CN1337398A - 用于电化学电池的氟代烷基磷酸盐 - Google Patents
用于电化学电池的氟代烷基磷酸盐 Download PDFInfo
- Publication number
- CN1337398A CN1337398A CN01123298A CN01123298A CN1337398A CN 1337398 A CN1337398 A CN 1337398A CN 01123298 A CN01123298 A CN 01123298A CN 01123298 A CN01123298 A CN 01123298A CN 1337398 A CN1337398 A CN 1337398A
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- Prior art keywords
- fluoroalkyl phosphate
- solvent
- preparation
- alkyl
- phosphate
- Prior art date
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- -1 Fluoroalkyl phosphate Chemical compound 0.000 title claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 35
- 239000010452 phosphate Substances 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000010 aprotic solvent Substances 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 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 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 229940099204 ritalin Drugs 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000005911 methyl carbonate group Chemical group 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 23
- 239000000243 solution Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001349 alkyl fluorides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010572 single replacement reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/13—Amines containing three or more amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
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Abstract
本发明涉及氟代烷基磷酸盐,涉及其制备方法以及涉及将其用作电池组、电容器、超级电容器和原电池的导电盐。
Description
本发明涉及氟代烷基磷酸盐、氟代烷基磷酸盐的制备以及将其用作电池组、电容器、超级电容器和原电池的导电盐。
便携式电子设备,如膝上型电脑、掌上型电脑、移动电话或录象机等的发展,因此对轻量和高性能的电池组的需求,近几年来在全世界得到显著的增加。
鉴于对电池组的这一突然增加的需求以及所产生的生态问题,发展使用寿命长的可再充电电池的重要性日益增加。
锂离子电池和双层高容量的电容器(所谓的超级电容器)是最近的发展现状。在这两种情况下,以LiPF6或N(C2H5)4BF4形式的对水解敏感的和热不稳定的物质常用作导电盐。这些物质同湿空气或同溶剂中残余水份接触时,可很快生成HF。除了毒性外,HF对电池组循环性能,因而对电化学电池的工作性能也有很不利的影响。
已经提出的替代品是酰亚胺,如双(三氟甲磺酰)亚胺或双(五氟乙磺酰)亚胺或甲烷化物,如三(三氟甲磺酰)甲烷化物和它们的衍生物。这些盐显示出高度的正电极稳定性,同有机非质子溶剂生成高导电性溶液。但是,这些酰亚胺的缺点是,它们不能将作为电池负电极的电流收集器的铝金属钝化。相反,甲烷化物只能很费劲地制备和纯化(Turowsky,Seppelt,无机化学(Inorg.Chem.),1988,2135)。此外,电化学性质,如氧化稳定性和铝的钝化,强烈依赖于甲烷化物的纯度。
因此,本发明的目的是提供电化学稳定的、并且制备简单的导电盐。本发明的另一目的是延长和改进电池组、电容器、超级电容器和原电池的服务寿命和性能。
令人吃惊地是,经过制取下面通式(I)的氟代烷基磷酸盐可以达到这一目的:
Mn+[PFx(CyF2y+1-zHz)6-x]n - (I)
式中,
1≤x≤6
1≤y≤8
0≤z≤2y+1
0≤n≤5以及
Mn+是一价到三价的阳离子,尤其是:
NR1R2R3R4,
PR1R2R3R4,
P(NR1R2)kR3 mR4 4-k-m(其中k=1-4,m=0-3和k+m≤4),
C(NR1R2)(NR3R4)(NR5R6),
C(芳基)3、Rb或鎓
其中R1-R8是H、烷基或芳基(C1-C8),后者可以由F、Cl或Br部分取代,
其中的Mn+=Li+、Na+、Cs+、K+和Ag+除外,
优选为下面通式的氟代烷基磷酸盐
N(C2H5)4[PF3(C2F5)3],
N(CH3)4[PF3(C4F9)3],
[N(CH3)4][PF3(C4F9)3],
[N(C2H5)4][PF3(C2F5)3],
P[N(CH3)2]4[PF3(C2F5)3],
P[N(CH3)2]4[PF3(C4F9)3],,
[P(CH3)4]+[PF3(C2F5)3]-,
[P(C2H5)4]+[PF3(C2F5)3]-,
[P(CH3)4]+[PF3[C4F9]3]-,
[P(C2H5)4]+[PF3[C4F9]3]-,
C[N(CH3)2]3[PF3(C2F5)3]以及
C[N(CH3)2]3[PF3(C4F9)3]。
已经发现,本发明的化合物具有很高的电化学稳定性。本发明的通式(I)的氟代烷基磷酸盐可以以纯的形式和其混合物形式用作为原电池和二次电池组、电容器、超级电容器和原电池的导电盐。本发明的氟代烷基磷酸盐还可以同该领域已知的其它盐一起用作导电盐。
本发明的氟代烷基磷酸盐优选以纯的形式用作导电盐,因为这种形式使用可以得到重复性很好的电化学性质。
氟代烷基磷酸盐的制备是以正膦为原料,正膦的制备方法在DE 196411 38中讨论过。在溶剂中制成0.01-4摩尔,优选为0.5-3摩尔,特别优选为1.5-2.5摩尔的正膦或氟代烷基磷酸盐的溶液或悬浮液,溶剂优选为有机非质子溶剂,特别优选的是选自碳酸酯、酯、醚、腈、酰胺、酮、磺酸酯、磺酰胺、亚砜、磷酸酯、正膦、氯代烷烃以及它们的混合物。优选的溶剂是可以直接适用于原电池或二次电池、电容器、超级电容器或原电池中的溶剂或它们的混合物,例如,碳酸二甲酯、碳酸二乙酯、碳酸异丙烯酯、碳酸亚乙酯、碳酸甲乙酯、碳酸甲丙酯、1,2二甲氧基乙烷、1,2二乙氧基乙烷、醋酸甲酯、γ-丁内酯、醋酸乙酯、丙酸甲酯、丙酸乙酯、丁酸甲酯、丁酸乙酯、二甲基亚砜、二氧戊环、环丁砜、乙腈、丙烯腈、四氢呋喃、2-甲基四氢呋喃或它们的混合物。
为了同氟代烷基磷酸盐反应,加入等摩尔量的或稍微过量的金属或非金属氟化物、氯化物、四氟硼酸盐或六氟磷酸盐,优选选自[NR1R2R3R4]F、[NR1R2R3R4]Cl、[PR1R2R3R4]F、[PR1R2R3R4]Cl、[P(NR1R2)4]F、[P(NR1R2)4]Cl、[C(NR1R2)3]Cl以及[C(NR1R2)3]F,如果需要,将其以溶液配方加入。对于同正膦的反应,N(CH3)4F、N(C2H5)4F、[P[(CH3)2]4]F或C[N(CH3)2]3F以等摩尔量或稍微过量加入。将混合物在液态范围下,优选在0℃-50℃,特别优选为在室温下搅拌。搅拌进行0.5-48小时,优选为2-12小时。如果本发明的氟代烷基磷酸盐由复分解制备,则得到的副产物通过将反应混合物冷却随后过滤分离出来。如果在反应中没有副产物生成,则反应混合物可以再直接使用。
得到的电解质适用于原电池、二次电池、电容器、超级电容器和原电池,同样也是本发明的主题。
在这些电解质中本发明的氟代烷基磷酸盐的浓度优选为0.01-4摩尔/升,特别优选为0.5-3摩尔/升。
本发明还涉及至少含一种本发明的通式(I)的氟代烷基磷酸盐和任选的其它盐和/或添加剂的原电池、二次电池、电容器、超级电容器和原电池。这些其它的盐和添加剂都是本领域的人员所熟悉的,例如,由DoronAurbach:非水电化学,Marc Dekker Inc.,New York 1999;D.Linden:电池组手册(Handbook of Batteries),Second Edition,McGraw-HillInc.,New York 1995,以及G.Mamantov and A.I.Popov:非水溶液的化学,最近的进展(Chemistry of Nonaqueous Solutions,CurrentProgress),VCH Verlagsgemeinschaft Weinheim 1994。因此这些文献在此引为参考,并作为本发明的一个组成部分。
本发明的的氟代烷基磷酸盐可以同传统的电解质一起使用。适宜的电解质的实例是选自LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2和LiC(CF3SO2)3以及它们的混合物的导电盐。这些电解质还可包括有机异氰酸酯(DE19944603)以减少水含量。下面通式的锂络合物盐可以存在:
Mx+[EZ]x/y y-式中:x和y是1,2,3,4,5或6Mx+是金属离子E是选自BR1R2R3、AlR1R2R3、PR1R2R3R4R5、AsR1R2R3R4R5和VR1R2R3R4R5的路易斯酸,R1-R5可相同或不同,任选通过单键或双键直接相互键合,并且每个单独或一起,是卤素(F、Cl或Br),可以部分或完全由F、Cl或Br取代的烷基或烷氧基(C1-C8),任选通过氧键合的芳环,如可由烷基(C1-C8)或单或六取代的或未取代的苯基、萘基、蒽基和菲基,和任选通过氧键合的芳族杂环,如由烷基(C1-C8)或F、Cl或Br单取代或四取代的或未取代的吡啶基、吡唑基、嘧啶基,以及Z是OR6、NR6R7、CR6R7R8、OSO2R6、N(SO2R6)(SO2R7)、C(SO2R6)(SO2R7)(SO2R8)或OCOR6,其中,R6-R8可相同或不同,任选通过单键或双键直接相互键合,并且每个可单独或一起是氢或按R1-R5所定义,该络合物盐是通过相应的硼或磷路易斯酸/溶剂加合物同锂或四烷基铵酰亚胺甲烷化物或三氟甲基磺酸盐反应而制成。
下面通式的硼酸盐(DE19959722)也可以存在:式中:M是金属离子或四烷基铵离子,x和y是1、2、3、4、5或6,R1-R4可相同或不同,任选通过单键或双键直接相互键合的烷氧基或羧基(C1-C8)。这些硼酸盐是通过四烷氧基硼酸锂或烷氧基锂同硼酸盐的1∶1的混合物同适宜的羟基或羧基化合物在非质子溶剂中以2∶1或4∶1比例反应得到。
添加剂,如下面通式的硅烷化合物也可以存在
SiR1R2R3R4其中R1-R4是H,CyF2Y+1-ZHZOCyF2Y+1-ZHZOC(O)CyF2Y+1-ZHZOSO2CyF2Y+1-ZHZ和 1≤x<6
1≤y≤8和
0≤z≤2y+1和R1-R4可相同或不同并且是可由F、CyF2Y+1-ZHZ、OCyF2Y+1-ZHZ、OC(O)CyF2Y+1-ZHZ、OSO2CyF2Y+1-ZHZ或N(CnF2n+1-ZHZ)2单取代或多取代的或未取代的苯基和萘基组成的芳环基团,或是每一个可以由F、CyF2Y+1-ZHZ、OCyF2Y+1-ZHZ、OC(O)CyF2Y+1-ZHZ、OSO2CyF2Y+1-ZHZ或N(CnF2n+1-ZHZ)2单取代或多取代(DE10027626)的吡啶基、吡唑基和嘧啶基组成的杂环芳环基团。
本发明的化合物也可以用在包括下面通式的氟代烷基磷酸锂的电解质中:
Li+[PFx(CyF2Y+1-ZHZ)6-x]-式中,1≤x≤53≤y≤80≤z≤2y+1和配体(CyF2Y+1-ZHZ)可相同或不同,只是下面通式的化合物除外
Li+[PFa(CHbFc(CF3)d)e]-其中,a是2-5的整数,b=0或1,c=0或1,d=2和e是1-4的整数,条件是,b和c不能同时为0,a+e的总和等于6,配体(CHbFc(CF3)d)可相同或不同(DE10008955)。氟代烷基磷酸锂的制法的特征在于,至少将下面通式中之一的化合物HmP(CnH2n+1)3-mOP(CnH2n+1)3,ClmP(CnH2n+1)3-m,FmP(CnH2n+1)3-m,CloP(CnH2n+1)5-o,FoP(CnH2n+1)5-o,在上述的通式中每一个,
0≤m≤2,3≤n≤8和0≤o≤4,
在氟化氢中电解氟化,所得到的氟化产物的混合物通过提取、相分离和/或蒸馏进行分离,得到的氟化的烷基正膦是同氟化锂在非质子溶剂混合物中在没有湿气的存在下反应,得到的盐用常规的方法进行纯化和分离。
本发明的化合物也可以用在包括下面通式盐的电解质中
Li[P(OR1)a(OR2)b(OR3)c(OR4)dFe]
式中,0<a+b+c+d≤5和a+b+c+d+e=6,以及R1-R4相互无关地是烷基、芳基或杂芳基,其中R1-R4中至少两个可以通过单键或双键直接相互连接(DE10016801)。这种化合物的制备是通过下面通式的磷(V)化合物
P(OR1)a(OR2)b(OR3)c(OR4)dFe式中0<a+b+c+d≤5和a+b+c+d+e=5,以及R1-R4如上定义,在有机溶剂存在下同氟化锂反应。
下面通式的离子液体也可存在于电解质中
K+A-,
式中,
K+是选自下面的阳离子 其中R1-R5可相同或不同,任选通过单键或双键直接相互键合,每一个单独或一起具有下列意义-H,-卤素,-可以被其它基团、F、Cl、N(CnF(2n+1-x)Hx)2、O(CnF(2n+1-x)Hx)、SO2(CnF(2n+1-x)Hx)或CnF(2n+1-x)Hx,(其中1<n<6和0<x<13)部分或完全取代的烷基(C1-C8),以及A-是选自下面通式的阴离子
[B(OR1)n(OR2)m(OR3)o(OR4)p]-其中0≤n,m,o,p≤4,以及m+n+o+p=4其中R1-R4是不同的或成对相同的,任选通过单键或双键直接相互键合的,每个单独或一起是,被CnF(2n+1-x)HX(其中1<n<6和0<x≤13)或卤素(F、Cl或Br)单取代或多取代的或未取代的苯基、萘基和蒽基和菲基组成的芳环基团,被CnF(2n+1-x)HX、(其中1<n<6和0<x≤13)或卤素(F、Cl或Br)单取代或多取代的或未取代的吡啶基、吡唑基、嘧啶基组成的的芳族杂环基团,被其它基团,优选被F、Cl、N(CnF(2n+1-x)HX)2、O(CnF(2n+1-x)HX)、SO2(CnF(2n+1-x)HX)或CnF(2n+1-x)HX(其中1<n<6和0<x≤13)部分取代或完全取代的烷基(C1-C8),或OR1-OR4单独或一起是可以被其它基团,优选为F、Cl、N(CnF(2n+1-x)HX)2、O(CnF(2n+1-x)HX)、SO2(CnF(2n+1-x)HX)或CnF(2n+1-x)HX(其中1<n<6和0<x≤13)部分或全部取代的芳族或脂族羧基、二羧基、含氧磺酰基或含氧羰基(DE10026565)。离子液体K+A-也可以存在(DE10027995),其中K+是如上所定义的,A是选自下面基团的阴离子,
[PFx(CyF2Y+1-zHz)6-x]-和1≤x<61≤y≤8和0≤z≤2y+1。
本发明的化合物还可以存在于包括下面通式化合物的电解质中:
NR1R2R3式中R1和R2是H、CyF2Y+1-zHz或(CnF2n-mHm)X,其中X是芳族或杂环基团,和R3是(CnF2n-mHm)Y,其中Y是杂环基团,或(CoF2o-pHp)Z,其中Z是芳族基团,以及其中的n、m、o、p、y、z满足下面的条件;0≤n≤6,0≤m≤2n,2≤o≤6,0≤p≤2o1≤y≤8以及,0≤z≤2y+1,用于降低电化学电池中的非质子电解质***的酸含量。
电解质还可包括下面成分的混合物a)至少一种下面通式的氟代烷基磷酸锂Li+[PFX(CyF2Y+1-zHz)6-X]-式中,1≤x≤5,1≤y≤8,和0≤z≤2y+1以及配体(CyF2Y+1-zHz)在每种情况下都是相同的或不同的,以及b)至少一种聚合物(DE10058264)。
这种电解质还可包括下面通式的四氟代烷基硼酸盐:
Mn+([BF4]-)n式中,Mn+是一价、二价或三价的阳离子,配体R在每种情况下都是相同的和是(CxF2x+1),其中1≤x≤8和n=1,2或3(DE10055811)。四氟代烷基硼酸盐的制法的特征在于,至少一种通式为Mn+([B(CN)4]-)n的化合物(其中,Mn+和n如上定义),在至少一种溶剂中同至少一种氟化剂反应进行氟化,得到的氟化化合物通过常规的方法纯化和分离。
这种电解质还可包括下面通式的硼酸盐Mn+[BFx(CyF2Y+1-zHz)4-X]- n式中1<x<3,1≤y≤8和0≤z≤2y+1,以及M是一价到三价的阳离子(1≤n≤3),钾和钡除外,特别是:Li,NR1R2R3R4、PR5R6R7R8、P(NR5R6)kR7 mR8 4-k-m(其中k=1-4,m=0-3和k+m≤4),或C(NR5R6)(NR7R8)(NR9R10),其中R1-R4是CyF2Y+1-zHz和R5-R10是H或CyF2Y+1-zHz,或芳族杂环阳离子,尤其是含氮和/或含氧和/或含硫的芳族杂环阳离子(DE10103189)。
制备这些化合物的方法的特征在于,a)BF3/溶剂络合物同烷基锂1∶1在冷却下进行反应,在缓慢加温后将大多数溶剂除去,随后将固体滤出,并用适宜的溶剂洗涤,或b)在适宜的溶剂中锂盐同B(CF3)F3盐以1∶1进行反应,将混合物在高温下搅拌,将溶剂除去,将非质子非水溶剂,优选用于电化学电池的溶剂,加到反应混合物中,将混合物干燥,或c)B(CF3)F3盐同锂盐以1∶1-1∶1.5在水中在高温下反应,在沸点加热0.5-2小时,除去水,将优选用于电化学电池的非质子非含水溶剂加到反应混合物中,将混合物干燥。电解质还可包括下面通式的氟代烷基磷酸盐
Mn+([PFx(CyF2Y+1-zHz)6-x]-)n式中Mn+是一价、二价或三价的阳离子,1≤x≤51≤y≤8和0≤z≤2y+1,n=1,2或3,配体(CyF2Y+1-zHz)在每种情况下都是相同或不同的,其中氟代烷基磷酸盐,(其中Mn+是锂离子和盐),M+([PF4(CF3)2]-),其中M+=Cs+、Ag+或K+M+([PF4(C2F5)2]-),其中M+=Cs+,M+([PF3(C2F5)3]-),其中M+=Cs+、K+、Na+或对-Cl(C6H4)N2 +,M+([PF3(C3F7)3]-),其中M+=Cs+、K+、Na+或对-Cl(C6H4)N2 +或对-O2N(C6H4)N2 +除外(DE10055812)。制备这些氟代烷基磷酸盐方法的特征在于,至少下面通式之一的化合物在氟化氢中电解氟化,HrP(CsH2s+1)3-r,OP(CsH2s+1)3,ClrP(CsH2s+1)3-r,FrPCsH2s+1)3-r,CltP(CsH2s+1)5-t和/或FtPCsH2s+1)5-t,式中,在每种情况下0≤r≤23≤s≤8以及0≤t≤4,得到的氟化产物的混合物经分离,得到的氟化的烷基正膦同通式为Mn+(F-)n(其中Mn+和n是如上所定义)的化合物在非质子溶剂或溶剂混合物中在没有湿气的存在下进行反应,得到的氟代烷基磷酸盐用常规的方法纯化和分离。
本发明的化合物也可以存在于包括下面通式的氟代烷基磷酸盐的电解质中:(Ma+)b[(CnF2n+1-mHm)yPF5-y(CR1R2)xPF5-y(CnH2n+1-mHm)y](2-) (a*b/2)式中Ma+是一价、二价或三价的阳离子a=1、2或3,b=2,(对于a=1),b=2(对于a=3),b=1(对于a=2)在每种情况下1≤n≤80≤m≤2,对于n=1或20≤m≤4,对于3≤n≤81≤x≤120≤y≤2其中R1和R2在每种情况可相同或不同,选自氟、氢、烷基、氟代烷基和全氟烷基取代基,以及其中在每种情况下,取代基(CnF2n+1-mHm)是相同或不同的。这些化合物的制备是将至少一种氟代-α,ω-双(烷基氟代正膦合)烷烃同至少一种通式为(Ma+)[F-]a(其中Ma+的定义如上)的氟化物盐在溶液中反应,得到氟代烷基磷酸盐,如果需要,用常规的方法纯化和/或分离后者。
本发明的化合物可以用于含涂有选自Sb、Bi、Cd、In、Pb、Ga和锡或它们的合金的金属芯的正电极材料的电化学电池中的电解质(DE10016024)。制备这种正电极材料方法的特征在于,a)制备金属或合金芯在乌洛托品中的悬浮液或溶胶,b)用C5-C12烃乳化此悬浮液,c)将此乳液沉淀在金属或合金芯上,以及d)加热此***将金属氢氧化物或羟基氧化物转化成相应的氧化物。
本发明的化合物也能用于由普通的锂***和嵌入化合物制成的负电极,而且由涂以一层种或多种金属氧化物的锂混合氧化物颗粒组成的负电极材料的电化学电池的电解质中(DE19922522)。它们也可以由涂以一种或多种聚合物的锂混合氧化物颗粒组成(DE19946066)。本发明的化合物也可以用于由涂有一层或多层碱金属化合物和金属氧化物的锂混合氧化物颗粒组成的负电极***(DE10014884)。这些材料制备方法的特征在于,将颗粒悬浮在有机溶剂中,将悬浮在有机溶剂中的碱金属盐化合物加入,将溶解于有机溶剂中的金属氧化物加入,在悬浮液中加入水解溶液,随后将涂布的颗粒过滤、干燥和烧结。本发明的化合物也能用于包括掺有氧化锡的正电极材料的***中(DE10025761)。这种正电极材料的制备方法如下:a)在氯化锡溶液中加入脲,b)在此溶液中加入乌洛托品和适宜的掺杂化合物,c)在石油醚中乳化得到的溶胶,d)将得到的凝胶洗涤并用吸滤除去溶剂,e)干燥和加热凝胶。
本发明也能用于包括具有还原的氧化锡的正电极材料的***中(DE10025762)。这种正电极材料的制备方法是:a)在氯化锡溶液中加入脲,b)在此溶液中加入乌洛托品,c)在石油醚中乳化得到的溶胶,d)将得到的凝胶洗涤,并用吸滤除去溶剂,e)将凝胶干燥和加热,以及f)在充气炉中,将得到的SnO2曝露于还原气流中。
本发明的氟代烷基磷酸酯具有电化学稳定的优点。这一性质使包括本发明的化合物的导电盐可以用在电池组、电容器、超级电容器和原电池中。
实施例下面参考实施例说明本发明。这些实施例只作为解释本发明,而不是限制本发明的一般的发明思想。
实施例1
由Li[PF3(C2F5)3]制备N(C2H5)4[PF3(C2F5)3]
将等摩尔量的在二氯甲烷中的N(C2H5)4X(X=F或Cl)加到1.5-2.5摩尔的Li[PF3(C2F5)3]溶液中。在室温下将此溶液搅拌数小时,搅拌时有少量LiX沉积形成。然后将反应混合物保持在-30℃--10℃下2小时,在减压下在-30℃--10℃滤出得到的沉淀。将溶剂蒸馏出去。随后在减压下在100℃干燥后,得到的产品是无色颗粒。19F-NMR波谱(CD3CN;标准:CCl3F):-43.6分米(1F)-79.7米(3F)-81.3米(6F)-87.0分米(2F)-115.3米(4F)-115.7米(2F)
实施例2
由PF2(C2F5)3制备N(CH3)4[PF3(C2F5)3]
在二氯甲烷中在-40℃下将等摩尔量的N(CH3)4F加到10克的PF2(C2F5)3中(按照DE19846636的方法制备的)。将混合物搅拌数小时,并加温到室温,蒸馏除去溶剂,分离出N(CH3)4[PF3(C2F5)3]。19F-NMR波谱(CD3CN;标准:CCl3F):-44.0分米(1F)-80.0米(3F)-82米(6F)-87.5分米(2F)-115.8米(4F)-116.2米(2F)
实施例3
由PF2(C4F9)3制备N(CH3)4[PF3(C4F9)3]
制法相似于实施例2,原料用PF2(C4F9)3,所用的阳离子源是N(CH3)4F。
实施例4
制备P[N(CH3)2]4[PF3(C2F5)3]和P[N(CH3)2]4[PF3(C4F9)3]
制法相似于实施例2,所用的阳离子源是P[N(CH3)2]4F。
实施例5
制备P[N(CH3)2]4[PF3(C4F9)3]和P[N(CH3)2]4[PF3(C2F5)3]
制法相似于实施例1,所用的阳离子源是P[N(CH3)2]4Cl。
实施例6
制备C[N(CH3)2]3[PF3(C2F5)3]和C[N(CH3)2]3[PF3(C4F9)3]
制法相似于实施例1,所用的阳离子源是C[N(CH3)2]3Cl。
实施例7
电解质的电化学稳定性
在一个不锈钢、铂或金工作电极,锂反电极和锂参比电极的测量电池中,在每一情况下,相继记录5次循环的电位图。为此,电位首先从静止电位开始以10毫伏/秒或20毫伏/秒的速度增加到6伏(相对于Li/Li+),然后返回到静止电位。为了能利用最高可能的电化学视窗,用EC和DMC的1∶1混合物作溶剂。
所有的电解质显示出的正电极稳定性高于5伏,图1表示包括[PF3C2H5)3]-的电解质的这种情况。
Claims (12)
1.通式为下面的氟代烷基磷酸盐
Mn+[PFx(CyF2y+1-zHz)6-x]n - (I)
式中,
1≤x≤6
1≤y≤8
0≤z≤2y+1
1≤n≤5,以及
Mn+是一价-三价的阳离子,尤其是:
NR1R2R3R4,
PR1R2R3R4,
P(NR1R2)kR3 mR4 4-k-m(其中k=1-4,m=0-3,和k+m≤4),
C(NR1R2)(NR3R4)(NR5R6),
C(芳基)3、Rb或鎓
其中R1-R8是H、烷基或芳基(C1-C8),该烷基或芳基可以被F、Cl或Br部分取代,
其中Mn+=Li+、Na+、Cs+、K+,Ag+除外。
2.权利要求1的氟代烷基磷酸酯,它们是
a)N(C2H5)4[PF3(C2F5)3],
b)N(CH3)4[PF3(C4F9)3],
c)[N(CH3)4][PF3(C4F9)3],
d)[N(C2H5)4][PF3(C2F5)3],
e)P[N(CH3)2]4[PF3(C2F5)3],
f)P[N(CH3)2]4[PF3(C4F9)3],
g)[P(CH3)4]+[PF3(C2F5)3]-,
h)[P(C2H5)4]+[PF3(C2F5)3]-,
i)[P(CH3)4]+[PF3[C4F9]3]-,
k)[P(C2H5)4]+[PF3[C4F9]3]-,
l)C[N(CH3)2]3[PF3(C2F5)3]和
m)C[N(CH3)2]3[PF3(C4F9)3].
3.权利要求1的氟代烷基磷酸盐的制备方法,其特征在于,正膦同氟化物盐或氟代烷基磷酸盐在溶剂,优选在有机非质子溶剂中同Mn+的氟化物、氯化物、四氟硼酸、六氟磷酸或其它的阴离子组成的盐反应。
4.权利要求3的氟代烷基磷酸盐的制备方法,其特征在于,氟代烷基磷酸盐同[NR1R2R3R4]X、[P(NR1R2)4]X、[PR1R2R3R4]X或[C(NR1R2)3]X反应,式中X=F-、C1-、BF4 -或PF6 -,和R1-4的定义如上。
5.权利要求3的氟代烷基磷酸盐的制备方法,其特征在于,正膦同N(CH3)4F、N(C2H5)4F、[P[N(CH3)2]4]F或C[N(CH3)2]3F反应。
6.权利要求3-5中之一的氟代烷基磷酸盐的制备方法,其特征在于,氟化的烷基正膦在溶剂或溶剂混合物中反应,这些溶剂直接适用于原电池或二次电池组、电容器、超级电容器或原电池。
7.权利要求3-6的氟代烷基磷酸盐的制备方法,其特征在于,有机非质子溶剂选自碳酸酯、酯、醚、腈、酰胺、酮、磺酸酯、磺酰胺、亚砜、磷酸酯、正膦、氯代烷烃以及它们的混合物。
8.权利要求3-7的方法,其特征在于,所用的溶剂是碳酸二甲酯、碳酸二乙酯、碳酸异丙烯酯、碳酸亚乙酯、碳酸甲乙酯、碳酸甲丙酯、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、醋酸甲酯、γ-丁内酯、醋酸乙酯、丙酸甲酯、丙酸乙酯、丁酸甲酯、丁酸乙酯、二甲基亚砜、二氧戊环、环丁砜、乙腈、丙烯腈、四氢呋喃、2-甲基四氢呋喃或它们的混合物。
9.用权利要求3-8中之一的方法制得的氟代烷基磷酸盐。
10.使用权利要求1或9中之一的至少一种氟代烷基磷酸盐作为原电池、二次电池组、电容器、超级电容器和/或原电池的导电盐,任选也同其它的盐混合使用。
11.包括权利要求1或9中之一的至少一种氟代烷基磷酸盐的原电池组、二次电池组、电容器、超级电容器和/或原电池的电解质。
12.权利要求11的电解质,其特征在于,在电解质中氟代烷基磷酸盐的浓度为0.01-4摩尔/升,优选为0.5-3摩尔/升,特别优选为1.5-2.5摩尔/升。
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102652138A (zh) * | 2009-12-18 | 2012-08-29 | 默克专利股份公司 | 具有(全氟烷基)氟磷酸氢盐阴离子的化合物 |
CN102742064A (zh) * | 2010-02-10 | 2012-10-17 | Nec能源元器件株式会社 | 非水性电解质溶液,和具有所述非水性电解质溶液的锂离子二次电池 |
CN102742064B (zh) * | 2010-02-10 | 2015-11-25 | Nec能源元器件株式会社 | 非水性电解质溶液,和具有所述非水性电解质溶液的锂离子二次电池 |
US9312073B2 (en) | 2010-02-10 | 2016-04-12 | Nec Energy Devices, Ltd. | Nonaqueous electrolyte solution, and lithium ion secondary battery having the same |
US9847180B2 (en) | 2010-02-10 | 2017-12-19 | Nec Energy Devices, Ltd. | Nonaqueous electrolyte solution, and lithium ion secondary battery having the same |
CN102956362A (zh) * | 2011-08-17 | 2013-03-06 | 海洋王照明科技股份有限公司 | 双电层电容器电解液以及双电层电容器 |
CN102956362B (zh) * | 2011-08-17 | 2016-01-13 | 海洋王照明科技股份有限公司 | 双电层电容器电解液以及双电层电容器 |
Also Published As
Publication number | Publication date |
---|---|
JP5048898B2 (ja) | 2012-10-17 |
DE50108141D1 (de) | 2005-12-29 |
BR0103182A (pt) | 2002-03-19 |
DE10038858A1 (de) | 2002-02-14 |
US6841301B2 (en) | 2005-01-11 |
KR20020011932A (ko) | 2002-02-09 |
EP1178050A2 (de) | 2002-02-06 |
KR100801811B1 (ko) | 2008-02-11 |
EP1178050B1 (de) | 2005-11-23 |
CN1279046C (zh) | 2006-10-11 |
EP1178050A3 (de) | 2002-09-25 |
TW530432B (en) | 2003-05-01 |
RU2265609C2 (ru) | 2005-12-10 |
US20020022182A1 (en) | 2002-02-21 |
CA2354794A1 (en) | 2002-02-04 |
JP2002138095A (ja) | 2002-05-14 |
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