CA2660449A1 - Dissociating agents, formulations and methods providing enhanced solubility of fluorides - Google Patents
Dissociating agents, formulations and methods providing enhanced solubility of fluorides Download PDFInfo
- Publication number
- CA2660449A1 CA2660449A1 CA002660449A CA2660449A CA2660449A1 CA 2660449 A1 CA2660449 A1 CA 2660449A1 CA 002660449 A CA002660449 A CA 002660449A CA 2660449 A CA2660449 A CA 2660449A CA 2660449 A1 CA2660449 A1 CA 2660449A1
- Authority
- CA
- Canada
- Prior art keywords
- crown
- solvents
- solution
- group
- dissociating agent
- 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
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title abstract description 54
- 238000009472 formulation Methods 0.000 title abstract description 23
- 150000002222 fluorine compounds Chemical class 0.000 title description 15
- 239000002904 solvent Substances 0.000 claims abstract description 148
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 124
- 229910001506 inorganic fluoride Inorganic materials 0.000 claims abstract description 79
- 239000002879 Lewis base Substances 0.000 claims abstract description 42
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 42
- 239000002841 Lewis acid Substances 0.000 claims abstract description 41
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims description 101
- 229910052744 lithium Inorganic materials 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 48
- -1 OsF6 Chemical compound 0.000 claims description 40
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims description 21
- 159000000002 lithium salts Chemical class 0.000 claims description 21
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 16
- 150000003983 crown ethers Chemical class 0.000 claims description 16
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 8
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 8
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 8
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 8
- GQRWGIWRQMNZNT-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadecane Chemical compound O1CCOCCOCCOCCOC2CCCCC21 GQRWGIWRQMNZNT-UHFFFAOYSA-N 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001504 inorganic chloride Inorganic materials 0.000 claims description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 6
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 5
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 claims description 4
- XKEHLMZHBXCJGZ-UHFFFAOYSA-N 1,4,7,10,13,16,19-heptaoxacyclohenicosane Chemical compound C1COCCOCCOCCOCCOCCOCCO1 XKEHLMZHBXCJGZ-UHFFFAOYSA-N 0.000 claims description 4
- XIWRBQVYCZCEPG-UHFFFAOYSA-N 17-nitro-2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-triene Chemical compound O1CCOCCOCCOCCOC2=CC([N+](=O)[O-])=CC=C21 XIWRBQVYCZCEPG-UHFFFAOYSA-N 0.000 claims description 4
- LNNVNAOXLAULPK-UHFFFAOYSA-N 17-tert-butyl-2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-triene Chemical compound O1CCOCCOCCOCCOC2=CC(C(C)(C)C)=CC=C21 LNNVNAOXLAULPK-UHFFFAOYSA-N 0.000 claims description 4
- KEDVODGFVKTPLB-UHFFFAOYSA-N 17-tert-butyl-2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadecane Chemical compound O1CCOCCOCCOCCOC2CC(C(C)(C)C)CCC21 KEDVODGFVKTPLB-UHFFFAOYSA-N 0.000 claims description 4
- BDTDDXDRCOLVNJ-UHFFFAOYSA-N 2,3-naphtho-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC3=CC=CC=C3C=C21 BDTDDXDRCOLVNJ-UHFFFAOYSA-N 0.000 claims description 4
- DSFHXKRFDFROER-UHFFFAOYSA-N 2,5,8,11,14,17-hexaoxabicyclo[16.4.0]docosa-1(22),18,20-triene Chemical compound O1CCOCCOCCOCCOCCOC2=CC=CC=C21 DSFHXKRFDFROER-UHFFFAOYSA-N 0.000 claims description 4
- CQNGAZMLFIMLQN-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-trien-17-amine Chemical compound O1CCOCCOCCOCCOC2=CC(N)=CC=C21 CQNGAZMLFIMLQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 4
- 229910017049 AsF5 Inorganic materials 0.000 claims description 4
- 229910020187 CeF3 Inorganic materials 0.000 claims description 4
- 229910021562 Chromium(II) fluoride Inorganic materials 0.000 claims description 4
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 claims description 4
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 claims description 4
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 4
- 229910005270 GaF3 Inorganic materials 0.000 claims description 4
- 229910021620 Indium(III) fluoride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910020261 KBF4 Inorganic materials 0.000 claims description 4
- 229910021135 KPF6 Inorganic materials 0.000 claims description 4
- 229910002319 LaF3 Inorganic materials 0.000 claims description 4
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 claims description 4
- 229910017971 NH4BF4 Inorganic materials 0.000 claims description 4
- 229910017673 NH4PF6 Inorganic materials 0.000 claims description 4
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 4
- 229910020007 NaZnCl3 Inorganic materials 0.000 claims description 4
- 229910017557 NdF3 Inorganic materials 0.000 claims description 4
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 claims description 4
- 229910021174 PF5 Inorganic materials 0.000 claims description 4
- 229910004366 ThF4 Inorganic materials 0.000 claims description 4
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 4
- 229910007998 ZrF4 Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 4
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 4
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- RNFYGEKNFJULJY-UHFFFAOYSA-L chromium(ii) fluoride Chemical compound [F-].[F-].[Cr+2] RNFYGEKNFJULJY-UHFFFAOYSA-L 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 4
- JKCQOMAQPUYHPL-UHFFFAOYSA-N dibenzo-21-crown-7 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 JKCQOMAQPUYHPL-UHFFFAOYSA-N 0.000 claims description 4
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 claims description 4
- MXCSCGGRLMRZMF-UHFFFAOYSA-N dibenzo-30-crown-10 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C2OCCOCCOCCOCCOC2=CC=CC=C21 MXCSCGGRLMRZMF-UHFFFAOYSA-N 0.000 claims description 4
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 claims description 4
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 4
- 239000003049 inorganic solvent Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims description 4
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001541 potassium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 4
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 4
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 4
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 4
- UDDORTWORGMVNZ-UHFFFAOYSA-N sulfuric acid;1,4,7,10-tetrazacyclododecane Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.C1CNCCNCCNCCN1 UDDORTWORGMVNZ-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims description 4
- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 claims description 4
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 4
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 4
- SBWLCGZEBQGYRP-UHFFFAOYSA-N 1,4,7,10-tetrazacyclododecane;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.C1CNCCNCCNCCN1 SBWLCGZEBQGYRP-UHFFFAOYSA-N 0.000 claims description 3
- IWFZLIOEAYLIQY-UHFFFAOYSA-N 2,5,8,15,18,21,24-heptaoxatricyclo[23.4.0.09,14]nonacosane Chemical compound O1CCOCCOCCOC2CCCCC2OCCOCCOC2CCCCC21 IWFZLIOEAYLIQY-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 229910021608 Silver(I) fluoride Inorganic materials 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 3
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 3
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 claims description 3
- QMLGNDFKJAFKGZ-UHFFFAOYSA-N dicyclohexano-24-crown-8 Chemical compound O1CCOCCOCCOC2CCCCC2OCCOCCOCCOC2CCCCC21 QMLGNDFKJAFKGZ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005462 imide group Chemical group 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Inorganic materials [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- CRMPMTUAAUPLIK-UHFFFAOYSA-N tellurium tetrafluoride Chemical compound F[Te](F)(F)F CRMPMTUAAUPLIK-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- LAINPTZBIXYTIZ-UHFFFAOYSA-N 2-(3-hydroxy-2,4,5,7-tetraiodo-6-oxo-9-xanthenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C(O)=C(I)C=C21 LAINPTZBIXYTIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910014264 BrF Inorganic materials 0.000 claims description 2
- 229910014263 BrF3 Inorganic materials 0.000 claims description 2
- 229910014271 BrF5 Inorganic materials 0.000 claims description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 2
- 229910006158 GeF2 Inorganic materials 0.000 claims description 2
- 229910006160 GeF4 Inorganic materials 0.000 claims description 2
- 229910019787 NbF5 Inorganic materials 0.000 claims description 2
- 229910004546 TaF5 Inorganic materials 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 claims description 2
- 229910001633 beryllium fluoride Inorganic materials 0.000 claims description 2
- XHVUVQAANZKEKF-UHFFFAOYSA-N bromine pentafluoride Chemical compound FBr(F)(F)(F)F XHVUVQAANZKEKF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 claims description 2
- FMSYTQMJOCCCQS-UHFFFAOYSA-L difluoromercury Chemical compound F[Hg]F FMSYTQMJOCCCQS-UHFFFAOYSA-L 0.000 claims description 2
- GGJOARIBACGTDV-UHFFFAOYSA-N germanium difluoride Chemical compound F[Ge]F GGJOARIBACGTDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- FQZUXVBMUHSNRN-UHFFFAOYSA-L mercury(1+);difluoride Chemical compound [Hg]F.[Hg]F FQZUXVBMUHSNRN-UHFFFAOYSA-L 0.000 claims description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 2
- PPMWWXLUCOODDK-UHFFFAOYSA-N tetrafluorogermane Chemical compound F[Ge](F)(F)F PPMWWXLUCOODDK-UHFFFAOYSA-N 0.000 claims description 2
- FQFKTKUFHWNTBN-UHFFFAOYSA-N trifluoro-$l^{3}-bromane Chemical compound FBr(F)F FQFKTKUFHWNTBN-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 4
- 229910019804 NbCl5 Inorganic materials 0.000 claims 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims 2
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 claims 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims 1
- 125000001814 trioxo-lambda(7)-chloranyloxy group Chemical group *OCl(=O)(=O)=O 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000005755 formation reaction Methods 0.000 abstract description 8
- 238000010348 incorporation Methods 0.000 abstract description 5
- 230000009918 complex formation Effects 0.000 abstract description 4
- 238000010669 acid-base reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 94
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 44
- 239000000126 substance Substances 0.000 description 30
- 238000009830 intercalation Methods 0.000 description 28
- 239000000463 material Substances 0.000 description 25
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 18
- 239000010439 graphite Substances 0.000 description 18
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- 229910001416 lithium ion Inorganic materials 0.000 description 15
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- 239000000654 additive Substances 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 11
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
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- 238000002161 passivation Methods 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
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- 229910019239 CoFx Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910015471 FeFx Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910014913 LixSi Inorganic materials 0.000 description 1
- 101100001708 Mus musculus Angptl4 gene Proteins 0.000 description 1
- 229910006141 NiFx Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910008046 SnC14 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical group [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 229910001153 VF4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- 125000005621 boronate group Chemical class 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 230000000536 complexating effect Effects 0.000 description 1
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- 229910052805 deuterium Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
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- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 239000002608 ionic liquid Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical class [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052722 tritium Chemical group 0.000 description 1
- 238000004832 voltammetry Methods 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
- 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
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
- H01M6/04—Cells with aqueous electrolyte
-
- 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
-
- 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
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
Abstract
The present invention provides compositions, formulations and methods providing for the effective dissolution of inorganic fluorides in solvents via incorporation of a dissociating agent component. Dissociating agents of the present invention participate in chemical reactions in solution, such as complex formation, acid-base reactions, and adduct formation reactions, that result in enhancement in the dissolution of inorganic fluorides in a range of solvent environments. Dissociating agents comprising Lewis acids, Lewis bases, anion receptors, cation receptors or combinations thereof are provided that significantly increase the extent of dissolution of a range of inorganic fluorides, particularly inorganic fluorides, such as LiF, that are highly insoluble in many solvents in the absence of the dissociating agents of the present invention.
Description
DISSOCIATING AGENTS, FORMULATIONS AND METHODS PROVIDING
ENHANCED SOLUBILITY OF FLUORIDES
CROSS-REFERENCE TO RELATED APPLICATIONS
[001] This application claims the benefit of priority to U.S. Patent Application No.
60/837,174, filed August 11, 2006 and to U.S. Application 11/681,493 filed March 2, 2007, both of which are incorporated herein by reference in their entireties to the extent not inconsistent with the present description.
STATEMENT REGARDING FEDERALLY SPONSORED
RESEARCH OR DEVELOPMENT
ENHANCED SOLUBILITY OF FLUORIDES
CROSS-REFERENCE TO RELATED APPLICATIONS
[001] This application claims the benefit of priority to U.S. Patent Application No.
60/837,174, filed August 11, 2006 and to U.S. Application 11/681,493 filed March 2, 2007, both of which are incorporated herein by reference in their entireties to the extent not inconsistent with the present description.
STATEMENT REGARDING FEDERALLY SPONSORED
RESEARCH OR DEVELOPMENT
[002] Not applicable.
BACKGROUND OF INVENTION
BACKGROUND OF INVENTION
[003] Advances in electrochemical storage and conversion devices have significantly expanded the capabilities of these systems in a variety of fields including portable electronics, aerospace technologies, communications and biomedical instrumentation.
State of the art electrochemical storage and conversion devices are specifically engineered to have designs and performance attributes supporting specific target application requirements and operating environments. Such advanced electrochemical storage systems include high energy density batteries exhibiting low self discharge rates and high discharge reliability for implanted medical devices; inexpensive light weight rechargeable batteries for portable electronics, and high capacity batteries capable of providing high discharge rates over short time intervals for military and aerospace applications.
State of the art electrochemical storage and conversion devices are specifically engineered to have designs and performance attributes supporting specific target application requirements and operating environments. Such advanced electrochemical storage systems include high energy density batteries exhibiting low self discharge rates and high discharge reliability for implanted medical devices; inexpensive light weight rechargeable batteries for portable electronics, and high capacity batteries capable of providing high discharge rates over short time intervals for military and aerospace applications.
[004] Widespread implementation of this diverse suite of advanced electrochemical storage and conversion systems continues to motivate research directed to expanding the functionality of these systems to enable the next generation of high performance device applications. Growth in the demand for high power portable electronic products, for example, has created enormous interest in developing safe, light weight primary and secondary batteries with higher energy densities. The demand for miniaturization in the field of consumer electronics and instrumentation also continues to stimulate research Page 1 of 44 into novel design strategies for reducing the sizes, masses and form factors of high performance batteries. Further, developments in the fields of electric vehicles and aerospace engineering has also created a significant need for highly reliable batteries exhibiting high energy densities and high power densities for a range of useful operating environments.
[005] Many advances in electrochemical storage and conversion technology are directly attributable to discovery and integration of new materials for battery components. Lithium battery technology, for example, continues to rapidly develop, at least in part, due to the discovery of novel electrode and electrolyte materials for these systems. From the pioneering identification of intercalation host materials for positive and negative electrodes to the development of high performance non-aqueous electrolytes, the discovery and optimization of novel materials for lithium battery systems have revolutionized their design and performance capabilities. As a result of these advances, lithium based battery technology is currently preferred for certain commercially significant applications including primary and secondary electrochemical cells for portable electronic systems.
[006] Advances in materials strategies and cell designs for lithium battery technology have realized primary and secondary electrochemical cells capable of providing useful device performance including: (i) large energy densities (e.g., =150 Wh kg-'), (ii) high cell voltages (e.g. up to about 3.6 V), (iii) substantially constant (e.g., flat) discharge profiles, (iv) long shelf-life (e.g., up to 10 years), (v) good cycling characteristics, and (vi) compatibility with a range of operating temperatures (e.g., -20 to 60 degrees Celsius).
As a result of these beneficial characteristics, primary and secondary lithium batteries are widely employed as power sources for many portable electronic devices, such as cellular telephones and portable computers, and for other important device applications in the fields of biomedical engineering, sensing, military communications, and lighting.
As a result of these beneficial characteristics, primary and secondary lithium batteries are widely employed as power sources for many portable electronic devices, such as cellular telephones and portable computers, and for other important device applications in the fields of biomedical engineering, sensing, military communications, and lighting.
[007] Primary lithium battery systems typically utilize a lithium metal negative electrode for generating lithium ions. During discharge, lithium ions are transported from the negative electrode through a liquid phase or solid phase electrolyte and undergo intercalation reaction at a positive electrode comprising an intercalation host material. Dual intercalation lithium ion secondary batteries have also been developed, wherein lithium metal is replaced with a second lithium ion intercalation host material providing the negative electrode. In lithium ion secondary cells, simultaneous lithium ion Page 2 of 44 insertion and de-insertion reactions allow lithium ions to migrate between the positive and negative intercalation electrodes during discharge and charging cycles.
Incorporation of a lithium ion intercalation host material for the negative electrode has the significant advantage of avoiding the use of metallic lithium which is susceptible to safety problems upon recharging attributable to the highly reactive nature and non-epitaxial deposition properties of lithium. Useful intercalation host materials for electrodes in lithium cells include carbonaceous materials (e.g., graphite, cokes, subfluorinated carbons etc.), metal oxides, metal sulfides, metal nitrides, metal selenides and metal phosphides. U.S. Patents Nos. 6,852,446, 6,306,540, 6,489,055, and "Lithium Batteries Science and Technology" edited by Gholam-Abbas Nazri and Gianfranceo Pistoia, Kluer Academic Publishers, 2004, are directed to lithium and lithium ion battery systems which are hereby incorporated by reference in their entireties.
Incorporation of a lithium ion intercalation host material for the negative electrode has the significant advantage of avoiding the use of metallic lithium which is susceptible to safety problems upon recharging attributable to the highly reactive nature and non-epitaxial deposition properties of lithium. Useful intercalation host materials for electrodes in lithium cells include carbonaceous materials (e.g., graphite, cokes, subfluorinated carbons etc.), metal oxides, metal sulfides, metal nitrides, metal selenides and metal phosphides. U.S. Patents Nos. 6,852,446, 6,306,540, 6,489,055, and "Lithium Batteries Science and Technology" edited by Gholam-Abbas Nazri and Gianfranceo Pistoia, Kluer Academic Publishers, 2004, are directed to lithium and lithium ion battery systems which are hereby incorporated by reference in their entireties.
[008] Electrolytes for lithium electrochemical cells are limited to nonaqueous materials given the extremely reactive nature of lithium with water. Several classes of nonaqueous electrolytes have been successfully implemented for lithium electrochemical cells including: (i) solutions of lithium salts dissolved in organic or inorganic solvents, (ii) ionically conducting polymers, (iii) ionic liquids and (iv) fused lithium salts. Nonaqueous electrolyte solutions comprising lithium salts dissolved in polar organic solvents are currently the most widely adopted electrolytes for primary and secondary lithium cells. Useful solvents for these electrolytes include polar solvents that facilitate dissociation of lithium salts into their ionic components. Polar solvents exhibiting useful properties for lithium cell electrolytes include linear and cyclic esters (e.g., methyl formate, ethylene carbonate, dimethyl carbonate and propylene carbonate), linear and cyclic ethers (e.g., dimethoxiethane, and dioxolane) acetonitrile, and y-butyrolactone. Lithium salts in these electrolyte systems are typically salts comprising lithium and complex anions that have relatively low lattice energies so as to facilitate their dissociation in polar organic solvents. Lithium salts that have been successfully incorporated in electrolytes for these systems include LiCIO4, LiBF4, LiAsF6, LiSbF6, LiAICl4 and LiPF6 provided at concentrations ranging from 0.01 M to 1 M.
[009] Successful implementation of polar organic solvent based electrolyte systems for primary or secondary lithium batteries involves a number of considerations involving their chemical and physical properties. First, the electrolyte must be capable of forming a stable passivation layer on the surfaces of the electrode that does not result in a Page 3 of 44 significant voltage delay at the onset of discharge and is capable of rapid reformation upon high current discharge. Second, the electrolyte must be chemically stable with respect to electrolytic degradation for relevant electrode material and discharge conditions. Third, the electrolyte must exhibit a useful ionic conductivity.
State of the art electrolytes for these systems, for example, exhibit ionic conductivities at 25 degrees Celsius greater than or equal to about 0.005 S cm-'. Other physical properties of electrolytes useful for providing enhanced performance in electrochemical cells include thermal stability, low viscosity, low melting point, and high boiling point.
State of the art electrolytes for these systems, for example, exhibit ionic conductivities at 25 degrees Celsius greater than or equal to about 0.005 S cm-'. Other physical properties of electrolytes useful for providing enhanced performance in electrochemical cells include thermal stability, low viscosity, low melting point, and high boiling point.
[010] The power output of many state of the art lithium cells is currently limited by the conductivity of electrolytes which determines, in part, the internal resistance of these systems. Accordingly, substantial research is currently directed toward developing electrolytes for primary and secondary lithium cells providing large ionic conductivities for accessing higher device performance. A number of strategies have been developed for increasing the ionic conductivities of polar organic solvent based electrolyte systems for primary or secondary lithium batteries. Many of these strategies involve providing additives to the electrolyte to enhance dissolution of a lithium salt while at the same time maintaining chemical and electrochemical stability under discharge and charging conditions.
[011] Anion receptors are a class of compounds that have been recently developed as additives to increase the ionic conductivity of nonaqueous electrolyte solutions (See, e.g., U.S. Pat. Nos. 6,022,643, 6,120,941, and 6,352,798). Anion receptors enhance the ionic disassociation of lithium salts in low dielectric solvents by incorporating non-hydrogen bonded electrophilic groups that participate in complex formation reactions with anions of the lithium salt provided to the electrolyte. Some anion receptor additives have been demonstrated to enhance the dissolution of specific lithium salts in a manner resulting in an increase in solubility by several orders of magnitude. Anion receptor additives encompass a wide range of compounds including fluorinated boron-based anion receptors, such as boranes, boronates and borates having electron withdrawing ligands, polyammonium compounds, guanidiniums, calixarene compounds, and aza-ether compounds. Successful integration of anion receptors in lithium batteries, however, depends on a number of key factors. First, the anion receptor must be stable with respect to electrolyte decomposition under useful discharge and charging conditions. Second, anion receptors should be capable of releasing (or de-complexing) complexed anions so as not to hinder intercalation reactions at the electrodes. Third, Page 4 of 44 the anion receptor itself preferably should not participate in intercalation with the intercalation host material, and if it does participate in such intercalation reactions it should not result in mechanically induced degradation of the electrodes.
[012] Additives have also been developed to impart other useful chemical and physical characteristics to polar organic solvent based electrolytes for lithium cells. U.S.
Patent No. 6,306,540 (Hiroi et al.), for example, provides additives for improving the stability of nonaqueous electrolytes by minimizing gas formation decomposition reactions involving lithium salts and their dissociation products. This reference discloses electrolyte compositions having a LiF additive provided to a solution of LiPF6 in a nonaqueous organic solvent. At least partial dissolution of the LiF
additive generates fluoride ions in the nonaqueous electrolyte which is reported to suppress gas forming decomposition reactions involving PF6- anions. The reference notes, however, that very little fluoride ion is generated in the electrolyte due to the inherently low solubility of LiF in the nonaqueous organic solvents evaluated. The reference reports, for example, that due to the poor solubility of LiF in the electrolytic solution it was difficult to dissolve 0.2% by weight of LiF (- 0.077 M) at room temperature.
Patent No. 6,306,540 (Hiroi et al.), for example, provides additives for improving the stability of nonaqueous electrolytes by minimizing gas formation decomposition reactions involving lithium salts and their dissociation products. This reference discloses electrolyte compositions having a LiF additive provided to a solution of LiPF6 in a nonaqueous organic solvent. At least partial dissolution of the LiF
additive generates fluoride ions in the nonaqueous electrolyte which is reported to suppress gas forming decomposition reactions involving PF6- anions. The reference notes, however, that very little fluoride ion is generated in the electrolyte due to the inherently low solubility of LiF in the nonaqueous organic solvents evaluated. The reference reports, for example, that due to the poor solubility of LiF in the electrolytic solution it was difficult to dissolve 0.2% by weight of LiF (- 0.077 M) at room temperature.
[013] As will be clear from the foregoing, there exists a need in the art for nonaqueous electrolytes exhibiting chemical and physical properties useful for electrochemical conversion and storage systems. Nonaqueous electrolytes are needed that exhibit large ionic conductivities and good stability for use in primary and secondary lithium electrochemical cells. Specifically, a need exists for additives for enhancing the solubility and stability of lithium salts in nonaqueous electrolytes for primary and secondary lithium electrochemical cells.
[014] Further, there exists generally a need in the art for methods providing for enhanced solubility and/or dissolution of fluorides, including inorganic fluorides that typically exhibit very low solubilities in many solvent environments.
Processes and compositions providing enhanced solubility of fluorides are needed to allow new chemistries to take place in the solution phase, including aqueous and nonaqueous phases. A broad range of potential applications exists for methods and compositions for enhancing the solubility of fluorides including surface fluorination, and organic and inorganic fluorination using soft chemistry methods. One example of a class of such reactions involves surface fluorination for the purpose of enhancing corrosion Page 5 of 44 resistance. Sources of solution phase fluoride ions are particularly needed that do involve the use of, or formation of, highly corrosive HF in solution and/or gas phases.
Processes and compositions providing enhanced solubility of fluorides are needed to allow new chemistries to take place in the solution phase, including aqueous and nonaqueous phases. A broad range of potential applications exists for methods and compositions for enhancing the solubility of fluorides including surface fluorination, and organic and inorganic fluorination using soft chemistry methods. One example of a class of such reactions involves surface fluorination for the purpose of enhancing corrosion Page 5 of 44 resistance. Sources of solution phase fluoride ions are particularly needed that do involve the use of, or formation of, highly corrosive HF in solution and/or gas phases.
[015] Table 1 provides a summary of solubility data for a range of inorganic fluorides in water. As shown in Table 1, many solid state inorganic fluorides (MFn), for example CdF2, CoF2, FeF3, MnF2, NaF, NiF2, ZnF2, ZrF4, AIF3, BaF2, CaF2, CuF2, FeF2, InF3, LiF, MgF2, PbF2, SrF2, UF4, VF3-3H20, BiF3, CeF3, CrF2/CrF3, GaF3, LaF3, NdF3, and ThF4, are poorly soluble in water and many organic solvents. Other fluorides, such as CsF, RbF, KF, SbF3 and AgF, readily dissolve into water at the ambient temperatures. When hydrolysis is not a problem, insoluble element fluorides can be prepared as water precipitates by halide metathesis or by the reaction of aqueous hydrofluoric acid with the appropriate element oxide, hydroxide, carbonate or with the element itself. As discussed above, however, the use of hydrofluoric acid has significant drawbacks given its highly corrosive and toxic nature.
[016] Accordingly, the dissolution of insoluble fluorides is currently a great challenge in chemical science and technology. Among other advantages, it can provide fluorine rich solutions for new chemical synthesis through solution reactions or for appropriate physical properties of dissolved fluorinated species. Specifically, methods and compositions providing enhanced solubility of fluorides may provide an important tool for accessing solution phase fluoride compositions useful for solution phase and surface phase synthetic pathways. As discussed above, methods and compositions providing enhanced solubility of fluorides would also enable new electrolyte solutions for many applications, including electrosynthesis, electrodeposition, and electropassivation, and in electrochemical energy storage and conversion systems such as primary and secondary batteries, electrochemical double-layer capacitors and fuel cells.
Page 6 of 44 [017] Table 1: Summary Of Solubility Data For A Range Of Inorganic Fluorides >iL,t;iigin ~'.;~r ~,.iIi?rin ;t0 rr" ru ?er.;r,~;`
<g;eyVe;k j _ tl = i:?F E13 u! . ..
':; iia ~-:r N-A
+iis PiaF 3tt ErFd:`? `.t 72 _r...
YiJ 1F 2..
e?.ri t'%Vcrj s-...
4S ~=~ 02 223_ i:s 7or5 \'.1k :r`.
VS Sa F4 C36 _:
4 G.;a Fe=;: 5~2 ~ 457~_ 1.u_ ~.=`
'JaF 4.?S is,;
s ViF: :E,~
ti Z..-v 1.E15 r:...
.... zr:..? ... li:
Page 6 of 44 [017] Table 1: Summary Of Solubility Data For A Range Of Inorganic Fluorides >iL,t;iigin ~'.;~r ~,.iIi?rin ;t0 rr" ru ?er.;r,~;`
<g;eyVe;k j _ tl = i:?F E13 u! . ..
':; iia ~-:r N-A
+iis PiaF 3tt ErFd:`? `.t 72 _r...
YiJ 1F 2..
e?.ri t'%Vcrj s-...
4S ~=~ 02 223_ i:s 7or5 \'.1k :r`.
VS Sa F4 C36 _:
4 G.;a Fe=;: 5~2 ~ 457~_ 1.u_ ~.=`
'JaF 4.?S is,;
s ViF: :E,~
ti Z..-v 1.E15 r:...
.... zr:..? ... li:
[018]
Page 7 of 44 (Table 1 - continued) ;.'L;; E;3i~
::L3 >_z,F2 lRi~:~
tiFLO .. . U:? ; ti,' 7 4 ;.t~. F_F
uL'1 I:-ir:3 0_.`~
u'Ls 41c>1 35z:
?.LS :i:K,:
.L5 FIL,F 3 61 7 VL.vs Sr~2 i DD i k+'L.Y_i 8F4 '4L
I?;:s0 1 ,'_1e;
:e.=
Nr;:
T:^Fw f~ iD
;{ Fj :1 2u~"sF?
eJ Pd ..=usl ::~s.=u ~:_~=FF
d F4''SFi;, ary:` =
d TeF4 `_iF6 d ':; c-+
Page 7 of 44 (Table 1 - continued) ;.'L;; E;3i~
::L3 >_z,F2 lRi~:~
tiFLO .. . U:? ; ti,' 7 4 ;.t~. F_F
uL'1 I:-ir:3 0_.`~
u'Ls 41c>1 35z:
?.LS :i:K,:
.L5 FIL,F 3 61 7 VL.vs Sr~2 i DD i k+'L.Y_i 8F4 '4L
I?;:s0 1 ,'_1e;
:e.=
Nr;:
T:^Fw f~ iD
;{ Fj :1 2u~"sF?
eJ Pd ..=usl ::~s.=u ~:_~=FF
d F4''SFi;, ary:` =
d TeF4 `_iF6 d ':; c-+
[019]
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[020] The present invention provides compositions, formulations and methods providing for the effective dissolution of inorganic fluorides (i.e., an inorganic salt containing one or more fluoride groups) in solvents via incorporation of a dissociating agent component. Dissociating agents of the present invention participate in chemical reactions in solution, such as complex formation, acid-base reactions and adduct formation reactions, that result in enhancement in the dissolution of inorganic fluorides in a range of solvent environments. Dissociating agents comprising Lewis acids, Lewis bases, anion receptors, cation receptors or combinations thereof are provided that significantly increase the extent of dissolution of a range of inorganic fluorides, particularly inorganic fluorides, such as LiF, that are highly insoluble in many solvents in the absence of the dissociating agents of present invention. The compositions, formulations and methods of the present invention are versatile and, thus, are useful for making solutions containing dissolved inorganic fluorides, including aqueous solutions, nonaqueous organic solutions and nonaqueous inorganic solutions. Dissociating Page 8 of 44 agents, formulations and methods of the present invention are useful for producing fluoride ion rich solutions having selected chemical, electronic and physical properties.
For example, the present invention provides compositions useful for providing solution phase reagents for chemical synthesis applications. Further, the present invention provides compositions useful for in electrochemical conversion and storage systems, electrosynthesis, electrodeposition (electroplating) , electropassivation, electro-etching, and electrochemical detection and analysis, such as enhanced F- ions sensors and specific electrodes applications. The methods and compositions of the present are also useful for sensing systems, including electrochemical sensing systems such as fluoride ion specific electrodes.
For example, the present invention provides compositions useful for providing solution phase reagents for chemical synthesis applications. Further, the present invention provides compositions useful for in electrochemical conversion and storage systems, electrosynthesis, electrodeposition (electroplating) , electropassivation, electro-etching, and electrochemical detection and analysis, such as enhanced F- ions sensors and specific electrodes applications. The methods and compositions of the present are also useful for sensing systems, including electrochemical sensing systems such as fluoride ion specific electrodes.
[021] The present invention also provides a new class of nonaqueous electrolytes for electrochemical devices, particularly for primary and secondary lithium electrochemical cells. Electrolyte formulations of this embodiment provide for effective dissolution of lithium salts having inherently low solubilities in many nonaqueous organic solvents.
This aspect of the present invention provides electrolyte compositions having chemical and physical properties, such as high ionic conductivities, good chemical and electrochemical stability and useful fluoride ion containing solution phase compositions, that are otherwise inaccessible in these systems. Dissociating agents comprising Lewis acids, Lewis bases, anion receptors, cation receptors or combinations thereof are provided in electrolyte formulations of the present invention that significantly increase the extent of dissolution and solubility of lithium salts, such as LiF, in polar nonaqueous organic solvents such as polar carbonates and y-butyrolactone. The present nonaqueous electrolyte compositions and dissociating agents are chemically stable in contact with metallic lithium and also exhibit high voltage stabilities over a useful range of discharge and charging potentials. Nonaqueous electrolytes of the present invention enable primary and secondary electrochemical cells, including primary and secondary lithium batteries, exhibiting advanced performance characteristics relative to conventional systems, including large discharge rates and power output capabilities.
This aspect of the present invention provides electrolyte compositions having chemical and physical properties, such as high ionic conductivities, good chemical and electrochemical stability and useful fluoride ion containing solution phase compositions, that are otherwise inaccessible in these systems. Dissociating agents comprising Lewis acids, Lewis bases, anion receptors, cation receptors or combinations thereof are provided in electrolyte formulations of the present invention that significantly increase the extent of dissolution and solubility of lithium salts, such as LiF, in polar nonaqueous organic solvents such as polar carbonates and y-butyrolactone. The present nonaqueous electrolyte compositions and dissociating agents are chemically stable in contact with metallic lithium and also exhibit high voltage stabilities over a useful range of discharge and charging potentials. Nonaqueous electrolytes of the present invention enable primary and secondary electrochemical cells, including primary and secondary lithium batteries, exhibiting advanced performance characteristics relative to conventional systems, including large discharge rates and power output capabilities.
[022] In an aspect, the present invention provides a solution having a dissociating agent for enhancing dissolution of one or more inorganic fluorides provided to a solvent or combination of solvents. A solution of this aspect of the present invention is a multi-component formulation comprising: (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents; and (iii) one or more inorganic fluorides dissolved in the one or more solvents having the dissociating agent. Useful dissociating agents in Page 9 of 44 this aspect of the present invention include Lewis acids, Lewis bases, anion receptors, cation receptors and combinations of these. This aspect of the present invention further provides methods of dissolving an inorganic fluoride in a solvent or combination of solvents comprising the steps of providing a dissociating agent to the solvent(s) and dissolving the inorganic fluoride into the solvent(s) containing the dissociating agent.
[023] Incorporation of a dissociating agent component in solutions of this aspect of the present invention increases the extent of dissolution of the inorganic fluoride in the solvent(s) by participating in chemical reactions in solution, including complex formation, acid-base reactions and adduct formation reactions, that affect the solubility equilibrium conditions in a manner to provide for dissolution of inorganic fluoride(s). In an embodiment, for example, the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M. For some applications, the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of the inorganic fluoride dissolved in the one or more solvents selected over the range of 0.15 M to 3M, and preferably for particular applications selected over the range of 0.5 M to 1 M. Dissociating agents preferred for some applications exhibit a significant enhancement of the dissolution of the inorganic fluoride on a mole-to-mole basis. In an embodiment, for example, the molar ratio of inorganic fluoride dissolved in the one or more solvents to dissociating agent dissolved in the one or more solvents:
[Inorganic Fluoride I [024] Molar Ratio = dissolved [Dissociating Agent ] dissolved [025] is greater than or equal to 0.1, and preferably for some applications selected over the range of 0.1 to 10.
[026] The present formulations, dissociating agents and methods are applicable to a broad range of inorganic fluorides, particularly those exhibiting low solubilities in pure solvent or solvent combinations. Classes of inorganic fluorides useful in the present solutions, formulations and methods include alkali metal fluorides, alkaline earth metal fluorides, transition metal fluorides and ammonium fluorides. The present invention provides solutions of dissolved fluorides having the formula:
Page 10 of 44 [027] MFn or BFy;
[028] (F1) (F2) [029] wherein M is a metal selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sn Pb, and Sb, and n is the oxidation state of M; and wherein B is a polyatomic cation selected from the group consisting of NH4+ (i.e., ammonium ion) and N(RlR2R3R4)+ (quaternary ammonium), wherein Rl, R2, R3, and R4 are each selected independently from the group consisting of a H atom, an alkyl group, an acetyl group and an aromatic (phenyl) group, and wherein y is the charge state of B. In an embodiment, for example, a solution of the present invention comprises an inorganic fluoride component selected from the group consisting of CdF2, CoF2, FeF3, MnF2, NaF, NiF2, ZnF2, ZrF4, AIF3, BaF2, CaF2, CuF2, FeF2, InF3, LiF, MgF2, PbF2, SrF2, UF4, VF3-3H203 BiF3, CeF3, CrF2/CrF3, GaF3, LaF3, NdF3, ThF4, AgF, CsF, RbF, SbF3, TIF, BeF2, KF, NH4F, SnF2, TaF5, VF4, BF3, BrF, BrF3, BrF5, CoF3, GeF2/GeF4, Hg2F2/HgF2, NbF5, OsF6, PF3/PF5, RhF3, SF4/SF6, SnF4, TeF4, UF6, VF5, and WF6.. In an embodiment, for example, a solution of the present invention comprises an inorganic fluoride component selected from the group consisting of: CdF2, CoF2, FeF3, MnF2, NaF, NiF2, ZnF2, ZrF4, AIF3, BaF2, CaF2, CuF2, FeF2, InF3, LiF, MgF2, PbF2, SrF2, UF4, VF3-3H20, BiF3, CeF3, CrF2/CrF3, GaF3, LaF3, NdF3, and ThF4.
[030] In another aspect, the present invention provides a solution containing one or more dissociating agents having chemical properties specifically tailored for dissolving a LiF salt in a solvent or combination of solvents. In an embodiment, a solution of this aspect comprises: (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents, the dissociating agent comprising one or more compounds selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether;
and (iii) LiF
dissolved in the one or more solvents having the dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M. Specific embodiments of this aspect of the present invention provide for the dissolution of LiF so as to generate a concentration of dissolved LiF in the solvent(s) selected over the range of 0.15 M to 3M, preferably for some applications selected over the range of 0.5 M to 1 M. This aspect of the present invention further provides methods of dissolving LiF in a solvent or combination of solvents comprising the steps of providing a dissociating agent comprising a Lewis acid, a Lewis base, a crown ether or Page 11 of 44 combination of these to the solvent(s) and dissolving the LiF into the solvent(s) containing the dissociating agent.
[031] Selection of the composition and concentration of the dissociating agent determines, at least in part, the composition, chemical properties and/or physical properties of the solutions and formulations of this aspect of the present invention. For example, the composition and concentration of dissociating agents in solutions and methods of the present invention are important parameters for achieving a desired extent of dissolution of an inorganic fluoride such as LiF. Useful dissociating agents in some embodiments include Lewis acids, Lewis bases, anion receptors, cation receptors, complexing agents, adduct formation agents and combinations of these compounds. In some embodiments, the dissociating agent is provided in the one or more solvents at a concentration selected over the range of 0.01 M to 10 M, and preferably for some applications selected over the range of 0.1 M to 5 M, and more preferably for some applications selected over the range of 0.5 M to 1.5 M. Other properties of dissociating agents useful for some embodiments include chemical stability (for example in the presence of lithium metal), electrochemical stability under discharge or charge conditions in an electrochemical cell, low viscosity impact when provided to solution, thermal stability and an enhancement in ionic conductivity when provided to solution. In some embodiments for lithium battery applications, dissociating reagents do not significantly undergo intercalation reactions at the electrodes.
[032] Lewis acids and Lewis bases are a particularly useful class of dissociating agents in the present solutions, formulations and methods. As used herein, the term "Lewis acid" refers to a substance which, in solution, is able to generate a cation or combine with an anion, and/or a molecule which can accept a pair of electrons and form a coordinate covalent bond, and the term "Lewis base" refers to a substance which, in solution, is able to generate an anion or combine with a cation, and/or a molecule or ion that can form a coordinate covalent bond by donating a pair of electrons.
Useful Lewis base or Lewis acid dissociating agents provided to solutions of the present invention include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. In an embodiment, for example, the dissociating agent is one or more Lewis base selected from the group consisting of AIC14 , C104-, SnC162-, BF4 , PF6-, and AsF6 . In an embodiment, for example, the dissociating agent is one or more Lewis acid selected from the group consisting of BF3, PF5, SbF5, AsF5, AIC13, SnC14, FeCl3, NbCI5, TiCl4, and ZnC12.
Page 12 of 44 [033] In an embodiment, a dissociating agent comprising one or more Lewis acid and/or Lewis base is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.5M to 3M. Lewis acids and bases may be provided to solutions of the present invention via providing a precursor compound to the solution. In the context of the description the term "precursor compound" refers to a substance that generates a Lewis acid, Lewis base or both in solution when provided to a solvent or combination of solvents. In an embodiment, for example, the dissociating agent is provided by dissolving a precursor compound in the one or more solvents to generate a Lewis base, a Lewis acid or a combination of a Lewis acid and a Lewis base, wherein the precursor compound comprises an alkali metal salt, alkaline earth metal salt; a transition metal salt, a rare earth metal salt, or an ammonium salt having the formula:
[034] AX:
[035] (F3);
[036] wherein A is selected from the group consisting of a metal, a metal cation and an ammonium group; and wherein X is selected from the group consisting of a fluorinated anion, a perchlorate group, an imide group, a carbide group, a carbonate group, an oxide group and a chloride group. Lithium salts are precursors useful for generating Lewis acids and/or Lewis bases in some solutions and methods of the present invention. Precursor compounds useful in the present solutions, formulations and methods include, but are not limited to, LiPF6, LiBF4, LiAsF6, LiCIO4, LiSnCI5, LiAICl4, LiFeCl4, LiNbCl6, LiTiCI5, LiZnCl3, NaPF6, NaBF4, NaAsF6, NaCIO4, NaSnCI5, NaAICl4, NaFeCl4, NaNbCl6, NaTiCI5, NaZnCl3, KPF6, KBF4, KAsF6, KCIO4, KSnCI5, KAIC14, KFeCl4, KNbCl6, KTiCI5, KZnCl3, NH4PF6, NH4BF4, NH4AsF6, NH4CIO4, NH4SnCI5, NH4AICI4, NH4FeCI4, NH4NbCI6, NH4TiCI5, NH4ZnCI3, N(CH3)4CIO4, N(CH3)4SnCI5, N(CH3)4AIC14, N(CH3)4FeCI4, N(CH3)4NbCI6, N(CH3)4TiCI5, N(CH3)4ZnCI3, N(C2H7)4C104, N(C2H7)4SnCI5, N(C2H7)4AIC14, N(C2H7)4FeCI4, N(C2H7)4NbCI6, N(C2H7)4TiCI5, and N(C2H7)4ZnCI3.
[037] Cation receptors are another particularly useful class of dissociating agents in the present solutions, formulations and methods. As used herein, the term "cation receptor" refers to a molecule or ion which can bind or otherwise take up a cation in solution. Some solutions of the present invention comprise one or more cation receptors selected from the group consisting of a crown ether, a Lewis base, and a Page 13 of 44 cation complexing agent. In an embodiment, a dissociating agent comprising one or more cation receptor is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.3M to 5M.
[038] Crown ethers are a class of cation receptor exhibiting chemical and physical properties beneficial for enhancing the dissolution of inorganic fluorides, including LiF.
These compounds are useful for complexing with metal ions in solution. Crown ether cation receptors useful in the present invention include, but are not limited to, Benzo-15-crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-1 5-crown-5, Dibenzo-1 8-crown-6, Dicyclohexyl-1 8-crown-6, Di-t-butyldibenzo-1 8-crown-6, 4,4i (5i )-Di-tert-butyldibenzo-24-crown-8, 4-Aminobenzo-15-Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert-Butylbenzo-15-crown-5, 4-tert-Butylcyclohexano-15-crown-5, 18-Crown-6, Cyclohexano-15-crown-5, Di-2,3-naphtho-30-crown-10, 4,4'(5')-Di-tert-butyldibenzo18-crown-6, 4'-(5')-Di-tert-butyldicyclohexano-18-crown-6, 4,4'(5')-Di-tert-butyldicyclohexano-24-crown-8, 4,10-Diaza-15-crown-5, Dibenzo-1 8-crown-6, Dibenzo-21 -crown-7, Dibenzo-24-crown-8, Dibenzo-30-crown-10, Dicyclohexano-18-crown-6, Dicyclohexano-21-crown-7,Dicyclohexano-24-crown-8, 2,6-Diketo-18-crown-6, 2,3-Naphtho-15-crown-5, 4'-Nitrobenzo-15-crown-5, Tetraaza-12-crown-4 tetrahydrochloride, Tetraaza-12-crown-4 tetrahydrogen sulfate, 1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane, 12-crown-4, 15-crown-5, and 21-crown-7. In an embodiment, a crown ether dissociating agent is provided to the solvent at a concentration in the solution selected over the range of 0.1 M
to 10M, a preferably for some applications selected over the range of 0.5M to 3M.
[039] Anion receptors are another particularly useful class of dissociating agents in the present solutions, formulations and methods. As used herein, the term anion receptor refers to a molecule or ion which can bind or otherwise take up an anion in solution. Anion receptors useful in the present solutions, formulations and methods include, but are not limited to fluorinated and semifluorinated borate compounds, fluorinated and semifluorinated boronate compounds, fluorinated and semifluorinated boranes, phenyl boron compounds, aza-ether boron compounds, Lewis acids, cyclic polyammonium compounds, guanidinium compounds, calixarene compounds, aza-ether compounds, quaternary ammonium compounds, amines, imidazolinium based receptors, mercury metallacycle compounds, silicon containing cages, and macrocycles. In an embodiment, a dissociating agent comprising one or more anion Page 14 of 44 receptor is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.5M to 3M.
[040] Examples of calixarene compounds include cobaltocenium-based receptors, ferrocene-based receptors, rr-metallated cationic hosts, calix[4]arenes, and calix[6]arenes. Examples of aza-ether anion receptors include linear aza-ethers, multi-branched aza-ethers, and cyclic aza-crown ethers. Examples of mercury metallacycle anion receptors include mercuracarborands and perfluoro-o-phenylenemercury metallacycles. Examples of anion receiving silicon-containing cages and macrocycles includes silsesquioxane cages and crown silanes. Other examples of useful anion receptors can generally be found in the art [See, e.g., Dietrich, Pure & Appl.
Chem., Vol 65, No. 7, pp. 1457-1464, 1993; U.S. Pat. No. 5,705,689; U.S. Pat. No.
6,120,941;
Matthews and Beer, Calixarene Anion Receptors, in Calixarenes 2001, pp. 421-439, Kluwer Academic Publishers, The Netherlands; Rodionov, State of the Art in Anion Receptor Design, American Chemical Society Division of Organic Chemistry Fellowship Awardee Essay 2005-2006; H.S. Lee, X.Q. Yang, C.L. Xiang, J. McBreen, L.S.
Choi, "The Synthesis of a New Family of Boron-Based Anion Receptors and the Study of Their Effect on Ion Pair Dissociation and Conductivily of Lithium Salts in Nonaqueous Solutions", J. Electrochem. Soc., Vol. 145, No. 8, August 1998; H.S. Lee, Z.F.
Ma, X.Q.
Yang, X. Sun and J. McBreen, "Synthesis of a Series of Fluorinated Boronate Compounds and Their Use as Additives in Lithium Battery Electrolytes", Journal of The Electrochemical Society, 151 (9) A1429-A1435 (2004); and X. Sun, H.S. Lee, S.
Lee, X.Q. Yang and J. Mc Breen, "A Novel Lithium Battery Electrolyte Based on Lithium Fluoride and a Tris(pentafluorophenyl) Borane Anion Receptor in DME"
Electrochemical and Solid-State Letters, 1(6) 239-240 (1998), all of which are incorporated by reference to the extent not inconsistent with the present description..
[041] Solutions, formulations, and methods of the present invention are compatible with a range of solvents, including water, nonaqueous organic solvents and nonaqueous inorganic solvents. In some embodiments useful for providing electrolytes for electrochemical cells, such as lithium electrochemical cells, the solvent(s) comprises one or more polar nonaqueous solvents, such as linear and cyclic esters, linear and cyclic ethers and polar carbonates. Electrolytes of the present invention may comprise a single nonaqueous solvent or a combination of nonaqueous solvents provided in relative proportions useful for a given electrochemical device or application.
The composition of nonaqueous solvents in some embodiments of the present invention is Page 15 of 44 selected to provide electrolyte formulations having desired physical, electronic and chemical properties, such as ionic conductivities, viscosities, melting points, freezing points and stability with respect to electrolytic decomposition and/or reaction with lithium metal. Useful solvents in the present invention include, but are not limited to, one or more of y-butyrolactone, propylene carbonate, dimethyl carbonate, ethylene carbonate, acetonitrile, 1,2, -dimethoxy ethane, N,N-dimethyl formamide, dimethyl sulfoxide, 1,3-diolane, methyl formate, nitromethane, phosphoroxichloride, thionylchloride, sulfurylchloride, diethyl ether, diethoxy ethane, 1,3 -dioxolane, tetrahydrofuran, 2-methyl-THF, diethyl carbonate, ethyl methyl carbonate, methylacetate and tratahydrofurane.
[042] In another aspect, solutions and formulations of the present invention provide electrolyte compositions useful for electrochemical storage and conversion applications.
In these embodiments, inorganic fluoride, dissociating agent and solvent components are selected to provide solution properties useful for a target electrochemical device application. In some embodiments of this aspect, for example, the composition of solution components of an electrolyte are selected to establish useful chemical and physical properties, such as large ionic conductivities, and enhanced solubility for solutions containing inorganic fluorides that are relatively insoluble in pure nonaqueous organic solvents. The present invention includes electrolytes, including nonaqueous electrolytes, exhibiting a high degree of chemical and electrochemical stability. In an embodiment, for example, an electrolyte of the present invention has a high voltage stability window over 5V vs. Li+ /Li. In another embodiment, electrolyte formulations of the present invention are stable with respect to contact with Li metal under discharge or charging conditions. A electrolyte of the present invention has an ionic conductivity at 25 degrees Celsius greater than or equal to 10-4 S cm-', preferably for some applications greater than or equal to 10-3 S cm-', and more preferably for some applications greater than or equal to 5 x 10-3 S cm-'. A nonaqueous electrolyte of the present invention has a viscosity at 25 degrees Celsius less than or equal to 5 cP, more preferably for some applications less than or equal to 3 cP.
[043] Although the present invention encompasses electrolytes comprising a broad range of inorganic fluorides, a preferred class of electrolytes for lithium electrochemical cells comprises LiF and a dissociating agent provided in one or more nonaqueous organic solvents. In this aspect, the present invention provides electrolyte formulations having an inorganic fluoride component comprising LiF salt and a dissociating agent Page 16 of 44 capable of significantly enhancing the dissociation and solubility of LiF in organic solvent(s). Embodiments of this aspect are particularly useful for electrolytes of electrochemical cells because F is the most electronegative element and Li is the most electropositive element. Therefore, electrolytes of the present invention comprising LiF
are particularly attractive for providing electrochemical cells having enhanced cell voltages and specific capacities relative to conventional lithium electrochemical cells.
Dissociating agents of the present invention are capable of increasing the conductivity of LiF in a selected nonaqueous organic solvent or combination of nonaqueous organic solvents, at 25 C, to a value equal to or greater than 10-4 S cm-', preferably equal to or greater 5 x 10-4 S cm-', and more preferably equal to or greater 10-3 S cm-'.
In an embodiment, dissociating agents of the present invention increase the solubility of LiF in a selected nonaqueous organic solvent (or combination of solvents) from a low value (e.g., on the order of micromolar) to 0.1 M or greater, preferably 0.5 M or greater, and preferably 1 M or greater. In an embodiment, LiF solubility at a temperature of about 25 C in an electrolyte of the present invention is increased by addition of a dissociating agent to a value greater than about 0.1 M, including between about 0.1 M to 5 M, and between about 1 M to 2 M.
[044] The present invention includes electrochemical devices comprising the present electrolytes, such as nonaqueous electrolytes, including, but not limited to, primary electrochemical cells, secondary electrochemical cells, capacitors, supercapacitors and fuel cells. In addition, the solutions, dissociating agents and methods of the present invention are also useful for sensing systems, including electrochemical sensing systems. Solutions and dissociating agents of the present invention, for example, are useful for reducing interference and enhancing the selectivity of fluoride ion specific electrodes. In an embodiment, the present invention provides an electrochemical cell comprising: (i) a positive electrode; (ii) a negative electrode; and (iii) an electrolyte of the present invention provided between the positive electrode and the negative electrode.
As will be appreciated by those having skill in the art of electrochemistry, electrolytes useful in electrochemical devices of the present invention include those provided throughout the present description. In an embodiment, an electrolyte of an electrochemical device of the present invention comprises (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents; and (iii) an inorganic fluoride dissolved in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate Page 17 of 44 a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M.
[045] As will be appreciate by those of skill in the art a wide range of electrode materials and configurations can be used in electrochemical devices of the present invention, including metallic and semiconducting materials. Use of nanostructured and/or intercalating electrodes is useful for some applications. In an embodiment, the negative electrode comprises lithium metal, a carbonaceous material, such as graphite, coke, multiwalled carbon nanotubes, multi-layered carbon nanofibers, multi-layered carbon nanoparticles, carbon nanowhiskers and carbon nanorods having lithium storage capability or a lithium metal alloy. In an embodiment, the positive electrode comprises a carbonaceous material, such as graphite, coke, multiwalled carbon nanotubes, multi-layered carbon nanofibers, multi-layered carbon nanoparticles, carbon nanowhiskers and carbon nanorods having fluoride ion storage capability. In an embodiment, positive electrode comprises a carbonaceous material comprises a subfluorinated carbonaceous material having an average stoichiometry CFX, wherein x is the average atomic ratio of fluorine atoms to carbon atoms and is selected from the range of about 0.3 to about 1.0;
the subfluorinated carbonaceous material being a multiphase material having an unfluorinated carbon component. In an embodiment, positive electrode comprises a fluorinated element such a transition metal or a rare earth metal having reversible fluorine ion storage capability.
[046] Solutions, dissociating agents and methods of the present invention providing enhanced solubility of fluorides have significant applications in addition to their use as electrolytes in electrochemical devices and systems. The compositions and methods of the present invention are beneficial for accessing solution phase compositions and properties (e.g., chemical, physical and/or electrochemical) useful for enabling a broad class of surface phase and solution synthetic pathways and other processes.
Fluoride containing solutions of the present invention, for example, may provide solution phase reagents for important synthetic chemistries, including organic and inorganic fluorination, for example by soft chemistry methods, and surface fluorination reactions.
Fluoride containing solutions of the present invention may also be useful for accessing solution properties (e.g., ionic conductivities, ionic strength, etc.) critical for accessing important solution phase processes, including electrosynthesis, electrodeposition, and electropassivation.
Page 18 of 44 [047] In another aspect, the present invention provides a method for dissolving an inorganic fluoride in one or more solvents comprising the steps of: (i) providing the one or more solvents; (ii) providing a dissociating agent to the one or more solvents; and (iii) dissolving the inorganic fluoride in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M, thereby dissolving the inorganic fluoride into the one or more solvents.
[048] In another aspect, the present invention provides a method for dissolving LiF in one or more solvents, comprising the steps of: (i) providing the one or more solvents; (ii) providing a dissociating agent to the one or more solvents, the dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and dissolving LiF in the one or more solvents having the dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M, and optionally greater than or equal to 0.5M.
[049] In another aspect, the present invention provides a method of making an electrolyte for an electrochemical device, the method comprising the steps of:
(i) providing one or more solvents; (ii) providing a dissociating agent to the one or more solvents; and (iii) dissolving an inorganic fluoride in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M, thereby making the electrolyte for the electrochemical device.
[050] In another aspect, the present invention provides a method of making an electrolyte for an electrochemical device, the method comprising the steps of:
(i) providing one or more solvents; (ii) providing a dissociating agent to the one or more solvents, the dissociating agent comprising one or more compounds selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and (iii) dissolving LiF in the one or more solvents having the dissociating agent, thereby making the electrolyte for the electrochemical device.
[051] In another aspect, the present invention provides a solution having LiF
dissolved in one or more solvents, said solution comprising: (i) said one or more Page 19 of 44 solvents; and (ii) LiF dissolved in said one or more solvents; wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
[052] Without wishing to be bound by any particular theory, there can be discussion herein of beliefs or understandings of underlying principles relating to the invention. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.
BRIEF DESCRIPTION OF THE DRAWINGS
[053] Figure 1. Comparative (normalized) discharge profile of Li/electrolyte/graphite-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M
LiPF6 solution in EC-DMC.
[054] Figure 2. Shows the cyclic voltammogram obtained with the LiF containing electrolyte cell between 2.1 and 4.8V under 15mV/mn sweeping rate. It shows oxidation and reduction peaks corresponding to negatively charged species intercalation and de-intercalation into graphite.
[055] Figure 3. Comparative (normalized) discharge profile of Li/electrolyte/graphite fluoride (CFo.53)-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF6 solution in EC-DMC.
[056] Figure 4 depicts the current provided by the cell containing LiPF6 during a charge/discharge cycle.
[057] Figure 5 depicts the current provided by the cell containing LiF and 12-crown-4 during a charge/discharge cycle.
DETAILED DESCRIPTION OF THE INVENTION
[058] Referring to the drawings, like numerals indicate like elements and the same number appearing in more than one drawing refers to the same element. In general the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the invention.
Page 20 of 44 [059] "Standard electrode potential" (E ) refers to the electrode potential when concentrations of solutes are 1 M, the gas pressures are 1 atm and the temperature is 25 degrees Celsius. As used herein standard electrode potentials are measured relative to a standard hydrogen electrode.
[060] "Intercalation" refers to refers to the process wherein an ion inserts into a host material to generate an intercalation compound via a host/guest solid state redox reaction involving electrochemical charge transfer processes coupled with insertion of mobile guest ions, such as fluoride ions. Major structural features of the host material are preserved after insertion of the guest ions via intercalation. In some host materials, intercalation refers to a process wherein guest ions are taken up with interlayer gaps (e.g., galleries) of a layered host material. Examples of intercalation compounds include fluoride ion intercalation compounds wherein fluoride ions are inserted into a host material, such as a layered fluoride host material or carbon host material.
Host materials useful for forming intercalation compounds for electrodes of the present invention include, but are not limited to, CFX, FeFx, MnFx, NiFx, CoFx, LiC6, LixSi, and LixGe.
[061] The term "electrochemical cell" refers to devices and/or device components that convert chemical energy into electrical energy or electrical energy into chemical energy.
Electrochemical cells have two or more electrodes (e.g., positive and negative electrodes) and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes. Electrochemical cells include, but are not limited to, primary batteries, secondary batteries and electrolysis systems.
General cell and/or battery construction is known in the art, see e.g., U.S. Pat. Nos.
6,489,055, 4,052,539, 6,306,540, Seel and Dahn J. Electrochem. Soc. 147(3) 892-898 (2000).
[062] The term "capacity" is a characteristic of an electrochemical cell that refers to the total amount of electrical charge an electrochemical cell, such as a battery, is able to hold. Capacity is typically expressed in units of ampere-hours. The term "specific capacity" refers to the capacity output of an electrochemical cell, such as a battery, per unit weight. Specific capacity is typically expressed in units of ampere-hours kg-'.
[063] The term "discharge rate" refers to the current at which an electrochemical cell is discharged. Discharge current can be expressed in units of ampere-hours.
Alternatively, discharge current can be normalized to the rated capacity of the electrochemical cell, and expressed as C/(X t), wherein C is the capacity of the Page 21 of 44 electrochemical cell, X is a variable and t is a specified unit of time, as used herein, equal to 1 hour.
[064] "Current density" refers to the current flowing per unit electrode area.
[065] The term "open circuit voltage" refers to the difference in potential between terminals (i.e. electrodes) of an electrochemical cell when the circuit is open (i.e. no load conditions). Under certain conditions the open circuit voltage can be used to estimate the composition of an electrochemical cell. The present methods and system utilize measurements of open circuit voltage for thermochemically stabilized conditions of an electrochemical cell to determine thermodynamic parameters, materials properties and electrochemical properties of electrodes, electrochemical cells and electrochemical systems.
[066] The expression "state of charge" is a characteristic of an electrochemical cell or component thereof (e.g. electrode - cathode and/or anode) referring to its available capacity, such as a battery, expressed as a percentage of its rated capacity.
[067] Electrode refers to an electrical conductor where ions and electrons are exchanged with electrolyte and an outer circuit. "Positive electrode" and "cathode" are used synonymously in the present description and refer to the electrode having the higher electrode potential in an electrochemical cell (i.e. higher than the negative electrode). "Negative electrode" and "anode" are used synonymously in the present description and refer to the electrode having the lower electrode potential in an electrochemical cell (i.e. lower than the positive electrode). Cathodic reduction refers to a gain of electron(s) of a chemical species, and anodic oxidation refers to the loss of electron(s) of a chemical species. Positive electrodes and negative electrodes of the present electrochemical cell may further comprise a conductive diluent, such as acetylene black, carbon black, powdered graphite, coke, carbon fiber, and metallic powder, and/or may further comprises a binder, such as a polymer binder.
Useful binders for positive electrodes in some embodiments comprise a fluoropolymer such as polyvinylidene fluoride (PVDF). Positive and negative electrodes of the present invention may be provided in a range of useful configurations and form factors as known in the art of electrochemistry and battery science, including thin electrode designs, such as thin film electrode configurations. Electrodes are manufactured as disclosed herein and as known in the art, including as disclosed in, for example, U.S. Pat.
Nos.
4,052,539, 6,306,540, 6,852,446. For some embodiments, the electrode is typically Page 22 of 44 fabricated by depositing a slurry of the electrode material, an electrically conductive inert material, the binder, and a liquid carrier on the electrode current collector, and then evaporating the carrier to leave a coherent mass in electrical contact with the current collector.
[068] "Electrode potential" refers to a voltage, usually measured against a reference electrode, due to the presence within or in contact with the electrode of chemical species at different oxidation (valence) states.
[069] "Electrolyte" refers to an ionic conductor which can be in the solid state, the liquid state (most common) or more rarely a gas (e.g., plasma). In the context of an electrochemical cell, the electrolyte provides ionic conductivity between two or more electrodes of an electrochemical cell.
[070] "Cation" refers to a positively charged ion, and "anion" refers to a negatively charged ion.
[071] "Lewis acid" refers to a substance which, in solution, is able to generate a cation or combine with an anion, and/or a molecule which can accept a pair of electrons and form a coordinate covalent bond. Useful classes of Lewis acids include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. Examples of inorganic fluoride Lewis acids are BF3, PF5, SbF5, and AsF5.
Examples of inorganic chloride Lewis acids are AIC13, SnCl4, FeCl3, NbCI5, TiCl4, and ZnCl2.
[072] "Lewis base" refers to a substance which, in solution, is able to generate an anion or combine with a cation, and/or a molecule or ion that can form a coordinate covalent bond by donating a pair of electrons. Useful classes of Lewis bases include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. Examples of inorganic chloride Lewis bases are AIC14 , C104-, and SnC162-. Examples of inorganic fluoride Lewis bases are BF4 , PF6-, and AsF6 .
[073] "Lewis acid precursor" or "precursor" and "Lewis base precursor" or "precursor"
refers to a substance which is able to generate Lewis acids and/or Lewis bases when introduced into a solvent and/or solution. Examples of Lewis acid/base precursors are LiPF6, LiBF4, LiAsF6, LiCIO4, LiSnCI5, LiAICl4, LiFeCl4, LiNbCl6, LiTiCI5, LiZnCl3, NaPF6, NaBF4, NaAsF6, NaCIO4, NaSnCI5, NaAICl4, NaFeCl4, NaNbCl6, NaTiCI5, NaZnCl3, KPF6, KBF4, KAsF6, KCIO4, KSnCI5, KAICI4, KFeCl4, KNbCl6, KTiCI5, KZnCl3, NH4PF6, Page 23 of 44 NH4BF4, NH4AsF6, NH4CIO4, NH4SnCI5, NH4AICI4, NH4FeCI4, NH4NbCI6, NH4TiCI5, and NH4ZnCI3 and others.
[074] "Anion receptor" refers to a molecule or ion which can bind or otherwise take up an anion. Useful classes of anion receptors include, but are not limited to, fluorinated and semifluorinated borate compounds, fluorinated and semifluorinated boronate compounds, fluorinated and semifluorinated boranes, Lewis acids, cyclic polyammonium compounds, guanidiniums, calixarene compounds, aza-ether compounds, quaternary ammonium, amine, and imidazolinium based receptors, mercury metallacycles, and silicon containing cages and macrocycles. Examples of cyclic polyammonium anion receptors include polyammonium macrocycles, polyammonium macrobicycles, polyammonium macrotricycles, azacrown compounds, protonated tetra-, penta- and hexaamines. Examples of calixarene compounds include cobaltocenium-based receptors, ferrocene-based receptors, Tr-metallated cationic hosts, calix[4]arenes, and calix[6]arenes. Examples of aza-ether anion receptors include linear aza-ethers, multi-branched aza-ethers, and cyclic aza-crown ethers. Examples of mercury metallacycle anion receptors include mercuracarborands and perfluoro-o-phenylenemercury metallacycles. Examples of anion receiving silicon-containing cages and macrocycles include silsesquioxane cages and crown silanes. Other examples of useful anion receptors can generally be found in the art [See, e.g., Dietrich, Pure & Appl.
Chem., Vol 65, No. 7, pp. 1457-1464, 1993; U.S. Pat. No. 5,705,689; U.S. Pat. No.
6,120,941;
Matthews and Beer, Calixarene Anion Receptors, in Calixarenes 2001, pp. 421-439, Kluwer Academic Publishers, The Netherlands; Rodionov, State of the Art in Anion Receptor Design, American Chemical Society Division of Organic Chemistry Fellowship Awardee Essay 2005-2006; H.S. Lee, X.Q. Yang, C.L. Xiang, J. McBreen, L.S.
Choi, "The Synthesis of a New Family of Boron-Based Anion Receptors and the Study of Their Effect on Ion Pair Dissociation and Conductivily of Lithium Salts in Nonaqueous Solutions", J. Electrochem. Soc., Vol. 145, No. 8, August 1998; H.S. Lee, Z.F.
Ma, X.Q.
Yang, X. Sun and J. McBreen, "Synthesis of a Series of Fluorinated Boronate Compounds and Their Use as Additives in Lithium Battery Electrolytes", Journal of The Electrochemical Society, 151 (9) A1429-A1435 (2004); and X. Sun, H.S. Lee, S.
Lee, X.Q. Yang and J. Mc Breen, "A Novel Lithium Battery Electrolyte Based on Lithium Fluoride and a Tris(pentafluorophenyl) Borane Anion Receptor in DME"
Electrochemical and Solid-State Letters, 1(6) 239-240 (1998).
Page 24 of 44 [075] "Cation receptor" refers to a molecule or ion which can bind or otherwise take up a cation. Useful classes of cation receptors include, but are not limited to, crown ethers, Lewis bases, and other cation complexing agents. Examples of crown ether cation receptors include, but are not limited to, Benzo-15-crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-15-crown-5, Dibenzo-18-crown-6, Dicyclohexyl-18-crown-6, Di-t-butyldibenzo-18-crown-6, 4,4i (5i )-Di-tert-butyldibenzo-24-crown-8, 4-Aminobenzo-15-Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert-Butylbenzo-15-crown-5, 4-tert-Butylcyclohexano-15-crown-5, 18-Crown-6, Cyclohexano-15-crown-5, Di-2,3-naphtho-30-crown-10, 4,4'(5')-Di-tert-butyldibenzo18-crown-6, 4'-(5')-Di-tert-butyldicyclohexano-18-crown-6, 4,4'(5')-Di-tert-butyldicyclohexano-24-crown-8, 4,10-Diaza-15-crown-5, Dibenzo-18-crown-6, Dibenzo-21-crown-7, Dibenzo-24-crown-8, Dibenzo-30-crown-10, Dicyclohexano-18-crown-6, D icycloh exa no-21 -crown -7, D icycloh exa no-24-crown -8, 2,6-Diketo-18-crown-6, 2,3-Naphtho-15-crown-5, 4'-Nitrobenzo-15-crown-5, Tetraaza-crown-4 tetrahydrochloride, Tetraaza-12-crown-4 tetrahydrogen sulfate, 1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane, 12-crown-4, 15-crown-5, and 21-crown-7.
[076] "Dissociating agent" and "dissociation agent" are used synonymously and refer to a compound added to a solution, solvent, and/or electrolyte to increase the solubility and/or dissolution of a salt. Dissociating agents of the present invention are useful for increasing the dissolution of inorganic fluorides, particularly inorganic fluorides, generally regarded to be relatively insoluble, such as LiF.
[077] The present invention provides methods for generating solutions containing large concentrations of dissolved fluoride salts which are generally regarded as insoluble. In another aspect, the present invention provides solutions, solvents, and electrolytes containing large concentrations of dissolved fluoride salts which are generally regarded as insoluble. In an embodiment, compounds are provided to the solutions, solvents, and electrolytes which facilitate dissolution of the fluoride salts.
These compounds can be regarded as dissolution, dissolving, dissociating, or dissociation agents, since they provide a means for dissolving normally insoluble compounds. In an embodiment, the fluoride salts are present as solutes in solution at concentrations much larger than that which occurs at a natural equilibrium in a solution that does not contain the dissociating agents. In an embodiment, the fluoride salts are a minor solute component. In another embodiment, the fluoride salts are the most abundant solute present in the solution, solvent, or electrolyte.
Page 25 of 44 [078] The present invention provides additives and methods for dissolving element fluorides (MFn) such as LiF. In an embodiment, for example, organic solutions of lithium salts (LiX), such as LiPF6, LiBF4, LiAsF6 and LiCIO4, in carbonate or gamma butyro-lactone (y-BL) based liquid solvents dissolve a significant amount LiF, whereas, the same solvents without the presence of the LiX salt do not appreciably dissolve LiF. The present methods apply to a variety of other insoluble fluorides (MFn) thus providing a large range of `complex-type' solutions of MFn + AX, A=alkali metal or NH4, and X=fluorinated anion, perchlorate, imide, carbide. Compositions of the present invention also provide a new family of electrolytes for lithium batteries applications containing LiF
dissolved at significant solubilities in nonaqueous organic solvents.
Example 1: Electrolytes and Dissociating Agents for Electrochemical Cells [079] To demonstrate the chemical properties and utility of the present additives, compositions, formulations and methods, electrolytes of the present invention were prepared and integrated into lithium electrochemical cells. The electrolytes evaluated comprise LiF and an appropriate dissociating agent dissolved in a selected nonaqueous organic solvent or combination of nonaqueous organic solvents. The electronic performance of the electrochemical cells was evaluated to demonstrate the beneficial chemical and physical properties of electrolytes of the present invention.
[080] 1. Preparation of the mother solutions: 1 M solutions of LiPF6 in EC-DMC
and of LiBF4 in y-BL and of LiAsF6 and of LiCIO4 in PC were prepared in a dry box filled with argon. (EC=ethylene carbonate, DMC=dimethyl carbonate and PC=propylene carbonate). These solutions are called `mother solutions' throughout this description.
[081] 2. Dissolving LiF in mother solutions: In a dry box filled with argon, a sample of 5 milliliters (5x10-3 mole of LiX) was taken from each of the above described mother solutions and 65 milligrams (2.5x10-3 mole) of LiF was added to it. The solution was stirred magnetically until full dissolution of LiF occurred, i.e., the solution becomes clear.
The molar ratio LiF/LiX in these solutions is 0.5, with an absolute LiF
concentration of 0.5 M.
[082] 3. Electrochemical tests: Coin cells were created in a dry box, consisting of a metallic lithium disc (negative pole), a polypropylene microporous separator wet with `electrolyte', and a composite electrode (positive pole). Two types of composite cathode electrodes were used: a graphite based electrode and a graphite fluoride based Page 26 of 44 electrode. The `electrolyte' is either the LiPF6 in EC-DMC mother solution or the LiF
dissolved in LiPF6 in EC-DMC mother solution.
[083] 3a)graphite based cells: The cells were first discharged under a constant current of 10 mA/g-graphite to 250 mV. The 250 mV vs. Li+/Li Potential was chosen between that of the first passivation (solid electrolyte interphase: SEI
formation usually at >500 mV vs. Li+/Li) and that of the lithium intercalation (usually at <200 mV vs. Li+/Li).
The cells were then charged to 5V vs. Li+/Li under the same 10 mA/g-graphite rate. A
constant 5V was then applied for several hours to further charge. The cells were then allowed to rest for several hours and were then discharged to 3V under the same 10 mA/g-graphite rate. Following this, the cells were cycled between 3V and 5V
several times under the same procedure described above.
[084] Linear voltammetry under a 15mV/min sweeping rate was also performed on the cell with LiF containing electrolyte in the 2.1-4.8V voltage window.
[085] 3b) graphite fluoride based cells: The CFX material tested here is CF0.53 obtained from graphite. The cells were discharged to different depths of discharge (DOD=10, 20, 30,...100%) under constant current (C/20 rate: i.e., 32.1 mA/g-CFo.53).
The cells were then charged to 4.8V and to 5.OV and allowed to rest for several hours the same constant voltage was applied ( 4.8 or 5.OV) for several hours to further charge.
After this, the cells were discharged to 3V and then recharged to 4.8 V or 5.0 V following the same procedure described above.
[086] 4. Results:
4a) Graphite based electrodes: Figure 1 provides a comparative (normalized) discharge profile of Li/electrolyte/graphite-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF6 solution in EC-DMC. Figure 1 shows the voltage versus discharge/charge ratio of the graphite based cells using mother solution electrolyte (no LiF) and LiF dissolved in mother electrolyte (LiF) with charge voltage up to 4.8V. These results indicate that the LiF containing electrolyte has a higher discharge voltage and relative capacity than the non LiF containing electrolyte.
[087] Figure 2 shows a cyclic voltammogram obtained with the Li/0.5M LiF+1 M
LiPF6 in EC-DMC/graphite cell, obtained between 2.1 and 4.8 V under a 15mV/min sweeping rate. Visible in Figure 2 are oxidation and reduction peaks corresponding to the intercalation and de-intercalation of the negatively charged species into graphite. These Page 27 of 44 positive current (oxidation) peaks and negative current peaks (reduction) peaks correspond to reversible charging and discharging of the cell. The peaks may be associated with negatively charged species (or anions) intercalation and de-intercalation, respectively.
[088] 4b) Graphite fluoride based electrodes: Figure 3 provides a comparative (normalized) discharge profile of Li/electrolyte/graphite fluoride (CFo.53)-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF6 solution in EC-DMC. Figure 3 shows the voltage versus discharge/charge capacity ratio of the graphite fluoride (CFo.53) based cells using mother solution electrolyte (no LiF) and LiF dissolved in mother electrolyte (LiF) with charge voltage up to 4.8V. These results indicate that the LiF containing electrolyte has a higher discharge voltage and relative capacity than the non-LiF containing electrolyte.
[089] 5. Conclusions: New electrolyte solutions based on element fluoride LiF
were successfully prepared. The solutions are light transparent and stable under an argon atmosphere. Dissolution of LiF was achieved in different organic liquid media comprised of polar solvents chosen among carbonates such as EC, DMC, PC or y-butyrolactone and containing a dissolved lithium salt such as LiPF6, LiBF4, LiAsF6 and LiCIO4. Electrolyte solutions with LiF have a high voltage stability window over 5V vs.
Li+/Li. They are also stable in contact with metallic lithium. LiF containing electrolyte solutions show enhanced electrochemical performances of electrode materials for batteries applications such as those based on pure graphite or graphite fluoride positive electrodes. Dissolution of many insoluble element fluorides can be achieved using the same principle of `mother solution' electrolytes.
Example 2: Comparison of fluorinated carbon electrode lithium half-cells with and without LiF
[090] Two fluorinated carbon electrode (CFo.125) lithium half cells were prepared. One cell contained an electrolyte of 1 M LiPF6 in propylene carbonate (PC); the other cell contained an electrolyte of 1 M LiF and 1 M 12-crown-4 in PC. The crown ether acts as a cation receptor to allow LiF to dissolve in the PC. The cells were cycled between about 3.2V and 5.5V at a rate of 1 mV/s.
Page 28 of 44 [091] Figure 4 depicts the current provided by the cell containing LiPF6 during a charge/discharge cycle and shows no clear oxidation or reduction peaks. This cell has a much higher charge capacity than discharge, indicating a large irreversibility.
[092] Figure 5 depicts the current provided by the cell containing LiF during a charge/discharge cycle and shows oxidation peaks at about 3.6V and 4.15V and a reduction peak at about 4 V. This cell has similar charge and discharge capacities, indicating good reversibility.
[093] These results indicate that the presence of dissolved LiF makes fluorinated carbon a suitable cathode for high voltage, high cycleability, rechargeable, fluoride ion batteries, since F- is able to reversibly intercalate into a fluorinated carbon cathode.
[094] Example 3: Fluoride Solutions having Dissociating Agents [095] Table 2 provides a summary of experimental conditions useful for making fluorides solutions of the present invention from a variety of fluoride salts, including NH4F, NaF, KF, MgF2 and AIF3.
Page 29 of 44 [096] Table 2: Example Fluoride Solutions :=:t F_.'~: ` r~o~:- ~zhrr :3.:,;c:, r~>_s~~;
W 4i= 5 is solaed i>g FC, \c; in <NH':JF 31:s :.'., t~N}'c tiHa:- w7-= S.2g Lt ;a,^^.
SS:F'2~ C:v=rr91`JI`i;3'?2tu\:?
fiaF \ [Yl:aaCt:Ved wi3s 3i.`::'vd axas zS sc:r=
M~Ii. .t<e,_ a:r,l := _ tz' vnhri -&. ~ tz:zr; salwi;~^
F :C CYI3Sq:SE.C:
31Td 4 18_ i.1RPr21,:R!i~
~h: 7~=.".:. -1e So:itil=cr'i R?F2 ; :s,06~E1":l`eb_lv cobr ai,~\::JS{ Y.
, ... t.'~.'.C~PI1E47 y,;
~.=cr3ryz :tr}S :E;:=1JZiA'2 in =,r~;;:=ti:. 0. -3: .=2, avxi=
ns:\eci ,a:h ?he cc:?;;hm =:;'3 3A~ zl> ri;
a,}`;:
[097]
STATEMENTS REGARDING INCORPORATION BY REFERENCE
AND VARIATIONS
[098] All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).
[099] The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such Page 30 of 44 terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices, device components, methods steps set forth in the present description. As will be obvious to one of skill in the art, methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps.
[0100] When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of the group members, are disclosed separately.
When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. Additionally, unless otherwise specified, all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure.
For example, it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium. Isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use. Methods for making such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.
[0101] Many of the molecules disclosed herein contain one or more ionizable groups [groups from which a proton can be removed (e.g., -COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules Page 31 of 44 and salts thereof are intended to be included individually in the disclosure herein. With regard to salts of the compounds herein, one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.
[0102] Every formulation or combination of components described or exemplified herein can be used to practice the invention, unless otherwise stated.
[0103] Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.
[0104] All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains.
References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art.
For example, when composition of matter are claimed, it should be understood that compounds known and available in the art prior to Applicant's invention, including compounds for which an enabling disclosure is provided in the references cited herein, are not intended to be included in the composition of matter claims herein.
[0105] As used herein, "comprising" is synonymous with "including,"
"containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of' excludes any element, step, or ingredient not specified in the claim element. As used herein, "consisting essentially of' does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms "comprising", "consisting essentially of' and "consisting of' may be replaced with either of the other two terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
Page 32 of 44 [0106] One of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.
Page 33 of 44
[Inorganic Fluoride I [024] Molar Ratio = dissolved [Dissociating Agent ] dissolved [025] is greater than or equal to 0.1, and preferably for some applications selected over the range of 0.1 to 10.
[026] The present formulations, dissociating agents and methods are applicable to a broad range of inorganic fluorides, particularly those exhibiting low solubilities in pure solvent or solvent combinations. Classes of inorganic fluorides useful in the present solutions, formulations and methods include alkali metal fluorides, alkaline earth metal fluorides, transition metal fluorides and ammonium fluorides. The present invention provides solutions of dissolved fluorides having the formula:
Page 10 of 44 [027] MFn or BFy;
[028] (F1) (F2) [029] wherein M is a metal selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sn Pb, and Sb, and n is the oxidation state of M; and wherein B is a polyatomic cation selected from the group consisting of NH4+ (i.e., ammonium ion) and N(RlR2R3R4)+ (quaternary ammonium), wherein Rl, R2, R3, and R4 are each selected independently from the group consisting of a H atom, an alkyl group, an acetyl group and an aromatic (phenyl) group, and wherein y is the charge state of B. In an embodiment, for example, a solution of the present invention comprises an inorganic fluoride component selected from the group consisting of CdF2, CoF2, FeF3, MnF2, NaF, NiF2, ZnF2, ZrF4, AIF3, BaF2, CaF2, CuF2, FeF2, InF3, LiF, MgF2, PbF2, SrF2, UF4, VF3-3H203 BiF3, CeF3, CrF2/CrF3, GaF3, LaF3, NdF3, ThF4, AgF, CsF, RbF, SbF3, TIF, BeF2, KF, NH4F, SnF2, TaF5, VF4, BF3, BrF, BrF3, BrF5, CoF3, GeF2/GeF4, Hg2F2/HgF2, NbF5, OsF6, PF3/PF5, RhF3, SF4/SF6, SnF4, TeF4, UF6, VF5, and WF6.. In an embodiment, for example, a solution of the present invention comprises an inorganic fluoride component selected from the group consisting of: CdF2, CoF2, FeF3, MnF2, NaF, NiF2, ZnF2, ZrF4, AIF3, BaF2, CaF2, CuF2, FeF2, InF3, LiF, MgF2, PbF2, SrF2, UF4, VF3-3H20, BiF3, CeF3, CrF2/CrF3, GaF3, LaF3, NdF3, and ThF4.
[030] In another aspect, the present invention provides a solution containing one or more dissociating agents having chemical properties specifically tailored for dissolving a LiF salt in a solvent or combination of solvents. In an embodiment, a solution of this aspect comprises: (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents, the dissociating agent comprising one or more compounds selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether;
and (iii) LiF
dissolved in the one or more solvents having the dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M. Specific embodiments of this aspect of the present invention provide for the dissolution of LiF so as to generate a concentration of dissolved LiF in the solvent(s) selected over the range of 0.15 M to 3M, preferably for some applications selected over the range of 0.5 M to 1 M. This aspect of the present invention further provides methods of dissolving LiF in a solvent or combination of solvents comprising the steps of providing a dissociating agent comprising a Lewis acid, a Lewis base, a crown ether or Page 11 of 44 combination of these to the solvent(s) and dissolving the LiF into the solvent(s) containing the dissociating agent.
[031] Selection of the composition and concentration of the dissociating agent determines, at least in part, the composition, chemical properties and/or physical properties of the solutions and formulations of this aspect of the present invention. For example, the composition and concentration of dissociating agents in solutions and methods of the present invention are important parameters for achieving a desired extent of dissolution of an inorganic fluoride such as LiF. Useful dissociating agents in some embodiments include Lewis acids, Lewis bases, anion receptors, cation receptors, complexing agents, adduct formation agents and combinations of these compounds. In some embodiments, the dissociating agent is provided in the one or more solvents at a concentration selected over the range of 0.01 M to 10 M, and preferably for some applications selected over the range of 0.1 M to 5 M, and more preferably for some applications selected over the range of 0.5 M to 1.5 M. Other properties of dissociating agents useful for some embodiments include chemical stability (for example in the presence of lithium metal), electrochemical stability under discharge or charge conditions in an electrochemical cell, low viscosity impact when provided to solution, thermal stability and an enhancement in ionic conductivity when provided to solution. In some embodiments for lithium battery applications, dissociating reagents do not significantly undergo intercalation reactions at the electrodes.
[032] Lewis acids and Lewis bases are a particularly useful class of dissociating agents in the present solutions, formulations and methods. As used herein, the term "Lewis acid" refers to a substance which, in solution, is able to generate a cation or combine with an anion, and/or a molecule which can accept a pair of electrons and form a coordinate covalent bond, and the term "Lewis base" refers to a substance which, in solution, is able to generate an anion or combine with a cation, and/or a molecule or ion that can form a coordinate covalent bond by donating a pair of electrons.
Useful Lewis base or Lewis acid dissociating agents provided to solutions of the present invention include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. In an embodiment, for example, the dissociating agent is one or more Lewis base selected from the group consisting of AIC14 , C104-, SnC162-, BF4 , PF6-, and AsF6 . In an embodiment, for example, the dissociating agent is one or more Lewis acid selected from the group consisting of BF3, PF5, SbF5, AsF5, AIC13, SnC14, FeCl3, NbCI5, TiCl4, and ZnC12.
Page 12 of 44 [033] In an embodiment, a dissociating agent comprising one or more Lewis acid and/or Lewis base is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.5M to 3M. Lewis acids and bases may be provided to solutions of the present invention via providing a precursor compound to the solution. In the context of the description the term "precursor compound" refers to a substance that generates a Lewis acid, Lewis base or both in solution when provided to a solvent or combination of solvents. In an embodiment, for example, the dissociating agent is provided by dissolving a precursor compound in the one or more solvents to generate a Lewis base, a Lewis acid or a combination of a Lewis acid and a Lewis base, wherein the precursor compound comprises an alkali metal salt, alkaline earth metal salt; a transition metal salt, a rare earth metal salt, or an ammonium salt having the formula:
[034] AX:
[035] (F3);
[036] wherein A is selected from the group consisting of a metal, a metal cation and an ammonium group; and wherein X is selected from the group consisting of a fluorinated anion, a perchlorate group, an imide group, a carbide group, a carbonate group, an oxide group and a chloride group. Lithium salts are precursors useful for generating Lewis acids and/or Lewis bases in some solutions and methods of the present invention. Precursor compounds useful in the present solutions, formulations and methods include, but are not limited to, LiPF6, LiBF4, LiAsF6, LiCIO4, LiSnCI5, LiAICl4, LiFeCl4, LiNbCl6, LiTiCI5, LiZnCl3, NaPF6, NaBF4, NaAsF6, NaCIO4, NaSnCI5, NaAICl4, NaFeCl4, NaNbCl6, NaTiCI5, NaZnCl3, KPF6, KBF4, KAsF6, KCIO4, KSnCI5, KAIC14, KFeCl4, KNbCl6, KTiCI5, KZnCl3, NH4PF6, NH4BF4, NH4AsF6, NH4CIO4, NH4SnCI5, NH4AICI4, NH4FeCI4, NH4NbCI6, NH4TiCI5, NH4ZnCI3, N(CH3)4CIO4, N(CH3)4SnCI5, N(CH3)4AIC14, N(CH3)4FeCI4, N(CH3)4NbCI6, N(CH3)4TiCI5, N(CH3)4ZnCI3, N(C2H7)4C104, N(C2H7)4SnCI5, N(C2H7)4AIC14, N(C2H7)4FeCI4, N(C2H7)4NbCI6, N(C2H7)4TiCI5, and N(C2H7)4ZnCI3.
[037] Cation receptors are another particularly useful class of dissociating agents in the present solutions, formulations and methods. As used herein, the term "cation receptor" refers to a molecule or ion which can bind or otherwise take up a cation in solution. Some solutions of the present invention comprise one or more cation receptors selected from the group consisting of a crown ether, a Lewis base, and a Page 13 of 44 cation complexing agent. In an embodiment, a dissociating agent comprising one or more cation receptor is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.3M to 5M.
[038] Crown ethers are a class of cation receptor exhibiting chemical and physical properties beneficial for enhancing the dissolution of inorganic fluorides, including LiF.
These compounds are useful for complexing with metal ions in solution. Crown ether cation receptors useful in the present invention include, but are not limited to, Benzo-15-crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-1 5-crown-5, Dibenzo-1 8-crown-6, Dicyclohexyl-1 8-crown-6, Di-t-butyldibenzo-1 8-crown-6, 4,4i (5i )-Di-tert-butyldibenzo-24-crown-8, 4-Aminobenzo-15-Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert-Butylbenzo-15-crown-5, 4-tert-Butylcyclohexano-15-crown-5, 18-Crown-6, Cyclohexano-15-crown-5, Di-2,3-naphtho-30-crown-10, 4,4'(5')-Di-tert-butyldibenzo18-crown-6, 4'-(5')-Di-tert-butyldicyclohexano-18-crown-6, 4,4'(5')-Di-tert-butyldicyclohexano-24-crown-8, 4,10-Diaza-15-crown-5, Dibenzo-1 8-crown-6, Dibenzo-21 -crown-7, Dibenzo-24-crown-8, Dibenzo-30-crown-10, Dicyclohexano-18-crown-6, Dicyclohexano-21-crown-7,Dicyclohexano-24-crown-8, 2,6-Diketo-18-crown-6, 2,3-Naphtho-15-crown-5, 4'-Nitrobenzo-15-crown-5, Tetraaza-12-crown-4 tetrahydrochloride, Tetraaza-12-crown-4 tetrahydrogen sulfate, 1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane, 12-crown-4, 15-crown-5, and 21-crown-7. In an embodiment, a crown ether dissociating agent is provided to the solvent at a concentration in the solution selected over the range of 0.1 M
to 10M, a preferably for some applications selected over the range of 0.5M to 3M.
[039] Anion receptors are another particularly useful class of dissociating agents in the present solutions, formulations and methods. As used herein, the term anion receptor refers to a molecule or ion which can bind or otherwise take up an anion in solution. Anion receptors useful in the present solutions, formulations and methods include, but are not limited to fluorinated and semifluorinated borate compounds, fluorinated and semifluorinated boronate compounds, fluorinated and semifluorinated boranes, phenyl boron compounds, aza-ether boron compounds, Lewis acids, cyclic polyammonium compounds, guanidinium compounds, calixarene compounds, aza-ether compounds, quaternary ammonium compounds, amines, imidazolinium based receptors, mercury metallacycle compounds, silicon containing cages, and macrocycles. In an embodiment, a dissociating agent comprising one or more anion Page 14 of 44 receptor is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.5M to 3M.
[040] Examples of calixarene compounds include cobaltocenium-based receptors, ferrocene-based receptors, rr-metallated cationic hosts, calix[4]arenes, and calix[6]arenes. Examples of aza-ether anion receptors include linear aza-ethers, multi-branched aza-ethers, and cyclic aza-crown ethers. Examples of mercury metallacycle anion receptors include mercuracarborands and perfluoro-o-phenylenemercury metallacycles. Examples of anion receiving silicon-containing cages and macrocycles includes silsesquioxane cages and crown silanes. Other examples of useful anion receptors can generally be found in the art [See, e.g., Dietrich, Pure & Appl.
Chem., Vol 65, No. 7, pp. 1457-1464, 1993; U.S. Pat. No. 5,705,689; U.S. Pat. No.
6,120,941;
Matthews and Beer, Calixarene Anion Receptors, in Calixarenes 2001, pp. 421-439, Kluwer Academic Publishers, The Netherlands; Rodionov, State of the Art in Anion Receptor Design, American Chemical Society Division of Organic Chemistry Fellowship Awardee Essay 2005-2006; H.S. Lee, X.Q. Yang, C.L. Xiang, J. McBreen, L.S.
Choi, "The Synthesis of a New Family of Boron-Based Anion Receptors and the Study of Their Effect on Ion Pair Dissociation and Conductivily of Lithium Salts in Nonaqueous Solutions", J. Electrochem. Soc., Vol. 145, No. 8, August 1998; H.S. Lee, Z.F.
Ma, X.Q.
Yang, X. Sun and J. McBreen, "Synthesis of a Series of Fluorinated Boronate Compounds and Their Use as Additives in Lithium Battery Electrolytes", Journal of The Electrochemical Society, 151 (9) A1429-A1435 (2004); and X. Sun, H.S. Lee, S.
Lee, X.Q. Yang and J. Mc Breen, "A Novel Lithium Battery Electrolyte Based on Lithium Fluoride and a Tris(pentafluorophenyl) Borane Anion Receptor in DME"
Electrochemical and Solid-State Letters, 1(6) 239-240 (1998), all of which are incorporated by reference to the extent not inconsistent with the present description..
[041] Solutions, formulations, and methods of the present invention are compatible with a range of solvents, including water, nonaqueous organic solvents and nonaqueous inorganic solvents. In some embodiments useful for providing electrolytes for electrochemical cells, such as lithium electrochemical cells, the solvent(s) comprises one or more polar nonaqueous solvents, such as linear and cyclic esters, linear and cyclic ethers and polar carbonates. Electrolytes of the present invention may comprise a single nonaqueous solvent or a combination of nonaqueous solvents provided in relative proportions useful for a given electrochemical device or application.
The composition of nonaqueous solvents in some embodiments of the present invention is Page 15 of 44 selected to provide electrolyte formulations having desired physical, electronic and chemical properties, such as ionic conductivities, viscosities, melting points, freezing points and stability with respect to electrolytic decomposition and/or reaction with lithium metal. Useful solvents in the present invention include, but are not limited to, one or more of y-butyrolactone, propylene carbonate, dimethyl carbonate, ethylene carbonate, acetonitrile, 1,2, -dimethoxy ethane, N,N-dimethyl formamide, dimethyl sulfoxide, 1,3-diolane, methyl formate, nitromethane, phosphoroxichloride, thionylchloride, sulfurylchloride, diethyl ether, diethoxy ethane, 1,3 -dioxolane, tetrahydrofuran, 2-methyl-THF, diethyl carbonate, ethyl methyl carbonate, methylacetate and tratahydrofurane.
[042] In another aspect, solutions and formulations of the present invention provide electrolyte compositions useful for electrochemical storage and conversion applications.
In these embodiments, inorganic fluoride, dissociating agent and solvent components are selected to provide solution properties useful for a target electrochemical device application. In some embodiments of this aspect, for example, the composition of solution components of an electrolyte are selected to establish useful chemical and physical properties, such as large ionic conductivities, and enhanced solubility for solutions containing inorganic fluorides that are relatively insoluble in pure nonaqueous organic solvents. The present invention includes electrolytes, including nonaqueous electrolytes, exhibiting a high degree of chemical and electrochemical stability. In an embodiment, for example, an electrolyte of the present invention has a high voltage stability window over 5V vs. Li+ /Li. In another embodiment, electrolyte formulations of the present invention are stable with respect to contact with Li metal under discharge or charging conditions. A electrolyte of the present invention has an ionic conductivity at 25 degrees Celsius greater than or equal to 10-4 S cm-', preferably for some applications greater than or equal to 10-3 S cm-', and more preferably for some applications greater than or equal to 5 x 10-3 S cm-'. A nonaqueous electrolyte of the present invention has a viscosity at 25 degrees Celsius less than or equal to 5 cP, more preferably for some applications less than or equal to 3 cP.
[043] Although the present invention encompasses electrolytes comprising a broad range of inorganic fluorides, a preferred class of electrolytes for lithium electrochemical cells comprises LiF and a dissociating agent provided in one or more nonaqueous organic solvents. In this aspect, the present invention provides electrolyte formulations having an inorganic fluoride component comprising LiF salt and a dissociating agent Page 16 of 44 capable of significantly enhancing the dissociation and solubility of LiF in organic solvent(s). Embodiments of this aspect are particularly useful for electrolytes of electrochemical cells because F is the most electronegative element and Li is the most electropositive element. Therefore, electrolytes of the present invention comprising LiF
are particularly attractive for providing electrochemical cells having enhanced cell voltages and specific capacities relative to conventional lithium electrochemical cells.
Dissociating agents of the present invention are capable of increasing the conductivity of LiF in a selected nonaqueous organic solvent or combination of nonaqueous organic solvents, at 25 C, to a value equal to or greater than 10-4 S cm-', preferably equal to or greater 5 x 10-4 S cm-', and more preferably equal to or greater 10-3 S cm-'.
In an embodiment, dissociating agents of the present invention increase the solubility of LiF in a selected nonaqueous organic solvent (or combination of solvents) from a low value (e.g., on the order of micromolar) to 0.1 M or greater, preferably 0.5 M or greater, and preferably 1 M or greater. In an embodiment, LiF solubility at a temperature of about 25 C in an electrolyte of the present invention is increased by addition of a dissociating agent to a value greater than about 0.1 M, including between about 0.1 M to 5 M, and between about 1 M to 2 M.
[044] The present invention includes electrochemical devices comprising the present electrolytes, such as nonaqueous electrolytes, including, but not limited to, primary electrochemical cells, secondary electrochemical cells, capacitors, supercapacitors and fuel cells. In addition, the solutions, dissociating agents and methods of the present invention are also useful for sensing systems, including electrochemical sensing systems. Solutions and dissociating agents of the present invention, for example, are useful for reducing interference and enhancing the selectivity of fluoride ion specific electrodes. In an embodiment, the present invention provides an electrochemical cell comprising: (i) a positive electrode; (ii) a negative electrode; and (iii) an electrolyte of the present invention provided between the positive electrode and the negative electrode.
As will be appreciated by those having skill in the art of electrochemistry, electrolytes useful in electrochemical devices of the present invention include those provided throughout the present description. In an embodiment, an electrolyte of an electrochemical device of the present invention comprises (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents; and (iii) an inorganic fluoride dissolved in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate Page 17 of 44 a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M.
[045] As will be appreciate by those of skill in the art a wide range of electrode materials and configurations can be used in electrochemical devices of the present invention, including metallic and semiconducting materials. Use of nanostructured and/or intercalating electrodes is useful for some applications. In an embodiment, the negative electrode comprises lithium metal, a carbonaceous material, such as graphite, coke, multiwalled carbon nanotubes, multi-layered carbon nanofibers, multi-layered carbon nanoparticles, carbon nanowhiskers and carbon nanorods having lithium storage capability or a lithium metal alloy. In an embodiment, the positive electrode comprises a carbonaceous material, such as graphite, coke, multiwalled carbon nanotubes, multi-layered carbon nanofibers, multi-layered carbon nanoparticles, carbon nanowhiskers and carbon nanorods having fluoride ion storage capability. In an embodiment, positive electrode comprises a carbonaceous material comprises a subfluorinated carbonaceous material having an average stoichiometry CFX, wherein x is the average atomic ratio of fluorine atoms to carbon atoms and is selected from the range of about 0.3 to about 1.0;
the subfluorinated carbonaceous material being a multiphase material having an unfluorinated carbon component. In an embodiment, positive electrode comprises a fluorinated element such a transition metal or a rare earth metal having reversible fluorine ion storage capability.
[046] Solutions, dissociating agents and methods of the present invention providing enhanced solubility of fluorides have significant applications in addition to their use as electrolytes in electrochemical devices and systems. The compositions and methods of the present invention are beneficial for accessing solution phase compositions and properties (e.g., chemical, physical and/or electrochemical) useful for enabling a broad class of surface phase and solution synthetic pathways and other processes.
Fluoride containing solutions of the present invention, for example, may provide solution phase reagents for important synthetic chemistries, including organic and inorganic fluorination, for example by soft chemistry methods, and surface fluorination reactions.
Fluoride containing solutions of the present invention may also be useful for accessing solution properties (e.g., ionic conductivities, ionic strength, etc.) critical for accessing important solution phase processes, including electrosynthesis, electrodeposition, and electropassivation.
Page 18 of 44 [047] In another aspect, the present invention provides a method for dissolving an inorganic fluoride in one or more solvents comprising the steps of: (i) providing the one or more solvents; (ii) providing a dissociating agent to the one or more solvents; and (iii) dissolving the inorganic fluoride in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M, thereby dissolving the inorganic fluoride into the one or more solvents.
[048] In another aspect, the present invention provides a method for dissolving LiF in one or more solvents, comprising the steps of: (i) providing the one or more solvents; (ii) providing a dissociating agent to the one or more solvents, the dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and dissolving LiF in the one or more solvents having the dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M, and optionally greater than or equal to 0.5M.
[049] In another aspect, the present invention provides a method of making an electrolyte for an electrochemical device, the method comprising the steps of:
(i) providing one or more solvents; (ii) providing a dissociating agent to the one or more solvents; and (iii) dissolving an inorganic fluoride in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M, thereby making the electrolyte for the electrochemical device.
[050] In another aspect, the present invention provides a method of making an electrolyte for an electrochemical device, the method comprising the steps of:
(i) providing one or more solvents; (ii) providing a dissociating agent to the one or more solvents, the dissociating agent comprising one or more compounds selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and (iii) dissolving LiF in the one or more solvents having the dissociating agent, thereby making the electrolyte for the electrochemical device.
[051] In another aspect, the present invention provides a solution having LiF
dissolved in one or more solvents, said solution comprising: (i) said one or more Page 19 of 44 solvents; and (ii) LiF dissolved in said one or more solvents; wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
[052] Without wishing to be bound by any particular theory, there can be discussion herein of beliefs or understandings of underlying principles relating to the invention. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.
BRIEF DESCRIPTION OF THE DRAWINGS
[053] Figure 1. Comparative (normalized) discharge profile of Li/electrolyte/graphite-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M
LiPF6 solution in EC-DMC.
[054] Figure 2. Shows the cyclic voltammogram obtained with the LiF containing electrolyte cell between 2.1 and 4.8V under 15mV/mn sweeping rate. It shows oxidation and reduction peaks corresponding to negatively charged species intercalation and de-intercalation into graphite.
[055] Figure 3. Comparative (normalized) discharge profile of Li/electrolyte/graphite fluoride (CFo.53)-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF6 solution in EC-DMC.
[056] Figure 4 depicts the current provided by the cell containing LiPF6 during a charge/discharge cycle.
[057] Figure 5 depicts the current provided by the cell containing LiF and 12-crown-4 during a charge/discharge cycle.
DETAILED DESCRIPTION OF THE INVENTION
[058] Referring to the drawings, like numerals indicate like elements and the same number appearing in more than one drawing refers to the same element. In general the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the invention.
Page 20 of 44 [059] "Standard electrode potential" (E ) refers to the electrode potential when concentrations of solutes are 1 M, the gas pressures are 1 atm and the temperature is 25 degrees Celsius. As used herein standard electrode potentials are measured relative to a standard hydrogen electrode.
[060] "Intercalation" refers to refers to the process wherein an ion inserts into a host material to generate an intercalation compound via a host/guest solid state redox reaction involving electrochemical charge transfer processes coupled with insertion of mobile guest ions, such as fluoride ions. Major structural features of the host material are preserved after insertion of the guest ions via intercalation. In some host materials, intercalation refers to a process wherein guest ions are taken up with interlayer gaps (e.g., galleries) of a layered host material. Examples of intercalation compounds include fluoride ion intercalation compounds wherein fluoride ions are inserted into a host material, such as a layered fluoride host material or carbon host material.
Host materials useful for forming intercalation compounds for electrodes of the present invention include, but are not limited to, CFX, FeFx, MnFx, NiFx, CoFx, LiC6, LixSi, and LixGe.
[061] The term "electrochemical cell" refers to devices and/or device components that convert chemical energy into electrical energy or electrical energy into chemical energy.
Electrochemical cells have two or more electrodes (e.g., positive and negative electrodes) and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes. Electrochemical cells include, but are not limited to, primary batteries, secondary batteries and electrolysis systems.
General cell and/or battery construction is known in the art, see e.g., U.S. Pat. Nos.
6,489,055, 4,052,539, 6,306,540, Seel and Dahn J. Electrochem. Soc. 147(3) 892-898 (2000).
[062] The term "capacity" is a characteristic of an electrochemical cell that refers to the total amount of electrical charge an electrochemical cell, such as a battery, is able to hold. Capacity is typically expressed in units of ampere-hours. The term "specific capacity" refers to the capacity output of an electrochemical cell, such as a battery, per unit weight. Specific capacity is typically expressed in units of ampere-hours kg-'.
[063] The term "discharge rate" refers to the current at which an electrochemical cell is discharged. Discharge current can be expressed in units of ampere-hours.
Alternatively, discharge current can be normalized to the rated capacity of the electrochemical cell, and expressed as C/(X t), wherein C is the capacity of the Page 21 of 44 electrochemical cell, X is a variable and t is a specified unit of time, as used herein, equal to 1 hour.
[064] "Current density" refers to the current flowing per unit electrode area.
[065] The term "open circuit voltage" refers to the difference in potential between terminals (i.e. electrodes) of an electrochemical cell when the circuit is open (i.e. no load conditions). Under certain conditions the open circuit voltage can be used to estimate the composition of an electrochemical cell. The present methods and system utilize measurements of open circuit voltage for thermochemically stabilized conditions of an electrochemical cell to determine thermodynamic parameters, materials properties and electrochemical properties of electrodes, electrochemical cells and electrochemical systems.
[066] The expression "state of charge" is a characteristic of an electrochemical cell or component thereof (e.g. electrode - cathode and/or anode) referring to its available capacity, such as a battery, expressed as a percentage of its rated capacity.
[067] Electrode refers to an electrical conductor where ions and electrons are exchanged with electrolyte and an outer circuit. "Positive electrode" and "cathode" are used synonymously in the present description and refer to the electrode having the higher electrode potential in an electrochemical cell (i.e. higher than the negative electrode). "Negative electrode" and "anode" are used synonymously in the present description and refer to the electrode having the lower electrode potential in an electrochemical cell (i.e. lower than the positive electrode). Cathodic reduction refers to a gain of electron(s) of a chemical species, and anodic oxidation refers to the loss of electron(s) of a chemical species. Positive electrodes and negative electrodes of the present electrochemical cell may further comprise a conductive diluent, such as acetylene black, carbon black, powdered graphite, coke, carbon fiber, and metallic powder, and/or may further comprises a binder, such as a polymer binder.
Useful binders for positive electrodes in some embodiments comprise a fluoropolymer such as polyvinylidene fluoride (PVDF). Positive and negative electrodes of the present invention may be provided in a range of useful configurations and form factors as known in the art of electrochemistry and battery science, including thin electrode designs, such as thin film electrode configurations. Electrodes are manufactured as disclosed herein and as known in the art, including as disclosed in, for example, U.S. Pat.
Nos.
4,052,539, 6,306,540, 6,852,446. For some embodiments, the electrode is typically Page 22 of 44 fabricated by depositing a slurry of the electrode material, an electrically conductive inert material, the binder, and a liquid carrier on the electrode current collector, and then evaporating the carrier to leave a coherent mass in electrical contact with the current collector.
[068] "Electrode potential" refers to a voltage, usually measured against a reference electrode, due to the presence within or in contact with the electrode of chemical species at different oxidation (valence) states.
[069] "Electrolyte" refers to an ionic conductor which can be in the solid state, the liquid state (most common) or more rarely a gas (e.g., plasma). In the context of an electrochemical cell, the electrolyte provides ionic conductivity between two or more electrodes of an electrochemical cell.
[070] "Cation" refers to a positively charged ion, and "anion" refers to a negatively charged ion.
[071] "Lewis acid" refers to a substance which, in solution, is able to generate a cation or combine with an anion, and/or a molecule which can accept a pair of electrons and form a coordinate covalent bond. Useful classes of Lewis acids include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. Examples of inorganic fluoride Lewis acids are BF3, PF5, SbF5, and AsF5.
Examples of inorganic chloride Lewis acids are AIC13, SnCl4, FeCl3, NbCI5, TiCl4, and ZnCl2.
[072] "Lewis base" refers to a substance which, in solution, is able to generate an anion or combine with a cation, and/or a molecule or ion that can form a coordinate covalent bond by donating a pair of electrons. Useful classes of Lewis bases include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. Examples of inorganic chloride Lewis bases are AIC14 , C104-, and SnC162-. Examples of inorganic fluoride Lewis bases are BF4 , PF6-, and AsF6 .
[073] "Lewis acid precursor" or "precursor" and "Lewis base precursor" or "precursor"
refers to a substance which is able to generate Lewis acids and/or Lewis bases when introduced into a solvent and/or solution. Examples of Lewis acid/base precursors are LiPF6, LiBF4, LiAsF6, LiCIO4, LiSnCI5, LiAICl4, LiFeCl4, LiNbCl6, LiTiCI5, LiZnCl3, NaPF6, NaBF4, NaAsF6, NaCIO4, NaSnCI5, NaAICl4, NaFeCl4, NaNbCl6, NaTiCI5, NaZnCl3, KPF6, KBF4, KAsF6, KCIO4, KSnCI5, KAICI4, KFeCl4, KNbCl6, KTiCI5, KZnCl3, NH4PF6, Page 23 of 44 NH4BF4, NH4AsF6, NH4CIO4, NH4SnCI5, NH4AICI4, NH4FeCI4, NH4NbCI6, NH4TiCI5, and NH4ZnCI3 and others.
[074] "Anion receptor" refers to a molecule or ion which can bind or otherwise take up an anion. Useful classes of anion receptors include, but are not limited to, fluorinated and semifluorinated borate compounds, fluorinated and semifluorinated boronate compounds, fluorinated and semifluorinated boranes, Lewis acids, cyclic polyammonium compounds, guanidiniums, calixarene compounds, aza-ether compounds, quaternary ammonium, amine, and imidazolinium based receptors, mercury metallacycles, and silicon containing cages and macrocycles. Examples of cyclic polyammonium anion receptors include polyammonium macrocycles, polyammonium macrobicycles, polyammonium macrotricycles, azacrown compounds, protonated tetra-, penta- and hexaamines. Examples of calixarene compounds include cobaltocenium-based receptors, ferrocene-based receptors, Tr-metallated cationic hosts, calix[4]arenes, and calix[6]arenes. Examples of aza-ether anion receptors include linear aza-ethers, multi-branched aza-ethers, and cyclic aza-crown ethers. Examples of mercury metallacycle anion receptors include mercuracarborands and perfluoro-o-phenylenemercury metallacycles. Examples of anion receiving silicon-containing cages and macrocycles include silsesquioxane cages and crown silanes. Other examples of useful anion receptors can generally be found in the art [See, e.g., Dietrich, Pure & Appl.
Chem., Vol 65, No. 7, pp. 1457-1464, 1993; U.S. Pat. No. 5,705,689; U.S. Pat. No.
6,120,941;
Matthews and Beer, Calixarene Anion Receptors, in Calixarenes 2001, pp. 421-439, Kluwer Academic Publishers, The Netherlands; Rodionov, State of the Art in Anion Receptor Design, American Chemical Society Division of Organic Chemistry Fellowship Awardee Essay 2005-2006; H.S. Lee, X.Q. Yang, C.L. Xiang, J. McBreen, L.S.
Choi, "The Synthesis of a New Family of Boron-Based Anion Receptors and the Study of Their Effect on Ion Pair Dissociation and Conductivily of Lithium Salts in Nonaqueous Solutions", J. Electrochem. Soc., Vol. 145, No. 8, August 1998; H.S. Lee, Z.F.
Ma, X.Q.
Yang, X. Sun and J. McBreen, "Synthesis of a Series of Fluorinated Boronate Compounds and Their Use as Additives in Lithium Battery Electrolytes", Journal of The Electrochemical Society, 151 (9) A1429-A1435 (2004); and X. Sun, H.S. Lee, S.
Lee, X.Q. Yang and J. Mc Breen, "A Novel Lithium Battery Electrolyte Based on Lithium Fluoride and a Tris(pentafluorophenyl) Borane Anion Receptor in DME"
Electrochemical and Solid-State Letters, 1(6) 239-240 (1998).
Page 24 of 44 [075] "Cation receptor" refers to a molecule or ion which can bind or otherwise take up a cation. Useful classes of cation receptors include, but are not limited to, crown ethers, Lewis bases, and other cation complexing agents. Examples of crown ether cation receptors include, but are not limited to, Benzo-15-crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-15-crown-5, Dibenzo-18-crown-6, Dicyclohexyl-18-crown-6, Di-t-butyldibenzo-18-crown-6, 4,4i (5i )-Di-tert-butyldibenzo-24-crown-8, 4-Aminobenzo-15-Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert-Butylbenzo-15-crown-5, 4-tert-Butylcyclohexano-15-crown-5, 18-Crown-6, Cyclohexano-15-crown-5, Di-2,3-naphtho-30-crown-10, 4,4'(5')-Di-tert-butyldibenzo18-crown-6, 4'-(5')-Di-tert-butyldicyclohexano-18-crown-6, 4,4'(5')-Di-tert-butyldicyclohexano-24-crown-8, 4,10-Diaza-15-crown-5, Dibenzo-18-crown-6, Dibenzo-21-crown-7, Dibenzo-24-crown-8, Dibenzo-30-crown-10, Dicyclohexano-18-crown-6, D icycloh exa no-21 -crown -7, D icycloh exa no-24-crown -8, 2,6-Diketo-18-crown-6, 2,3-Naphtho-15-crown-5, 4'-Nitrobenzo-15-crown-5, Tetraaza-crown-4 tetrahydrochloride, Tetraaza-12-crown-4 tetrahydrogen sulfate, 1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane, 12-crown-4, 15-crown-5, and 21-crown-7.
[076] "Dissociating agent" and "dissociation agent" are used synonymously and refer to a compound added to a solution, solvent, and/or electrolyte to increase the solubility and/or dissolution of a salt. Dissociating agents of the present invention are useful for increasing the dissolution of inorganic fluorides, particularly inorganic fluorides, generally regarded to be relatively insoluble, such as LiF.
[077] The present invention provides methods for generating solutions containing large concentrations of dissolved fluoride salts which are generally regarded as insoluble. In another aspect, the present invention provides solutions, solvents, and electrolytes containing large concentrations of dissolved fluoride salts which are generally regarded as insoluble. In an embodiment, compounds are provided to the solutions, solvents, and electrolytes which facilitate dissolution of the fluoride salts.
These compounds can be regarded as dissolution, dissolving, dissociating, or dissociation agents, since they provide a means for dissolving normally insoluble compounds. In an embodiment, the fluoride salts are present as solutes in solution at concentrations much larger than that which occurs at a natural equilibrium in a solution that does not contain the dissociating agents. In an embodiment, the fluoride salts are a minor solute component. In another embodiment, the fluoride salts are the most abundant solute present in the solution, solvent, or electrolyte.
Page 25 of 44 [078] The present invention provides additives and methods for dissolving element fluorides (MFn) such as LiF. In an embodiment, for example, organic solutions of lithium salts (LiX), such as LiPF6, LiBF4, LiAsF6 and LiCIO4, in carbonate or gamma butyro-lactone (y-BL) based liquid solvents dissolve a significant amount LiF, whereas, the same solvents without the presence of the LiX salt do not appreciably dissolve LiF. The present methods apply to a variety of other insoluble fluorides (MFn) thus providing a large range of `complex-type' solutions of MFn + AX, A=alkali metal or NH4, and X=fluorinated anion, perchlorate, imide, carbide. Compositions of the present invention also provide a new family of electrolytes for lithium batteries applications containing LiF
dissolved at significant solubilities in nonaqueous organic solvents.
Example 1: Electrolytes and Dissociating Agents for Electrochemical Cells [079] To demonstrate the chemical properties and utility of the present additives, compositions, formulations and methods, electrolytes of the present invention were prepared and integrated into lithium electrochemical cells. The electrolytes evaluated comprise LiF and an appropriate dissociating agent dissolved in a selected nonaqueous organic solvent or combination of nonaqueous organic solvents. The electronic performance of the electrochemical cells was evaluated to demonstrate the beneficial chemical and physical properties of electrolytes of the present invention.
[080] 1. Preparation of the mother solutions: 1 M solutions of LiPF6 in EC-DMC
and of LiBF4 in y-BL and of LiAsF6 and of LiCIO4 in PC were prepared in a dry box filled with argon. (EC=ethylene carbonate, DMC=dimethyl carbonate and PC=propylene carbonate). These solutions are called `mother solutions' throughout this description.
[081] 2. Dissolving LiF in mother solutions: In a dry box filled with argon, a sample of 5 milliliters (5x10-3 mole of LiX) was taken from each of the above described mother solutions and 65 milligrams (2.5x10-3 mole) of LiF was added to it. The solution was stirred magnetically until full dissolution of LiF occurred, i.e., the solution becomes clear.
The molar ratio LiF/LiX in these solutions is 0.5, with an absolute LiF
concentration of 0.5 M.
[082] 3. Electrochemical tests: Coin cells were created in a dry box, consisting of a metallic lithium disc (negative pole), a polypropylene microporous separator wet with `electrolyte', and a composite electrode (positive pole). Two types of composite cathode electrodes were used: a graphite based electrode and a graphite fluoride based Page 26 of 44 electrode. The `electrolyte' is either the LiPF6 in EC-DMC mother solution or the LiF
dissolved in LiPF6 in EC-DMC mother solution.
[083] 3a)graphite based cells: The cells were first discharged under a constant current of 10 mA/g-graphite to 250 mV. The 250 mV vs. Li+/Li Potential was chosen between that of the first passivation (solid electrolyte interphase: SEI
formation usually at >500 mV vs. Li+/Li) and that of the lithium intercalation (usually at <200 mV vs. Li+/Li).
The cells were then charged to 5V vs. Li+/Li under the same 10 mA/g-graphite rate. A
constant 5V was then applied for several hours to further charge. The cells were then allowed to rest for several hours and were then discharged to 3V under the same 10 mA/g-graphite rate. Following this, the cells were cycled between 3V and 5V
several times under the same procedure described above.
[084] Linear voltammetry under a 15mV/min sweeping rate was also performed on the cell with LiF containing electrolyte in the 2.1-4.8V voltage window.
[085] 3b) graphite fluoride based cells: The CFX material tested here is CF0.53 obtained from graphite. The cells were discharged to different depths of discharge (DOD=10, 20, 30,...100%) under constant current (C/20 rate: i.e., 32.1 mA/g-CFo.53).
The cells were then charged to 4.8V and to 5.OV and allowed to rest for several hours the same constant voltage was applied ( 4.8 or 5.OV) for several hours to further charge.
After this, the cells were discharged to 3V and then recharged to 4.8 V or 5.0 V following the same procedure described above.
[086] 4. Results:
4a) Graphite based electrodes: Figure 1 provides a comparative (normalized) discharge profile of Li/electrolyte/graphite-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF6 solution in EC-DMC. Figure 1 shows the voltage versus discharge/charge ratio of the graphite based cells using mother solution electrolyte (no LiF) and LiF dissolved in mother electrolyte (LiF) with charge voltage up to 4.8V. These results indicate that the LiF containing electrolyte has a higher discharge voltage and relative capacity than the non LiF containing electrolyte.
[087] Figure 2 shows a cyclic voltammogram obtained with the Li/0.5M LiF+1 M
LiPF6 in EC-DMC/graphite cell, obtained between 2.1 and 4.8 V under a 15mV/min sweeping rate. Visible in Figure 2 are oxidation and reduction peaks corresponding to the intercalation and de-intercalation of the negatively charged species into graphite. These Page 27 of 44 positive current (oxidation) peaks and negative current peaks (reduction) peaks correspond to reversible charging and discharging of the cell. The peaks may be associated with negatively charged species (or anions) intercalation and de-intercalation, respectively.
[088] 4b) Graphite fluoride based electrodes: Figure 3 provides a comparative (normalized) discharge profile of Li/electrolyte/graphite fluoride (CFo.53)-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF6 solution in EC-DMC. Figure 3 shows the voltage versus discharge/charge capacity ratio of the graphite fluoride (CFo.53) based cells using mother solution electrolyte (no LiF) and LiF dissolved in mother electrolyte (LiF) with charge voltage up to 4.8V. These results indicate that the LiF containing electrolyte has a higher discharge voltage and relative capacity than the non-LiF containing electrolyte.
[089] 5. Conclusions: New electrolyte solutions based on element fluoride LiF
were successfully prepared. The solutions are light transparent and stable under an argon atmosphere. Dissolution of LiF was achieved in different organic liquid media comprised of polar solvents chosen among carbonates such as EC, DMC, PC or y-butyrolactone and containing a dissolved lithium salt such as LiPF6, LiBF4, LiAsF6 and LiCIO4. Electrolyte solutions with LiF have a high voltage stability window over 5V vs.
Li+/Li. They are also stable in contact with metallic lithium. LiF containing electrolyte solutions show enhanced electrochemical performances of electrode materials for batteries applications such as those based on pure graphite or graphite fluoride positive electrodes. Dissolution of many insoluble element fluorides can be achieved using the same principle of `mother solution' electrolytes.
Example 2: Comparison of fluorinated carbon electrode lithium half-cells with and without LiF
[090] Two fluorinated carbon electrode (CFo.125) lithium half cells were prepared. One cell contained an electrolyte of 1 M LiPF6 in propylene carbonate (PC); the other cell contained an electrolyte of 1 M LiF and 1 M 12-crown-4 in PC. The crown ether acts as a cation receptor to allow LiF to dissolve in the PC. The cells were cycled between about 3.2V and 5.5V at a rate of 1 mV/s.
Page 28 of 44 [091] Figure 4 depicts the current provided by the cell containing LiPF6 during a charge/discharge cycle and shows no clear oxidation or reduction peaks. This cell has a much higher charge capacity than discharge, indicating a large irreversibility.
[092] Figure 5 depicts the current provided by the cell containing LiF during a charge/discharge cycle and shows oxidation peaks at about 3.6V and 4.15V and a reduction peak at about 4 V. This cell has similar charge and discharge capacities, indicating good reversibility.
[093] These results indicate that the presence of dissolved LiF makes fluorinated carbon a suitable cathode for high voltage, high cycleability, rechargeable, fluoride ion batteries, since F- is able to reversibly intercalate into a fluorinated carbon cathode.
[094] Example 3: Fluoride Solutions having Dissociating Agents [095] Table 2 provides a summary of experimental conditions useful for making fluorides solutions of the present invention from a variety of fluoride salts, including NH4F, NaF, KF, MgF2 and AIF3.
Page 29 of 44 [096] Table 2: Example Fluoride Solutions :=:t F_.'~: ` r~o~:- ~zhrr :3.:,;c:, r~>_s~~;
W 4i= 5 is solaed i>g FC, \c; in <NH':JF 31:s :.'., t~N}'c tiHa:- w7-= S.2g Lt ;a,^^.
SS:F'2~ C:v=rr91`JI`i;3'?2tu\:?
fiaF \ [Yl:aaCt:Ved wi3s 3i.`::'vd axas zS sc:r=
M~Ii. .t<e,_ a:r,l := _ tz' vnhri -&. ~ tz:zr; salwi;~^
F :C CYI3Sq:SE.C:
31Td 4 18_ i.1RPr21,:R!i~
~h: 7~=.".:. -1e So:itil=cr'i R?F2 ; :s,06~E1":l`eb_lv cobr ai,~\::JS{ Y.
, ... t.'~.'.C~PI1E47 y,;
~.=cr3ryz :tr}S :E;:=1JZiA'2 in =,r~;;:=ti:. 0. -3: .=2, avxi=
ns:\eci ,a:h ?he cc:?;;hm =:;'3 3A~ zl> ri;
a,}`;:
[097]
STATEMENTS REGARDING INCORPORATION BY REFERENCE
AND VARIATIONS
[098] All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).
[099] The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such Page 30 of 44 terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices, device components, methods steps set forth in the present description. As will be obvious to one of skill in the art, methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps.
[0100] When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of the group members, are disclosed separately.
When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. Additionally, unless otherwise specified, all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure.
For example, it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium. Isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use. Methods for making such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.
[0101] Many of the molecules disclosed herein contain one or more ionizable groups [groups from which a proton can be removed (e.g., -COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules Page 31 of 44 and salts thereof are intended to be included individually in the disclosure herein. With regard to salts of the compounds herein, one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.
[0102] Every formulation or combination of components described or exemplified herein can be used to practice the invention, unless otherwise stated.
[0103] Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.
[0104] All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains.
References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art.
For example, when composition of matter are claimed, it should be understood that compounds known and available in the art prior to Applicant's invention, including compounds for which an enabling disclosure is provided in the references cited herein, are not intended to be included in the composition of matter claims herein.
[0105] As used herein, "comprising" is synonymous with "including,"
"containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of' excludes any element, step, or ingredient not specified in the claim element. As used herein, "consisting essentially of' does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms "comprising", "consisting essentially of' and "consisting of' may be replaced with either of the other two terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
Page 32 of 44 [0106] One of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.
Page 33 of 44
Claims (51)
1. A solution having an inorganic fluoride dissolved in one or more solvents, said solution comprising:
said one or more solvents;
a dissociating agent provided to said one or more solvents; and said inorganic fluoride dissolved in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M.
said one or more solvents;
a dissociating agent provided to said one or more solvents; and said inorganic fluoride dissolved in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M.
2. The solution of claim 1 wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of said inorganic fluoride dissolved in said one or more solvents selected over the range of 0.15 M
to 3M.
to 3M.
3. The solution of claim 1 wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of said inorganic fluoride dissolved in said one or more solvents selected over the range of 0.5 M to 1M.
4. The solution of claim 1 wherein the molar ratio of inorganic fluoride dissolved in said one or more solvents to dissociating agent dissolved in said one or more solvents is greater than or equal to 0.1.
5. The solution of claim 1 wherein the molar ratio of inorganic fluoride dissolved in said one or more solvents to dissociating agent dissolved in said one or more solvents is selected over the range of 0.1 to 10.
6. The solution of claim 1 wherein said inorganic fluoride has the formula:
MF n or BF y;
(F1) (F2) wherein M is a metal selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sn Pb, and Sb, and n is the oxidation state of M; and wherein B is a polyatomic cation selected from the group consisting of NH4+
and N(R1R2R3R4)+, wherein R1, R2, R3, and R4 are each selected independently from the group consisting of a H atom, an alkyl group, an acetyl group and an aromatic (phenyl) group.
MF n or BF y;
(F1) (F2) wherein M is a metal selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sn Pb, and Sb, and n is the oxidation state of M; and wherein B is a polyatomic cation selected from the group consisting of NH4+
and N(R1R2R3R4)+, wherein R1, R2, R3, and R4 are each selected independently from the group consisting of a H atom, an alkyl group, an acetyl group and an aromatic (phenyl) group.
7. The solution of claim 1 wherein said inorganic fluoride is selected from the group consisting of CdF2, CoF2, FeF3, MnF2, NaF, NiF2, ZnF2, ZrF4, AlF3, BaF2, CaF2, CuF2, FeF2, InF3, LiF, MgF2, PbF2, SrF2, UF4, VF3-3H20, BiF3, CeF3, CrF2/CrF3, GaF3, LaF3, NdF3, ThF4, AgF, CsF, RbF, SbF3, TIF, BeF2, KF, NH4F, SnF2, TaF5, VF43 BF3, BrF, BrF3, BrF5, CoF3, GeF2/GeF4, Hg2F2/HgF2, NbF5, OsF6, PF3/PF5, RhF3, SF4/SF6, SnF4, TeF4, UF6, VF5, and WF6.
8. The solution of claim 1 wherein said dissociating agent is provided in said one or more solvents at a concentration selected over the range of 0.1 M to 10 M.
9. The solution of claim 1 wherein said dissociating agent is one or more compounds selected from the group consisting of a Lewis acid, a Lewis base, an anion receptor, and a cation receptor.
10. The solution of claim 9 wherein said dissociating agent is one or more Lewis bases or Lewis acids selected from the group consisting of an inorganic fluoride, an inorganic chloride, an inorganic carbonate, and an inorganic oxide.
11. The solution of claim 9 wherein said dissociating agent is one or more Lewis bases selected from the group consisting of AlCl4-, ClO4-, SnCl6 2-, BF4-, PF6-, and AsF6-.
12. The solution of claim 9 wherein said dissociating agent is one or more Lewis acids selected from the group consisting of BF3, PF5, SbF5, AsF5, AlCl3, SnCl4, FeCl3, NbCl5, TiCl4, and ZnCl2.
13. The solution of claim 9 wherein said dissociating agent is provided by dissolving a precursor compound in said one or more solvents to generate a Lewis base, a Lewis acid or a Lewis acid and a Lewis base, said precursor compound comprising an alkali metal salt, alkaline earth metal salt; a transition metal salt or an ammonium salt having the formula:
AX:
(F3) wherein A is selected from the group consisting of a metal, a metal cation and an ammonium group; and wherein X is selected from the group consisting of a fluorinated anion, a perchlorate group, an imide group, a carbide group, a carbonate group, an oxide group and a chloride group.
AX:
(F3) wherein A is selected from the group consisting of a metal, a metal cation and an ammonium group; and wherein X is selected from the group consisting of a fluorinated anion, a perchlorate group, an imide group, a carbide group, a carbonate group, an oxide group and a chloride group.
14. The solution of claim 13 wherein said precursor compound is one or more lithium salt.
15. The solution of claim 13 wherein said precursor compound is one or more salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiClO4, LiSnCl5, LiAlCl4, LiFeCl4, LiNbCl6, LiTiCl5, LiZnCl3, NaPF6, NaBF4, NaAsF6, NaClO4, NaSnCl5, NaAlCl4, NaFeCl4, NaNbCl6, NaTiCl5, NaZnCl3, KPF6, KBF4, KAsF6, KClO4, KSnCl5, KAlCl4, KFeCl4, KNbCl6, KTiCl5, KZnCl3, NH4PF6, NH4BF4, NH4AsF6, NH4ClO4, NH4SnCl5, NH4AlCl4, NH4FeCl4, NH4NbCl6, NH4TiCl5, NH4ZnCl3, N(CH3)4ClO4, N(CH3)4SnCl5, N(CH3)4AlCl4, N(CH3)4FeCl4, N(CH3)4NbCl6, N(CH3)4TiCl5, N(CH3)4ZnCl3, N(C2H7)4ClO4, N(C2H7)4SnCl5, N(C2H7)4AlCl4, N(C2H7)4FeCl4, N(C2H7)4NbCl6, N(C2H7)4TiCl5, and N(C2H7)4ZnCl3.
16. The solution of claim 1 wherein said dissociating agent comprises one or more anion receptors.
17. The solution of claim 1 wherein said dissociating agent comprises one or more cation receptors.
18. The solution of claim 17 wherein said cation receptor is one or more compound selected from the group consisting of a crown ether, a Lewis base, and a cation complexing agent.
19. The solution of claim 18 wherein said cation receptor is one or more crown ether selected from the group consisting of Benzo-15-crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-15-crown-5, Dibenzo-18-crown-6, Dicyclohexyl-18-crown-6, Di-t-butyldibenzo-18-crown-6, 4,4i~(5i~)-Di-tert-butyldibenzo-24-crown-8, 4-Aminobenzo-15-Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert-Butylbenzo-15-crown-5, 4-tert-Butylcyclohexano-15-crown-5, 18-Crown-6, Cyclohexano-15-crown-5, Di-2,3-naphtho-30-crown-10, 4,4'(5')-Di-tert-butyldibenzo18-crown-6, 4'-(5')-Di-tert-butyldicyclohexano-18-crown-6, 4,4'(5')-Di-tert-butyldicyclohexano-24-crown-8, 4,10-Diaza-15-crown-5, Dibenzo-18-crown-6, Dibenzo-21-crown-7, Dibenzo-24-crown-8, Dibenzo-30-crown-10, Dicyclohexano-18-crown-6, Dicyclohexano-21-crown-7, Dicyclohexano-24-crown-8, 2,6-Diketo-18-crown-6, 2,3-Naphtho-15-crown-5, 4'-Nitrobenzo-15-crown-5, Tetraaza-12-crown-4 tetrahydrochloride, Tetraaza-12-crown-4 tetrahydrogen sulfate, 1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane, 12-crown-4, 15-crown-5, and 21-crown-7.
20. The solution of claim 1 wherein said one or more solvents is selected from the group consisting of water, a nonaqueous organic solvent and a nonaqueous inorganic solvent.
21. The solution of claim 1 wherein said one or more solvents comprise one or more polar nonaqueous solvents.
22. The solution of claim 1 wherein said one or more solvents comprise one or more solvents selected from the group consisting of .gamma.-butyrolactone, propylene carbonate, dimethyl carbonate, ethylene carbonate, acetonitrile, 1,2, -dimethoxy ethane, N,N-dimethyl formamide, dimethyl sulfoxide, 1,3-diolane, methyl formate, nitromethane, phosphoroxichloride, thionylchloride, sulfurylchloride, diethyl ether, diethoxy ethane, 1,3 -dioxolane, tetrahydrofuran, 2-methyl-THF, diethyl carbonate, ethyl methyl carbonate, methylacetate and tratahydrofurane.
23. The solution of claim 1 wherein said one or more solvents comprise one or more polar carbonates.
24. An electrolyte comprising the solution of claim 1.
25. An electrochemical device comprising the solution of claim 1.
26. A method for dissolving an inorganic fluoride in one or more solvents, said method comprising the steps of:
providing said one or more solvents;
providing a dissociating agent to said one or more solvents; and dissolving said inorganic fluoride in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M, thereby dissolving said inorganic fluoride into said one or more solvents.
providing said one or more solvents;
providing a dissociating agent to said one or more solvents; and dissolving said inorganic fluoride in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M, thereby dissolving said inorganic fluoride into said one or more solvents.
27. A solution comprising LiF dissolved in one or more solvents, said solution comprising:
said one or more solvents;
a dissociating agent provided to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and said LiF dissolved in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
said one or more solvents;
a dissociating agent provided to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and said LiF dissolved in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
28. The solution of claim 27 wherein said dissociating agent and LiF are provided in amounts sufficient to generate a concentration of LiF dissolved in said one or more solvents selected over the range of 0.15 M to 3M.
29. The solution of claim 27 wherein said dissociating agent and LiF are provided in amounts sufficient to generate a concentration of LiF dissolved in said one or more solvents selected over the range of 0.5 M to 1M.
30. The solution of claim 27 wherein said dissociating agent is provided in said one or more solvents at a concentration selected over the range of 0.1 M to 10 M.
31. The solution of claim 27 wherein said dissociating agent is one or more Lewis base or Lewis acid selected from the group consisting of an inorganic fluoride, an inorganic chloride, an inorganic carbonate, and an inorganic oxide.
32. The solution of claim 27 wherein said dissociating agent is one or more Lewis base selected from the group consisting of AlCl4-, ClO4 , SnCl62-, BF4-, PF6-, and AsF6-.
33. The solution of claim 27 wherein said dissociating agent is one or more Lewis acid selected from the group consisting of BF3, PF5, SbF5, AsF5, AlCl3, SnCl4, FeCl3, NbCl5, TiCl4, and ZnCl2.
34. The solution of claim 27 wherein said dissociating agent is provided by dissolving a precursor compound in said one or more solvents to generate a Lewis base, a Lewis acid or a Lewis acid and a Lewis base, said precursor compound comprising an alkali metal salt, alkaline earth metal salt; a transition metal salt or an ammonium salt having the formula:
AX:
(F3) wherein A is selected from the group consisting of a metal, a metal cation and a ammonium group; and wherein X is selected from the group consisting of a fluorinated anion, a perchlorate group, an imide group, a carbide group, a carbonate group, an oxide group and a chloride group.
AX:
(F3) wherein A is selected from the group consisting of a metal, a metal cation and a ammonium group; and wherein X is selected from the group consisting of a fluorinated anion, a perchlorate group, an imide group, a carbide group, a carbonate group, an oxide group and a chloride group.
35. The solution of claim 34 wherein said precursor compound is one or more lithium salt.
36. The solution of claim 34 wherein said precursor compound is one or more salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiClO4, LiSnCl5, LiAlCl4, LiFeCl4, LiNbCl6, LiTiCl5, LiZnCl3, NaPF6, NaBF4, NaAsF6, NaClO4, NaSnCl5, NaAlCl4, NaFeCl4, NaNbCl6, NaTiCl5, NaZnCl3, KPF6, KBF4, KAsF6, KClO4, KSnCl5, KAlCl4, KFeCl4, KNbCl6, KTiCl5, KZnCl3, NH4PF6, NH4BF4, NH4AsF6, NH4ClO4, NH4SnCl5, NH4AlCl4, NH4FeCl4, NH4NbCl6, NH4TiCl5, NH4ZnCl3, N(CH3)4ClO4, N(CH3)4SnCl5, N(CH3)4AlCl4, N(CH3)4FeCl4, N(CH3)4NbCl6, N(CH3)4TiCl5, N(CH3)4ZnCl3, N(C2H7)4ClO4, N(C2H7)4SnCl5, N(C2H7)4AlCl4, N(C2H7)4FeCl4, N(C2H7)4NbCl6, N(C2H7)4TiCl5, and N(C2H7)4ZnCl3.
37. The solution of claim 27 wherein said dissociating agent is one or more crown ether selected from the group consisting of Benzo-15-crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-15-crown-5, Dibenzo-18-crown-6, Dicyclohexyl-18-crown-6, Di-t-butyldibenzo-18-crown-6, 4,4i~(5i~)-Di-tert-butyldibenzo-24-crown-8, 4-Aminobenzo-15-Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert-Butylbenzo-15-crown-5, 4-tert-Butylcyclohexano-15-crown-5, 18-Crown-6, Cyclohexano-15-crown-5, Di-2,3-naphtho-30-crown-10, 4,4'(5')-Di-tert-butyldibenzo18-crown-6, 4'-(5')-Di-tert-butyldicyclohexano-18-crown-6, 4,4'(5')-Di-tert-butyldicyclohexano-24-crown-8, 4,10-Diaza-15-crown-5, Dibenzo-18-crown-6, Dibenzo-21-crown-7, Dibenzo-24-crown-8, Dibenzo-30-crown-10, Dicyclohexano-18-crown-6, Dicyclohexano-21-crown-7,Dicyclohexano-24-crown-8, 2,6-Diketo-18-crown-6, 2,3-Naphtho-15-crown-5, 4'-Nitrobenzo-15-crown-5, Tetraaza-12-crown-4 tetrahydrochloride, Tetraaza-12-crown-4 tetrahydrogen sulfate, 1,4,10,13-Tetraoxa-7,16-diazacyclooctadecane, 12-crown-4, 15-crown-5, and 21-crown-7.
38. The solution of claim 27 wherein said one or more solvents is selected from the group consisting of water, a nonaqueous organic solvent and a nonaqueous inorganic solvent.
39. The solution of claim 27 wherein said one or more solvents comprise one or more polar nonaqueous solvents.
40. The solution of claim 27 wherein said one or more solvents comprise one or more solvents selected from the group consisting of .gamma.-butyrolactone, propylene carbonate, dimethyl carbonate, ethylene carbonate, acetonitrile, 1,2, -dimethoxy ethane, N,N-dimethyl formamide, dimethyl sulfoxide, 1,3-diolane, methyl formate, nitromethane, phosphoroxichloride, thionylchloride, sulfurylchloride, diethyl ether, diethoxy ethane, 1,3 -dioxolane, tetrahydrofuran, 2-methyl-THF, diethyl carbonate, ethyl methyl carbonate, methylacetate and tratahydrofurane.
41. The solution of claim 27 wherein said one or more solvents comprise one or more polar carbonates.
42. An electrolyte comprising the solution of claim 27.
43. An electrochemical device comprising the solution of claim 27
44. A method for dissolving LiF in one or more solvents, said method comprising the steps of:
providing said one or more solvents;
providing a dissociating agent to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and dissolving LiF in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
providing said one or more solvents;
providing a dissociating agent to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and dissolving LiF in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
45. An electrolyte for an electrochemical device, said electrolyte comprising:
one or more solvents;
a dissociating agent provided to said one or more solvents; and an inorganic fluoride dissolved in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M.
one or more solvents;
a dissociating agent provided to said one or more solvents; and an inorganic fluoride dissolved in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M.
46. An electrochemical cell comprising: a positive electrode; a negative electrode; and the electrolyte of claim 45; said electrolyte provided between said positive electrode and said negative electrode.
47. An electrolyte for an electrochemical device, said electrolyte comprising:
one or more solvents;
a dissociating agent provided to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and LiF dissolved in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
one or more solvents;
a dissociating agent provided to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and LiF dissolved in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
48. An electrochemical cell comprising: a positive electrode; a negative electrode; and the electrolyte of claim 47; said electrolyte provided between said positive electrode and said negative electrode.
49. A method of making an electrolyte for an electrochemical device, said method comprising the steps of:
providing one or more solvents;
providing a dissociating agent to said one or more solvents; and dissolving an inorganic fluoride in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M, thereby making said electrolyte for said electrochemical device.
providing one or more solvents;
providing a dissociating agent to said one or more solvents; and dissolving an inorganic fluoride in said one or more solvents having said dissociating agent;
wherein said dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in said one or more solvents greater than or equal to 0.15 M, thereby making said electrolyte for said electrochemical device.
50. A method of making an electrolyte for an electrochemical device, said method comprising the steps of:
providing one or more solvents;
providing a dissociating agent to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether.
dissolving LiF in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M, thereby making said electrolyte for said electrochemical device.
providing one or more solvents;
providing a dissociating agent to said one or more solvents, said dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether.
dissolving LiF in said one or more solvents having said dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M, thereby making said electrolyte for said electrochemical device.
51. A solution having LiF dissolved in one or more solvents, said solution comprising:
said one or more solvents; and LiF dissolved in said one or more solvents; wherein the concentration of LiF
dissolved in said one or more solvents is greater than or equal to 0.15 M.
said one or more solvents; and LiF dissolved in said one or more solvents; wherein the concentration of LiF
dissolved in said one or more solvents is greater than or equal to 0.15 M.
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PCT/US2007/075697 WO2008105916A2 (en) | 2006-08-11 | 2007-08-10 | Dissociating agents, formulations and methods providing enhanced solubility of fluorides |
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WO2013157189A1 (en) | 2012-04-16 | 2013-10-24 | パナソニック株式会社 | Electrochemical energy storage device, active substance using same, and production method therefor |
DE102013218681A1 (en) * | 2013-09-18 | 2015-03-19 | Robert Bosch Gmbh | Method for operating a battery cell |
CN106030891B (en) * | 2013-12-18 | 2018-11-23 | 丰田自动车株式会社 | The manufacturing method of fluoride ion conducting electrolyte liquid and the manufacturing method of fluoride ion battery |
JP6067631B2 (en) * | 2014-08-06 | 2017-01-25 | トヨタ自動車株式会社 | Electrolyte for fluoride ion battery and fluoride ion battery |
JP6050290B2 (en) * | 2014-08-06 | 2016-12-21 | トヨタ自動車株式会社 | Electrolyte for fluoride ion battery and fluoride ion battery |
RU2592646C2 (en) * | 2014-11-14 | 2016-07-27 | Открытое Акционерное Общество " Научно-исследовательский и проектно-технологический институт электроугольных изделий" | Low-temperature lithium-fluocarbon element |
JP6342837B2 (en) * | 2015-04-03 | 2018-06-13 | トヨタ自動車株式会社 | Electrolyte for fluoride ion battery and fluoride ion battery |
JP6521902B2 (en) | 2016-06-02 | 2019-05-29 | トヨタ自動車株式会社 | Fluoride ion battery electrolyte and fluoride ion battery |
US10950893B2 (en) * | 2016-12-19 | 2021-03-16 | Honda Motor Co., Ltd. | Liquid electrolyte for battery |
JP7176256B2 (en) * | 2018-07-05 | 2022-11-22 | トヨタ自動車株式会社 | Fluoride ion battery and non-aqueous electrolyte |
JP7243508B2 (en) * | 2019-07-25 | 2023-03-22 | トヨタ自動車株式会社 | Fluoride ion battery and non-aqueous electrolyte |
JP7432906B2 (en) | 2022-03-03 | 2024-02-19 | 国立大学法人京都大学 | Electrode active materials, electrodes, electrochemical devices, modules and methods |
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US5705689A (en) * | 1995-06-19 | 1998-01-06 | Associated Universities, Inc. | Aza compounds as anion receptors |
TW434923B (en) * | 1998-02-20 | 2001-05-16 | Hitachi Ltd | Lithium secondary battery and liquid electrolyte for the battery |
EP1058331A4 (en) * | 1998-12-22 | 2004-07-07 | Mitsubishi Electric Corp | Electrolytic solution for celles and cells made by using the same |
EP1442489B1 (en) * | 2001-11-09 | 2009-09-16 | Yardney Technical Products, Inc. | Non-aqueous electrolytes for lithium electrochemical cells |
US6580006B1 (en) * | 2002-05-02 | 2003-06-17 | 3M Innovative Properties Company | Catalytic process for preparing perfluoroethanesulfonyl fluoride and/or perfluorodiethylsulfone |
US9184428B2 (en) * | 2005-03-15 | 2015-11-10 | Uchicago Argonne Llc | Non-aqueous electrolytes for lithium ion batteries |
-
2007
- 2007-08-10 EP EP07873790A patent/EP2054961A4/en not_active Withdrawn
- 2007-08-10 WO PCT/US2007/075697 patent/WO2008105916A2/en active Application Filing
- 2007-08-10 CA CA002660449A patent/CA2660449A1/en not_active Abandoned
- 2007-08-10 KR KR1020097005018A patent/KR20090064382A/en not_active Application Discontinuation
- 2007-08-10 JP JP2009524011A patent/JP2010500725A/en active Pending
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EP2054961A4 (en) | 2012-02-29 |
KR20090064382A (en) | 2009-06-18 |
WO2008105916A3 (en) | 2008-11-13 |
WO2008105916A2 (en) | 2008-09-04 |
JP2010500725A (en) | 2010-01-07 |
EP2054961A2 (en) | 2009-05-06 |
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