CN1276792A - 含多氟醇根配体的弱配位阴离子 - Google Patents
含多氟醇根配体的弱配位阴离子 Download PDFInfo
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- CN1276792A CN1276792A CN98810370A CN98810370A CN1276792A CN 1276792 A CN1276792 A CN 1276792A CN 98810370 A CN98810370 A CN 98810370A CN 98810370 A CN98810370 A CN 98810370A CN 1276792 A CN1276792 A CN 1276792A
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- 150000001450 anions Chemical class 0.000 title claims abstract description 78
- 239000003446 ligand Substances 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims description 45
- -1 p-tert-butylPhenyl Chemical group 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims description 17
- 159000000002 lithium salts Chemical class 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
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- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 5
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- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
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- 229910052715 tantalum Inorganic materials 0.000 claims description 4
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- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
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- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 150000001768 cations Chemical class 0.000 description 38
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- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 29
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
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- 238000012360 testing method Methods 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 18
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- 229910001416 lithium ion Inorganic materials 0.000 description 14
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- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 12
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
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- 239000000706 filtrate Substances 0.000 description 11
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- 239000013078 crystal Substances 0.000 description 10
- 125000001153 fluoro group Chemical group F* 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
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- 239000011734 sodium Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910003004 Li-O2 Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910010084 LiAlH4 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 4
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- 125000001424 substituent group Chemical group 0.000 description 4
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- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- 238000011925 1,2-addition Methods 0.000 description 3
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- IZPIZCAYJQCTNG-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)C1=CC=CC=C1 IZPIZCAYJQCTNG-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
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- XZNOAVNRSFURIR-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol Chemical compound FC(F)(F)C(O)(C(F)(F)F)C(F)(F)F XZNOAVNRSFURIR-UHFFFAOYSA-N 0.000 description 1
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000006347 bis(trifluoromethyl)hydroxymethyl group Chemical group [H]OC(*)(C(F)(F)F)C(F)(F)F 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
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- 125000001072 heteroaryl group Chemical group 0.000 description 1
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- 238000009616 inductively coupled plasma Methods 0.000 description 1
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- 238000004255 ion exchange chromatography Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 150000002602 lanthanoids Chemical class 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 238000005649 metathesis reaction Methods 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- LYGJENNIWJXYER-FIBGUPNXSA-N nitromethane-d3 Chemical compound [2H]C([2H])([2H])[N+]([O-])=O LYGJENNIWJXYER-FIBGUPNXSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000003211 polymerization photoinitiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001472 pulsed field gradient Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供包含下式的多氟化阴离子的化合物及其用途:[M1(XC(CFa(R1)b)(CFc(R2)d)R3)m(R4)n]-p。具体地,本发明提供包含一种阴离子的化合物,所述阴离子包含与过渡金属或第Ⅲ、Ⅳ或Ⅴ族元素配位的多氟化醇根。
Description
发明领域
本发明涉及含多氟醇根(polyfluroalkoxide)的化合物及其用途,特别是用于电池中。
发明背景
含弱配位阴离子(即仅与阳离子弱配位的阴离子)的化合物适用于各种应用包括作为电解质和在各种有机反应中作为催化剂的抗衡离子。Barbarich等在“LiAl(OC(Ph)(CF3)2)4:用于形成碳-碳键的反应的烃溶性催化剂”,Organometallics,1996,15,3776中描述了一些适用的含弱配位阴离子的催化剂,该文献引入本文供参考。
非常活泼的金属和非金属阳离子的研究不断刺激新弱配位阴离子的发展。参见例如Bochmann,Angew.Chem.,Int.Ed.Engl.1992,31,1181;Strauss,Chem.Rev.1993,93,927;Strauss,Chemtracts-Inorganic Chem.1994,6,1;和Seppelt,Angew.Chem.,Int.Ed.Engl.1993,32,1025。弱配位阴离子最重要的用途之一是增强金属阳离子的催化活性。近年来受到相当多关注的两个实例是金属茂催化的烯烃聚合,和锂催化的Diels-Alder反应和1,4-共轭加成反应。参见EP-A-277 004(Turner,1988);Pellecchia等,Makromol.Chem.,Rapid Commun.1992,13,265;DuBay等,J.Org.Chem.1994,59,6898;Saidi等,Chem.Ber.1994,127,1761;Kobayashi等,Chem.Lett.1995,307;和Arai等,Angew.Chem.,Int.Ed.Engl.1996,15,3776。
适用的阴离子不仅必须弱配位,而且必须在高度亲电子阳离子存在下对氧化和/或裂解是稳定的。此外,理想的弱配位阴离子应有分散在由与弱碱性原子如氢或卤素的相对非极性键组成的大表面上的单一负电荷。符合这些标准中许多(但不是所有)标准的弱配位阴离子包括B(Arf)4 -(Arf=C6F5或3,5-C6H3(CF3)2)、CB11H12-nXn -(X=H或I)、CB9H10-nXn -(X=H、Cl、Br或M(OTeF5)n -(n=4,M=B;n=6,M=Nb、Sb))。
上述所有阴离子都有限制。一些是对于特定应用而言配位太强。一些是在使用它们的苛刻化学条件下不稳定。例如,BPh4 -的氟化衍生物可与强亲电子阳离子反应,导致(i)C-F键开裂而在氟原子和阳离子之间形成键,或者(ii)氟代芳基转移给阳离子。每种情况下,所述阳离子都不再有反应性或催化活性。
其它弱配位阴离子如ClO4 -、BF4 -、PF6 -、SbF6 -、B(OTeF5)4 -和Nb(OTeF5)6 -不是热稳定和/或水解稳定的。此外,这些阴离子的锂盐包括LiCF3SO3和LiPF6在有机溶剂尤其是在强还原剂如金属锂和相关的含锂电池的阳极溶液存在下稳定的有机溶剂中导电率低。此外,已知一些锂盐如LiPF6是不稳定的,过时分解。
其它的含有硼原子的阴离子和含有碳原子和硼原子簇的阴离子如碳硼烷(例如CB5、CB9、CB11),因由其形成的盐最多仅含一个与硼原子键合的氟原子而不是特别弱地配位。
近来,1998年3月27日申请的US专利申请09/049 420公开了弱配位且热和/或水解稳定的多氟化碳硼烷阴离子。
尽管在弱配位阴离子方面有进步,但仍需要新的弱配位阴离子。还需要在有机溶剂中有高导电率的弱配位阴离子。
发明概述
本发明涉及一类新的弱配位阴离子,包括至少一个有至少一个氟原子的配体。
更具体地,本发明提供下式的阴离子及其用途:
[M1(XC(CFa(R1)b)(CFc(R2)d)R3)m(R4)n]-p
其中M1为过渡金属或第III、IV或V族元素;
p为1或2;
每个X独立地为O、S、或NR5R6;
每个R1和R2独立地为H、卤离子或C1-C4烷基;
每个R3独立地为H、C1-C4烷基、或C4-C20芳基;
每个R4独立地为C1-C10烷基、C1-C10醇根(alkoxide)或C4-C20酚根(aryloxide);
每个R5和R6独立地为H或C1-C10烷基;
每个a和c独立地为0至3的整数;
a+b=3;
c+d=3;
m为2至8的整数;和
n为0至4的整数;
条件是a或c至少之一不为0。在本发明优选化合物中,p为1,每个R4独立地为C1-C10醇根或C4-C20酚根,当M1为Al且a和c为3时,R3不是苯基或对甲苯基。
本发明还提供用于电化学装置的电解质,包含有抗衡阳离子M的上式阴离子,其中M为金属阳离子、磷鎓阳离子、铵阳离子或硫鎓阳离子。
附图简述
图1为[2,6-(CH3)2C5H4N][Nb(HFIP)6]晶体的不对称单元中两个Nb(HFIP)6 -阴离子之一的X-射线晶体结构。
图2为LiAl(HFPP)4的X-射线晶体结构。
图3为通过非线性最小二乘方技术与VTF经验式拟合的导电率数据。
图4为LiAl(HFPP)4·O(C6H8)的X-射线晶体结构。
图5为TlAl(HFIP)4的X-射线晶体结构。
图6为LiAl(HFTB)4·OPPh3的X-射线晶体结构。
图7为TlAl(HFTB)4的X-射线晶体结构。
发明详述
本发明提供一种化合物及其用途,所述化合物包含下式的阴离子:
[M1(XC(CFa(R1)b)(CFc(R2)d)R3)m(R4)n]-p
其中M1为过渡金属或第III、IV或V族元素;
p为1或2;
每个X独立地为O、S、或NR5R6;
每个R1和R2独立地为H、卤离子或C1-C4烷基;
每个R3独立地为H、C1-C4烷基、或C4-C20芳基;
每个R4独立地为C1-C10烷基、C1-C10醇根或C4-C20酚根;
每个R5和R6独立地为H或C1-C10烷基;
每个a和c独立地为0至3的整数;
a+b=3;
c+d=3;
m为2至8的整数;和
n为0至4的整数;
条件是a或c至少之一不为0。在本发明优选化合物中,p为1,每个R4独立地为C1-C10醇根或C4-C20酚根,当M1为Al且a和c为3时,R3不是苯基或对甲苯基。更优选地,本发明化合物有多氟化阴离子,所述阴离子有至少两个多氟醇根基团。下文中“多氟化阴离子”意指上式的阴离子。
本发明的多氟阴离子本身未必包括化学上的化合物。的确,在不离析(isolable)化合物中,阴离子必须与阳离子成对以保持电中性。因此,本发明化合物更确切地为下式的化合物:Mp[M1(XC(CFa(R1)b)(CFc(R2)d)R3)m(R4)n]k。
M为1至4价的阳离子。M可以是任何阳离子,包括由以下衍生的阳离子:碱金属;碱土金属;过渡金属如Ag、Zn、Cu、Co、Fe、Mn、Cr、V、Ti、Zr、Rh、Pd、Cd、Hg、Os、Pt、Y、Nb、Sc、Ta、Hf、和Mo;镧系和锕系金属;铵部分如铵,四烃基铵(例如四丁基铵和四乙基铵),三烃基铵(例如三乙基铵、二异丙基乙基铵和三甲基铵),二烃基铵,氮杂芳族阳离子如2,6-二甲基吡啶鎓、甲基-2,6-二甲基吡啶鎓、甲基吡啶鎓和吡啶鎓,和亚铵(imminium)阳离子;磷鎓部分包括四烷基磷鎓、四芳基磷鎓和含烷基和芳基混合物的磷鎓离子;硫鎓部分如含烷基、芳基或其混合物的硫鎓离子;及其它适合的阳离子如铊。此外,M可以是相对稳定的碳阳离子如三苯甲游基部分和相关的碳阳离子(例如R3C+);及其它已知的阳离子如水合氢离子(H3O+)、H5O2 +、(Et2O)nH+、H9O4 +、和甲酰鎓(HCO+)。优选地,所述阳离子(即M)选自铊、碱金属阳离子、铵、一烃基铵、二烃基铵、三烃基铵、四烃基铵、氮杂芳族阳离子、四烃基磷鎓、水合氢、甲酰鎓、三苯甲游基和相关的碳阳离子;更优选选自三苯甲游基和相关的碳阳离子、铊、四烃基铵、碱金属阳离子、和氮杂芳族阳离子;最优选选自三苯甲游基、Li+、Tl+、2,6-二甲基吡啶鎓、四乙基铵、钠、钾、和甲基-2,6-二甲基吡啶鎓。本文所用“烃基”意指有至少一个碳原子的化合物,包括芳基、烷基、烯基和炔基。此外,烃基可以是直链、支化、或环状的。烃基也可被其它非氢或碳原子如卤素、氧、硫、氮或磷取代。
应当理解阳离子与本发明多氟化阴离子之摩尔比取决于所述阳离子的价态。这以p和k的值反映,例如,如果阳离子和阴离子均为一价,则k和p均为1,即阳离子和本发明多氟化阴离子间的摩尔比为1∶1。相反如果阳离子为二价而阴离子为一价,则k为2,p为1,阳离子和本发明多氟化阴离子间的摩尔比为1∶2。优选地,k为1至4的整数、更优选1至3,还更优选k为1或2、最优选1。优选p为1或2,更优选1。
应当理解由于本发明多氟化阴离子是弱缔合阴离子,所以与多氟化阴离子缔合的阳离子可容易地通过任何已知方法包括离子交换色谱法和其它离子交换法与其它阳离子交换。
本发明中所用第III、IV和V族元素是分别列在元素周期表第III、IV和V族中的那些元素。例如,第III族元素是B、Al、Ga、In和Tl;第IV族元素是C、Si、Ge、Sn、和Pb;第V族元素是N、P、As、Sb和Bi。优选地M1选自Al、B、V、Ti、Si、Zr、Ge、Sn、Cu、Y、Zn、Ga、Nb、Ta、Bi、P、As、Sc、Hf和Sb,更优选选自Al、B、Nb和Ta,最优选选自Al、B和Nb。
关于本文中所述分子式:
优选X为O(氧)。
优选R3选自H、甲基、三氟甲基、对叔丁基苯基、苯基、对甲苯基和邻羟苯基。本文中所用邻羟苯基意指在邻位有氧部分的苯基,所述氧部分还与M1键合。对于本发明化合物,优选R3选自H、甲基、三氟甲基、对叔丁基苯基、和苯基。
优选m为2、3、4或6。对于本发明化合物,优选m为2、4或6。
优选n为0或1。
优选R4为C1-C10烷基或C4-C20酚根。当R4为C1-C10烷基时,优选所述烷基选自甲基和乙基。当R4为C4-C20酚根时,优选R4为取代或未取代的二羟苯基,更优选邻二羟根苯基。本发明中所用二羟根苯基意指邻苯二酚衍生的基团,其中两个羟根均与M1键合。“取代或未取代”分别意指在所述苯基(或其它适合的)环上分别存在或不存在一或多个取代基。该取代基可以是卤素;烷基包括环烷基和卤代烷基;和芳基包括卤代芳基和杂芳基。
根据本发明,烷基为脂族烃,可以是直链或支链基团。烷基可选地被一或多个取代基如卤素、烯基、炔基、芳基、羟基、烷氧基、羧基、氧基或环烷基取代。可选地在烷基中插有一或多个氧、硫、或取代或未取代的氮原子。烷基的例子包括甲基、乙基、异丙基、正丁基、叔丁基、氟甲基、二氟甲基、三氟甲基、氯甲基、三氯甲基、和五氟乙基。芳基为碳环或杂环的芳环部分。芳基可被一或多个取代基如卤素、烯基、烷基、炔基、羟基、烷氧基或环烷基取代。芳基的例子包括苯基、对甲苯基、对叔丁基苯基、噻吩基、呋喃基、嘧啶基、吡啶基、噁唑基、异噁唑基、和苯硫基(thiophenyl)。
在另一实施方案中,每个a和c独立地为0至3的整数,其中a或c至少之一为1至3的整数。优选地,a或c至少之一为3。因此,本发明多氟化阴离子的M1可含有多氟化醇根和未氟化醇根配体的混合物。更优选地,a和c均为3。
本发明多氟化阴离子还可包括一或多个螯合的多醇根如二-和/或三-醇根。此外,本发明多氟化阴离子还可包括一或多个烷基或芳基代替一或多个上述醇根。
下面结合含Nb(HFIP)6 -阴离子的化合物的合成描述本发明多氟化阴离子的制备方法。该方法涉及相对不贵的商购化合物:锂、NbCl5、和六氟-2-丙醇。制备含Nb(HFIP)6 -的化合物的一般反应式如下所示:
其它抗衡阳离子物质包括其它金属阳离子如K、Na、Mg、Ca、和Cs;三苯甲游基阳离子;吡啶鎓阳离子如2,6-吡啶鎓阳离子;和2,6-二甲基吡啶鎓阳离子,可通过阳离子交换反应制备,例如LiNb(HFIP)6与CPh3Cl在1,2-二氯乙烷中的复分解作用可制备所述三苯甲游基(CPh3 +)盐。
如图1中所示,[2,6-(CH3)2C5H4N][Nb(HFIP)6]即Nb(HFIP)6 -阴离子的2,6-吡啶鎓盐似乎有以NbO6为中心的似八面体几何形状,与Tl2Zr(HFIP)6中Zr(HFIP)6 2-结构特征的似八面体ZrO6中心相似。不受任何理论限制,据信LiNb(HFIP)6中的Li+离子大概与几个醇根氧原子键合并可能与几个CF3-基的氟原子键合,与Tl2Zr(HFIP)6中的Tl-离子相似。如图2中所示,相关化合物LiAl(HFPP)4(HFPP=六氟-2-苯基-2-丙醇根)的固态结构似乎显示Li+离子与两个醇根氧原子和来自所给Al(HFPP)4 -阴离子的四个CF3-基氟原子键合。相比,据信未氟化的盐LiNb(OEt)6中的Li+离子仅与来自两个相邻Nb(OEt)6 -阴离子的四个乙醇根氧原子键合形成似四面体的LiO4中心。
含本发明多氟化阴离子的化合物具有很高的导电率,使之特别适用作电化学装置的电解质。电化学装置的例子包括电池如锂电池或用于各种应用的锂离子电池;其它类型的电池;燃料电池;双层电容;传感器;和电色(electrochromic)显示。这些电化学装置可用于各种应用包括用于电车、lap top计算机和需要能源的其它应用的电化学装置。如表1所示,本发明多氟化阴离子的锂盐在有机溶剂中有很高的导电率。具体地,本发明化合物与其它含氟锂盐如LiCF3SO3相比在四氢呋喃(THF)和甘醇二甲醚(glyme)中有很高的导电率。
表1 导电率
化合物 | 浓度(M) | 溶剂 | 导电率(μScm-1) | 当量电导率(Scm2mol-1) |
Li(HFIP) | 0.0100 | THF | 0.315 | 0.0315 |
Li(HFIP) | 0.0100 | 甘醇二甲醚 | 0 | |
LiOTf | 0.0100 | THF | 1.47 | 0.147 |
LiOTf | 0.0100 | 甘醇二甲醚 | 3.90 | 0.390 |
LiOTf/1.36eq.冠 | 0.0100 | 甘醇二甲醚 | 7.00 | 0.700 |
LiOTf/>50eq.冠 | 0.0100 | 甘醇二甲醚 | 31.0 | 3.10 |
LiOTf | 0.0100 | PC | 195 | 19.5 |
LiAl(HFPP)4 | 0.0100 | THF | 258 | 25.8 |
LiAl(HFPP)4 | 0.0100 | DFB | 2.72 | 0.272 |
LiAl(HFPP)4 | 0.0100 | 甘醇二甲醚 | 250 | 25.0 |
LiAl(HFPP)4 | 0.0100 | PC | 130 | 13.0 |
LiAl(t-BuHFPP) | 0.0100 | 甘醇二甲醚 | 238 | 23.8 |
LiNb(HFIP)6 | 0.0100 | THF | 337 | 33.7 |
LiNb(HFIP)6 | 0.0100 | 甘醇二甲醚 | 360 | 36.0 |
LiNb(HFIP)6/1.34eq.冠 | 0.0100 | 甘醇二甲醚 | 338 | 33.8 |
LiNb(HFIP)6 | 0.0100 | PC | 126 | 12.6 |
1HFIP=OCH(CF3)2;HFPP=OC(Ph)(CF3)2;冠=12-冠-4;t-BuHFPP=OC(p-C(CH3)3Ph)(CF3)2;THF=四氢呋喃;PC=丙二醇碳酸酯;OTf=CF3SO3;DFB=1,2-二氟代苯。
特别适用于电池中的本发明化合物的锂盐包括LiAl(OC(C6H5)(CF3)2)4、LiNb(OCH(CF3)2)6、和LiAl(t-BuHFPP)。
再参考表1,本发明多氟化阴离子的锂盐比lithium triflate在THF和甘醇二甲醚中的导电率高至少两个数量级。因此,为在有机溶剂如THF或甘醇二甲醚中获得相同的导电率,在电化学装置中本发明化合物的需要量为其它含氟电解质如LiCF3SO3和LiPF6需要量的约1%。
本发明多氟化阴离子的锂盐在约25℃、约0.01M浓度下在THF中的导电率为至少约50μScm-1,优选至少约130μScm-1,更优选至少约190μScm-1,最优选至少约250μScm-1。或者,本发明多氟化阴离子的锂盐在约25℃、约0.01M浓度下在甘醇二甲醚中的导电率为至少约50μScm-1,优选至少约130μScm-1,更优选至少约190μScm-1,最优选至少约250μScm-1。
据信LiAl(HFPP)4的结构包含罕见的在所述Li+阳离子周围的三棱柱形配位区,有两个Li-O(C、Al)键和四个Li-F(C)键,参见图2。不受任何理论的限制,据信Li+阳离子和CF3基之间的弱键合导致在低介电溶剂中具有高导电率。的确,相信高度氟化和所述C-F键中Li+阳离子间的弱配位使本发明锂盐不同于其它含氟锂盐,例如LiNb(HFIP)6含有空前的36个氟原子,据信其使单负电荷离域。
本发明多氟化阴离子也可用于各种有机反应催化剂,其中弱配位阴离子通过共轭加成和Diels-Alder反应中所含相应阳离子改善催化反应的产率、选择性和/或速率。本发明化合物包含弱配位阴离子即多氟化阴离子,它提高缔合金属阳离子的催化活性。近来引起广泛关注的催化反应的例子是锂催化的Diels-Alder反应和锂催化的1,4-共轭加成反应。如下面所示,用LiNb(HFIP)6(1)在甲硅烷基乙烯酮缩二乙醇(2)至空间位阻,
-不饱和羰基化合物(3)的1,4-共轭加成反应中作为催化剂,以93%的产率得到1,4-加成产品(4)。
反应条件:1,2-二氯乙烷(DCE)溶剂,0.1M(3)、0.2M(2),0.01MLiNb(HFIP)6和0.01M六甲基磷酰胺(HMPA)在24℃下30小时。
在这些条件下观察到仅形成所述1,4-加成产物(4)。有趣地,反应混合物中省去HMPA时,仅10分钟后就观察到(4)和所述1,2-加成产物(5)的混合物(单产率95%,(4)∶(5)之摩尔比=1∶5)。不受任何理论限制,据信Li+离子与HMPA配合产生空间位阻更大的烯酮(enone)-锂离子配合物,因此相对于所述乙烯酮加至所述羰基碳即1,2-加成反应,更利于在距羰基碳更远的位置加入所述乙烯酮即1,4-加成。
表2中示出LiNb(HFIP)6与两种其它锂催化剂增加1,4-共轭加成产物的形成的对比。Li(HMPA)+配合物的路易斯酸性较弱导致反应速率下降,表现在HMPA加入反应混合物时所需反应时间较长。用LiNb(HFIP)6得到的结果与使用活性非常高的催化剂LiCo(C2B9H11)2所得结果相当。用LiClO4作为催化剂时,产品的产率明显较低。此外,在助催化剂HMPA存在下使用LiClO4时,(4)∶(5)之比例仅改善至1.3∶1。不受任何理论限制,据信与ClO4 -相比Nb(HFIP)6 -的尺寸较大和/或与Li+的配位能力较弱导致LiClO4与LiNb(HFIP)6之间催化活性不同。
表2 (2)和(3)间的锂催化反应产生1,4-和
1,2-加成产物(4)和(5)的产率a
催化剂 | 助催化剂b | 时间 | (4)∶(5)之比 | %产率 |
LiNb(HFIP)6 | 无 | 10min | 1∶5 | 95% |
LiNb(HFIP)6 | 0.1M HMPA | 30h | 100∶0 | 93% |
LiCo(C2B9H11)2 | 无 | 20min | 1∶6 | 95% |
LiCo(C2B9H11)2 | 0.1M HMPA | 32h | 100∶0 | 96% |
LiClO4 | 无 | 10min | 1∶4.5 | 62% |
LiClO4 | 0.1M HMPA | 48h | 1.3∶1 | 69% |
a 反应条件:1,2-二氯乙烷,0.1M(3)、0.2M(2),0.1M催化剂和0.1M助催化剂(使用时),在25℃下。
b HMPA=六甲基磷酰胺。
c 这些结果来自DuBay等,J.Org.Chem.,1994,59,6898。
空间较庞大即比Nb(HFIP)6 -大的本发明多氟化阴离子提供在无HMPA下区域选择性和/或活性更高的锂阳离子催化剂。此外,本发明富对映体的多氟化阴离子(包含有手性中心的多氟化醇根)提供对映选择性的锂离子催化剂,即产生富对映体的产物。当然,碳原子的手性中心是四个不同基团与之相连的碳原子;而化合物手性的最终判据是镜像不重叠性。面选择性、对映选择性或立体选择性合成反应是其中主要地或仅形成一组立体异构体之一的那些反应。优选地,以至少约50%的对映体过剩量产生一种异构体。对映体过剩量是产品组合物中一种对映体与另一种对映体之差。对映体过剩量可由下式表示:%ee=(R-S)/(R+S),其中R为一种对映体的量,S为另一种对映体的量,例如,含有98%一种对映体和2%另一种对映体的产品组合物的%ee为96%。更优选地,以比另一种对映体至少约80%的对映体过剩量产生一种异构体,还更优选至少约90%的对映体过剩量,甚至更优选至少约95%的对映体过剩量,最优选至少约98%的过剩量。
可使本发明多氟化阴离子的锂盐与聚合物化合或混合制备表现出锂离子导电性的聚合物材料。这种材料(称为聚合物包盐型固体电解质或固态聚合物电解质)可作为电解质用于无溶剂高能密度锂基电池。聚合物还包括连接剂,通过在聚合物和本发明化合物之间形成化学键使本发明化合物与聚合物结构直接键合。适用于本发明的聚合物有橡胶态的物性。一般地,适合的聚合物有一种或多种以下鉴别特征:1)能溶解弱配位阴离子的锂盐和/或与弱配位阴离子的锂盐的锂阳离子配位(即使是弱配位);2)能在其中溶解不同量锂的情况下保持低玻璃化转变温度;和3)能具有高导电率,特别是高锂离子导电率,即在给定温度下比lithium triflate/聚合物混合物高。适用于本发明的聚合物的例子包括聚乙二醇;聚乙烯;聚丙烯;聚苯乙烯;聚丁二烯;聚氟乙烯;聚氯丁二烯;聚烷基硅氧烷如聚二甲基硅氧烷;聚氯乙烯;聚乙烯亚胺;和聚环氧烷如聚环氧丙烷、非晶形聚环氧乙烷和聚环氧乙烷。优选该聚合物选自非晶形聚环氧乙烷(aPEO)、聚环氧烷、聚烷基硅氧烷、聚氟乙烯、聚氯乙烯、聚氯丁二烯、聚丁二烯、聚乙烯和聚丙烯;更优选选自aPEO、聚氟乙烯、聚氯乙烯、聚氯丁二烯、聚丁二烯、聚乙烯和聚丙烯;最优选选自aPEO、聚丁二烯、聚乙烯和聚丙烯。
本发明还包括聚合物包盐型电解质,有含本发明多氟化阴离子的碱金属盐,所述多氟化阴离子包括如Nb(HFIP)6 -、Al(OCH(CF3)2)4 -、Al(OC(CH3)(CF3)2)4 -、Al(OCPh(CF3)2)4 -、和Al(OC(CF3)3)4 -等多氟化阴离子。包含这些多氟化阴离子的化合物具有优于含其它阴离子的化合物的玻璃化转变温度、阻抗值和阳离子迁移数。
本发明多氟化阴离子也可用作活化过渡金属催化的烯烃聚合的助催化剂和聚合光引发剂的抗衡离子。
在以下实施例的基础上,本发明的其它目的、优点和新特征对于本领域技术人员会更加清楚,这些实施例不用于限制本发明。
试验
所有制备和物理测量均在严格无空气和水的情况下进行。利用Schlenk、手套箱和高真空技术,需要惰性气氛时使用纯氮气。所有试剂和溶剂均为试剂级的或更好。锂金属丝(Aldrich,Milwaukee,WI)原样使用。三苯基氯甲烷CPh3Cl(Aldrich)从乙酸乙酯中重结晶。氯化铌(V)(Aldrich)在125℃真空下升华。六氟-2-丙醇(Central Glass,Ube,Japan)经活性4°A分子筛干燥并真空蒸馏。以下溶剂由所示干燥剂通过蒸馏干燥:四氢呋喃(Na);苯-d6(Na);丙酮-d6(活性4°A分子筛);乙腈-d3(P2O5);1,2-二甲氧基乙烷(Na);丙二醇碳酸酯(Na);六氟异丙醇(活性4°A分子筛);六氟-2-苯基-2-丙醇(活性4°A分子筛);二乙醚(Na);1,2-二氯乙烷(P2O5);1,2-二氯乙烷-d4(P2O5);甲苯-d8(Na);乙腈-d3(P2O5);硝基甲烷-d3(P2O5);氯仿-d(P2O5);一氯三氟甲烷(P2O5);四甲基甲硅烷(P2O5);六甲基磷酰胺(P2O5);二乙醚(Na);全氟代叔丁醇(活性4°A分子筛);六氟代叔丁醇(活性4°A分子筛);和六氟代苯(活性4°A分子筛)。在H2SO4上搅拌、流过活化的碱性氧化铝(Aldrich;150目),从钠金属中蒸馏,制备无水纯己烷。
用Bruker WP-300分光计或Bruker SY-200分光计记录NMR波谱。化学位移(Ω)是相对于SiMe4(对于1H NMR,Ω=0)和CFCl3(对于19F NMR,δ=0)。如前面所述,用Perkin Elmer P400分光计进行ICP-AES分析。
用Perkin Elmer DSC-7热分析仪通过示差扫描量热法测量玻璃化转变温度(Tg)。该仪器用四个标准(镓、环己烷、癸烷和庚烷)校准。对于每个试样使用四个不同的扫描速度,通过将线性的Tg对扫描速度线外推至0℃/min的扫描速度确定Tg(玻璃化转变认为是转折的中点)。
在10℃和100℃之间的温度下,在5Hz和5MHz之间的频率下,用Hewlett-Packard4192阻抗分析仪测量聚合物电解质的导电率。将试样压制成在两个钽电极之间的0.1cm Teflon隔板(内径1.0cm)内的片。为确保电极与试样间良好地接触,在进行介电测量之前将装载电池加热至80℃过夜。用Nyquist®曲线(虚对实阻抗)确定试样在各温度下的实际(0频率)d.c.导电率。
负-和正-离子电喷雾质谱法在Fisons VG Quattro-SQ质谱仪上进行。电导法用Yellow Springs Instrument Co.,Inc.31A型电导电桥和已对反向使用校准的YSI3403型电导池(电池常数k=1.113)进行。在手套箱中在5ml体积的烧瓶中用适合的无水溶剂制备用于电导测量的溶液。确定所有溶剂的电导均低于2×10-7φ-1,这是用此装置可测量最低电导。
试验1
LiNb(HFIP)6的合成
将新升华的Li(HFIP)(6.64g,38mmol)的25-ml六氟代苯溶液滴加至新升华的NbCl5(1.72g,6.4mmol)的25-ml六氟代苯溶液中。将反应混合物在25℃下搅拌17小时,然后用细玻璃料过滤除去固态LiCl和少量过剩的NbCl5。通过真空蒸发从无色滤液中除去挥发分,得到5.54g LiNb(HFIP)6,为白色固体(基于Li(HFIP)为79%)。
1H NMR(苯-d6:六氟代苯(1∶9 v∶v)):δ5.19(m)。
19F NMR波谱:δ-74.7(s)。
产品中铌与锂之摩尔比通过电感耦合等离子体原子发射光谱法(AES-ICP)确定。计算的Nb/Li=1.00。测得(六次测量)Nb/Li=1.03(1)。
试验2
[Ph3C][Nb(HFIP)6]的合成
将新制备的LiNb(HFIP)6(1.64g,1.49mmol)和Ph3CCl(0.42g,1.49mmol)溶解于35ml 1,2-二氯乙烷中。使该黄色溶液避光,搅拌24小时,然后用细玻璃料过滤除去固态LiCl。通过真空蒸发从滤液中除去挥发分,得到1.63g[Ph3C][Nb(HFIP)6],为黄色固体(基于LiNb(HFIP)6为82%)。
1H NMR(1,2-二氯乙烷-d4):δ8.29(t),7.88(t),7.66(d)和5.10(m)。
19F NMR:δ-74.6(s)。
试验3
该实施例说明含本发明多氟化阴离子的聚合物包盐型电解质的制备方法。
如下制备含不同化学计量LiNb(HFIP)6的aPEO试样。使聚合物试样(典型地0.13g,3.0mmol醚-氧原子)与四氢呋喃(7ml)混合。所得混合物与含不同量LiNb(HFIP)6的四氢呋喃溶液混合使醚-氧/锂之摩尔比为12、24、或30。将反应混合物搅拌15小时,然后观察到无色的均匀溶液。通过真空蒸发从反应混合物中除去挥发分,在烧瓶壁上得到无色透明的橡胶状固体。在60℃真空下将该橡胶状固体加热12小时确保四氢呋喃完全去除。以此方式制备的三种无色透明的橡胶状聚合物包盐型电解质为aPEO12 LiNb(HFIP)6、aPEO24 LiNb(HFIP)6、和aPEO30 LiNb(HFIP)6。
试验4
该实施例显示本发明固态聚合物包盐型电解质与其它含氟聚合物包盐型电解质间热和导电参数的对比。
分别通过示差扫描量热法和复合阻抗测量确定聚合物aPEO12LiNb(HFIP)6、aPEO24 LiNb(HFIP)6、和aPEO30 LiNb(HFIP)6的玻璃化转变温度Tg和与温度相关的导电率σ。通过非线性最小二乘方技术使图3所示导电率数据拟合VTF经验式:
因子A典型地与载电荷浓度相关,B为假活化能,据信与离子迁移所需聚合物膨胀系数相关,T0与聚合物电解质的玻璃化转变温度相关(典型地Tg-T0值为25-50°K),k为玻尔兹曼常数。通过试验和误差确定与数据的最佳适配固定参数T0。Tg、T0、和最小二乘方变量A和B(与它们相伴的评估标准偏差)与由aPEO和LiCF3SO3或NaCF3SO3组成的聚合物电解质的结果一起示于表3中。
对于给定的阳离子、聚合物和化学计量,一些聚合物包盐型电解质的离子导电率可能随阴离子而改变。导电率的变化可以是阴离子大小、极化率、和/或配位能力(即成离子对的能力)的函数,其中任何参数均可能影响聚合物链段的Tg、阳离子-阴离子簇或离子介导的瞬态交联。
对于aPEOnLiNb(HFIP)6和aPEOnLiCF3SO3在n不变的情况下,不能仅通过导电率测量确定的迁移数(即阳离子和阴离子所带电荷分数)可能不同。脉冲场梯度NMR测量显示aPEOnLiCF3SO3中Li+的迁移数可能低于0.1(即CF3SO3 -的迁移数可能大于0.9)。Nb(HFIP)6 -阴离子比CF3SO3 -的体积大导致在n不变的情况下aPEOnLiNb(HFIP)6的阴离子迁移数比aPEOnLiCF3SO3低。因而,即使aPEO24LiNb(HFIP)6和aPEO25LiCF3SO3的总导电率基本相同,aPEO24LiNb(HFIP)6的锂离子导电率也明显高于aPEO25LiCF3SO3的。
表3 固态聚合物包盐型电解质的热和导电参数a聚合物电解质 Tq b 106sc Ad Bd T0 d Tq-T0
(°K) (Scm-1) (Scm-1K1/2) (eV) (K) (K)aPEOe 211aPEO30LiNb(HFIP)6 219 5.0 0.40(2) 0.0745(6) 190 29aPEO24LiNb(HFIP)6 222 10 0.160(4) 0.0545(3) 200 22aPEO12LiNb(HFIP)6 227 1.4 2.4(2) 0.130(2) 180 47aPEO30LiCF3SO3 f 28aPEO25LiCF3SO3 f 33aPEO10LiCF3SO3 f 3.6aPEO9LiCF3SO3 e 252 0.82aPEO9NaCF3SO3 q 251 1.5 93 0.13 194 57aPEO12NaCF3SO3 h 236 1.6 4.0 0.080 211 25
a aPEO=非晶形聚环氧乙烷
b 玻璃化转变温度
c 在20℃下的D.C.导电率
d A和B为与VTF等式拟合的s对1/T曲线的最小二乘方参数(括号内的esds)。T0值定为通过连续反复获得数据的最佳适配确定的值。
e Besner等,Macromolecules,1992,25,6480。
f 参见Rockwell等,Inorg.Chimica Acta,1997,263,195的参考44。
g Wintergill等,Polymer,1989,30,1123。
h Doan等,Chem.Mater.,1990,2,539。
试验5
LiB[O(C6H4)C(CF3)2O]2的合成
向HO(C6H4)C(CF3)2OH(0.2242g,0.86mmol)的20ml蒸馏水溶液中加入LiOH·H2O(0.0181g,0.43mmol)和B(OH)3(0.0266g,0.43mmol)的水溶液。将反应混合物在氩气氛下在105℃搅拌22小时。用旋转蒸发器除去水得到无色透明的油。加入甲苯产生白色固体沉淀。在真空下除去甲苯,使所得白色粉末在180℃真空下升华得到LiB[O(C6H4)C(CF3)2O]2,为白色粉末。
1H NMR(CD3CN)δ7.37(d,1H),7.24(t,1H),6.79(t,1H),6.7(d,1H)。
19F NMR(CD3CN)δ115.78(s)。
低分辨质谱(负离子电喷雾,CH3CN溶液)。对于C18H8BF12O4计算:527.0]。测得:m/z527.1[(M-Li)-。
试验6
LiAl[O(C6H4)C(CF3)2O]2的合成
将约0.515g HO(C6H4)C(CF3)2OH(1.98mmol)和0.155g LiAlH4(4.09mmol)混入甲苯中,搅拌140小时。通过有Celite的Schlenk过滤器过滤反应混合物。将滤液在真空下浓缩得到棕色固体。
1H NMR(C6D6)δ7.76(d,1H),7.37(d,1H),6.93(t,1H),6.73(t,1H),6.65(t,1H),6.56(t,1H),6.45(d,1H),6.03(d,1H)。
19F NMR(C6D6)δ-72.47(m),-74.06(m),-78.15(m),-78.75(m)。
试验7
LiAl(HFPP)4的合成
将H[HFPP](5.3624g,22.0mmol)的20ml己烷溶液加入搅拌的LiAlH4(0.4220g,11.1mmol)的己烷(30ml)悬浮液中。观察到从无色浆液中放出气体(可推断为H2)。将混合物搅拌16小时,在此期间混合物的外观不变。然后通过中级玻璃过滤器过滤该混合物。剩余的固体用20ml己烷洗涤。滤液在真空下浓缩得到白色结晶固体(5.2445g,基于H[HFPP]为95%)。
1H NMR(C6D6):δ7.9(m,8H),7.0(m,12H)。
19F NMR(C6D6):δ-75.24(q,JF-Li=2.8Hz)。
7Li NMR(C6D6):δ-0.35(bs)。
13C NMR(甲基环己烷-d14):δ131.5(s),130.3(s),128.6(s),127.4(s),124.5(q,JC-F=289Hz)。
低分辨质谱(负离子电喷雾,CH3CN溶液)m/z998.9[(M-Li)-;对于C36H20AlF24O4计算:999.1]
LiAl(HFPP)4的X-射线结构示于图2中(为清楚起见省去氢原子)。未标注的画影线的圆圈为氟原子,而未标注的无影线圆圈为碳原子。所选原子间距离(°A)和角(°):Li-O1,1.978(8);Li-O2,1.966(8);Li-Fl,1.984(9);Li-F4,2.354(10);Li-F7,2.098(11);Li-F10,2.082(9);O1-Li-O2,79.9(3)。
试验8
LiAl(HFPP)4·O(C6H8)的合成
将LiAl(HFPP)4溶解于甲苯中,加入稍低于1当量的环己烯酮。
有配位的2-环己烯-1-酮的LiAl(HFPP)4的X-射线结构示于图4中(为清楚起见省去氢原子)。未标注的画影线的圆圈为氟原子,而未标注的无影线圆圈为碳原子。所选原子间距离(°A)和角(°):Li-O1,2.028(9);Li-O2,2.02(1);Li-O5,1.830(9);Li-F1,2.27(1);Li-F4,2.48(1);Li-F7,2.75(1);O5-C32,1.230(6);O1-Li-O2,78.1(3);O1-Al-O2,92.1(2);Li-O5-C32,154.1(6)。
试验9
[(C6H5)3C][Al(HFPP)4]的合成
将LiAl(HFPP)4(0.2082g,0.2069mmol)的CH2Cl2溶液加入-78℃的PhCCl3(0.0576g,0.2066mmol)的CH2Cl2溶液中,形成鲜橙色。使溶液升至室温,搅拌15小时,形成沉淀。通过盖有Celite的中级玻璃过滤器过滤该溶液得到鲜橙色溶液。将滤液浓缩得到黄色固体,再溶解于热CHCl3中。冷却至-40℃时,形成黄色晶体(0.2265g,88.2%)。
1H NMR(CD2Cl2):δ8.4(tt,3H),7.85(m,14H),7.61(dm,6H)7.27(tt,4H),7.16(tm)。
19F NMR(CH2Cl2):δ-74.8(s)。
试验10
TlAl(HFIP)4的合成
将Tl[HFIP](3.8849g,10.35mmol)的甲苯溶液从加料漏斗滴加至0℃下搅拌的AlCl3(0.3455g,2.59mmol)的甲苯浆液中。加料时形成白色沉淀,推断为TlCl。加完后,使溶液升至室温,将有白色沉淀的无色透明溶液搅拌5小时,在此期间未观察到变化。将反应混合物在真空下浓缩过夜,得到白色固体,该固体仍是湿的,推断有甲苯。在50℃真空下升华得到TlAl(HFIP)4,为白色固体(1.6072g,68.7%)。
1H NMR(C6D6):δ4.65(septet(7重峰),JH-F=6.3Hz)。
19F NMR(C6D6):δ-76.46(d,JH-F=6Hz)。
TlAl(HFPP)4的X-射线结构示于图5中。未标注的画影线的圆圈为氟原子,而未标注的无影线大圆圈为碳原子,未标注的无影线小圆圈为氢原子。所选原子间距离(°A)和角(°):Tl-O1,2.805(6);Tl-O2,2.855(6);Tl-O3’,2.992(6);Tl-F1,3.090(7);Tl-F4,3.398(7);Tl-F7,3.540(6);Tl-F10,2.967(6);其它Tl-F,3.045(6)至3.245(6)°A;O1-Tl-O2,54.3(2)。
试验11
TlB(HFIP)4的合成
将约0.3524g B(HFIP)3(0.688mmol)真空转移至Tl(HFIP)(0.2564g,0.690mmol)的冻甲苯溶液中。将混合物在室温下搅拌过夜(约18小时)。将反应混合物在真空下浓缩得到固体。使固体在45℃真空下升华得到TlB(HFIP)4,为白色固体(0.3187g,52.4%产率)。
1H NMR(CD2Cl2):δ4.80(septet)。
19F NMR(C6D6):δ-76.46(d,JH-F=6Hz)。
试验12
LiAl(HFTB)4的合成
将H[HFTB](2.3643g,13.0mmol)的10ml己烷溶液加入在室温下搅拌的LiAlH4(0.246g,6.49mmol)的己烷(40ml)溶液中。约52.5小时后,通过中级玻璃过滤器过滤反应混合物除去白色固体。将白色固体用30ml己烷洗涤。滤液在真空下浓缩得到LiAl(HFTB)4,为白色结晶固体(1.7561g,71%基于H[HFTB])。
1H NMR(C6D6):δ1.43(s)。
19F NMR(C6D6):δ-79.72(s)。
低分辨质谱(负离子电喷雾,CH3CN溶液)。对于C16H12AlF24O4计算:751.0。测得:m/z750.8[(M-Li)]-。
试验13
LiAl(HFTB)4·OP(C6H5)3的合成
将约1当量氧化三苯膦加入LiAl(HFTB)4的己烷溶液中。
配位有氧化三苯膦的LiAl(HFPP)4的X-射线结构示于图5中(为清楚起见省去氢原子)。未标注的画影线的圆圈为氟原子,而未标注的无影线圆圈为碳原子。所选原子间距离(°A)和角(°):Li-O1,2.045(9);Li-O2,2.018(9);Li-O5,1.822(9);Li-F1,2.885(10);Li-F4,2.308(11);Li-F7,2.732(11);Li-F8,2.993(9);Li-F19,2.827(12);O1-Li-O2,78.4(3);O1-Al-O2,92.5(2);Li-O5-P,155.6(4)。
试验14
TlAl(HFTB)4的合成
将Tl[HFTB](7.8089g,20.26mmol)的甲苯溶液用加料漏斗滴加至0℃下搅拌的AlCl3(0.6753g,5.065mmol)的甲苯浆液中。加料时立即形成白色沉淀,推断为TlCl。加完后,使溶液升至室温,将有白色沉淀的无色透明溶液搅拌16小时,在此期间未观察到变化。将反应混合物在真空下浓缩过夜,得到白色固体,该固体仍是湿的,推断有甲苯。使固体在60℃真空下升华得到TlAl(HFIP)4(4.1064g,84.9%)。
1H NMR(C6D6):δ1.57(s)。
19F NMR(C6D6):δ-77.89(s)。
TlAl(HFPP)4的X-射线结构示于图5中。未标注的画影线的圆圈为氟原子,而未标注的无影线大圆圈为碳原子,未标注的无影线小圆圈为氢原子。所选原子间距离(°A)和角(°): Tl-O1,2.731(9);Tl-O2,2.717(9);Tl-F1,3.987(10);Tl-F4,2.903(9);Tl-F7,2.952(10);Tl-F10,3.081(11);其它Tl-F,3.154(10)至3.471(10)°A;O1-Tl-O2,57.9(3)。
试验15
[(C6H5)3C][Al(HFTB)4]的合成
将TlAl(HFTB)4(3.994g,3.663mmol)的CH2Cl2溶液加入-78℃的Ph3CCl(1.0214g,3.664mmol)的CH2Cl2溶液中,变成鲜橙色并形成沉淀。使溶液升至室温,搅拌20小时。通过盖有Celite的中级玻璃过滤器过滤该溶液得到鲜橙色溶液。滤液在真空下浓缩得到黄色固体(3.2034g,87.9%)。将黄色固体用异辛烷洗涤。再溶解于热CHCl3中。冷却至-40℃重结晶,得到黄色晶体(2.4g,66.7%)。
1H NMR(CD2Cl2):δ8.4(t,3H),7.85(t,6H),7.61(d,6H)1.47(s,12H)。
19F NMR(CH2Cl2):δ-79.85(s)。
试验16
LiAl(t-BuHFPP)4的合成
将约0.9923g(t-BuHFPP)H(3.31mmol)和LiAlH4(0.1265g,3.34mmol)加入约50ml己烷中。将混合物在室温下搅拌18小时,过滤。将滤液浓缩得到0.2899g LiAl(t-BuHFPP)4。滤出的固体用甲苯洗涤又得到0.4783gLiAl(t-BuHFPP)4。总产率为47%。LiAl(t-BuHFPP)4为白色固体。
1H NMR(C6D6):δ7.95(d,2H),7.23(d,2H),1.12(s,9H)。
19F NMR(CH2Cl2):δ-75.32(s)。
试验17
LiAl(PFTB)4的合成
将H[PFTB](1.5577g,6.599mmol)的15ml CFC-113溶液加入搅拌的LiAlH4(0.1250g,3.299mmol)的CFC-113(30ml)浆液中。将反应混合物搅拌16.5小时,通过中级玻璃过滤器过滤。滤液在真空下浓缩得到白色结晶固体(1.2302g,76.6%基于H[PFTB])。
19F NMR(C6D6):δ-61.00(s)。
低分辨质谱(负离子电喷雾,CH3CN溶液)。对于C16AlF36O4计算:967.1。测得:m/z966.5(M-Li)-。
试验18
[2,6-二甲基吡啶鎓][Nb(HFIP)6]的合成
将新制备的LiNb(HFIP)6(0.20g,0.18mmol)和氯化2,6-二甲基吡啶鎓(0.026g,0.18mmol)的混合物溶解于25ml无水二氯甲烷中。在室温下剧烈搅拌反应2.5小时,通过细玻璃料过滤除去固体LiCl。在真空下使滤液体积降至约5ml直至开始从溶液中沉淀出产物。然后将溶液加热直至所有固体重新溶解。使此饱和溶液缓慢冷却至室温。18小时后,收集两批晶体之第一批。重复此过程,收集第二批晶体材料。使两部分混合(0.20g,93%基于LiNb(HFIP)6)。
图1中示出[2,6-(CH3)2C6H4N+][Nb(HFIP)6 -]晶体的不对称单元中两个Nb(HFIP)6 -阴离子之一的X-射线结构。未标注的带影线圆圈是氟原子,未标注的无影线大圆圈为碳原子,未标注的无影线小圆圈为氢原子。Nb-O距离在1.929(8)至1.998(8)°A的范围内。
试验19
[LiTa(HFIP)6]·3(C2H5)2O的合成
将新升华的TaCl5(1.51g,4.21mmol)和Li(HFIP)(4.39g,25.3mmol)的混合物溶解于40ml无水Et2O中。初始反应充分地放热使溶剂沸腾,但反应迅速冷却至室温。将反应混合物在25℃下搅拌15小时,然后用真空蒸发使反应混合物浓缩。将所得固体溶解于20ml无水C6F6中。通过细玻璃料过滤除去不溶的LiCl,利用一部分硅藻土辅助小颗粒的过滤。滤液在真空下浓缩得到4.64g LiTa(HFIP)6·3Et2O,为白色微晶固体(基于Li(HFIP)为78%)。
1HNMR(苯-d6:六氟代苯(1∶9 v∶v)):δ5.24,3.45(q,JH-H=7.0Hz)和1.08(t,JH-H=7.0Hz)。
19F NMR(苯-d6:六氟代苯(1∶9 v∶v)):δ-74.6。
本领域技术人员应当理解,对于本发明优选实施方案,可作各种改变和修改且在不背离本发明精神的情况下可作各种改变和修改。因此权利要求书包括落入本发明实际精神和范围的所有这种等同变化。
Claims (57)
1.一种化合物,包含下式的阴离子:
[M1(XC(CFa(R1)b)(CFc(R2)d)R3)m(R4)n]-1
其中M1为过渡金属或第III、IV或V族元素;
每个X独立地为O、S、或NR5R6;
每个R1和R2独立地为H、卤离子或C1-C4烷基;
每个R3独立地为H、C1-C4烷基、或C4-C20芳基;
每个R4独立地为C1-C10烷基、C1-C10醇根或C4-C20酚根;
每个R5和R6独立地为H或C1-C10烷基;
每个a和c独立地为0至3的整数;
a+b=3;
c+d=3;
m为2至8的整数;和
n为0至4的整数;
条件是a或c至少之一不为0,当M1为Al且a和c为3时,R3不是苯基或对甲苯基。
2.权利要求1的化合物,其中M1选自Al、B、V、Ti、Si、Zr、Ge、Sn、Cu、Y、Zn、Ga、Nb、Ta、Bi、P、As、Sc、Hf和Sb。
3.权利要求1的化合物,其中M1选自Al、B、Nb和Ta。
4.权利要求1的化合物,其中a和c为3。
5.权利要求1的化合物,其中X为O。
6.权利要求1的化合物,其中R3选自H、甲基、三氟甲基、对叔丁基苯基、和苯基。
7.权利要求1的化合物,其中m为2、4或6。
8.权利要求1的化合物,其中n为1。
9.权利要求1的化合物,其中X为O,a和c为3。
10.权利要求9的化合物,其中M1为Al。
11.权利要求10的化合物,其中m=2,n=1,R3为苯基,和R4为邻二羟根苯基。
12.权利要求10的化合物,其中m=4,n=0。
13.权利要求12的化合物,其中R3为H。
14.权利要求12的化合物,其中R3为甲基。
15.权利要求12的化合物,其中R3为三氟甲基。
16.权利要求12的化合物,其中R3为对叔丁基苯基。
17.权利要求9的化合物,其中M1为B。
18.权利要求17的化合物,其中m=4,n=0,和R3为H。
19.权利要求9的化合物,其中M1为Nb,m=6,n=0,R3为H。
20.权利要求9的化合物,其中M1为Ta,m=6,n=0,R3为H。
21.用于电化学装置的电解质,包括下式的化合物:
Mp[M1(XC(CFa(R1)b)(CFc(R2)d)R3)m(R4)n]
其中
M为金属、磷鎓、铵或硫鎓;
M1为过渡金属或第III、IV或V族元素;
每个X独立地为O、S、或NR5R6;
每个R1和R2独立地为H、卤离子或C1-C4烷基;
每个R3独立地为H、C1-C4烷基、或C4-C20芳基;
每个R4独立地为C1-C10烷基、C1-C10醇根或C4-C20酚根;
每个R5和R6独立地为H或C1-C10烷基;
每个a和c独立地为0至3的整数;
a+b=3;
c+d=3;
p为1或2;
m为2至8的整数;和
n为0至4的整数;
条件是a或c至少之一不为0。
22.权利要求21的电解质,其中p为1。
23.权利要求22的电解质,其中M1选自Al、B、V、Ti、Si、Zr、Ge、Sn、Cu、Y、Zn、Ga、Nb、Ta、Bi、P、As、Sc、Hf和Sb。
24.权利要求22的电解质,其中M1选自Al、B、Nb和Ta。
25.权利要求22的电解质,其中a和c为3。
26.权利要求22的电解质,其中X为O。
27.权利要求22的电解质,其中R3选自H、甲基、三氟甲基、对叔丁基苯基、和苯基。
28.权利要求22的电解质,其中m为2、3、4或6。
29.权利要求22的电解质,其中M为Li,n为1。
30.权利要求29的电解质,其中R4为C1-C10烷基。
31.权利要求29的电解质,其中R4选自甲基和乙基。
32.权利要求22的电解质,其中X为O,a和c为3。
33.权利要求32的电解质,其中M为Li,M1为Al。
34.权利要求33的电解质,其中m=2,n=1,R3为苯基,和R4为取代的邻二羟根苯基。
35.权利要求33的电解质,其中m=2,n=1,R3为苯基,和R4为邻二羟根苯基。
36.权利要求33的电解质,其中m=4,n=0。
37.权利要求36的电解质,其中R3为H。
38.权利要求36的电解质,其中R3为甲基。
39.权利要求36的电解质,其中R3为三氟甲基。
40.权利要求36的电解质,其中R3为对叔丁基苯基。
41.权利要求36的电解质,其中R3为对甲基苯基。
42.权利要求36的电解质,其中R3为苯基。
43.权利要求33的电解质,其中m=3,n=1,和R3为苯基。
44.权利要求43的电解质,其中R4为甲基。
45.权利要求43的电解质,其中R4为乙基。
46.权利要求32的电解质,其中M为Li,M1为B。
47.权利要求46的电解质,其中m=4,n=0,和R3为H。
48.权利要求32的电解质,其中M为Li,M1为Nb,m=6,n=0,R3为H。
49.权利要求32的电解质,其中M为Li,M1为Ta,m=6,n=0,R3为H。
50.包含权利要求21的电解质的固体聚合物。
51.权利要求50的固体聚合物,还包含选自以下的聚合物:聚乙二醇、聚乙烯、聚丙烯、聚苯乙烯、聚丁二烯、聚氟乙烯、聚氯丁二烯、聚二甲基硅氧烷、聚氯乙烯、聚乙烯亚胺、聚环氧丙烷、非晶形聚环氧乙烷、聚环氧乙烷及其混合物。
52.包含权利要求50的固体聚合物的电化学装置。
53.用于电化学装置的电解质,包含金属阴离子的锂盐,所述阴离子包含至少一个多氟醇根配体。
54.权利要求53的电解质,其中所述锂盐在0.01M浓度下在THF中的导电率为至少50μScm-1。
55.权利要求53的电解质,其中所述锂盐在0.01M浓度下在甘醇二甲醚中的导电率为至少50μScm-1。
56.包含有至少两个多氟化醇根配体的金属阴离子的化合物,其中所述化合物的锂盐在25℃、0.01M浓度下在THF中的导电率为至少约50μScm-1。
57.包含有至少两个多氟化醇根配体的金属阴离子的化合物,其中所述化合物的锂盐在25℃、0.01M浓度下在甘醇二甲醚中的导电率为至少约50μScm-1。
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1998
- 1998-09-11 AT AT98947054T patent/ATE285413T1/de not_active IP Right Cessation
- 1998-09-11 EP EP98947054A patent/EP1025110B1/en not_active Expired - Lifetime
- 1998-09-11 CA CA002302559A patent/CA2302559A1/en not_active Abandoned
- 1998-09-11 WO PCT/US1998/019268 patent/WO1999012938A1/en not_active Application Discontinuation
- 1998-09-11 JP JP2000510745A patent/JP4275311B2/ja not_active Expired - Fee Related
- 1998-09-11 CN CN98810370A patent/CN1276792A/zh active Pending
- 1998-09-11 DE DE69828303T patent/DE69828303T2/de not_active Expired - Fee Related
- 1998-09-11 US US09/151,852 patent/US6221941B1/en not_active Expired - Lifetime
- 1998-09-11 AU AU93928/98A patent/AU9392898A/en not_active Abandoned
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CN108350151A (zh) * | 2015-09-02 | 2018-07-31 | 维也纳科技大学 | 新的引发剂及其用于阳离子光聚合的用途 |
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EP1025110A4 (en) | 2001-03-07 |
JP2001515908A (ja) | 2001-09-25 |
WO1999012938A1 (en) | 1999-03-18 |
ATE285413T1 (de) | 2005-01-15 |
KR20010086196A (ko) | 2001-09-10 |
US6221941B1 (en) | 2001-04-24 |
EP1025110B1 (en) | 2004-12-22 |
DE69828303D1 (de) | 2005-01-27 |
CA2302559A1 (en) | 1999-03-18 |
EP1025110A1 (en) | 2000-08-09 |
AU9392898A (en) | 1999-03-29 |
DE69828303T2 (de) | 2005-12-08 |
JP4275311B2 (ja) | 2009-06-10 |
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