CN104245708A - 硅酸锂类 - Google Patents
硅酸锂类 Download PDFInfo
- Publication number
- CN104245708A CN104245708A CN201380017318.4A CN201380017318A CN104245708A CN 104245708 A CN104245708 A CN 104245708A CN 201380017318 A CN201380017318 A CN 201380017318A CN 104245708 A CN104245708 A CN 104245708A
- Authority
- CN
- China
- Prior art keywords
- lithium
- compound
- perfluoroalkyl
- formula
- ionogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 title 1
- 229910052912 lithium silicate Inorganic materials 0.000 title 1
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 lithium perfluoroalkyl silicates Chemical class 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003990 capacitor Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 35
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 28
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 6
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 28
- 239000000203 mixture Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 229910003002 lithium salt Inorganic materials 0.000 description 11
- 159000000002 lithium salts Chemical class 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 238000004611 spectroscopical analysis Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000007788 liquid Chemical class 0.000 description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- KLZDCUBZWUSEGO-UHFFFAOYSA-N CC.F.F.F.F.F Chemical compound CC.F.F.F.F.F KLZDCUBZWUSEGO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000001447 compensatory effect Effects 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000001983 dialkylethers Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000005684 open-chain carbonates Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910008416 Li-Ti Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910006861 Li—Ti Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910003691 SiBr Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 240000007591 Tilia tomentosa Species 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical group N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JKTHTZCPLANQBH-UHFFFAOYSA-N n,n-dimethylthiohydroxylamine Chemical compound CN(C)S JKTHTZCPLANQBH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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Abstract
本发明涉及全氟烷基氟硅酸锂、其制备及其在电化学电池中,更具体是在锂电池组、锂离子电池组或锂离子电容器中作为导电盐的用途,还涉及包含所述全氟烷基氟硅酸锂的电解质或电化学电池。
Description
本发明涉及全氟烷基氟硅酸锂、其制备及其在电化学电池中,更具体是在锂电池组、锂离子电池组或锂离子电容器中作为导电盐的用途,还涉及包含这些全氟烷基氟硅酸锂的电解质或电化学电池。
电化学器件的关键组分是电解质。它决定性地影响例如锂离子电池组的寿命、可靠性和性能。
以在有机溶剂中的溶液包含锂盐的电解质的导电性由该锂盐的性质决定,即由其溶解性和解离成游离或溶剂化阳离子和阴离子的能力决定。解离的离子在电化学电池中负责电荷转移。
在锂电池组或锂离子电池组中通常使用六氟磷酸锂作为导电盐,例如如W.A.van Schalkwijk和B.Scrosati(编辑),“Advances in Lithium-IonBatteries”,Kluwer Academic/Plenum Publisher,N.Y.,2002,第5章,第155-183页中所述。缺点是该盐对水解的稳定性较低。因此为找到该盐的替代物进行了各种尝试。
JP 63239780描述了在锂电池组用非水或聚合物电解质中作为可能导电盐的六氟硅酸锂。
六氟硅酸锂具有化学式Li2SiF6。文献通常使用化学式LiSiF6,但这在化学上是不正确的—例如在EP 1172877 A1中。六氟硅酸锂在有机溶剂中的溶解度非常低。JP 63239780例如制备了Li2SiF6在碳酸亚乙酯和2-甲基四氢呋喃的体积比为1:1的混合物中的0.02M溶液。
EP 1172877 A1描述了具有非水电解质的蓄电池,其中一种电解质盐为四氟硼酸锂且另一种电解质盐在许多可能性中为六氟硅酸锂。
在硅上引入全氟烷基提高了在有机溶剂中的溶解性。
例如在N.Maggiarosa等,Angew.Chem.Int.Ed.1999,38(15),2252-2253中将具有阴离子[(CH3)3Si(CF3)F]和[(CH3)3Si(CF3)2]的四甲基铵盐描述为高度反应性物质,它们以中间体化合物形式特别适合三氟甲基的转移。
例如可以分离三(二甲氨基)锍二(三氟甲基)三甲基硅酸盐,其在至多0℃的温度下稳定。然而,从0℃到5℃的温度下该化合物如A.Kolomeisev等,Chem.Commun.1999,1017-1018所述发生放热分解。因此,该类阴离子不适合新的导电盐。
因此,本发明的目的是要提供适合用于电化学电池中所用电解质的导电盐,它们在有机溶剂中稳定并且具有较低分子量,从而有利于制备在有机溶剂中的1M溶液。
H.Beckers在BergischeGesamthochschule Wuppertal于1987年进行的试验未能证实三氟甲基四氟硅酸盐的合成。他的报告在第15页描述了下列分解:
惊人地发现全氟烷基氟硅烷可以与氟化锂在有机溶剂存在下反应并发生反应而形成全氟烷基氟硅酸锂。因此,本发明的目的按照本发明借助全氟烷基氟硅酸锂实现。
因此,本发明首先提供了式(I)和/或(II)的锂盐:
Li[(Rf)nSiF5-n] (I)
Li2[(Rf)nSiF6-n] (II),
其中
Rf每次出现时独立地为具有2-12个碳原子的直链或支化全氟烷基,以及n为1-4的整数。
具有2-12个碳原子的全氟烷基对应于具有2-12个碳原子的直链或支化烷基,其中所有H原子已经被F原子替代。
具有2-12个碳原子的烷基例如为乙基、异丙基、丙基、丁基、仲丁基或叔丁基,戊基,1-、2-或3-甲基丁基,1,1-、1,2-或2,2-二甲基丙基,1-乙基丙基,正己基,正庚基,正辛基,正壬基,正癸基,正十一烷基或正十二烷基。
优选的全氟烷基Rf在每种情况下相互独立地为具有2-6个碳原子的直链或支化全氟烷基。特别优选的全氟烷基Rf在每种情况下相互独立地为五氟乙基、七氟正丙基、九氟正丁基或全氟正己基。
在本发明的一个优选实施方案中,全氟烷基Rf相同。
变量n优选为1、2或3。变量n更优选为2或3。变量n非常优选为3。
因此,如上所述的优选式(I)化合物为如下盐:三(五氟乙基)二氟硅酸锂、二(五氟乙基)三氟硅酸锂、三(七氟正丙基)二氟硅酸锂、二(七氟正丙基)三氟硅酸锂、三(九氟正丁基)二氟硅酸锂、二(九氟正丁基)三氟硅酸锂、三(十三氟正己基)二氟硅酸锂或二(十三氟正己基)三氟硅酸锂。
因此,如上所述的优选式(II)化合物是如下盐:三(五氟乙基)三氟硅酸二锂、二(五氟乙基)四氟硅酸二锂、三(七氟正丙基)三氟硅酸二锂、二(七氟正丙基)四氟硅酸二锂、三(九氟正丁基)三氟硅酸二锂、二(九氟正丁基)四氟硅酸二锂、三(十三氟正己基)三氟硅酸二锂或二(十三氟正己基)四氟硅酸二锂。
按照本发明特别优选的锂盐是三(五氟乙基)二氟硅酸锂和二(五氟乙基)三氟硅酸锂。
按照本发明尤其优选的锂盐是三(五氟乙基)二氟硅酸锂。
如上所述的式(I)化合物可以通过使相应硅烷与氟化锂反应而合成。
因此,本发明进一步提供了一种制备如上所述或作为优选描述的式(I)化合物的方法,其中使式(III)的(全氟烷基)氟硅烷与氟化锂在干燥空气或惰性气体条件下在有机溶剂存在下反应:
(Rf)nSiF4-n (III)
其中Rf和n具有上述定义或作为优选显示的定义之一。
该反应优选在干燥气氛中,如在干燥空气、氮气或氩气下进行。特别优选该反应在干燥空气或干燥氮气气氛下进行。
该反应优选在干燥有机溶剂中进行。合适的有机溶剂例如选自碳酸二甲酯、碳酸二乙酯、碳酸亚丙酯、碳酸亚乙酯、碳酸乙基·甲基酯、二甲氧基乙烷、乙醚、甲基叔丁基醚、γ-丁内酯、四氢呋喃、2-甲基四氢呋喃、乙酸乙酯或所述溶剂的混合物。优选在碳酸二甲酯中进行该反应。
氟化锂优选在-169℃至室温的温度下,更优选在-169℃下引入有机溶剂中,并且冷凝式(III)化合物。然后在加热至10-40℃的温度过程中进行实际反应。该反应优选在室温(25℃)下进行。
式(III)化合物不能市购,但可以如实施例部分所述制备或者通过相应于所需硅烷改性的方法制备。
其中n为3且Rf在每次出现时为五氟乙基的式(III)化合物,即可三(五氟乙基)氟硅烷例如可以通过使三(五氟乙基)溴硅烷与SbF3在室温下反应而制备。详细的反应条件以及还有三(五氟乙基)溴硅烷的制备如实施例部分所述。
其中n为2且Rf在每次出现时为五氟乙基的式(III)化合物,即二(五氟乙基)二氟硅烷例如可以通过使甲基三(五氟乙基)硅烷与氟反应,然后分凝而得到。详细的反应条件描述于实施例部分。
其中n为4且Rf在每次出现时为五氟乙基的式(III)化合物,即四(五氟乙基)硅烷例如可以通过使乙基三(五氟乙基)硅烷与氟反应而得到。详细的反应条件描述于实施例部分。
或者,式(I)和/或(II)化合物还可以通过使四氯化硅与相应的全氟烷基锂反应而制备。
因此,本发明进一步提供了一种制备如上所述或作为优选描述的式(I)和/或(II)化合物的方法,其中使四氯化硅与全氟烷基锂反应,其中全氟烷基对应于具有2-12个碳原子的全氟烷基。
该反应优选在-78℃至-40℃的温度下在有机溶剂中进行。合适溶剂的实例是二烷基醚,此时烷基各自相互独立地可以具有1-4个碳原子且可以是线性或支化的,或二烷基醚与己烷的混合物。优选的溶剂是乙醚或乙醚和己烷的混合物。
四氯化硅可市购。相应的全氟烷基锂化合物例如可以根据P.G.Gassmann,N.J.O’Reilly,Tetrahedron Lett.1985,26,第5243页;H.Uno,S.-i.Okada,T.Ono,Y.Shiraishi,H.Suzuki,J.Org.Chem.1992,57,第1504页;H.Uno,H.Suzuki,Synlett,1993,第91页;K.Maruoka,I.Shimada,M.Akakura,H.Yamamoto,Synlett,1994,第847页中所述方法制备。
该替换反应通常产生式(I)化合物和式(II)化合物的混合物。有关优先形成何种化合物的控制通过所用原料的比例并通过选择后处理而实现。式(I)的盐例如同样可以作为与溶剂如二甲氧基乙烷的固体或液体配合物分离。
本发明进一步提供了至少一种如上所述或作为优选描述的式(I)和/或(II)化合物在电化学电池中作为导电盐的用途。
优选的电化学电池是锂电池组、锂离子电池组或锂电容器。
本发明的锂盐也可以没有进一步限制地与其他导电盐或添加剂组合用于电化学电池中。取决于它们在电解质中的浓度,本发明锂盐还可以是添加剂。
本发明进一步提供了一种包含至少一种如上所述或作为优选描述的式(I)和/或(II)化合物的电解质。
在化学上讲,电解质是任何包含自由离子且因此导电的物质。典型的电解质是离子溶液,但熔融电解质和固体电解质同样是可能的。
因此,本发明的电解质或相应电解质配制剂是导电介质,这主要是由于存在至少一种呈溶解和/或熔融状态的物质,即通过离子运动支持导电性。
本发明化合物可以完全类似于对该应用已知的替换锂化合物使用并且当使用它们时,它们显示出特别高的稳定性。相应的蓄电池组电池就电容和电压恒定性显示出最好性能,以及在超出平均的高充电/放电循环次数下也显示出不受限制的功能性。
因此,当将式(I)和/或(II)化合物在本发明电解质中用作导电盐时,所用溶液为该锂导电盐在非质子溶剂或溶剂混合物中的0.45-2M,优选1M溶液。
对本发明而言,摩尔浓度是指在25℃下的浓度。
当将式(I)化合物和/或式(II)化合物在本发明电解质中用作添加剂时,典型的浓度基于该电解质总重量为0.05-10重量%,优选0.05-5%。
除了该至少一种如上所述或作为优选描述的式(I)或(II)化合物外,本发明电解质可以包含任选的其他导电盐,优选选自锂盐和/或四烷基铵盐,其中各烷基相互独立地为具有1-4个碳原子的烷基。
在一个优选实施方案中,当将该电解质用于锂电池组或锂离子电池组和锂离子电容器中时,该导电盐为导电锂盐如LiPF6、LiBF4、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiF5P(C2F5)、LiF5P(C3F7)、LiF5P(C4F9)、LiF3P(C2F5)3、LiF4P(C2F5)2、LiF3P(C4F9)3、LiB(C2O4)2或LiF2B(C2O4)。
当将包含至少一种如上所述或作为优选描述的式(I)或(II)化合物的电解质在双层电容器或超级电容器中用作添加剂时,该导电盐优选为选自[N(C2H5)4]BF4、[N(C2H5)4]PF6、[N(C2H5)3(CH3)]BF4、[N(C2H5)3(CH3)]PF6、[N(C2H5)4][N(SO2CF3)2]、[N(C2H5)3(CH3)][N(SO2CF3)2]、[N(C2H5)4][PF3(C2F5)3]、[N(C2H5)3(CH3)][PF3(C2F5)3]、[N(C2H5)4][PF4(C2F5)2]、[N(C2H5)3(CH3)][PF4(C2F5)2]、[N(C2H5)4][PF5(C2F5)]和[N(C2H5)3(CH3)][PF5(C2F5)]的四烷基铵盐。
优选使用该导电锂盐或导电锂盐的混合物在非质子溶剂或溶剂混合物中的0.45-2M溶液,更优选1M溶液。
本发明电解质优选包含非质子溶剂或溶剂混合物,并且还任选包含其他添加剂。它们可以与其他导电盐和/或添加剂组合用作聚合物电解质或相转移介质的一部分。
该电解质的非质子溶剂优选由开链或环状碳酸酯、羧酸酯、腈类、硅烷类或磺酸酯或其混合物构成。
优选的开链或环状碳酸酯是碳酸二乙酯、碳酸二甲酯、碳酸乙基·甲基酯、碳酸亚乙酯或碳酸亚丙酯。
优选的羧酸酯是乙酸乙酯或丙酸甲酯。
优选的腈类是己二腈、戊二腈和乙腈;特别优选乙腈。
该有机溶剂优选以5-90重量%,优选40-90重量%存在于该电解质中,其中重量百分数值基于整个电解质。
其他添加剂例如可以选自已知添加剂碳酸亚乙烯基酯、丙磺酸内酯、乙酸乙烯酯、联苯、环己基苯,有机胺,例如三烷基胺、二烷基苯基胺,或N-甲硅烷基化胺,如作为N-甲硅烷基化环状胺的实例的三甲基甲硅烷基咪唑,或各种砜,实例是二苯基砜,并且上述胺中的烷基各自可以相互独立地为具有1-20个碳原子的直链或支化烷基。
在一个优选实施方案中,除了如上所述的本发明式(I)和/或(II)的盐外,该电解质还包含所述组的添加剂碳酸亚乙烯基酯、丙磺酸内酯、乙酸乙烯酯、联苯、环己基苯、有机胺、N-甲硅烷基化胺或砜,其中上述胺中的烷基各自可以相互独立地为具有1-20个碳原子的直链或支化烷基。
另一类可以存在的添加剂是对于那些已知为凝胶电解质的电解质引起胶凝的添加剂,凝胶电解质是呈准固体的电解质。它们具有固体电解质的结构性能,但像液体电解质一样保留导电性能。
这类凝胶添加剂例如可以选自无机颗粒状材料,如SiO2、TiO2或Al2O3。本发明的电解质可以基于整个电解质以0.01-20重量%,优选1-10重量%包含该类凝胶添加剂。
当溶剂存在于本发明的电解质中时,还可以存在聚合物,此时该聚合物是聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯或聚偏二氟乙烯-六氟丙烯-一氯三氟乙烯共聚物、Nafion、聚氧化乙烯、聚甲基丙烯酸甲酯、聚丙烯腈、聚丙烯、聚苯乙烯、聚丁二烯、聚乙二醇、聚乙烯基吡咯烷酮、聚苯胺、聚吡咯或聚噻吩。将这些聚合物加入电解质中以将液体电解质转化成准固体或固体电解质并且因此改善溶剂保留,尤其是在老化时。
本发明的电解质通过电解质生产领域熟练技术人员熟知的方法制备,通常通过将该导电盐溶于相应溶剂混合物中并加入其他助剂而制备。
本发明进一步提供了一种电化学电池,包含至少一种如上所述或作为优选描述的式(I)和/或(II)化合物。
该电化学电池优选为锂电池组、锂离子电池组或锂离子电容器。
锂电池组为其中将锂金属电极用作负电极的电池组。
作为其负电极,锂离子电池组使用其中可以插入或可逆除去锂的材料。该类材料的实例是石墨、硅或硅-碳复合材料、锡氧化物或锂钛氧化物。
该类电化学电池的一般结构是已知的且为该领域熟练技术人员熟知—对于电池组,例如在Linden's Handbook of Batteries(ISBN 978-0-07-162421-3)中已知。
阳极例如由碳/石墨构成,阴极由锂金属氧化物或锂(铁)磷酸盐构成,而隔片由聚丙烯/聚乙烯或陶瓷薄膜构成。
甚至在没有进一步观察下,假定熟练技术人员能够最大程度利用上述说明。因此,优选实施方案和实例例仅解释为说明性公开,决不具有任何限制作用。
所得化合物由元素分析和NMR光谱法表征。
NMR光谱使用来自Bruker,德国Karlsruhe的Avance 250和AvanceII 300分光计记录。将丙酮-D6在毛细管中用作锁场物质。定位使用外部参考完成:TMS用于1H和13C光谱;CCl3F—用于19F光谱;以及85%H3PO4—用于31P光谱。
实施例1.制备二乙氨基三(五氟乙基)硅烷
将100ml乙醚和34ml在己烷中的1.6M(54mmol)正丁基锂引入Schlenk烧瓶中并在-85℃下脱气。在冷凝56mmol五氟乙烷之后将该溶液在-80℃下搅拌45分钟。然后缓慢滴加3.1g(15mmol)Et2NSiCl3。在冷藏浴中将反应混合物由-80℃缓慢温热至室温(RT),可能的话补偿压力。所得沉淀通过在双端玻璃料上过滤除去。在旋转蒸发器上除去溶剂。使该轻微黄色残留物进行分馏。在66毫巴的压力和98℃的顶部温度下以清澈无色液体得到(C2F5)3SiNEt2。产量:5.7g(12.4mmol),82%(基于SiCl3NEt2)。
(C2F5)3SiNEt2在CDCl3中的NMR光谱数据,RT。
实施例2.制备四(五氟乙基)硅烷
将124mg(0.3mmol)(C2F5)3SiC2H5在FEP反应器中冷凝并在-120℃下与3mmol F2(5%,在He中)混合。借助泵将气态反应混合物在室温下在用F2钝化的不锈钢装置(316)中循环2小时。然后在-196℃下冻析所有可冷凝成分。在-78℃下分离出所有挥发性成分,并在戊烷中通过NMR光谱法分析被少量HF污染的液态残余物。发现它为由Si(C2F5)4和(C2F5)3SiF以10:1的比例构成的产物混合物。
产物混合物的29Si NMR光谱数据(溶剂:戊烷)
产物混合物的19F NMR光谱数据(溶剂:戊烷)
实施例3:制备三(五氟乙基)溴硅烷
Et2NSi(C2F5)3+2HBr→(C2F5)3SiBr+[H2NEt2]Br
将二乙氨基三(五氟乙基)硅烷(22.9g,50mmol)引入Schlenk烧瓶中,并冷凝溴化氢(140mmol)。将烧瓶内容物温热至室温。通过冷凝将挥发性成分转移到温度为-196℃的冷阱中。过量HBr通过使用冷却至-78℃的冷阱分凝而除去。以无色液体得到三(五氟乙基)溴硅烷(0.688g,1.48mmol,89%)。产量:22.7g(12.4mmol),98%(基于Et2NSi(C2F5)3)。
Si(C2F5)3Br在戊烷中的NMR光谱数据,RT
实施例4:制备三(五氟乙基)氟硅烷
在具有杨氏塞(Young tap)的100ml烧瓶中引入0.9g(5mmol)SbF3并冷凝1.6g(3.5mmol)(C2F5)3SiBr。搅拌1天后可以作为清澈无色液体冷凝出(C2F5)3SiF。产量:1.2g(3.0mmol),86%(基于(C2F5)3SiBr)。
(C2F5)3SiF作为纯物质的NMR光谱数据,RT。
实施例5.制备甲基三(五氟乙基)硅烷
将150ml乙醚和52ml在戊烷中的2M(104mmol)正丁基锂引入Schlenk烧瓶并在-85℃下脱气。在冷凝120mmol五氟乙烷之后将该溶液在-80℃下搅拌45分钟。然后缓慢滴加5g(33mmol)CH3SiCl3。在冷藏浴中将反应混合物由-80℃缓慢温热至RT,可能的话补偿压力。所得沉淀通过在双端玻璃料上过滤分离。使用Claisen桥蒸除溶剂。使该轻微黄色残留物进行分馏。在大气压力和56℃的顶部温度下以清澈无色液体得到CH3Si(C2F5)3。产量:7.6g(19mmol),57%(基于CH3SiCl3)。
Si(C2F5)3CH3在CDCl3中的NMR光谱数据,RT
实施例6:制备三(五氟乙基)氟硅烷
将(C2F5)3SiCH3(340mg,0.85mmol)冷凝到反应容器中,与F2混合4次,每次1mmol F2,并在室温下搅拌1小时。然后将所有挥发性物质冷凝到冷阱中。相应气体空间在-75℃下排出并丢弃。通过NMR光谱法分析残留物(0.306g)。
在室温下14小时之后,(C2F5)3SiCF3的初始量的90%转化成(C2F5)3SiF,消去C2F4和C3F6。
反应混合物的29Si NMR光谱数据(无溶剂)
反应混合物的19F NMR光谱数据(无溶剂)
实施例7.制备三(五氟乙基)二氟硅酸(-1)锂,Li[(C2F5)3SiF2]
在Schlenk烧瓶中在N2气氛下将624.5mg(24mmol)LiF引入24ml(25.77g)碳酸二甲酯(DMC)中,引入(CH3O)2CO(在分子筛上干燥并新蒸)并在-196℃下冷凝9.723g(24mmol)(C2F5)3SiF。当在搅拌下温热至RT时,该LiF进入溶液中。Li[(C2F5)3SiF2]的产率是定量的。
使用-D6丙酮作为外部锁场物质时Li[Si(C2F5)3F2]
在(CH3O)2CO中的NMR光谱数据,RT。
10.3g(24mmol)Li[(C2F5)3SiF2]在24ml碳酸二甲酯中的溶液的导电率如下:
实施例8.制备三(五氟乙基)三氟硅酸(-2)二锂,Li2[Si(C2F5)3F3]
将50ml乙醚和10ml在己烷中的1.6M(16mmol)正丁基锂的混合物在-92℃下脱气并冷凝20mmol五氟乙烷。然后将该无色溶液在-90℃下搅拌15分钟并冷凝0.32g(1.9mmol)SiCl4。在冷藏浴中将反应混合物由-80℃缓慢温热至RT,并通过NMR光谱法表征该产物。
Li2[Si(C2F5)3F3]在Et2O中在室温下的NMR光谱数据:
Claims (10)
1.式(I)和/或(II)化合物:
Li[(Rf)nSiF5-n] (I)
Li2[(Rf)nSiF6-n] (II)
其中
Rf每次出现时独立地为具有2-12个碳原子的直链或支化全氟烷基,以及n为1-4的整数。
2.根据权利要求1的化合物,其中变量n为1、2或3。
3.根据权利要求1或2的化合物,其中变量n为2或3。
4.根据权利要求1-3中任一项的化合物,其中全氟烷基Rf在每次出现时相同。
5.一种制备根据权利要求1-4中任一项的式(I)化合物的方法,其中使式(III)的(全氟烷基)氟硅烷与氟化锂在干燥空气或惰性气体条件下在有机溶剂存在下反应:
(Rf)nSiF4-n (III)
其中Rf和n具有权利要求1-3中所述的定义。
6.一种制备根据权利要求1-4中任一项的式(I)和/或(II)化合物的方法,其中使四氯化硅与全氟烷基锂反应,其中全氟烷基对应于具有2-12个碳原子的全氟烷基。
7.至少一种根据权利要求1-4中任一项的化合物在电化学电池中作为导电盐的用途。
8.根据权利要求7的用途,其中所述电化学电池为锂电池组或锂离子电池组或锂离子电容器。
9.一种电解质,包含至少一种根据权利要求1-4中任一项的化合物。
10.一种电化学电池,包含至少一种根据权利要求1-4中任一项的化合物。
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