WO2006078866A2 - Electric current-producing device having sulfone-based electrolyte - Google Patents
Electric current-producing device having sulfone-based electrolyte Download PDFInfo
- Publication number
- WO2006078866A2 WO2006078866A2 PCT/US2006/001975 US2006001975W WO2006078866A2 WO 2006078866 A2 WO2006078866 A2 WO 2006078866A2 US 2006001975 W US2006001975 W US 2006001975W WO 2006078866 A2 WO2006078866 A2 WO 2006078866A2
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- WO
- WIPO (PCT)
- Prior art keywords
- och
- ocf
- electrolyte
- propyl
- group
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 113
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 50
- -1 cyclic sulfone Chemical class 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 33
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 239000002000 Electrolyte additive Substances 0.000 claims abstract 7
- 239000006184 cosolvent Substances 0.000 claims abstract 7
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 14
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 10
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 125000006002 1,1-difluoroethyl group Chemical group 0.000 claims description 5
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 5
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 5
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 150000008117 polysulfides Polymers 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000006091 1,3-dioxolane group Chemical class 0.000 claims description 4
- LFJJGHGXHXXDFT-UHFFFAOYSA-N 3-bromooxolan-2-one Chemical compound BrC1CCOC1=O LFJJGHGXHXXDFT-UHFFFAOYSA-N 0.000 claims description 4
- PUEFXLJYTSRTGI-UHFFFAOYSA-N 4,4-dimethyl-1,3-dioxolan-2-one Chemical compound CC1(C)COC(=O)O1 PUEFXLJYTSRTGI-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 229910012226 MBF4 Inorganic materials 0.000 claims description 4
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 4
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005077 polysulfide Substances 0.000 claims description 4
- 229920001021 polysulfide Polymers 0.000 claims description 4
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- KFJPWGWEQDFGDD-UHFFFAOYSA-N 4-fluoro-1,3,2-dioxathiolane 2-oxide Chemical compound FC1COS(=O)O1 KFJPWGWEQDFGDD-UHFFFAOYSA-N 0.000 claims 2
- 229910018374 MN(SO2CF3)2 Inorganic materials 0.000 claims 2
- 229910016079 MPF6 Inorganic materials 0.000 claims 2
- 125000006342 heptafluoro i-propyl group Chemical group FC(F)(F)C(F)(*)C(F)(F)F 0.000 claims 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000011241 protective layer Substances 0.000 abstract 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
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- 159000000002 lithium salts Chemical class 0.000 description 15
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 15
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 229910003092 TiS2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- XMVHIXPXKJRKRE-UHFFFAOYSA-N methoxy(methylsulfonyl)methane Chemical compound COCS(C)(=O)=O XMVHIXPXKJRKRE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- QJDUDPQVDAASMV-UHFFFAOYSA-M sodium;ethanethiolate Chemical compound [Na+].CC[S-] QJDUDPQVDAASMV-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates in general to nonaqueous electrolyte solvents for use in electric current- producing devices and, more particularly, to non-aqueous electrolyte solvents having a non-symmetrical, non-cyclic sulfone, which are suitable for use in electric current- producing devices .
- Batteries are commonly used to power many types of motors and electronic devices for use in portable applications .
- the battery may be rechargeable or disposable (one-shot usage) type .
- the battery provides operating power for integrated circuits in portable electronic systems , or provides an electromotive force to drive motors for industrial applications .
- Battery-powered automobiles offer many interesting possibilities for fulfilling transportation needs , while reducing energy consumption, and minimizing hazard to the environment .
- Automobile batteries must be rechargeable and preferably deliver high voltages , e . g . greater than 4.5 VDC, to provide adequate power to the motor .
- the battery should also have good electrochemical stability, safety and longevity.
- Sulfones can generally be divided into two types : the aromatic sulfones and the aliphatic sulfones .
- the aliphatic sulfones can also be divided into two types-the cyclic (commonly referred to as sulfolanes ) and non-cyclic .
- the non-cyclic aliphatic sulfones form a potentially-attractive group of organic solvents that present a high chemical and thermal stability.
- EMS ethyl methyl sulfone
- 2M LiPF ⁇ /EMS has been used as the supporting electrolyte in a dual graphite cell which operates around 5.5v
- IM LiPF 6 /EMS has been used as the electrolyte in Li/T2- Lia /3 [Nii /3 Mn 2/3 _ O 2 cell which operates up to 5.4v.
- EMS applications are limited by a shortcoming, i . e .
- the present invention is an electrolyte element for use in an electric current-producing device comprising one or more ionic electrolyte salts and a non-aqueous electrolyte solvent including one or more nonsymmetrical, non-cyclic sulfones of the general formula : Rl- SO2-R2.
- the Rl group is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms .
- the R2 group which is different in formulation than the Rl group, is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms .
- the present invention is an electric current-producing device comprising a cathode and an anode .
- a non-aqueous electrolyte element is disposed between the cathode and anode .
- the non-aqueous electrolyte element includes an electrolyte salt and a non-symmetrical , non- cyclic sulfone of the general formula : R1-SO2-R2.
- Rl is an alkyl group
- R2 is an alkyl group including oxygen .
- the present invention is an electrolyte for a electric current-producing device comprising an non-aqueous electrolyte solvent including an non-symmetrical , non-cyclic sulfone of the general formula : R1-SO2-R2.
- Rl is an alkyl group
- R2 is an alkyl group including oxygen .
- the present invention is a method of forming an electric current-producing device, comprising the steps of providing a cathode, providing an anode, and providing a non-aqueous electrolyte element disposed between the cathode and anode .
- the non-aqueous electrolyte element includes an electrolyte salt and a nonsymmetrical , non-cyclic sulfone of the general formula : Rl- SO2-R2.
- Rl is an alkyl group
- R2 is an alkyl group including oxygen .
- FIG . 1 illustrates a lithium battery providing power to a load
- FIG . 2 illustrates non-symmetrical , non-cyclic sulfone group coupled with a Rl alkyl group and R2 oxygen containing alkyl group;
- FIG . 3 is a graph of conductivities of IM LiTFSI in different sulfones ;
- FIGs . 4a-4b are graphs of electrochemical stability ranges ( "windows" ) for IM LiTFSI in different sulfone solutions ;
- FIG . 5 is a graph of performance of the cell MCMB25-28 I 1M LiPF 6 /EMES
- FIGs . 6a-6b are graphs of cell performance under different current densities ;
- FIG . 7 is a graph of charge/discharge capacity and coulomb efficiency of the cell LiCr 0 - OI sMn L 985 O 4 I lM LiPF 6 /EMES
- FIGs . 8a-8b are graphs of charge and discharge profile of half cell of Li
- FIGs . 9a-9b are graphs of temperature dependence of ionic conductivities of 1.
- OM lithium salts A) 1. OM lithium salts in EMES containing 5wt% carbonates (EC and DMC) and ethylene sulfite (ES) ; B) 1.0MLiPF 6 in EMES containing different percentage of EC;
- FIGs . 1Oa-IOd are graphs of cyclic voltammograms for IM LiPF 6 in different EMES/EC mixtures , A) 5wt% EC; B) 10wt% EC; C) 20wt% EC; D) 30wt% EC;
- FIGs . lla-lld are graphs of cyclic voltammograms for IM LiPF 6 in different EMES/DMC mixtures, A) 5wt% DMC; B) 10wt% DMC; C) 20wt% DMC; D) 30wt% DMC;
- FIG . 12 is a graph of a first lithium intercalation and de-intercalation profile on graphite electrode using different 1.
- OM LiPF 6 electrolyte solutions
- FIG . 13 is a graph of a first charge and discharge profile of full cell of graphite
- FIG . 14 is a graph of an electrochemical window for IM LiClO 4 in EMES/ES mixture .
- FIG . 1 illustrates electric current-producing device 10 providing electrical power to load 12.
- the electric current-producing device 10 is a battery or other voltaic cell .
- the electric current-producing device 10 is a supercapacitor .
- Device 10 may include a lithium-ion cell or lithium metal cell, or plurality of such cells .
- Device 10 has anode 14 , cathode 16, and electrolyte 18. Anode 14 and cathode 16 are connected to load 12 to provide electrical power to the load.
- Electrolyte 18 contains a non-aqueous electrolyte element comprising a non-symmetrical, non-cyclic sulfone component , as described fully hereinafter, that is stable in the presence of the anode and cathode .
- Load 12 may be an electronic system, equipment in an industrial application, or motor for an automobile, j ust to name a few .
- the material of anode 14 has one or more metals or metal alloys selected from the Group IA and HA metals in the Periodic Table .
- anode 14 may be made with lithium or sodium.
- the anode may also be alkali-metal intercalated carbon, such as LiCx where x is equal to or greater than 2.
- alkali- metal intercalated conductive polymers such as lithium, sodium or potassium doped polyacetylenes , polyphenylenes , polyquinolines , and the like .
- Examples of other suitable anode material are lithium metal, lithium-aluminum alloys , lithium-tin alloys , lithium-intercalated carbons , lithium- intercalated graphites , calcium metal, aluminum, sodium, and sodium alloys .
- Cathode 16 may be made with any of the commonly used cathode active materials .
- suitable cathode active materials are inorganic insertion oxides and sulfides , metal chalcogenides , elemental sulfur, organo-sulfur and carbon-sulfur polymers , conjugated polymers , and liquid cathodes .
- Useful inorganic insertion oxides include Co02 , NiO2 , Mn02 , Mn204 , V6O13 , V2O5 , and blends thereof .
- Useful inorganic sulfides include TiS2 , MoS2 , and the like .
- Suitable conj ugated polymers include polyacetylene, poly (phenylene vinylene ) , and polyaniline .
- Useful liquid cathodes include S02 , S0C12 , SO2C12 , and POC13.
- Useful organo-sulfur materials include those disclosed in U . S . Patent Nos . 4 , 833 , 048 ; 4 , 917 , 974 ; 5 , 324 , 599; and 5 , 516, 598.
- Further examples of useful cathode active materials include organo-sulfur polymer materials , as described in U . S . Patent No .
- Sulfur containing cathode active organic materials as described in these disclosures comprise, in their oxidized state, a polysulfide moiety of the formula, -5m- , wherein m is an integer equal to or greater than 3.
- Cathode 16 may further comprise one or more materials selected from the group consisting of: binders , electrolytes , and conductive additives , usually to improve or simplify their fabrication as well as improve their electrical and electrochemical characteristics .
- Useful conductive additives are those known to one skilled in the art of electrode fabrication and are such that they provide electrical connectivity to the maj ority of the electroactive materials in the composite cathode . Examples of useful conductive fillers include conductive carbons
- binder and conductive filler can vary widely and the amounts present will depend on the desired performance .
- the amount of binder will vary greatly, but will generally be less than about 15 wt% of the composite cathode .
- the amount of conductive filler used will also vary greatly and will typically be less than 20 wt% of the composite cathode .
- Useful amounts of conductive additives are generally less than 12 wt% .
- binder material may vary widely so long as it is inert with respect to the composite cathode materials .
- Useful binders are those materials , usually polymeric, that allow for ease of processing of battery electrode composites .
- useful binders are organic polymers such as polytetrafluoroethylenes (TEFLONTM) , polyvinylidine fluorides ( PVF2 or PVDF) , ethylene-propylene- diene (EPDM) rubbers, polyethylene oxides ( PEO) , UV curable acrylates , UV curable methacrylates , and UV curable divinylethers , and the like .
- Electrolyte 18 plays an important role in the electrochemical performance of electric current- producing device 10 , including the ability to generate high output voltages for maximum power transfer .
- Electrolyte elements are useful in electrolytic cells , rechargeable batteries , electric capacitors , fuel cells , and function as a medium for storage and transport of ions .
- electrolyte element relates to an element of an electric current-producing device which comprises an electrolyte solvent, one or more electrolyte salts , and optionally other additives including polymer electrolytes and gel-polymer electrolytes .
- Any liquid, solid, or solid-like material capable of storing and transporting ions may be used, so long as the material is chemically inert with respect to anode 14 and cathode 16, and the material facilitates the transportation of ions between the anode and the cathode .
- these materials may additionally function as separator materials between the anode and cathode .
- the electrolyte elements of the present invention include one or more ionic electrolyte salts and a non-aqueous electrolyte solvent .
- the non-aqueous electrolyte solvent contains one or more non-symmetrical, non-cyclic sulfones , and optionally other additives , such as one or more electrolyte co-solvents , gelling agents , ionically conductive solid polymers , and/or other additives .
- the electrolyte elements may be prepared by dissolving one or more ionic electrolyte salts in one or more non-aqueous electrolyte solvents .
- a new sulfone is introduced into the composition of electrolyte 18.
- the sulfones are provided in the battery electrolyte to increase the possible output voltage and available power from the battery .
- sulfones with different length of oligo ethylene glycol segments have been synthesized and tested for use in rechargeable lithium batteries .
- Relative to the model compound EMS which has a melting point of 36.5°C, the new sulfones have low melting points , mostly depressed below room temperature . Their conductivities are lower than that of EMS .
- the highest ambient temperature conductivity of 10 "2 > 58 S . cm "1 is obtained for 0.7M LiTFSI/MEMS solution .
- the sulfones show wide electrochemical stability windows , in excess of 5. Ov vs Li/Li + , increasing with decreasing length of the oligoether chains . A cell with lithium metal anode and manganate cathode performed well, maintaining high coulomb efficiency over 200 cycles .
- the non-aqueous electrolyte solvents include a nonsymmetrical, non-cyclic sulfone, suitable for use in electric current-producing devices , such as device 10. As shown in FIG . 2 , the non-symmetrical, non-cyclic sulfone has the general formula : R1-SO2-R2.
- the SO2 group 20 represents the sulfone group .
- the Rl group 22 is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms .
- the R2 group 24 is a linear or branched or partially or fully fluorinated linear or branched alkyl group containing oxygen and having 1 to 7 carbon atoms .
- the Rl and R2 groups each have 1 to 4 carbon atoms .
- the SO2 sulfone group is the same group that occurs in the following compounds : ethylmethyl sulfone (EMSF, CH3CH2-SO2-CH3 ) , ethyl-iso-propyl sulfone (EiPSF, CH3CH2-SO2- CH (CH3 ) 2 ) , ethyl-sec-butyl sulfone (EsB SF, CH3CH2-SO2- CH (CH3 ) (CH2CH3 ) ) , ethyl-iso-butyl sulfone (EiBSF) .
- Rl alkyl group examples are : methyl (-CH 3 ) ; ethyl (-CH 2 CH 3 ) ; n-propyl (-CH 2 CH 2 CH 3 ) ; n-butyl ( -CH 2 CH 2 CH 2 CH 3 ) ; n-pentyl (-CH 2 CH 2 CH 2 CH 2 CH 3 ) ; n-hexyl ( -CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) ; n- heptyl ( -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) ; iso-propyl (-CH (CH 3 ) 2 ) ; iso- butyl (-CH 2 CH (CH 3 ) 2 ) ; sec-butyl (-CH (CH 3 ) CH 2 CH 3 ) ; tert-butyl (- C (CH 3 ) 3 ) ; iso-pentyl ( -CH 2 CH 2 CH (
- R2 oxygen containing alkyl group examples are: -CH 2 OCH 3 ; -CF 2 OCH 3 ; -CF 2 OCF 3 ; -CH 2 CH 2 OCH 3 ; -CH 2 CF 2 OCH 3 ; -CF 2 CH 2 OCH 3 ; -CF 2 CF 2 OCH 3 ; -CF 2 CH 2 OCF 3 ; -CH 2 CF 2 OCF 3 ; -CH 2 CH 2 OCF 3 ; -CHFCF 2 OCF 2 H; -CF 2 CF 2 OCF (CF 3 ) 2 ; -CF 2 CH 2 OCF (CF 3 ) 2 ; - CH 2 CF 2 OCF (CF 3 ) 2 ; - CH 2 CF 2 OCF (CF 3 ) 2 ; -CH 2 CH 2 OCF (CF 3 ) 2 ; -CH 2 CH 2 OCF (CF 3 ) 2 ; -CF 2 CF 2 OC (CF 3 ) 3 ; -CF 2 CH 2 OC
- the Rl alkyl group may also contain oxygen, e.g. using any one of the formulations described for the R2 group.
- the Rl and R2 groups will each have a different formulation from the other, e.g. in terms of chemical structure or length of segments.
- One group of electrolyte salts includes MC104, MPF ⁇ , MPF x (C n F 2n+ I) 6 -X, MBF4 , MBF 4 -X (CnF 2n+ I) x , MAsF ⁇ , MSCN, MB (CO 2 ) 4 ("LiBOB”) , and MSO3CF3, where "M” represents lithium or sodium. Also available are electrolyte solutions including MN ( SO2CF3 ) 2 as the electrolyte salt , which exhibits exceptionally high conductivity combined with high chemical and electrochemical stability .
- the electrolyte elements may further include one or more liquid electrolye co-solvents ( i . e . , in addition to a non-symmetrical, non-cyclic sulfone) , gelling agents, ionically conductive solid polymers , and other additives .
- suitable electrolyte co-solvents , gelling agents or ionically conductive solid polymers include any of those commonly used with lithium metal and lithium-ion cells .
- suitable liquid electrolyte co-solvents for use in the electrolyte elements include any one of the commonly used electrolyte solvents .
- Examples of useful liquid electrolyte co-solvents include carbonates , N-methyl acetamide , acetonitrile, symmetric sulfones , sulfolanes , 1 , 3-dioxolanes , glymes , polyethylene glycols , siloxanes , and ethylene oxide grafted siloxanes , and blends thereof .
- Examples of useful carbonates include ethylene carbonate (EC) and propylene carbonate ( PC) .
- Examples of useful glymes includes tetraethyleneglycol dimethyl ether (TEGDME) and 1 , 2- dimethoxyethane .
- Liquid electrolyte elements are often used in combination with one of the common porous separators .
- Liquid electrolyte solvents or plasticizing agents are often themselves useful as gel forming agents for gel-polymer electrolytes .
- gelling agents which are useful in the electrolyte elements are those prepared from polymer matrices derived from polyethylene oxides ( PEO) , polypropylene oxides , polyacrylonitriles , polysiloxanes , polyimides , polyethers , sulfonated polyimides , perfluorinated membranes (NafionTM resins ) , polyethylene glycols, polyethylene glycol-bis- (methyl acrylates ) , polyethylene glycol-bis (methyl methacrylates ) , derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, blends of the foregoing, and the like .
- Examples of ionically conductive solid polymers suitable for use in the electrolyte elements are those having polyethers , polyethylene oxides ( PEO) , polyimides , polyphosphazenes , polyacrylonitriles ( PAN) , polysiloxanes , polyether grafted polysiloxanes , derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing, to which is added an appropriate ionic electrolyte salt .
- Ionically conductive solid polymers electrolytes may additionally function as separator materials between the anode and cathode .
- additives which are useful in the electrolyte elements include soluble additives , such as : vinylene carbonate (VC) , ethylene sulfite (ES) , propylene sulfite
- the non-aqueous electrolyte solvents are particularly useful in electrolytic cells, rechargeable batteries , electric capacitors , fuel cells , and the like, which comprise non-aqueous electrolyte elements and which require high energy storage capacity, long shelf life, and a low rate of self-discharge .
- the electrolyte solvents are particularly useful in electrolytic cells comprising alkali- metal-containing electrodes , and particularly to lithium intercalation electrodes .
- the high oxidation resistance of the ambient temperature electrolyte solutions of the present invention result from the stability of the -SO2- group when in a non- cyclic, non-symmetric sulfone structure, characterized by freezing temperatures low enough to enable utilization in ambient temperature applications .
- FIG . 3 illustrates the DC electrical conductivities of electrolytes of various solutions of alkali metal salts in sulfones .
- Glass transition temperature T g was measured using a DTA instrument .
- the heating rate was 10K/min .
- T 9 was defined as the onset temperature of the heat capacity jump and T m was defined as the temperature at which the melting peak reaches its maximum. The boiling point was recorded during the distillation process .
- Electrolyte solutions of different salt concentrations were prepared by dissolving calculated amount of lithium salts in the respective sulfones .
- the measurement of DC conductivity was carried out using an automated frequency impedance analyzer . The measurements were made automatically during heating of the precooled samples at lK/min by means of a programmed controller .
- To determine electrochemical characteristics cyclic voltammetry was performed using a potentiostat/galvanostat with a three- electrode cell .
- the working electrode was a platinum wire, and the counter and reference electrodes were lithium foil in the voltage range of -0.3-6. OV. Most scans were made at room temperature at a typical scan rate of lmv/s .
- Electrochemical half cells Li
- were constructed using fiberglass paper as the separator .
- the cathode solution consisting of 82% active material, 10% carbon black and 8% PVdF in N-methylpyrrolindone was cast directly on the pre-weighed stainless steel electrode . The electrode was dried, first at room temperature and then at 100 0 C under vacuum for two days . The weight of the electrode was determined inside the dry box, and the weight of active material obtained by difference .
- the anode composite electrodes were made in a similar way from a slurry of 90% MCMB25-28 and 10% PVdF in N-methylpyrrolindone .
- the cell construction and the tests were all carried out in an argon- filled glove box .
- the voltage profile of the charge/discharge process was monitored using a battery cycler .
- a constant current ranging from 0.01 ⁇ 0.1 mA/cm 2 was used with pre-set cut-off voltage of 0.01-2.
- cell At these cut-off voltages a computerized cycler automatically switched the test cells to charge or discharge .
- the glass transition temperatures of the new sulfones are described as follows .
- the glass transition temperature increases with increasing ether chain length, see Table 1 , implying that the increasing molecular weight effect offsets the decrease in T g expected from the dilution of the cohesive sulfone groups .
- FIG . 4a shows EMES
- FIG. 4b is EMEES
- the cyclic voltammetry scans are well above 5.
- FIGs . 4a-4b also show that, with increasing ether chain length, the electrochemical stability decreases , from 5.6v for EMES , 5.3v for EMEES , (vs 5.9v for EMS ) showing that stability advantage of sulfone, as a class of solvent, is diminishing with increasing ether group concentration .
- FIG . 4a shows EMES
- FIG. 4b shows EMEES
- the cyclic voltammetry scans are well above 5.
- FIGs . 4a-4b also show that, with increasing ether chain length, the electrochemical stability decreases , from 5.6v for EMES , 5.3v for EMEES , (vs 5.9v for EMS ) showing that stability advantage of s
- FIG. 5 shows a test of the ether sulfone-based solutions for reversible intercalation into the graphite designated MCMB25-28 , for the first three cycles of the cell MCMB25-28
- the corresponding charge and discharge capacities of the first three cycles are 343.0 , (202.8 ) ; 251.4 , (200.5 ) ; 219.2 , ( 193.0 ) mAh/g, respectively.
- the performance of the new solutions with lithium metal anodes and Cr 3+ -modified LiMn 2 O 4 spinel intercalation cathodes are tested .
- FIG ⁇ a-6b compare the cell performance using different IM lithium salts in EMES during the first cycle under different current densities .
- FIG . 6a shows data from the cell using IM LiTFSI/EMES electrolyte .
- FIG . 6b shows data from the cell using IM LiPFg/EMES electrolyte .
- Each cell shows two well-defined discharge plateaus , around 4.0 and 4.1v versus Li/Li , + respectively. It is also seen that the capacities decrease with increasing current density.
- FIG. 7 The corresponding cell performance under the current density of 0.092mA cm "2 using IM LiPF 6 /EMES in terms of charge/discharge capacities and coulomb efficiency is shown in FIG . 7.
- This cell showed excellent cyclability, more than 200 cycles , tending to stabilize after 200 cycles at a discharge capacity around 50 mAh/g and a stable coulomb efficiency around 0.86.
- the novel non-cyclic, nonsymmetrical sulfones are substituted with perfluoromethyl (trifluoromethyl, -CF3) or perfluoromethylene (-CF2 ) groups .
- Substitution of a methyl, -CH3 , group by a perfluoromethyl, - CF3 is surprisingly found to advantageously decrease the viscosity of the sulfone, thereby increasing the conductivity of the electrolyte solutions and increasing the penetration of the electrolytes into the cathode and separator in electrolytic cells at ambient conditions .
- CF3CH2SO2CH3 (2 , 2 , 2-trifluoroethylmethyl sulfone, CF3MMSF) and CF3CH2CH2SO2CH3 (CF3EMSF) .
- CF3MMSF which exhibits very high conductivity, for example, in lithium chlorate solutions .
- the fluorinated non-symmetrical , non-cyclic sulfone further offers superior wetting, penetration and other surfactant properties .
- Example 1 involving preparation of methoxyethyl methyl sulfone (MEMS ) , 45.6 g thiourea was dissolved in 150ml water, 28.8ml dimethyl sulfate was added and the solution was refluxed for lhour . After cooling to room temperature, 48g NaOH in 75 ml distilled water was added and the solution was stirred for 1 hour, then 55g chloroethyl methyl ether (ClCH 2 CH 2 OCH 3 ) was added dropwise . After addition the solution was slowly heated to reflux for 10 hours .
- MEMS methoxyethyl methyl sulfone
- the upper organic layer was separated to obtain the methoxyethyl methyl sulfide (CH 3 OCH 2 CH 2 SCH 3 ) with a yield of 55% .
- the sulfide was set to oxidation with 30wt% H 2 O 2 in acetic acid . On completion of oxidation, most of the solvent was removed. Dilute NaOH aqueous solution was added to neutralize excess acetic acid . Water was removed by rotary evaporation and the residual paste was extracted with chloroform at least three times . The chloroform was combined and dried over anhydrous sodium sulfate . Finally chloroform was removed and the crude product was distilled under vacuum at 95-100 0 C to obtain the pure product MEMS .
- Example 2 involving preparation of MEMS, pre- weighed empty bottle was cooled in dry ice acetone solution and Methane thiol was slowly charged into the bottle .
- the net weight of methanethiol was obtained by the difference before and after weighing as 21.5g . 71. ⁇ g 25wt% NaOH aqueous solution was charged into stainless steel pressure vessel and cooled with ice water .
- the vessel was vacuumed and then under stirring methanethiol was slowly charged into the vessel .
- the solution was stirred for lhr before 38g chloroethyl methyl ether (ClCH 2 CH 2 OCH 3 ) was added.
- Example 3 involving characterization of MEMS, glass transition temperature T 9 was measured using a DTA instrument .
- the heating rate used was 10K/min .
- T g was defined as the onset temperature of the heat capacity j ump and T m was defined as the temperature at which the melting peak reaches its maximum.
- the boiling point was recorded during the distillation process .
- the T 9 and T m of MEMS are - 89.5 0 C and 15°C respectively, as shown in Table 1.
- the boiling point of MEMS is estimated as 275°C at atmosphere pressure .
- Electrolyte solutions of different salts were prepared by dissolving calculated amount of lithium salts in MEMS at about 80 0 C, in the case of LiPF 6 salt the temperature is controlled around 50 0 C .
- the measurement of DC conductivity was carried out using a frequency impedance analyzer .
- the measurements were made automatically during heating of the pre-cooled samples at lK/min by means of a programmed controller .
- the temperature dependence curve for MEMS containing 1. OM LiTFSI is shown in FIG . 3.
- the T g and room temperature ionic conductivities of 1. OM different lithium salts in MEMS are shown in Table 2.
- Table 2 shows glass transition temperature (T g /°C) and room temperature conductivity log ( ⁇ 2 s/S cm "1 ) of IM different lithium salt solution in different sulfones .
- Example 4 involving preparation of ethyl methoxyethyl sulfone (EMES ) , 57g NaOH was dissolved in 57g H 2 O and cooled with ice water, 88.4g ethanethiol was added to the solution slowly . The solution was stirred for half hour before 135g chloroethyl methyl ether (ClCH 2 CH 2 OCH 3 ) was added. After addition the solution was stirred at room temperature for several hours before it was heated to reflux for overnight . The reaction was stopped and cooled to room temperature .
- EMES ethyl methoxyethyl sulfone
- Ethyl methoxyethyl sulfide ( CH 3 CH 2 SCH 2 CH 2 OCH 3 ) in the upper organic layer was separated, 156g, yield 91% .
- lOOg Ethyl methoxyethyl sulfide was set up for oxidation with 17Og 50wt% H 2 O 2 and 200ml acetic acid. After work up as in Example 1 the crude sulfone was distilled and the fraction at 85-88 0 C /0.3Torr is collected.
- Example 5 involving characterization of EMES, the T g and T m of EMES are -91. O 0 C and 2 0 C respectively, as shown in Table 1.
- the boiling point of MEMS is estimated as 28 ⁇ °C at atmosphere pressure .
- Salt solutions of EMES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3.
- the temperature dependence curve for EMES containing 1. OM LiTFSI is shown in FIG . 3.
- the T g and room temperature ionic conductivities of 1. OM of different lithium salts in EMES are shown in Table 2.
- Example 6 involving an electric current- producing device employing EMES electrolytes , electrochemical half cells , Li
- are constructed using fiber glass paper as the separator .
- the cathode solution consisting of 82% active material, 10% carbon black and 8% PVdF in N-methylpyrrolindone is cast directly on the pre- weighed stainless steel electrode .
- the electrode is dried, first at room temperature and then at 100 0 C under vacuum for two days .
- the weight of the electrode is determined inside the dry box, and the weight of active material obtained by difference .
- the MCMB25-28 composite electrodes are made in a similar way from slurry of 90% MCMB25-28 and 10% PVdF in N- methylpyrrolindone .
- Test cells were constructed by using Whatman glass fiber filter soaked in the electrolyte solution of Example 5 as the separator and a lithium anode and (or MCMB25-28 ) cathode . The tests were all carried out in an argon-filled glove box . The voltage profile of the charge/discharge process was monitored using a battery cycler . A constant current ranging from 0.01 ⁇ 0.1 mA/cm 2 were used with pre-set cut-off voltage of 0.01-2. OV for Li
- FIGs . 5 , 6a-b, and 7 The test results are shown in FIGs . 5 , 6a-b, and 7 , respectively.
- Another set of experiments are performed using commercial electrode sheets ( synthetic graphite and LiCoO 2 ) .
- the electrodes are cut into disc with area of 0.72 cm 2 and assembled either in a half cell of Li
- LiCoO 2 A constant current density of 0.14 mA/cm 2 was used for both charging and discharging with pre-set cut-off voltage of 0.01-2.
- LiCoO 2 cell The result is shown in FIGs . 8a-8b .
- Example 7 involving characterization of mixtures of EMES with carbonates, the mixtures of EMES with carbonates were prepared by mixing different weight percentage of either ethylene carbonate (EC) or dimethyl carbonate ( DMC) in EMES .
- EC ethylene carbonate
- DMC dimethyl carbonate
- OM LiPF 6 electrolyte solution was prepared by dissolving the salt in the mixtures at about 50 0 C, as described in Example 3.
- the ionic conductivities were measured using the method described in Example 3 and their temperature dependence curves are shown in FIGs . 9a-9b . Addition of EC to the electrolyte solution increases the ionic conductivities in all cases due to the higher dielectric constant of EC .
- FIGs . 1Oa-IOd and lla-lld are graphs of cyclic voltammograms for IM LiPF ⁇ in different EMES/EC mixtures .
- FIGs . lla-lld are graphs of cyclic voltammograms for IM LiPF ⁇ in different EMES/DMC mixtures .
- Note that the electrochemical stability windows are all higher than 5.2v.
- Example 8 ethylene sulfite (ES) is chosen as an additive and mixed with EMES at the composition of 5wt% .
- ES ethylene sulfite
- OM LiClO 4 electrolyte was prepared by dissolving the salt in the mixture of EMES/ES at about 80 0 C, as described in Example 3. The ionic conductivities were measured using the method described in Example 3 and its temperature dependence curve shown in FIGs . 9a-9b is higher than that of 1.
- OM LiPF 5 /EMES solution a
- Example 9 involving synthesis of ethyl methoxyethoxyethyl sulfone (EMEES ) , 4Og NaOH was dissolved in 4Og H 2 O and cooled with ice water . 62g ethanethiol was added to the solution slowly.
- EEES ethyl methoxyethoxyethyl sulfone
- Example 10 involving characterization of ethyl methoxyethoxyethyl sulfone (EMEES) , the T g of EMEES is -87.6°C as shown in Table 1. Salt solutions of EMEES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3. The temperature dependence curve for EMEES containing 1. OM LiTFSI is shown in FIG . 3. The T 9 and room temperature ionic conductivities of 1. OM of different lithium salts in EMEES are shown in Table 2. The cyclic voltammogram of IM LiTFSI/EMEES electrolyte was measured, as described in Example 5 , which is shown in FIG. 4b .
- Example 11 involving synthesis of ethyl methoxyethoxyethoxyethyl sulfone (EMEEES) , 4Og NaOH was dissolved in 4Og H 2 O and cooled with ice water, 62g ethanethiol was added to the solution slowly. The solution was stirred for half hour before 182.5g chloroethyl methoxyethoxyethyl ether ( CICH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ) was added . After addition the solution was stirred at room temperature for several hours before it was heated to reflux for overnight . The reaction was stopped and cooled to room temperature .
- EEEES ethyl methoxyethoxyethoxyethyl sulfone
- Ethyl methoxyethoxyethoxyethyl sulfide ( CH 3 CH 2 SCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ) in the upper organic layer was separated with a yield of 95% .
- the sulfide was further oxidized with H 2 O 2 and acetic acid, as described in Example 1 , to obtain the ethyl methoxyethoxyethoxyethyl sulfone ( EMEEES ) .
- Example 12 involving characterization of ethyl methoxyethoxyethoxyethyl sulfone (EMEEES ) , the T 9 of EMEEES is -82.5 0 C, as shown in Table 1.
- Salt solutions of EMEEES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3.
- the temperature dependence curve for EMEEES containing 1. OM LiTFSI is shown in FIG . 3.
- the T 9 and room temperature ionic conductivities of 1. OM of different lithium salts in EMEEES are shown in Table 2.
- Example 13 involving synthesis of dimethoxyethyl sulfone ( DMES ) , 50ml 2-chloroethyl methyl ether, 70g Na 2 S .9H 2 O, 17. ⁇ g tetrabutylammonium bromide and 50ml H 2 O were mixed into a three-neck flask equipped with magnetic stirrer and reflux condenser, and heated at 70 0 C with vigorous stirring . The reaction was continued for overnight . The organic layer was separated and dissolved in chloroform, washed with distilled water several times to remove the ammonium salt and dried over anhydrous sodium sulfate .
- DMES dimethoxyethyl sulfone
- Example 14 involving characterization of dimethoxyethyl sulfone (DMES ) , the T 9 and T m of DMES are - 90.7 0 C and 47. O 0 C, respectively, as shown in Table 1.
- Salt solutions of DMES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3.
- the temperature dependence curve for DMES containing 1. OM LiTFSI is shown in FIG . 3.
- the T 9 and room temperature ionic conductivities of 1. OM of different lithium salts in DMES are shown in Table 2.
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Abstract
A battery has electrolyte disposed between an anode and a cathode. The electrolyte contains ionic electrolyte salts and a non-aqueous electrolyte solvent which includes a nonsymmetrical, non-cyclic sulfone. The sulfone has the general formula: R1-SO2-R2, wherein Rl is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms, and R2 is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms. The electrolyte further includes an electrolyte co-solvent and an electrolyte additive for protective layer formation. The present sulfone is useful for generating higher output voltages for the battery.
Description
Electric Current-Producing Device having Sulfone-based Electrolyte
Statement Regarding Federally-Sponsored Research or Development
[0001] The U . S . Government has a paid-up license in the present invention and the right in limited circumstances to require the patent owner to license others on fair and reasonable terms as provided by the terms of Grant No . DEFG039ER14378-003 and DEFG03945541 awarded by the US Department of Energy .
Claim to Domestic Priority
[0002] The present non-provisional patent application claims priority to provisional application serial no . 60/645 , 536 entitled "New Sulfone Electrolytes for Rechargeable Lithium Batteries", filed on January 19, 2005 , by Xiao-Guang Sun et al .
Field of the Invention
[0003] The present invention relates in general to nonaqueous electrolyte solvents for use in electric current- producing devices and, more particularly, to non-aqueous electrolyte solvents having a non-symmetrical, non-cyclic sulfone, which are suitable for use in electric current- producing devices .
Background of the Invention
[0004] Batteries are commonly used to power many types of motors and electronic devices for use in portable applications . The battery may be rechargeable or disposable (one-shot usage) type . The battery provides operating power for integrated circuits in portable electronic systems , or provides an electromotive force to drive motors for industrial applications .
[0005] One area of particular interest is automotive power trains . Battery-powered automobiles offer many interesting possibilities for fulfilling transportation needs , while reducing energy consumption, and minimizing hazard to the environment . Automobile batteries must be rechargeable and preferably deliver high voltages , e . g . greater than 4.5 VDC, to provide adequate power to the motor . The battery should also have good electrochemical stability, safety and longevity.
[0006] Common types of rechargeable battery are known as lithium-ion cell and lithium metal cell . U . S . Patent Nos . 5 , 460 , 905 ; 5 , 462 , 566 ; 5 , 582 , 623 ; and 5 , 587 , 253 describe the basic elements and performance requirements of lithium batteries and their components . A key issue in the development of high energy batteries is the choice of the electrolyte element to improve the possible output voltage, stability, cycle life, and safety of the battery. A large number of non-aqueous organic solvents have been suggested and investigated as electrolytes in connection with various types of cells containing lithium electrodes . U . S . Patent Nos . 3 , 185 , 590 ; 3 , 578 , 500 ; 3, 778 , 310 ; 3 , 877 , 983 ; 4 , 163 , 829 ; 4 , 118 , 550 ; 4 , 252 , 876; 4 , 499, 161 ; 4 , 740 , 436; and 5 , 079, 109 describe many possible electrolyte element combinations and electrolyte solvents , such as borates , substituted and
unsubstituted ethers , cyclic ethers , polyethers , esters , sulfones , alkylene carbonates, organic sulfites , organic sulfates , organic nitrites and organic nitro compounds . [0007] One class of organic electrolyte solvents that have received attention as a component of electrolyte elements for electrochemical cells and other devices are the sulfones . Sulfones can generally be divided into two types : the aromatic sulfones and the aliphatic sulfones . The aliphatic sulfones can also be divided into two types-the cyclic (commonly referred to as sulfolanes ) and non-cyclic . The non-cyclic aliphatic sulfones form a potentially-attractive group of organic solvents that present a high chemical and thermal stability.
[0008] In particular, ethyl methyl sulfone (EMS ) has shown remarkable electrochemical stability, reaching 5.8v vs . Li/Li+ by a conservative stability criterion . For example, 2M LiPFβ/EMS has been used as the supporting electrolyte in a dual graphite cell which operates around 5.5v, and IM LiPF6/EMS has been used as the electrolyte in Li/T2- Lia/3 [Nii/3Mn2/3_ O2 cell which operates up to 5.4v. Despite its success as solvent in those cases , EMS applications are limited by a shortcoming, i . e . its relatively high melting point, 36.5°C, which eliminates its use as a single solvent in electronic devices whose range of operation includes temperatures much below ambient . To overcome this limitation EMS must be blended with other high stability solvents that yield low-melting eutectics with EMS, or be replaced by alternative sulfones with lower melting points . [0009] A eutectic mixture of EMS with dimethyl sulfone melts at 25°C, and the mixture has been used in lithium salt solution conductivity studies extending well below ambient, however, crystallization takes place on long exposure to low temperatures . Since single solvent electrolytes are
desirable for a variety of reasons , and since alternative second components to provide lower-melting eutectics than the above are also desirable, a need exists to further study the synthesis of sulfone-containing molecular liquids .
Summary of the Invention
[0010] In one embodiment, the present invention is an electrolyte element for use in an electric current-producing device comprising one or more ionic electrolyte salts and a non-aqueous electrolyte solvent including one or more nonsymmetrical, non-cyclic sulfones of the general formula : Rl- SO2-R2. The Rl group is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms . The R2 group, which is different in formulation than the Rl group, is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms . [0011] In another embodiment, the present invention is an electric current-producing device comprising a cathode and an anode . A non-aqueous electrolyte element is disposed between the cathode and anode . The non-aqueous electrolyte element includes an electrolyte salt and a non-symmetrical , non- cyclic sulfone of the general formula : R1-SO2-R2. Rl is an alkyl group, and R2 is an alkyl group including oxygen . [0012] In another embodiment, the present invention is an electrolyte for a electric current-producing device comprising an non-aqueous electrolyte solvent including an non-symmetrical , non-cyclic sulfone of the general formula : R1-SO2-R2. Rl is an alkyl group, and R2 is an alkyl group including oxygen .
[0013] In another embodiment, the present invention is a method of forming an electric current-producing device,
comprising the steps of providing a cathode, providing an anode, and providing a non-aqueous electrolyte element disposed between the cathode and anode . The non-aqueous electrolyte element includes an electrolyte salt and a nonsymmetrical , non-cyclic sulfone of the general formula : Rl- SO2-R2. Rl is an alkyl group, and R2 is an alkyl group including oxygen .
Brief Description of the Drawings
[0014] FIG . 1 illustrates a lithium battery providing power to a load;
FIG . 2 illustrates non-symmetrical , non-cyclic sulfone group coupled with a Rl alkyl group and R2 oxygen containing alkyl group;
FIG . 3 is a graph of conductivities of IM LiTFSI in different sulfones ;
FIGs . 4a-4b are graphs of electrochemical stability ranges ( "windows" ) for IM LiTFSI in different sulfone solutions ;
FIG . 5 is a graph of performance of the cell MCMB25-28 I 1M LiPF6/EMES | Li under the current density of 0.013mA cm"2;
FIGs . 6a-6b are graphs of cell performance under different current densities ;
FIG . 7 is a graph of charge/discharge capacity and coulomb efficiency of the cell LiCr0 - OIsMnL 985O4 I lM LiPF6/EMES | Li under the current density of 0.092mA cm"2;
FIGs . 8a-8b are graphs of charge and discharge profile of half cell of Li | | Graphite and full cell of Graphite I I LiCoO2 using 1. OM LiPF6/EMES as the electrolyte, respectively;
FIGs . 9a-9b are graphs of temperature dependence of ionic conductivities of 1. OM lithium salts , A) 1. OM lithium salts in EMES containing 5wt% carbonates (EC and DMC) and ethylene sulfite (ES) ; B) 1.0MLiPF6 in EMES containing different percentage of EC;
FIGs . 1Oa-IOd are graphs of cyclic voltammograms for IM LiPF6 in different EMES/EC mixtures , A) 5wt% EC; B) 10wt% EC; C) 20wt% EC; D) 30wt% EC;
FIGs . lla-lld are graphs of cyclic voltammograms for IM LiPF6 in different EMES/DMC mixtures, A) 5wt% DMC; B) 10wt% DMC; C) 20wt% DMC; D) 30wt% DMC;
FIG . 12 is a graph of a first lithium intercalation and de-intercalation profile on graphite electrode using different 1. OM LiPF6 electrolyte solutions ;
FIG . 13 is a graph of a first charge and discharge profile of full cell of graphite | | LiCoθ2 using different 1. OM LiPF6 electrolyte solutions ; and
FIG . 14 is a graph of an electrochemical window for IM LiClO4 in EMES/ES mixture .
Detailed Description of the Drawings
[0015] The present invention is described in one or more embodiments in the following description with reference to the Figures , in which like numerals represent the same or similar elements . While the invention is described in terms of the best mode for achieving the invention' s obj ectives , it will be appreciated by those skilled in the art that it is intended to cover alternatives , modifications , and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims and their equivalents as supported by the following disclosure and drawings .
[0016] Batteries are commonly used to power many types of electronics , motors , and other devices for use in portable applications . The battery may be rechargeable or disposable one-shot usage type . The battery provides operating power for integrated circuits in portable electronic systems , or an electromotive force to drive motors for industrial and automotive applications .
[0017] FIG . 1 illustrates electric current-producing device 10 providing electrical power to load 12. In one embodiment , the electric current-producing device 10 is a battery or other voltaic cell . Alternatively, the electric current-producing device 10 is a supercapacitor . Device 10 may include a lithium-ion cell or lithium metal cell, or plurality of such cells . Device 10 has anode 14 , cathode 16, and electrolyte 18. Anode 14 and cathode 16 are connected to load 12 to provide electrical power to the load. Electrolyte 18 contains a non-aqueous electrolyte element comprising a non-symmetrical, non-cyclic sulfone component , as described fully hereinafter, that is stable in the presence of the anode and cathode . Load 12 may be an electronic system, equipment in an industrial application, or motor for an automobile, j ust to name a few .
[0018] The material of anode 14 has one or more metals or metal alloys selected from the Group IA and HA metals in the Periodic Table . For example, anode 14 may be made with lithium or sodium. The anode may also be alkali-metal intercalated carbon, such as LiCx where x is equal to or greater than 2. Also useful as anode materials are alkali- metal intercalated conductive polymers , such as lithium, sodium or potassium doped polyacetylenes , polyphenylenes , polyquinolines , and the like . Examples of other suitable anode material are lithium metal, lithium-aluminum alloys , lithium-tin alloys , lithium-intercalated carbons , lithium-
intercalated graphites , calcium metal, aluminum, sodium, and sodium alloys .
[0019] Cathode 16 may be made with any of the commonly used cathode active materials . Examples of suitable cathode active materials are inorganic insertion oxides and sulfides , metal chalcogenides , elemental sulfur, organo-sulfur and carbon-sulfur polymers , conjugated polymers , and liquid cathodes . Useful inorganic insertion oxides include Co02 , NiO2 , Mn02 , Mn204 , V6O13 , V2O5 , and blends thereof . Useful inorganic sulfides include TiS2 , MoS2 , and the like . Suitable conj ugated polymers include polyacetylene, poly (phenylene vinylene ) , and polyaniline . Useful liquid cathodes include S02 , S0C12 , SO2C12 , and POC13. Useful organo-sulfur materials include those disclosed in U . S . Patent Nos . 4 , 833 , 048 ; 4 , 917 , 974 ; 5 , 324 , 599; and 5 , 516, 598. [0020] Further examples of useful cathode active materials include organo-sulfur polymer materials , as described in U . S . Patent No . 5 , 441 , 831, and carbon-sulfur materials , as described in U . S . Patent Nos . 5 , 601 , 947 and 5 , 529 , 860. Sulfur containing cathode active organic materials as described in these disclosures comprise, in their oxidized state, a polysulfide moiety of the formula, -5m- , wherein m is an integer equal to or greater than 3. Further useful composite cathode compositions including organo-sulfur or elemental sulfur . Cathode 16 may further comprise one or more materials selected from the group consisting of: binders , electrolytes , and conductive additives , usually to improve or simplify their fabrication as well as improve their electrical and electrochemical characteristics . [0021] Useful conductive additives are those known to one skilled in the art of electrode fabrication and are such that they provide electrical connectivity to the maj ority of the electroactive materials in the composite cathode . Examples
of useful conductive fillers include conductive carbons
(e . g . , carbon black) , graphites , metal flakes , metal powders , electrically conductive polymers , and the like .
[0022] In those cases where binder and conductive filler are desired, the amounts of binder and conductive filler can vary widely and the amounts present will depend on the desired performance . Typically, when binders and conductive fillers are used, the amount of binder will vary greatly, but will generally be less than about 15 wt% of the composite cathode . The amount of conductive filler used will also vary greatly and will typically be less than 20 wt% of the composite cathode . Useful amounts of conductive additives are generally less than 12 wt% .
[0023] The choice of binder material may vary widely so long as it is inert with respect to the composite cathode materials . Useful binders are those materials , usually polymeric, that allow for ease of processing of battery electrode composites . Examples of useful binders are organic polymers such as polytetrafluoroethylenes (TEFLONTM) , polyvinylidine fluorides ( PVF2 or PVDF) , ethylene-propylene- diene (EPDM) rubbers, polyethylene oxides ( PEO) , UV curable acrylates , UV curable methacrylates , and UV curable divinylethers , and the like .
[0024] For the case of the automotive application, battery-powered motors offer many interesting possibilities for fulfilling transportation needs with greater efficiency and reduced harm to the environment . Automobile batteries must be rechargeable and preferably deliver high voltages , e . g . greater than 4.5 VDC, to provide adequate power to the motor . The battery should also have good electrochemical stability and longevity. Electrolyte 18 plays an important role in the electrochemical performance of electric current- producing device 10 , including the ability to generate high
output voltages for maximum power transfer . [0025] Electrolyte elements are useful in electrolytic cells , rechargeable batteries , electric capacitors , fuel cells , and function as a medium for storage and transport of ions . The term "electrolyte element, " as used herein, relates to an element of an electric current-producing device which comprises an electrolyte solvent, one or more electrolyte salts , and optionally other additives including polymer electrolytes and gel-polymer electrolytes . Any liquid, solid, or solid-like material capable of storing and transporting ions may be used, so long as the material is chemically inert with respect to anode 14 and cathode 16, and the material facilitates the transportation of ions between the anode and the cathode . In the special case of solid electrolytes , these materials may additionally function as separator materials between the anode and cathode . [0026] The electrolyte elements of the present invention include one or more ionic electrolyte salts and a non-aqueous electrolyte solvent . The non-aqueous electrolyte solvent contains one or more non-symmetrical, non-cyclic sulfones , and optionally other additives , such as one or more electrolyte co-solvents , gelling agents , ionically conductive solid polymers , and/or other additives . The electrolyte elements may be prepared by dissolving one or more ionic electrolyte salts in one or more non-aqueous electrolyte solvents .
[0027] As a feature of the present invention, a new sulfone is introduced into the composition of electrolyte 18. The sulfones are provided in the battery electrolyte to increase the possible output voltage and available power from the battery . In particular, sulfones with different length of oligo ethylene glycol segments have been synthesized and tested for use in rechargeable lithium batteries . Relative
to the model compound EMS , which has a melting point of 36.5°C, the new sulfones have low melting points , mostly depressed below room temperature . Their conductivities are lower than that of EMS . The highest ambient temperature conductivity of 10"2 > 58S . cm"1 is obtained for 0.7M LiTFSI/MEMS solution . The sulfones show wide electrochemical stability windows , in excess of 5. Ov vs Li/Li+, increasing with decreasing length of the oligoether chains . A cell with lithium metal anode and manganate cathode performed well, maintaining high coulomb efficiency over 200 cycles . [0028] The non-aqueous electrolyte solvents include a nonsymmetrical, non-cyclic sulfone, suitable for use in electric current-producing devices , such as device 10. As shown in FIG . 2 , the non-symmetrical, non-cyclic sulfone has the general formula : R1-SO2-R2. The SO2 group 20 represents the sulfone group . The Rl group 22 is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms . The R2 group 24 is a linear or branched or partially or fully fluorinated linear or branched alkyl group containing oxygen and having 1 to 7 carbon atoms . In another embodiment , the Rl and R2 groups each have 1 to 4 carbon atoms .
[0029] The SO2 sulfone group is the same group that occurs in the following compounds : ethylmethyl sulfone (EMSF, CH3CH2-SO2-CH3 ) , ethyl-iso-propyl sulfone (EiPSF, CH3CH2-SO2- CH (CH3 ) 2 ) , ethyl-sec-butyl sulfone (EsB SF, CH3CH2-SO2- CH (CH3 ) (CH2CH3 ) ) , ethyl-iso-butyl sulfone (EiBSF) . [0030] Examples of the Rl alkyl group are : methyl (-CH3) ; ethyl (-CH2CH3) ; n-propyl (-CH2CH2CH3) ; n-butyl ( -CH2CH2CH2CH3) ; n-pentyl (-CH2CH2CH2CH2CH3) ; n-hexyl ( -CH2CH2CH2CH2CH2CH3 ) ; n- heptyl ( -CH2CH2CH2CH2CH2CH2CH3 ) ; iso-propyl (-CH (CH3) 2) ; iso- butyl (-CH2CH (CH3) 2) ; sec-butyl (-CH (CH3) CH2CH3) ; tert-butyl (- C (CH3) 3) ; iso-pentyl ( -CH2CH2CH (CH3) 2) ; trifluoromethyl ( -CF3) ;
2,2,2-trifluoroethyl (-CH2CF3) ; 1, 1-dif luoroethyl (-CF2CH3) ; perfluoroethyl (-CF2CF3) ; 3, 3, 3-trifluoro-n-propyl (- CH2CH2CF3) ; 2, 2-dif luoro-n-propyl (-CH2CF2CH3) ; 1, 1-dif luoro-n- propyl (-CF2CH2CH3) ; 1, 1, 3, 3, 3-pentaf luoro-n-propyl (- CF2CH2CF3) ; 2, 2, 3, 3, 3- pentaf luoro-n-propyl (-CH2CF2CF3) ; perf luoro-n-propyl (-CF2CF2CF3) ; perf luoro-n-butyl (- CF2CF2CF2CF3) ; perf luoro-n-pentyl (-CF2CF2CF2CF2CF3) ; perfluoro- n-hexyl (-CF2CF2CF2CF2CF2CF3) ; perf luoro-n-heptyl (- CF2CF2CF2CF2CF2CF2CF3) ; -CF (CH3) 2; -CH(CH3)CF3; -CF (CF3) 2; - CH (CF3) 2 ; -CH2CF (CH3) 2 ; -CF2CH (CH3) 2; -CH2CH(CH3)CF3; - CH2CH(CF3)2; -CF2CF(CF3J2; -C (CF3) 3.
[0031] Examples of the R2 oxygen containing alkyl group are: -CH2OCH3; -CF2OCH3; -CF2OCF3; -CH2CH2OCH3; -CH2CF2OCH3; - CF2CH2OCH3; -CF2CF2OCH3; -CF2CF2OCF3; -CF2CH2OCF3; -CH2CF2OCF3; - CH2CH2OCF3; -CHFCF2OCF2H; -CF2CF2OCF (CF3) 2; -CF2CH2OCF (CF3) 2; - CH2CF2OCF (CF3) 2 ; -CH2CH2OCF (CF3) 2; -CF2CF2OC (CF3) 3; - CF2CH2OC ( CF3 ) 3 ; -CH2CF2OC ( CF3 ) 3 ; -CH2CH2OC ( CF3 ) 3 ; -CH2CH2OCH2CH3 ; CH2CH2OCH2CF3; -CH2CH2OCF2CH3; -CH2CH2OCF2CF3; -CH2CF2OCH2CH3; -
CH2CF2OCF2CH3 ; -CH2CF2OCH2CF3; -CH2CF2OCF2CF3; -CF2CH2OCH2CH3; -
CF2CH2OCF2CH3 ; -CF2CH2OCH2CF3; -CF2CH2OCF2CF3; -CF2CF2OCH2CH3; -
CF2CF2OCF2CH3 ; -CF2CF2OCH2CF3; -CF2CF2OCF2CF3; -CF2CF2CF2OCH3; -
CF2CF2CH2OCH3; -CF2CH2CF2OCH3; -CH2CF2CF2OCH3; -CH2CF2CH2OCH3; -
CH2CH2CF2OCH3; -CF2CH2CH2OCH3; -CH2CH2CH2OCH3; -CF2CF2CF2OCF3; -
CF2CF2CH2OCF3; -CF2CH2CF2OCF3; -CH2CF2CF2OCF3; -CH2CH2CF2OCF3; -
CH2CF2CH2OCF3; -CF2CH2CH2OCF3; -CH2CH2CH2CH2OCH3; -
CH2CH2CH2CH2CH2OCH3 ; -CH2CH2CH2CH2CH2CH2OCH3 ; -CH2CH2OCH2CH2OCH3 ;
CH2CH2OCH2CH2OCH2CH2OCH3.
[0032] In an alternate embodiment, the Rl alkyl group may also contain oxygen, e.g. using any one of the formulations described for the R2 group. However, the Rl and R2 groups will each have a different formulation from the other, e.g. in terms of chemical structure or length of segments.
[0033] One group of electrolyte salts includes MC104,
MPFβ, MPFx (CnF2n+I) 6-X, MBF4 , MBF4-X (CnF2n+I) x, MAsFβ, MSCN, MB (CO2) 4 ("LiBOB") , and MSO3CF3, where "M" represents lithium or sodium. Also available are electrolyte solutions including MN ( SO2CF3 ) 2 as the electrolyte salt , which exhibits exceptionally high conductivity combined with high chemical and electrochemical stability .
[0034] The electrolyte elements may further include one or more liquid electrolye co-solvents ( i . e . , in addition to a non-symmetrical, non-cyclic sulfone) , gelling agents, ionically conductive solid polymers , and other additives . Suitable electrolyte co-solvents , gelling agents or ionically conductive solid polymers include any of those commonly used with lithium metal and lithium-ion cells . For example, suitable liquid electrolyte co-solvents for use in the electrolyte elements include any one of the commonly used electrolyte solvents . Examples of useful liquid electrolyte co-solvents include carbonates , N-methyl acetamide , acetonitrile, symmetric sulfones , sulfolanes , 1 , 3-dioxolanes , glymes , polyethylene glycols , siloxanes , and ethylene oxide grafted siloxanes , and blends thereof . Examples of useful carbonates include ethylene carbonate (EC) and propylene carbonate ( PC) . Examples of useful glymes includes tetraethyleneglycol dimethyl ether (TEGDME) and 1 , 2- dimethoxyethane .
[0035] Liquid electrolyte elements are often used in combination with one of the common porous separators . Liquid electrolyte solvents or plasticizing agents are often themselves useful as gel forming agents for gel-polymer electrolytes . Examples of gelling agents which are useful in the electrolyte elements are those prepared from polymer matrices derived from polyethylene oxides ( PEO) , polypropylene oxides , polyacrylonitriles , polysiloxanes , polyimides , polyethers , sulfonated polyimides , perfluorinated
membranes (NafionTM resins ) , polyethylene glycols, polyethylene glycol-bis- (methyl acrylates ) , polyethylene glycol-bis (methyl methacrylates ) , derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, blends of the foregoing, and the like .
[0036] Examples of ionically conductive solid polymers suitable for use in the electrolyte elements are those having polyethers , polyethylene oxides ( PEO) , polyimides , polyphosphazenes , polyacrylonitriles ( PAN) , polysiloxanes , polyether grafted polysiloxanes , derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing, to which is added an appropriate ionic electrolyte salt . Ionically conductive solid polymers electrolytes may additionally function as separator materials between the anode and cathode .
[0037] Other additives which are useful in the electrolyte elements include soluble additives , such as : vinylene carbonate (VC) , ethylene sulfite (ES) , propylene sulfite
( PS ) , fluoroethylen sulfite ( FEC) , α-bromo-γ-butyrolactone, methyl chloroformate, t-butylene carbonate, 12-crown-4 , carbon dioxide (CO2) , sulfur dioxide ( SO2) , sulfur trioxide and other inorganic additives ; acid anhydrides to reduce or eliminate the presence of water; reaction products of carbon disulfide and lithium, possibly a soluble sulfide, as disclosed in U . S . Patent No . 3, 532 , 543 ; high concentrations of water as described in U . S . Patent Nos . 5 , 432 , 425 and 5 , 436, 549 ; and polysulfide additives .
[0038] The non-aqueous electrolyte solvents are particularly useful in electrolytic cells, rechargeable batteries , electric capacitors , fuel cells , and the like, which comprise non-aqueous electrolyte elements and which
require high energy storage capacity, long shelf life, and a low rate of self-discharge . The electrolyte solvents are particularly useful in electrolytic cells comprising alkali- metal-containing electrodes , and particularly to lithium intercalation electrodes .
[0039] The high oxidation resistance of the ambient temperature electrolyte solutions of the present invention result from the stability of the -SO2- group when in a non- cyclic, non-symmetric sulfone structure, characterized by freezing temperatures low enough to enable utilization in ambient temperature applications . When such a sulfone is utilized as a solvent to dissolve inorganic electrolyte salts of highly oxidation resistant anions such as C104 , CF3SO3 (triflate) , and in particular, bis (trifluoromethane sulfonyl) imide ( -N (CF3SO2 ) 2 , lithium imide ) , then solutions which combine exceptional oxidation resistance with high ambient temperature conductivity are obtained as , for example, shown in FIG . 3. In general, FIG . 3 illustrates the DC electrical conductivities of electrolytes of various solutions of alkali metal salts in sulfones . As seen in the figure, at 25°C the conductivity of EMS is more than half order of magnitude higher than those of the oligoether sulfones of the present work, indicating the great advantage of EMS as a single solvent in the sulfone family.
[0040] The process of making, using, and testing electric current-producing device 10, including anode 14 , cathode 16, and electrolyte 18 containing the non-aqueous electrolyte solvents having non-symmetrical, non-cyclic sulfone groups defined above by R1-SO2-R2 is now described in detail . [0041] Oligoether-containing sulfides were synthesized by reacting halide compounds of oligoethylene glycols with sodium methanethiolate or with sodium ethanethiolate . Sulfones with structures listed in Table 1 were obtained by
oxidation of the synthesized sulfides with H2O2. Table 1 is summary of physical properties of synthesized sulfones , wherein note1 is estimated melting point, note2 is boiling point under atmosphere pressure estimated by nomograph, and note3 is estimated boiling point .
Table 1
[0042] Glass transition temperature Tg was measured using a DTA instrument . The heating rate was 10K/min . T9 was defined as the onset temperature of the heat capacity jump and Tm was defined as the temperature at which the melting peak reaches its maximum. The boiling point was recorded during the distillation process .
[0043] Electrolyte solutions of different salt concentrations were prepared by dissolving calculated amount of lithium salts in the respective sulfones . The measurement of DC conductivity was carried out using an automated frequency impedance analyzer . The measurements were made automatically during heating of the precooled samples at lK/min by means of a programmed controller . To determine electrochemical characteristics , cyclic voltammetry was performed using a potentiostat/galvanostat with a three- electrode cell . The working electrode was a platinum wire, and the counter and reference electrodes were lithium foil in the voltage range of -0.3-6. OV. Most scans were made at room temperature at a typical scan rate of lmv/s .
[0044] Electrochemical half cells , Li | | sulfone electrolyte I I MCMB25-28 (MCMB for mesocarbon microbeads ) , and Li | I sulfone electrolyte | |
were constructed using fiberglass paper as the separator . The cathode solution consisting of 82% active material, 10% carbon black and 8% PVdF in N-methylpyrrolindone was cast directly on the pre-weighed stainless steel electrode . The electrode was dried, first at room temperature and then at 1000C under vacuum for two days . The weight of the electrode was determined inside the dry box, and the weight of active material obtained by difference . The anode composite electrodes were made in a similar way from a slurry of 90% MCMB25-28 and 10% PVdF in N-methylpyrrolindone . The cell construction and the tests were all carried out in an argon- filled glove box . The voltage profile of the charge/discharge process was monitored using a battery cycler . A constant current ranging from 0.01~0.1 mA/cm2 was used with pre-set cut-off voltage of 0.01-2. OV for Li | | electrolyte | | MCMB25-28 cell and 3.0-4.3V for Li | | electrolyte | |
cell . At these cut-off voltages a computerized cycler automatically switched the test cells to charge or discharge .
[0045] All of the ether fragment additions caused the lowering of melting point relative to EMS except for one case (dimethoxyethyl sulfone) in which symmetry was retained. Indeed, in some cases crystallization was not observed at all . For instance, introduction of the smallest fragment , the methoxy group, at the ethyl end of EMS yielding methoxyethylmethyl sulfone (MEMS) , lowers the melting point to 150C . The subambient melting of the compound formed by adding the same group to the symmetric dimethyulsulfone ( DMS) (mp = 1100C) yielding methoxymethylmethyl-sulphone (MMMS) , the
change in melting point being 9OK. Attaching the methoxy group to one end of the symmetric diethyl sulfone ( DES) gives ethyl methoxy ethyl sulfone (EMES ) with an even lower melting point , 20C, vs 74 °C for the symmetric compound. These data, along with data for several other variants, are summarized in Table 1.
[0046] The glass transition temperatures of the new sulfones are described as follows . For the mono asymmetric sulfones such as EMES, EMEES (ethyl methoxyethoxyethyl sulfone) and EMEEES (ethyl methoxyethoxyethoxyethyl sulfone) , the glass transition temperature increases with increasing ether chain length, see Table 1 , implying that the increasing molecular weight effect offsets the decrease in Tg expected from the dilution of the cohesive sulfone groups . [0047] The ionic conductivities , at any temperature, follow the order : EMS>MEMS>EMES>DMES>EMEES>EMEEES , and appear to follow the order of the respective sulfone viscosities . Of the possible synthesized sulfones , the room temperature conductivities of lithium salt solutions of MEMS and EMES are the highest . Since the difference is not large, and the ease of synthesis and purification greater in the case of EMES, the latter is adopted for making solutions for the electrochemical stability and cell performance tests . [0048] In FIGs . 4a-4b, the cyclic voltammetry scans from which the electrochemical windows for 1. OM LiTFSI solutions at Pt working electrode under the scan rate of lmv/s in EMES, EMEES are obtained. FIG . 4a shows EMES, while FIG . 4b is EMEES . The cyclic voltammetry scans are well above 5. Ov vs . Li+/Li . FIGs . 4a-4b also show that, with increasing ether chain length, the electrochemical stability decreases , from 5.6v for EMES , 5.3v for EMEES , (vs 5.9v for EMS ) showing that stability advantage of sulfone, as a class of solvent, is diminishing with increasing ether group concentration .
[0049] FIG . 5 shows a test of the ether sulfone-based solutions for reversible intercalation into the graphite designated MCMB25-28 , for the first three cycles of the cell MCMB25-28 | 1M LiPFg/EMES | Li during cycling at constant current density of 0.013 mA. crrf2. The corresponding charge and discharge capacities of the first three cycles are 343.0 , (202.8 ) ; 251.4 , (200.5 ) ; 219.2 , ( 193.0 ) mAh/g, respectively. [0050] Next, the performance of the new solutions with lithium metal anodes and Cr3+-modified LiMn2O4 spinel intercalation cathodes are tested . FIGs . βa-6b compare the cell performance using different IM lithium salts in EMES during the first cycle under different current densities . FIG . 6a shows data from the cell using IM LiTFSI/EMES electrolyte . FIG . 6b shows data from the cell using IM LiPFg/EMES electrolyte . Each cell shows two well-defined discharge plateaus , around 4.0 and 4.1v versus Li/Li , + respectively. It is also seen that the capacities decrease with increasing current density.
[0051] When the charge/discharge rates are raised, there is progressively less time for lithium ions to diffuse through the LiMn2O4 crystallites . At higher rates , only lithium ions located in the outer regions of the grains are accessible for reaction, causing a reduction in capacity. However, comparatively the cell using IM LiPFg electrolyte exhibited a higher capacity than the cell using IM LiTFSI/EMES electrolyte under similar current densities . In addition it has been shown that the charge/discharge capacities for the cells using LiTFSI/EMES decreases very quickly with cycling due to its failure to form effective SEI layers , thus LiPFg is useful as the lithium salt for full cell test . The corresponding cell performance under the current density of 0.092mA cm"2 using IM LiPF6/EMES in terms of charge/discharge capacities and coulomb efficiency is shown
in FIG . 7. This cell showed excellent cyclability, more than 200 cycles , tending to stabilize after 200 cycles at a discharge capacity around 50 mAh/g and a stable coulomb efficiency around 0.86.
[0052] It is further noted that improved performance may be obtained when the present hybrid sulfones are mixed with fluorinated sulfones on the one hand or with alkyl carbonates on the other . The incorporation of oligoether segments into molecular sulfones lowers the freezing point to sub-ambient values , without decreasing the electrochemical window, but may increase the viscosity with consequent lowering of lithium salt solution conductivities . However, any decrease in conductivity can be compensated by fluorination of the Rl and R2 alkyl groups . The oligoether-containing sulfones retain high electrochemical stability with "windows" well above 5. Ov versus Li+/Li . It is possible that Li+ may be intercalated/de-intercalated into graphite electrode by using oligoether-containing sulfones .
[0053] In another embodiment, the novel non-cyclic, nonsymmetrical sulfones are substituted with perfluoromethyl (trifluoromethyl, -CF3) or perfluoromethylene (-CF2 ) groups . Substitution of a methyl, -CH3 , group by a perfluoromethyl, - CF3 , is surprisingly found to advantageously decrease the viscosity of the sulfone, thereby increasing the conductivity of the electrolyte solutions and increasing the penetration of the electrolytes into the cathode and separator in electrolytic cells at ambient conditions . [0054] Useful are the novel fluorinated sulfones CF3CH2SO2CH3 (2 , 2 , 2-trifluoroethylmethyl sulfone, CF3MMSF) and CF3CH2CH2SO2CH3 (CF3EMSF) . Also available is CF3MMSF which exhibits very high conductivity, for example, in lithium chlorate solutions . The fluorinated non-symmetrical , non-cyclic sulfone further offers superior wetting,
penetration and other surfactant properties . [0055] Several embodiments of the present invention are described in the following examples , which are offered by way of illustration and not by way of limitation .
[0056] In Example 1 , involving preparation of methoxyethyl methyl sulfone (MEMS ) , 45.6 g thiourea was dissolved in 150ml water, 28.8ml dimethyl sulfate was added and the solution was refluxed for lhour . After cooling to room temperature, 48g NaOH in 75 ml distilled water was added and the solution was stirred for 1 hour, then 55g chloroethyl methyl ether (ClCH2CH2OCH3) was added dropwise . After addition the solution was slowly heated to reflux for 10 hours . The upper organic layer was separated to obtain the methoxyethyl methyl sulfide (CH3OCH2CH2SCH3) with a yield of 55% . The sulfide was set to oxidation with 30wt% H2O2 in acetic acid . On completion of oxidation, most of the solvent was removed. Dilute NaOH aqueous solution was added to neutralize excess acetic acid . Water was removed by rotary evaporation and the residual paste was extracted with chloroform at least three times . The chloroform was combined and dried over anhydrous sodium sulfate . Finally chloroform was removed and the crude product was distilled under vacuum at 95-1000C to obtain the pure product MEMS .
[0057] In Example 2 , involving preparation of MEMS, pre- weighed empty bottle was cooled in dry ice acetone solution and Methane thiol was slowly charged into the bottle . The net weight of methanethiol was obtained by the difference before and after weighing as 21.5g . 71. βg 25wt% NaOH aqueous solution was charged into stainless steel pressure vessel and cooled with ice water . The vessel was vacuumed and then under stirring methanethiol was slowly charged into the vessel . The solution was stirred for lhr before 38g chloroethyl methyl ether (ClCH2CH2OCH3) was added. The
solution was stirred for overnight at room temperature and then heated to reflux for lOhrs before the process was stopped. The solution was cooled and the upper organic layer was separated to give a yield of 87% . The sulfide was then subj ected to oxidation with 12Og 30wt% H2O2 and 100ml acetic acid . After work up as in Example 1 the crude product was distilled under vacuum and 35g pure product was isolated with a yield 71% .
[0058] In Example 3 , involving characterization of MEMS, glass transition temperature T9 was measured using a DTA instrument . The heating rate used was 10K/min . Tg was defined as the onset temperature of the heat capacity j ump and Tm was defined as the temperature at which the melting peak reaches its maximum. The boiling point was recorded during the distillation process . The T9 and Tm of MEMS are - 89.50C and 15°C respectively, as shown in Table 1. The boiling point of MEMS is estimated as 275°C at atmosphere pressure .
[0059] Electrolyte solutions of different salts were prepared by dissolving calculated amount of lithium salts in MEMS at about 800C, in the case of LiPF6 salt the temperature is controlled around 500C . The measurement of DC conductivity was carried out using a frequency impedance analyzer . The measurements were made automatically during heating of the pre-cooled samples at lK/min by means of a programmed controller . The temperature dependence curve for MEMS containing 1. OM LiTFSI is shown in FIG . 3. The Tg and room temperature ionic conductivities of 1. OM different lithium salts in MEMS are shown in Table 2. In general, Table 2 shows glass transition temperature (Tg/°C) and room temperature conductivity log (σ2s/S cm"1) of IM different lithium salt solution in different sulfones .
Sulfone LiTFSI LiSO3CF3 LiClO4 LiBF4 LiPF6 LiSCN logσ25 T0 logσ2S Tq logσ25 T0 logσ25 logσ25 Tq Iogσ25
EMS -96.0 -2 .27 -103.0 -3.00 -110.0 -2.95 -111.0 -2.80 -86.2 -2.55 -101.5 -3.35
MEMS -81.0 -2 .83 -83.4 -3.00 -88 0 -2.93 -84 0 -3.03 -82.0 -2.91 -86 5 -3.15
EMES -83.3 .85 -87.5 -3.05 -88 0 -3.10 -85 5 -2.89 -88.7 -2.92 -82 5 -3.62
EMEES -73.4 -3 .12 -74.0 -3.71 -76 0 -3.39 -76 4 -3.48 -70.4 -3.61 -77 0 -3.92
EMEEES -71.6 -3 .25 -68.6 -3.85 -79 4 -3.50 -78 5 -3.55 -77.0 -3.80 -74 6 -3.96
DMES -84.0 -2 .99 -83.0 -3.70 -76 4 -3.16 -84 0 -3.30 -82.0 -3.09 -82 5 -3.72
Table 2
[0060] In Example 4 , involving preparation of ethyl methoxyethyl sulfone (EMES ) , 57g NaOH was dissolved in 57g H2O and cooled with ice water, 88.4g ethanethiol was added to the solution slowly . The solution was stirred for half hour before 135g chloroethyl methyl ether (ClCH2CH2OCH3) was added. After addition the solution was stirred at room temperature for several hours before it was heated to reflux for overnight . The reaction was stopped and cooled to room temperature . Ethyl methoxyethyl sulfide ( CH3CH2SCH2CH2OCH3 ) in the upper organic layer was separated, 156g, yield 91% . lOOg Ethyl methoxyethyl sulfide was set up for oxidation with 17Og 50wt% H2O2 and 200ml acetic acid. After work up as in Example 1 the crude sulfone was distilled and the fraction at 85-880C /0.3Torr is collected.
[0061] In Example 5 , involving characterization of EMES, the Tg and Tm of EMES are -91. O0C and 20C respectively, as shown in Table 1. The boiling point of MEMS is estimated as 28β°C at atmosphere pressure . Salt solutions of EMES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3. The temperature dependence curve for EMES containing 1. OM LiTFSI is shown in FIG . 3. The Tg and room temperature ionic conductivities of 1. OM of different lithium salts in EMES are shown in Table 2.
[0062] The cyclic voltammogram of IM LiTFSI/EMES electrolyte is recorded at 1.0mv/s at a Pt working electrode
with lithium as both counter and reference electrode using a potentiostat/galvanostat instrument, as shown in FIG . 4a . [0063] In Example 6, involving an electric current- producing device employing EMES electrolytes , electrochemical half cells , Li | | sulfone electrolyte | | MCMB25-28 , and Li | | sulfone electrolyte | |
are constructed using fiber glass paper as the separator . The cathode solution consisting of 82% active material, 10% carbon black and 8% PVdF in N-methylpyrrolindone is cast directly on the pre- weighed stainless steel electrode . The electrode is dried, first at room temperature and then at 1000C under vacuum for two days . The weight of the electrode is determined inside the dry box, and the weight of active material obtained by difference . The MCMB25-28 composite electrodes are made in a similar way from slurry of 90% MCMB25-28 and 10% PVdF in N- methylpyrrolindone .
[0064] Test cells were constructed by using Whatman glass fiber filter soaked in the electrolyte solution of Example 5 as the separator and a lithium anode and
(or MCMB25-28 ) cathode . The tests were all carried out in an argon-filled glove box . The voltage profile of the charge/discharge process was monitored using a battery cycler . A constant current ranging from 0.01~0.1 mA/cm2 were used with pre-set cut-off voltage of 0.01-2. OV for Li | | electrolyte | | MCMB25-28 cell and 3.0-4.3V for Li | | electrolyte | | LiCr0.oisMni.gssCU cell respectively . At these cut-off voltages a computerized cycler automatically switches the test cells to charge or discharge . The test results are shown in FIGs . 5 , 6a-b, and 7 , respectively. [0065] Another set of experiments are performed using commercial electrode sheets ( synthetic graphite and LiCoO2) . The electrodes are cut into disc with area of 0.72 cm2 and assembled either in a half cell of Li | | electrolyte | |
graphite or full cell of graphite | | electrolyte | | LiCoO2. A constant current density of 0.14 mA/cm2 was used for both charging and discharging with pre-set cut-off voltage of 0.01-2. OV for Li | | electrolyte | | graphite cell and 2.5-4.2V for graphite | | electrolyte | | LiCoO2 cell, respectively . The result is shown in FIGs . 8a-8b .
[0066] In Example 7 , involving characterization of mixtures of EMES with carbonates, the mixtures of EMES with carbonates were prepared by mixing different weight percentage of either ethylene carbonate (EC) or dimethyl carbonate ( DMC) in EMES . 1. OM LiPF6 electrolyte solution was prepared by dissolving the salt in the mixtures at about 500C, as described in Example 3. The ionic conductivities were measured using the method described in Example 3 and their temperature dependence curves are shown in FIGs . 9a-9b . Addition of EC to the electrolyte solution increases the ionic conductivities in all cases due to the higher dielectric constant of EC .
[0067] The cyclic voltammograms of IM LiPF6 in EMES/EC and EMES/DMC are measured, as described in Example 5 , which is shown in FIGs . 1Oa-IOd and lla-lld, respectively. FIGs . 10a- 1Od are graphs of cyclic voltammograms for IM LiPFβ in different EMES/EC mixtures . A) 5wt% EC; B) 10wt% EC; C) 20wt% EC; D) 30wt% EC . FIGs . lla-lld are graphs of cyclic voltammograms for IM LiPFβ in different EMES/DMC mixtures . A) 5wt% DMC; B) 10wt% DMC; C) 20wt% DMC; D) 30wt% DMC . Note that the electrochemical stability windows are all higher than 5.2v.
[0068] Half cell of Li | | electrolyte | | graphite or full cell of graphite | | electrolyte | | LiCoO2 were built using the IM LiPF6 electrolytes in EMES/EC and EMES/DMC, as described in Example 6. A constant current density of 0.14 mA/cm2 was used for both charging and discharging with pre-set cut-off
voltage of 0.01-2. OV for Li | | electrolyte | | graphite cell and 2.5-4.2V for graphite | | electrolyte | | LiCoO2 cell , respectively . The results are shown in FIGs . 12 and 13. There is no graphite exfoliations observed in all the cases studied under the charge/discharge current density of 0.14mA cm"2.
[0069] In Example 8 , involving characterization of EMES with additives , ethylene sulfite (ES) is chosen as an additive and mixed with EMES at the composition of 5wt% . 1. OM LiClO4 electrolyte was prepared by dissolving the salt in the mixture of EMES/ES at about 800C, as described in Example 3. The ionic conductivities were measured using the method described in Example 3 and its temperature dependence curve shown in FIGs . 9a-9b is higher than that of 1. OM LiPF5/EMES solution .
[0070] The cyclic voltammograms of IM LiClO4 in EMES/ES was measured, as described in Example 5 , which is shown in FIG . 14. The electrochemical stability is still higher than 5. Ov. [0071] Half cell of Li | | electrolyte | | graphite or full cell of graphite | | electrolyte | | LiCoO2 were built using the IM LiCl4 electrolytes in EMES/ES, as described in Example 6. A constant current density of 0.14 mA/cm2 was used for both charging and discharging with pre-set cut-off voltage of 0.01-2. OV for Li | | electrolyte | | graphite cell and 2.5-4.2V for graphite | | electrolyte | | LiCoO2 cell, respectively. The results are shown in FIGs . 12 and 13. Note that there is no graphite exfoliations observed in this case studied under the charge/discharge current density of 0.14mA cm"2. [0072] In Example 9, involving synthesis of ethyl methoxyethoxyethyl sulfone (EMEES ) , 4Og NaOH was dissolved in 4Og H2O and cooled with ice water . 62g ethanethiol was added to the solution slowly. The solution is stirred for half hour before 138.5g chloroethyl methoxyethyl ether
( CICH2CH2OCH2CH2OCH3 ) was added. After addition the solution was stirred at room temperature for several hours before it was heated to reflux for overnight . The reaction was stopped and cooled to room temperature . Ethyl methoxyethoxyethyl sulfide ( CH3CH2SCH2CH2OCH2CH2OCH3 ) in the upper organic layer was separated with a yield of 96% . The resuting compound was oxidized with H2O2 and acetic acid, as described in Example 1 , to yield ethy methoxyethoxyethyl sulfone (EMEES ) . [0073] In Example 10 , involving characterization of ethyl methoxyethoxyethyl sulfone (EMEES) , the Tg of EMEES is -87.6°C as shown in Table 1. Salt solutions of EMEES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3. The temperature dependence curve for EMEES containing 1. OM LiTFSI is shown in FIG . 3. The T9 and room temperature ionic conductivities of 1. OM of different lithium salts in EMEES are shown in Table 2. The cyclic voltammogram of IM LiTFSI/EMEES electrolyte was measured, as described in Example 5 , which is shown in FIG. 4b .
[0074] In Example 11 , involving synthesis of ethyl methoxyethoxyethoxyethyl sulfone (EMEEES) , 4Og NaOH was dissolved in 4Og H2O and cooled with ice water, 62g ethanethiol was added to the solution slowly. The solution was stirred for half hour before 182.5g chloroethyl methoxyethoxyethyl ether ( CICH2CH2OCH2CH2OCH2CH2OCH3 ) was added . After addition the solution was stirred at room temperature for several hours before it was heated to reflux for overnight . The reaction was stopped and cooled to room temperature . Ethyl methoxyethoxyethoxyethyl sulfide ( CH3CH2SCH2CH2OCH2CH2OCH2CH2OCH3 ) in the upper organic layer was separated with a yield of 95% . The sulfide was further oxidized with H2O2 and acetic acid, as described in Example 1 , to obtain the ethyl methoxyethoxyethoxyethyl sulfone
( EMEEES ) .
[0075] In Example 12 , involving characterization of ethyl methoxyethoxyethoxyethyl sulfone (EMEEES ) , the T9 of EMEEES is -82.50C, as shown in Table 1. Salt solutions of EMEEES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3. The temperature dependence curve for EMEEES containing 1. OM LiTFSI is shown in FIG . 3. The T9 and room temperature ionic conductivities of 1. OM of different lithium salts in EMEEES are shown in Table 2.
[0076] In Example 13 , involving synthesis of dimethoxyethyl sulfone ( DMES ) , 50ml 2-chloroethyl methyl ether, 70g Na2S .9H2O, 17. βg tetrabutylammonium bromide and 50ml H2O were mixed into a three-neck flask equipped with magnetic stirrer and reflux condenser, and heated at 700C with vigorous stirring . The reaction was continued for overnight . The organic layer was separated and dissolved in chloroform, washed with distilled water several times to remove the ammonium salt and dried over anhydrous sodium sulfate . Solvent was removed using a rotary evaporator, and dimethoxyethyl sulfide was obtained with a yield of 63% . The sulfide was oxidized with H2O2 and acetic acid, as described in Example 1 , to obtain the corresponding sulfone, dimethoxyethylsulfone (DMES ) .
[0077] In Example 14 , involving characterization of dimethoxyethyl sulfone (DMES ) , the T9 and Tm of DMES are - 90.70C and 47. O0C, respectively, as shown in Table 1. Salt solutions of DMES were prepared, as described in Example 3 , and their ionic conductivities were measured using the method described in Example 3. The temperature dependence curve for DMES containing 1. OM LiTFSI is shown in FIG . 3. The T9 and room temperature ionic conductivities of 1. OM of different lithium salts in DMES are shown in Table 2.
[0078] While one or more embodiments of the present invention have been illustrated in detail, the skilled artisan will appreciate that modifications and adaptations to those embodiments may be made without departing from the scope of the present invention as set forth in the following claims .
Claims
1. An electrolyte element for use in an electric current- producing device, comprising: one or more ionic electrolyte salts; and a non-aqueous electrolyte solvent including one or more non-symmetrical, non-cyclic sulfones of the general formula: R1-SO2-R2, wherein the Rl group is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms, and the R2 group, which is different in formulation than the Rl group, is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms.
2. The electrolyte element of claim 1, wherein the Rl group is selected from the group consisting of: methyl (-CH3) ; ethyl (-CH2CH3); n-propyl (-CH2CH2CH3); n-butyl (-CH2CH2CH2CH3); n- pentyl (-CH2CH2CH2CH2CH3) ; n-hexyl (-CH2CH2CH2CH2CH2CH3) ; n- heptyl (-CH2CH2CH2CH2CH2CH2CH3) ; iso-propyl (-CH (CH3) 2) ; iso- butyl (-CH2CH (CH3) 2) ; sec-butyl (-CH(CH3)CH2CH3) ; tert-butyl (- C (CH3) 3) ; iso-pentyl (-CH2CH2CH (CH3) 2) ; trif luoromethyl (-CF3) ; 2,2,2-trifluoroethyl (-CH2CF3) ; 1, 1-dif luoroethyl (-CF2CH3); perf luoroethyl (-CF2CF3) ; 3, 3, 3-trif luoro-n-propyl (- CH2CH2CF3); 2 , 2-dif luoro-n-propyl (-CH2CF2CH3) ; 1, 1-dif luoro-n- propyl (-CF2CH2CH3) ; 1, 1, 3, 3, 3-pentaf luoro-n-propyl (- CF2CH2CF3) ; 2, 2, 3, 3, 3- pentaf luoro-n-propyl (-CH2CF2CF3) ; perfluoro-n-propyl (-CF2CF2CF3) ; perf luoro-n-butyl (- CF2CF2CF2CF3) ; perf luoro-n-pentyl (-CF2CF2CF2CF2CF3) ; perfluoro- n-hexyl (-CF2CF2CF2CF2CF2CF3) ; perf luoro-n-heptyl (- CF2CF2CF2CF2CF2CF2CF3) ; -CF (CH3) 2; -CH(CH3)CF3; -CF (CF3) 2; - CH (CF3) 2; -CH2CF (CH3) 2; -CF2CH (CH3) 2; -CH2CH(CH3)CF3; - CH2CH (CF3)2; -CF2CF (CF3) 2; -C (CF3) 3 -
3. The electrolyte element of claim 1, wherein the R2 group is selected from the group consisting of: -CH2OCHs; -CF2OCHs; - CF2OCF3; -CH2CH2OCH3; -CH2CF2OCH3; -CF2CH2OCH3; -CF2CF2OCH3; - CF2CF2OCF3; -CF2CH2OCF3; -CH2CF2OCF3; -CH2CH2OCF3; -CHFCF2OCF2H; - CF2CF2OCF(CFs)2; -CF2CH2OCF (CF3) 2; -CH2CF2OCF (CF3) 2; - CH2CH2OCF(CFS)2; -CF2CF2OC(CFS)3; -CF2CH2OC(CFS)3; -CH2CF2OC(CFS)3; -CH2CH2OC (CF3) 3; -CH2CH2OCH2CH3; -CH2CH2OCH2CF3; -CH2CH2OCF2CH3; - CH2CH2OCF2CF3; -CH2CF2OCH2CH3; -CH2CF2OCF2CH3; -CH2CF2OCH2CF3; - CH2CF2OCF2CF3; -CF2CH2OCH2CH3; -CF2CH2OCF2CH3; -CF2CH2OCH2CF3; - CF2CH2OCF2CF3; -CF2CF2OCH2CH3; -CF2CF2OCF2CH3; -CF2CF2OCH2CFs; - CF2CF2OCF2CF3; -CF2CF2CF2OCH3; -CF2CF2CH2OCH3; -CF2CH2CF2OCH3; - CH2CF2CF2OCH3; -CH2CF2CH2OCH3; -CH2CH2CF2OCH3; -CF2CH2CH2OCH3; - CH2CH2CH2OCH3; -CF2CF2CF2OCF3; -CF2CF2CH2OCF3; -CF2CH2CF2OCF3; - CH2CF2CF2OCF3; -CH2CH2CF2OCF3; -CH2CF2CH2θCFs; -CF2CH2CH2OCF3; - CH2CH2CH2CH2OCH3; -CH2CH2CH2CH2CH2OCH3; -CH2CH2CH2CH2CH2CH2OCH3; - CH2CH2OCH2CH2OCH3 ; -CH2CH2OCH2CH2OCH2CH2OCH3.
4. The electrolyte element of claim 1, wherein the ionic electrolyte salt is selected from the group consisting of MC104, MPFβ, MPFx(CnF2n+I)6-X, MBF4, MBF4-X (CnF2n+1) x, MAsFβ, MSCN, MB (CO2) 4, MN(SO2CF3)2, and MSO3CF3, where "M" is lithium or sodium, or any mixture thereof.
5. The electrolyte element of claim 1, further including an electrolyte co-solvent.
6. The electrolyte element of claim 5, wherein the electrolyte co-solvent is selected from the group consisting of: co-solvents include carbonates, N-methyl acetamide, acetonitrile, symmetric sulfones, sulfolanes, 1, 3-dioxolanes, glymes, polyethylene glycols, siloxanes, and ethylene oxide grafted siloxanes .
7. The electrolyte element of claim 1 , further including an electrolyte additive .
8. The electrolyte element of claim 7 , wherein the electrolyte additive is selected from the group consisting of : vinylene carbonate (VC) , ethylene sulfite (ES) , propylene sulfite ( PS ) , fluoroethylen sulfite ( FEC) , α-bromo-γ- butyrolactone, methyl chloroformate, t-butylene carbonate, 12-crown~4 , carbon dioxide (CO2) , sulfur dioxide ( SO2) , sulfur trioxide ( SO3) , acid anhydrides , reaction products of carbon disulfide and lithium, polysulfide, and other inorganic additives .
9. An electric current-producing device, comprising : a cathode ; an anode; and a non-aqueous electrolyte element disposed between the cathode and anode, the non-aqueous electrolyte element including an electrolyte salt and a non-symmetrical , non- cyclic sulfone of the general formula : R1-SO2-R2 , wherein Rl is an alkyl group, and R2 is an alkyl group including oxygen .
10. The electric current-producing device of claim 9, wherein the device is a voltaic cell .
11. The electric current-producing device of claim 9, wherein the device is a supercapacitor .
12. The electric current-producing device of claim 9, wherein the alkyl group of Rl includes oxygen and has a different formulation than R2.
13. The electric current-producing device of claim 12, wherein the Rl or R2 group is selected from the group consisting of: -CH2OCH3; -CF2OCH3; -CF2OCF3; -CH2CH2OCH3; - CH2CF2OCH3; -CF2CH2OCH3; -CF2CF2OCH3; -CF2CF2OCF3; -CF2CH2OCF3; - CH2CF2OCF3; -CH2CH2OCF3; -CHFCF2OCF2H; -CF2CF2OCF (CF3) 2; - CF2CH2OCF (CF3) 2; -CH2CF2OCF (CF3) 2 ; -CH2CH2OCF (CF3) 2; - CF2CF2OC (CF3) 3; -CF2CH2OC (CF3) 3; -CH2CF2OC (CF3) 3; -CH2CH2OC (CF3) 3; -CH2CH2OCH2CH3; -CH2CH2OCH2CF3; -CH2CH2OCF2CH3; -CH2CH2OCF2CF3; - CH2CF2OCH2CH3; -CH2CF2OCF2CH3; -CH2CF2OCH2CF3; -CH2CF2OCF2CF3; - CF2CH2OCH2CH3; -CF2CH2OCF2CH3; -CF2CH2OCH2CF3; -CF2CH2OCF2CF3; - CF2CF2OCH2CH3; -CF2CF2OCF2CH3; -CF2CF2OCH2CF3; -CF2CF2OCF2CF3; - CF2CF2CF2OCH3; -CF2CF2CH2OCH3; -CF2CH2CF2OCH3; -CH2CF2CF2OCH3; - CH2CF2CH2OCH3; -CH2CH2CF2OCH3; -CF2CH2CH2OCH3; -CH2CH2CH2OCH3; - CF2CF2CF2OCF3; -CF2CF2CH2OCF3; -CF2CH2CF2OCF3; -CH2CF2CF2OCF3; - CH2CH2CF2OCF3; -CH2CF2CH2OCF3; -CF2CH2CH2OCF3; -CH2CH2CH2CH2OCH3; - CH2CH2CH2CH2CH2OCH3; -CH2CH2CH2CH2CH2CH2OCH3; -CH2CH2OCH2CH2OCH3; - CH2CH2OCH2CH2OCH2CH2OCH3.
14. The electric current-producing device of claim 9, wherein the Rl group is selected from the group consisting of: methyl (-CH3) ; ethyl (-CH2CH3) ; n-propyl (-CH2CH2CH3) ; n- butyl (-CH2CH2CH2CH3) ; n-pentyl (-CH2CH2CH2CH2CH3) ; n-hexyl (- CH2CH2CH2CH2CH2CH3) ; n-heptyl (-CH2CH2CH2CH2CH2CH2CH3) ; iso-propyl
(-CH (CH3) 2) ; iso-butyl (-CH2CH (CH3) 2) ; sec-butyl (-
CH(CH3)CH2CH3) ; tert -butyl (-C(CH3J3); iso-pentyl (-
CH2CH2CH (CH3) 2) ; trif luoromethyl (-CF3) ; 2, 2, 2-trif luoroethyl
(-CH2CF3) ; 1,1-dif luoroethyl (-CF2CH3) ; perf luoroethyl (- CF2CF3) ; 3,3, 3-trif luoro-n-propyl (-CH2CH2CF3) ; 2, 2-dif luoro-n- propyl (-CH2CF2CH3) ; 1, 1-dif luoro-n-propyl (-CF2CH2CH3) ; 1,1, 3, 3, 3-pentaf luoro-n-propyl (-CF2CH2CF3); 2,2,3,3,3- pentafluoro-n-propyl (-CH2CF2CF3) ; perf luoro-n-propyl (- CF2CF2CF3) ; perf luoro-n-butyl (-CF2CF2CF2CF3) ; perfluoro-n- pentyl (-CF2CF2CF2CF2CF3) ; perfluoro-n-hexyl (-
CF2CF2CF2CF2CF2CF3 ) ; perfluoro-n-heptyl ( -CF2CF2CF2CF2CF2CF2CF3 ) ; -CF (CHs) 2; -CH (CH3) CF3; -CF (CFs) 2; -CH (CF3) 2; -CH2CF (CHs) 2; - CF2CH (CHg) 2 ; -CH2CH (CH3) CF3; -CH2CH (CFs) 2; -CF2CF (CF3) 2; -C (CFs) 3 -
15. The electric current-producing device of claim 9, wherein the ionic electrolyte salt is selected from the group consisting of MC104 , MPF6, MPFx (CnF2n+1) 6_x, MBF4 , MBF4-. χ (CnF2n+1) x, MAsFβ, MSCN, MB (CO2) 4, MN ( SO2CF3 ) 2 , and MSO3CF3 , where "M" is lithium or sodium, or any mixture thereof .
16. The electric current-producing device of claim 9, wherein the electrolyte element further includes an electrolyte co-solvent .
17. The electric current-producing device of claim 16, wherein the electrolyte co-solvent is selected from the group consisting of : co-solvents include carbonates , N-methyl acetamide, acetonitrile, symmetric sulfones , sulfolanes , 1, 3- dioxolanes , glymes , polyethylene glycols , siloxanes, and ethylene oxide grafted siloxanes .
18. The electric current-producing device of claim 9, wherein the electrolyte element further includes an electrolyte additive .
19. The electric current-producing device of claim 18 , wherein the electrolyte additive is selected from the group consisting of : vinylene carbonate (VC) , ethylene sulfite (ES) , propylene sulfite (PS ) , fluoroethylene sulfite ( FEC) , α-bromo-γ-butyrolactone, methyl chloroformate, t-butylene carbonate, 12-crown-4 , carbon dioxide (CO2) , sulfur dioxide ( SO2) , sulfur trioxide ( SO3) , acid anhydrides , reaction products of carbon disulfide and lithium, polysulfide, and other inorganic additives.
20. An electrolyte for an electric current-producing device, comprising a non-aqueous electrolyte solvent including an non-symmetrical, non-cyclic sulfone of the general formula: R1-SO2-R2, wherein Rl is an alkyl group, and R2 is an alkyl group including oxygen.
21. The electrolyte of claim 20, wherein the alkyl group of Rl includes oxygen and has a different formulation than R2.
22. The electrolyte of claim 21, wherein the Rl or R2 group is selected from the group consisting of: -CH2OCH3; -CF2OCH3; - CF2OCF3; -CH2CH2OCH3; -CH2CF2OCH3; -CF2CH2OCH3; -CF2CF2OCH3; - CF2CF2OCF3; -CF2CH2OCF3; -CH2CF2OCF3; -CH2CH2OCF3; -CHFCF2OCF2H; - CF2CF2OCF(CFa)2; -CF2CH2OCF (CF3) 2; -CH2CF2OCF (CF3) 2; - CH2CH2OCF (CF3) 2; -CF2CF2OC (CF3) 3; -CF2CH2OC (CF3) 3; -CH2CF2OC (CF3) 3; -CH2CH2OC (CF3) 3; -CH2CH2OCH2CH3; -CH2CH2OCH2CF3; -CH2CH2OCF2CH3; - CH2CH2OCF2CF3; -CH2CF2OCH2CH3; -CH2CF2OCF2CH3; -CH2CF2OCH2CF3; - CH2CF2OCF2CF3; -CF2CH2OCH2CH3; -CF2CH2OCF2CH3; -CF2CH2OCH2CF3; - CF2CH2OCF2CF3; -CF2CF2OCH2CH3; -CF2CF2OCF2CH3; -CF2CF2OCH2CF3; - CF2CF2OCF2CF3; -CF2CF2CF2OCH3; -CF2CF2CH2OCH3; -CF2CH2CF2OCH3; - CH2CF2CF2OCH3; -CH2CF2CH2OCH3; -CH2CH2CF2OCH3; -CF2CH2CH2OCH3; - CH2CH2CH2OCH3; -CF2CF2CF2OCF3; -CF2CF2CH2OCF3; -CF2CH2CF2OCF3; - CH2CF2CF2OCF3; -CH2CH2CF2OCF3; -CH2CF2CH2OCF3; -CF2CH2CH2OCF3; - CH2CH2CH2CH2OCH3; -CH2CH2CH2CH2CH2OCH3; -CH2CH2CH2CH2CH2CH2OCH3; - CH2CH2OCH2CH2OCH3 ; -CH2CH2OCH2CH2OCH2CH2OCH3.
23. The electrolyte of claim 21, wherein the Rl group is selected from the group consisting of: methyl (-CH3) ; ethyl (- CH2CH3) ; n-propyl (-CH2CH2CH3) ; n-butyl (-CH2CH2CH2CH3) ; n- pentyl (-CH2CH2CH2CH2CH3); n-hexyl (-CH2CH2CH2CH2CH2CH3) ; n- heptyl (-CH2CH2CH2CH2CH2CH2CH3) ; iso-propyl (-CH (CH3) 2) ; iso- butyl (-CH2CH(CHs)2) ; sec-butyl (-CH(CH3)CH2CH3) ; tert-butyl (- C (CH3) 3) ; iso-pentyl (-CH2CH2CH (CH3) 2) ; trif luoromethyl (-CF3) ; 2, 2, 2-trif luoroethyl (-CH2CF3) ; 1, 1-dif luoroethyl (-CF2CH3) ; perf luoroethyl (-CF2CF3); 3, 3, 3-trif luoro-n-propyl (- CH2CH2CF3); 2 , 2-dif luoro-n-propyl (-CH2CF2CH3) ; 1, 1-dif luoro-n- propyl (-CF2CH2CH3) ; 1, 1, 3, 3, 3-pentaf luoro-n-propyl (- CF2CH2CF3) ; 2, 2, 3, 3, 3- pentaf luoro-n-propyl (-CH2CF2CF3) ; perf luoro-n-propyl (-CF2CF2CF3) ; perf luoro-n-butyl (- CF2CF2CF2CF3) ; perf luoro-n-pentyl (-CF2CF2CF2CF2CF3) ; perfluoro- n-hexyl (-CF2CF2CF2CF2CF2CF3) ; perf luoro-n-heptyl (- CF2CF2CF2CF2CF2CF2CF3) ; -CF(CH3)2; -CH(CH3)CF3; -CF(CF3)2; - CH (CF3) 2; -CH2CF (CH3) 2 ; -CF2CH (CH3) 2; -CH2CH(CH3)CF3; - CH2CH(CF3)2; -CF2CF (CF3) 2; -C(CF3J3-
24. The electrolyte of claim 20, wherein the ionic electrolyte salt is selected from the group consisting of MC1O4, MPF6, MPFx (CnF2n+I ) 6-x, MBF4, MBF4-* (CnF2n+I ) x, MAsFβ, MSCN, MB (CO2) 4, MN(SO2CF3)2, and MSO3CF3, where "M" is lithium or sodium, or any mixture thereof.
25. The electrolyte of claim 21, further including an electrolyte co-solvent.
26. The electrolyte of claim 25, wherein the electrolyte co- solvent is selected from the group consisting of: co-solvents include carbonates, N-methyl acetamide, acetonitrile, symmetric sulfones, sulfolanes, 1, 3-dioxolanes, glymes, polyethylene glycols, siloxanes, and ethylene oxide grafted siloxanes .
27. The electrolyte of claim 20, further including an electrolyte additive.
28. The electrolyte of claim 27, wherein the electrolyte additive is selected from the group consisting of: vinylene carbonate (VC) , ethylene sulfite (ES) , propylene sulfite (PS) , fluoroethylene sulfite (FEC) , α-bromo-γ-butyrolactone, methyl chlorof ormate, t-butylene carbonate, 12-crown~4, carbon dioxide (CO2) , sulfur dioxide (SO2) , sulfur trioxide (SO3) , acid anhydrides, reaction products of carbon disulfide and lithium, polysulfide, and other inorganic additives.
29. A method of forming an electric current-producing device, comprising: providing a cathode; providing an anode; and providing a non-aqueous electrolyte element disposed between the cathode and anode, the non-aqueous electrolyte element including an electrolyte salt and a non-symmetrical, non-cyclic sulfone of the general formula: R1-SO2-R2, wherein Rl is an alkyl group, and R2 is an alkyl group including oxygen.
30. The method of claim 29, wherein the alkyl group of Rl includes oxygen and has a different formulation than R2.
31. The method of claim 30, wherein the Rl or R2 group is selected from the group consisting of: -CH2OCH3; -CF2OCH3; - CF2OCF3; -CH2CH2OCH3; -CH2CF2OCH3; -CF2CH2OCH3; -CF2CF2OCH3; - CF2CF2OCF3; -CF2CH2OCF3; -CH2CF2OCF3; -CH2CH2OCF3; -CHFCF2OCF2H; - CF2CF2OCF(CFs)2; -CF2CH2OCF (CF3) 2; -CH2CF2OCF (CF3) 2; - CH2CH2OCF (CF3) 2; -CF2CF2OC (CF3) 3; -CF2CH2OC (CF3) 3; -CH2CF2OC (CF3) 3 ; -CH2CH2OC (CF3) 3; -CH2CH2OCH2CH3; -CH2CH2OCH2CF3; -CH2CH2OCF2CH3; - CH2CH2OCF2CF3; -CH2CF2OCH2CH3; -CH2CF2OCF2CH3; -CH2CF2OCH2CF3; - CH2CF2OCF2CF3; -CF2CH2OCH2CH3; -CF2CH2OCF2CH3; -CF2CH2OCH2CF3; - CF2CH2OCF2CF3; -CF2CF2OCH2CH3; -CF2CF2OCF2CH3; -CF2CF2OCH2CF3; -
CF2CF2OCF2CF3; -CF2CF2CF2OCH3; -CF2CF2CH2OCH3; -CF2CH2CF2OCH3; -
CH2CF2CF2OCH3; -CH2CF2CH2OCH3; -CH2CH2CF2OCH3; -CF2CH2CH2OCH3; -
CH2CH2CH2OCH3; -CF2CF2CF2OCF3; -CF2CF2CH2OCF3; -CF2CH2CF2OCF3; -
CH2CF2CF2OCF3; -CH2CH2CF2OCF3; -CH2CF2CH2OCF3; -CF2CH2CH2OCF3; - CH2CH2CH2CH2OCH3; -CH2CH2CH2CH2CH2OCH3; -CH2CH2CH2CH2CH2CH2OCH3; - CH2CH2OCH2CH2OCH3 ; -CH2CH2OCH2CH2OCH2CH2OCH3.
32. The method of claim 29, wherein the Rl group is selected from the group consisting of: methyl (-CH3) ; ethyl (-CH2CH3) ; n-propyl (-CH2CH2CH3); n-butyl (-CH2CH2CH2CH3); n-pentyl (- CH2CH2CH2CH2CH3) ; n-hexyl (-CH2CH2CH2CH2CH2CH3) ; n-heptyl (- CH2CH2CH2CH2CH2CH2CH3) ; iso-propyl (-CH (CH3) 2) ; iso-butyl (- CH2CH (CH3) 2) ; sec-butyl (-CH(CH3)CH2CH3) ; tert-butyl (-C (CH3) 3) ; iso-pentyl (-CH2CH2CH (CH3) 2) ; trif luoromethyl (-CF3) ; 2,2,2- trifluoroethyl (-CH2CF3); 1, 1-dif luoroethyl (-CF2CH3) ; perfluoroethyl (-CF2CF3) ; 3, 3, 3-trif luoro-n-propyl (- CH2CH2CF3) ; 2 , 2-dif luoro-n-propyl (-CH2CF2CH3) ; 1, 1-dif luoro-n- propyl (-CF2CH2CH3); 1, 1, 3, 3, 3-pentaf luoro-n-propyl (- CF2CH2CF3); 2 , 2 , 3 , 3, 3- pentaf luoro-n-propyl (-CH2CF2CF3) ; perfluoro-n-propyl (-CF2CF2CF3) ; perf luoro-n-butyl (- CF2CF2CF2CF3) ; perf luoro-n-pentyl (-CF2CF2CF2CF2CF3) ; perfluoro- n-hexyl (-CF2CF2CF2CF2CF2CF3) ; perf luoro-n-heptyl (- CF2CF2CF2CF2CF2CF2CF3) ; -CF(CH3)2; -CH(CH3)CF3; -CF(CF3)2; - CH (CF3) 2; -CH2CF(CH3)2; -CF2CH (CH3) 2; -CH2CH(CH3)CF3; - CH2CH (CF3) 2; -CF2CF (CF3) 2; -C(CF3J3.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06733765.9A EP1842250B1 (en) | 2005-01-19 | 2006-01-19 | Electric current-producing device having a sulfone-based electrolyte |
| KR1020077018778A KR101101001B1 (en) | 2005-01-19 | 2006-01-19 | Electric current-producing device having sulfone-based electrolyte |
| JP2007552279A JP5318420B2 (en) | 2005-01-19 | 2006-01-19 | Current generator having sulfone electrolyte |
| US11/780,416 US7833666B2 (en) | 2005-01-19 | 2007-07-19 | Electric current-producing device having sulfone-based electrolyte |
| US12/897,602 US20110020712A1 (en) | 2005-01-19 | 2010-10-04 | Electric current-producing device having sulfone-based electrolyte |
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| US64553605P | 2005-01-19 | 2005-01-19 | |
| US60/645,536 | 2005-01-19 |
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| US11/780,416 Continuation US7833666B2 (en) | 2005-01-19 | 2007-07-19 | Electric current-producing device having sulfone-based electrolyte |
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| US (2) | US7833666B2 (en) |
| EP (1) | EP1842250B1 (en) |
| JP (1) | JP5318420B2 (en) |
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- 2006-01-19 EP EP06733765.9A patent/EP1842250B1/en active Active
- 2006-01-19 CN CNA2006800025430A patent/CN101507023A/en active Pending
- 2006-01-19 WO PCT/US2006/001975 patent/WO2006078866A2/en active Application Filing
- 2006-01-19 KR KR1020077018778A patent/KR101101001B1/en active IP Right Grant
- 2006-01-19 JP JP2007552279A patent/JP5318420B2/en active Active
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2007
- 2007-07-19 US US11/780,416 patent/US7833666B2/en active Active
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| JP2000058076A (en) | 1998-08-05 | 2000-02-25 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte battery |
| US20010009744A1 (en) | 2000-01-21 | 2001-07-26 | Jin-Sung Kim | Electrolyte for lithium secondary battery and lithium secondary battary comprising same |
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| Title |
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| See also references of EP1842250A4 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7833666B2 (en) | 2005-01-19 | 2010-11-16 | Arizona Board of Regents for and behalf of Arizona State University | Electric current-producing device having sulfone-based electrolyte |
| CN100463287C (en) * | 2006-09-20 | 2009-02-18 | 广州天赐高新材料股份有限公司 | High rate electrolyte for lithium ion battery |
| US9853326B2 (en) | 2007-04-05 | 2017-12-26 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| US11616253B2 (en) | 2007-04-05 | 2023-03-28 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| EP2418723A1 (en) * | 2007-04-05 | 2012-02-15 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| US11367899B2 (en) | 2007-04-05 | 2022-06-21 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| US10468720B2 (en) | 2007-04-05 | 2019-11-05 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| US9093716B2 (en) | 2007-04-05 | 2015-07-28 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| US9590270B2 (en) | 2007-04-05 | 2017-03-07 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| EP2597717A1 (en) * | 2007-04-05 | 2013-05-29 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| US9281541B2 (en) | 2007-04-05 | 2016-03-08 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte for secondary battery and nonaqueous-electrolyte secondary battery employing the same |
| US20110143212A1 (en) * | 2007-09-28 | 2011-06-16 | Charles Austen Angell | Non-Aqueous Electrolyte Solution for Rechargeable Lithium Batteries |
| WO2009042958A1 (en) * | 2007-09-28 | 2009-04-02 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Non-aqueous electrolyte solution for rechargeable lithium batteries |
| CN102197024A (en) * | 2008-10-24 | 2011-09-21 | 住友精化株式会社 | Sulfone compound |
| US8372548B2 (en) | 2008-11-13 | 2013-02-12 | Samsung Sdi Co., Ltd. | Organic electrolytic solution and lithium battery employing the same |
| CN102216264B (en) * | 2008-11-17 | 2014-01-15 | 住友精化株式会社 | Sulfone compound |
| US8466324B2 (en) | 2008-11-17 | 2013-06-18 | Sumitomo Seika Chemicals Co., Ltd. | Sulfone compound |
| US8945765B2 (en) | 2008-12-08 | 2015-02-03 | Samsung Sdi Co., Ltd. | Secondary lithium battery electrolyte and secondary lithium battery including the same |
| EP2400588A4 (en) * | 2009-02-18 | 2014-04-02 | Asahi Kasei E Materials Corp | Electrolyte solution for lithium ion secondary battery, and lithium ion secondary battery |
| EP2400588A1 (en) * | 2009-02-18 | 2011-12-28 | Asahi Kasei E-materials Corporation | Electrolyte solution for lithium ion secondary battery, and lithium ion secondary battery |
| CN102459161A (en) * | 2009-06-09 | 2012-05-16 | 住友精化株式会社 | Process for preparation of alkyl sulfone compounds |
| US9118088B2 (en) | 2009-06-10 | 2015-08-25 | Asahi Kasei E-Materials Corporation | Electrolyte solution and lithium ion secondary battery using the same |
| CN102449842A (en) * | 2009-06-10 | 2012-05-09 | 旭化成电子材料株式会社 | Electrolytic solution and lithium ion secondary battery utilizing same |
| EP2450999A1 (en) * | 2010-11-03 | 2012-05-09 | Samsung Sdi Co., Ltd. | Electrolyte for lithium ion battery, and lithium ion battery including same |
| US9263764B2 (en) | 2010-11-03 | 2016-02-16 | Samsung Sdi Co., Ltd. | Electrolyte for lithium ion battery, and lithium ion battery including same |
| WO2012151618A1 (en) * | 2011-05-10 | 2012-11-15 | Cap-Xx Limited | Electrolyte |
| US10497970B2 (en) | 2013-03-14 | 2019-12-03 | Arizona Board Of Regents On Behalf Of Arizona State University | Alkali ion conducting plastic crystals |
| US11094963B2 (en) | 2013-03-14 | 2021-08-17 | Arizona Board Of Regents On Behalf Of Arizona State University | Alkali ion conducting plastic crystals |
| US11695153B2 (en) | 2013-03-14 | 2023-07-04 | Arizona Board Of Regents On Behalf Of Arizona State University | Alkali ion conducting plastic crystals |
| WO2017149204A3 (en) * | 2016-03-04 | 2017-12-21 | Broadbit Batteries Oy | Rechargeable sodium cells for high energy density battery use |
| US10686224B2 (en) | 2017-04-19 | 2020-06-16 | Arizona Board Of Regents On Behalf Of Arizona State University | Battery with aluminum-containing cathode |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1842250A2 (en) | 2007-10-10 |
| CN101507023A (en) | 2009-08-12 |
| EP1842250B1 (en) | 2013-09-04 |
| JP2008532209A (en) | 2008-08-14 |
| JP5318420B2 (en) | 2013-10-16 |
| EP1842250A4 (en) | 2010-12-15 |
| US20110020712A1 (en) | 2011-01-27 |
| US20070298326A1 (en) | 2007-12-27 |
| KR20080003774A (en) | 2008-01-08 |
| WO2006078866A3 (en) | 2009-04-23 |
| KR101101001B1 (en) | 2011-12-29 |
| US7833666B2 (en) | 2010-11-16 |
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