, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
US9819057B2 (en) | 2012-09-07 | 2017-11-14 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
US9848276B2 (en) | 2013-03-11 | 2017-12-19 | Rovi Guides, Inc. | Systems and methods for auto-configuring a user equipment device with content consumption material |
US9674563B2 (en) | 2013-11-04 | 2017-06-06 | Rovi Guides, Inc. | Systems and methods for recommending content |
WO2016039750A1 (en) | 2014-09-11 | 2016-03-17 | Halliburton Energy Services, Inc. | Cyanamide-based carbon dioxide and/or hydrogen sulfide scavengers and methods of use in subterranean operations |
KR20230034420A (en) * | 2015-03-25 | 2023-03-09 | 니폰 제온 가부시키가이샤 | All-solid secondary battery |
JP2015187992A (en) * | 2015-05-26 | 2015-10-29 | ハイドロ−ケベック | Novel lithium insertion electrode material based on orthosilicate derivative |
KR102446364B1 (en) * | 2015-09-03 | 2022-09-21 | 삼성에스디아이 주식회사 | Electrolyte for rechargeable lithium battery and rechargeable lithium battery |
US9972451B2 (en) * | 2015-11-30 | 2018-05-15 | City University Of Hong Kong | Polyelectrolyte and a method for manufacturing an energy storage device |
EP3471192A4 (en) * | 2016-06-08 | 2020-01-15 | Kaneka Corporation | Lithium-ion secondary battery and assembled battery |
DE102019208914A1 (en) * | 2019-06-19 | 2020-12-24 | Robert Bosch Gmbh | Salt with anion with unfluorinated dialkylamide sulfonyl and / or sulfoximide group and with perfluoroalkyl sulfonyl group |
WO2024035170A1 (en) * | 2022-08-12 | 2024-02-15 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte and lithium secondary battery comprising same |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4250092A (en) * | 1978-05-12 | 1981-02-10 | Crc Compagnia Di Ricerca Chimica S.A. | Derivatives of N-cyano-azomethines and process for their preparation |
US4303748A (en) * | 1978-11-22 | 1981-12-01 | Agence Nationale De Valorisation De La Recherche (Anvar) | Electrochemical generators for producing current and new materials for their manufacture |
US4581307A (en) * | 1984-03-28 | 1986-04-08 | Saft, S.A. | High specific energy electrochemical cell with low initial impedance |
US4816372A (en) * | 1986-09-26 | 1989-03-28 | Agfa-Gevaert Aktiengesellschaft | Heat development process and color photographic recording material suitable for this process |
US4899249A (en) * | 1988-04-21 | 1990-02-06 | Pennwalt Corporation | Fluorine-containing dielectric media and capacitors employing such media |
US5063124A (en) * | 1986-10-30 | 1991-11-05 | Societe Nationale Elf Aquitane | Ionically conductive material |
US5723664A (en) * | 1994-09-12 | 1998-03-03 | Central Glass Company, Limited | Method of preparing sulfonimide or its salt |
US6030720A (en) * | 1994-11-23 | 2000-02-29 | Polyplus Battery Co., Inc. | Liquid electrolyte lithium-sulfur batteries |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2300084A1 (en) * | 1973-01-02 | 1974-07-04 | Henkel & Cie Gmbh | Microbicidal guanidinsulphonic acid amides - prepd. by reacting N,N'-dialkyl-N'-chlorosulphonylchlorofromamidine and amines |
DE2831163A1 (en) * | 1978-07-15 | 1980-01-24 | Bbc Brown Boveri & Cie | ELECTROCHEMICAL STORAGE CELL |
DE3243959A1 (en) | 1982-02-06 | 1983-08-18 | Merck Patent Gmbh, 6100 Darmstadt | ODOR STABILIZATION OF THIOGLYCOLATE SOLUTIONS |
FR2527602A1 (en) * | 1982-06-01 | 1983-12-02 | Anvar | BIS PERHALOGENOACYL- OR SULFONYL- IMIDURES OF ALKALI METALS, THEIR SOLID SOLUTIONS WITH PLASTIC MATERIALS AND THEIR APPLICATION TO THE CONSTITUTION OF CONDUCTIVE ELEMENTS FOR ELECTROCHEMICAL GENERATORS |
FR2532476A1 (en) * | 1982-09-01 | 1984-03-02 | Commissariat Energie Atomique | IMPROVEMENT TO ELECTROCHEMICAL GENERATORS COMPRISING AN ORGANIC POLYMER AS AN ACTIVE ELECTRODE MATERIAL |
GB8312660D0 (en) * | 1983-05-09 | 1983-06-15 | Ici Plc | Piperazine bisbiguanides |
GB8312661D0 (en) * | 1983-05-09 | 1983-06-15 | Ici Plc | Bisbiguanide derivatives |
FR2606217B1 (en) * | 1986-10-30 | 1990-12-14 | Elf Aquitaine | NOVEL ION CONDUCTIVE MATERIAL CONSISTING OF A SALT SOLUTION IN A LIQUID ELECTROLYTE |
JP3760474B2 (en) * | 1993-04-22 | 2006-03-29 | ダイキン工業株式会社 | Method and apparatus for generating electric energy, and compound having NF bond used therefor |
DE4447389A1 (en) * | 1994-12-22 | 1996-06-27 | Schering Ag | Disubstituted p-fluorobenzenesulfonamides |
US5514493A (en) * | 1995-03-06 | 1996-05-07 | Minnesota Mining And Manufacturing Company | Perfluoroalkylsulfonates, sulfonimides, and sulfonyl methides, and electrolytes containing them |
US5723720A (en) * | 1995-06-07 | 1998-03-03 | J. R. Simplot Company | Process for the development of endophyte-infected plants |
JP3252705B2 (en) * | 1995-07-17 | 2002-02-04 | トヨタ自動車株式会社 | Electric double layer capacitor |
JP3500245B2 (en) * | 1995-08-01 | 2004-02-23 | 株式会社リコー | Gel-like solid electrolyte secondary battery |
JP3874435B2 (en) * | 1995-10-09 | 2007-01-31 | 旭化成エレクトロニクス株式会社 | Organosulfonylimide lithium |
JP3269396B2 (en) * | 1996-08-27 | 2002-03-25 | 松下電器産業株式会社 | Non-aqueous electrolyte lithium secondary battery |
JP4124487B2 (en) * | 1996-12-30 | 2008-07-23 | イドロ―ケベック | Five-membered ring anion salts or tetraazapentalene derivatives and their use as ion-conducting substances |
CA2197056A1 (en) | 1997-02-07 | 1998-08-07 | Hydro-Quebec | New ionically conductive material with improved conductivity and stability |
CA2215849A1 (en) * | 1997-09-11 | 1999-03-11 | Christophe Michot | New solvent and electrolytic composition with high conductivity and wide stability range |
-
1997
- 1997-09-11 CA CA002215849A patent/CA2215849A1/en not_active Abandoned
-
1998
- 1998-09-10 EP EP98402242A patent/EP0902492B1/en not_active Expired - Lifetime
- 1998-09-10 DE DE69838702T patent/DE69838702T2/en not_active Expired - Lifetime
- 1998-09-10 EP EP07014876.2A patent/EP1863109B1/en not_active Expired - Lifetime
- 1998-09-11 US US09/151,599 patent/US6296973B1/en not_active Expired - Lifetime
- 1998-09-11 JP JP25864198A patent/JP4699579B2/en not_active Expired - Lifetime
-
2001
- 2001-04-03 US US09/824,103 patent/US20010012591A1/en not_active Abandoned
-
2002
- 2002-12-12 US US10/317,222 patent/US20030162096A1/en not_active Abandoned
-
2006
- 2006-04-19 US US11/406,279 patent/US20060188788A1/en not_active Abandoned
-
2009
- 2009-04-23 US US12/428,701 patent/US20090206299A1/en not_active Abandoned
- 2009-12-30 US US12/650,135 patent/US20100112455A1/en not_active Abandoned
-
2011
- 2011-02-07 US US13/022,175 patent/US8737039B2/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4250092A (en) * | 1978-05-12 | 1981-02-10 | Crc Compagnia Di Ricerca Chimica S.A. | Derivatives of N-cyano-azomethines and process for their preparation |
US4303748A (en) * | 1978-11-22 | 1981-12-01 | Agence Nationale De Valorisation De La Recherche (Anvar) | Electrochemical generators for producing current and new materials for their manufacture |
US4581307A (en) * | 1984-03-28 | 1986-04-08 | Saft, S.A. | High specific energy electrochemical cell with low initial impedance |
US4816372A (en) * | 1986-09-26 | 1989-03-28 | Agfa-Gevaert Aktiengesellschaft | Heat development process and color photographic recording material suitable for this process |
US5063124A (en) * | 1986-10-30 | 1991-11-05 | Societe Nationale Elf Aquitane | Ionically conductive material |
US4899249A (en) * | 1988-04-21 | 1990-02-06 | Pennwalt Corporation | Fluorine-containing dielectric media and capacitors employing such media |
US5723664A (en) * | 1994-09-12 | 1998-03-03 | Central Glass Company, Limited | Method of preparing sulfonimide or its salt |
US6030720A (en) * | 1994-11-23 | 2000-02-29 | Polyplus Battery Co., Inc. | Liquid electrolyte lithium-sulfur batteries |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008040698A1 (en) * | 2006-10-02 | 2008-04-10 | Basf Se | Electrolyte for lithium ion batteries |
FR2925181A1 (en) * | 2007-12-12 | 2009-06-19 | Hydro Quebec | ELECTROCHROME OPTICAL LENS |
WO2009098415A1 (en) * | 2007-12-12 | 2009-08-13 | Hydro-Quebec | Electrochromic optical lens |
US8482839B2 (en) | 2007-12-12 | 2013-07-09 | Hydro-Quebec | Electrochromic optical lens |
US20130018257A1 (en) * | 2010-03-23 | 2013-01-17 | Henri Mehier | Device For Administering Heat To A Human Or Animal Tissue, Vessel Or Cavity |
Also Published As
Publication number | Publication date |
---|---|
US20100112455A1 (en) | 2010-05-06 |
JP4699579B2 (en) | 2011-06-15 |
US20090206299A1 (en) | 2009-08-20 |
US6296973B1 (en) | 2001-10-02 |
DE69838702D1 (en) | 2007-12-27 |
CA2215849A1 (en) | 1999-03-11 |
US8737039B2 (en) | 2014-05-27 |
EP0902492B1 (en) | 2007-11-14 |
DE69838702T2 (en) | 2008-10-30 |
US20110128674A1 (en) | 2011-06-02 |
EP1863109A2 (en) | 2007-12-05 |
EP1863109B1 (en) | 2016-09-07 |
US20030162096A1 (en) | 2003-08-28 |
JPH11171853A (en) | 1999-06-29 |
US20010012591A1 (en) | 2001-08-09 |
EP1863109A3 (en) | 2009-07-29 |
EP0902492A1 (en) | 1999-03-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8737039B2 (en) | Solvents and novel electrolytic compositions having a large range of stability and high conductivity | |
JP3878206B2 (en) | Ionic conductive material with good corrosion resistance | |
EP0731518B1 (en) | Perfluoroalkylsulfonates, sulfonimides, and sulfonyl methides, and electrolytes containing them | |
US6728096B1 (en) | Non-aqueous electrolyte | |
EP1602142B1 (en) | Energy storage devices | |
Hagiwara et al. | Ionic liquids for electrochemical devices | |
EP0731477B1 (en) | Electric double layer capacitor | |
EP1721900B1 (en) | Novel imidazolium compound | |
US8128833B1 (en) | Non-aqueous electrolyte | |
JP4858107B2 (en) | Electrolyte | |
CA2246955C (en) | Solvents and novel electrolytic compositions having a high stability domain and high conductivity | |
JP3730856B2 (en) | Electrolytes for electrochemical devices, electrolytes or solid electrolytes thereof, and batteries | |
JP3690065B2 (en) | Electric double layer capacitor | |
JP2020155278A (en) | Aqueous electrolyte solution for power storage device, and power storage device including the same | |
JP2020155279A (en) | Aqueous electrolyte solution for power storage device, and power storage device including the same | |
EP0130507A1 (en) | High conductivity thionyl chloride electrolytes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |