CN1280130A - 用于电化学电池的锂配盐的制备方法 - Google Patents
用于电化学电池的锂配盐的制备方法 Download PDFInfo
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- CN1280130A CN1280130A CN00120406A CN00120406A CN1280130A CN 1280130 A CN1280130 A CN 1280130A CN 00120406 A CN00120406 A CN 00120406A CN 00120406 A CN00120406 A CN 00120406A CN 1280130 A CN1280130 A CN 1280130A
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- Prior art keywords
- alkyl
- halogen
- lithium
- unsubstituted
- alkoxy
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000003839 salts Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 31
- 150000002367 halogens Chemical class 0.000 claims description 31
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 229910052794 bromium Inorganic materials 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004076 pyridyl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 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 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 125000005561 phenanthryl group Chemical group 0.000 claims description 10
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229960003742 phenol Drugs 0.000 claims description 8
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 125000005103 alkyl silyl group Chemical group 0.000 claims 1
- 239000000460 chlorine Substances 0.000 description 25
- 125000003545 alkoxy group Chemical group 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- -1 alkali metal salt Chemical class 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical class [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001915 proofreading effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical class OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- XEZXLXYRVOPMIO-UHFFFAOYSA-N 5-fluoro-2-hydroxybenzenesulfonic acid Chemical class OC1=CC=C(F)C=C1S(O)(=O)=O XEZXLXYRVOPMIO-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910002441 CoNi Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 230000004888 barrier function Effects 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 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
- 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
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 125000005911 methyl carbonate group Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000005412 pyrazyl group Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
Classifications
-
- 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
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Primary Cells (AREA)
Abstract
本发明涉及锂配盐的制备方法及其在电化学电池中的用途。
Description
本发明涉及锂配盐的制备方法和这种盐在电化学电池中的用途。
锂离子电池是最有希望的便携式应用体系中的一种,其应用领域从精密电子设备(例如移动电话、摄像机-录像机组合装置)拓展到电子驱动机动车用电池组。
这些电池组由阴极、阳极、隔膜和非水电解质组成。所使用的阴极通常是Li(MnMez)2O4、Li(CoMez)O2、Li(CoNixMez)O2或其它锂夹杂和嵌入化合物。阳极可由锂金属、碳质材料、石墨、石墨碳质材料或其它锂夹杂和嵌入化合物或合金化合物组成。所使用的电解质呈现含有锂盐例如LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2或LiC(CF3SO2)3和这些盐的混合物在非质子传递溶剂中的溶液形式。
普通的导电锂盐存在各种缺点。一些导电盐的循环产率较低(例如LiBF4)。其它导电盐的热稳定性较差(例如LiPF6),还有一些其它导电盐不特别适用,原因是它们具有毒性和环境安全性差(例如LiAsF6)。
因此,WO98/07729公开了一种新型导电盐-硼酸锂配合物。这些化合物在循环实验中得到特别好的结果,证明是特别稳定的。这些配合物在与其它盐混合时在氧化方面呈现出协同的稳定效果。
现有技术公开的双[5-氟-2-羟连(olato)-苯-磺化(sulfonato)(2)-O,O′]硼酸(1-)锂是一种导电盐,根据其特性,一定被认为是极有希望在锂离子电池组中应用的导电盐。但是,存在的问题是成本高并且前体的合成过程复杂。
唯一一份有关2-羟基苯磺酸和其衍生物合成方法的现有技术对比文献(Speier,“(羟基有机)-硅烷和有关化合物的制备和特性”,J.Am.Chem.Soc.74(1952),1003)公开了繁琐的三步法,总产率在40-70%的范围内。
因此,本发明的目的是提供一种合成锂配盐的简单方法。
R1和R2相同或不同,通过一个单键或双键彼此直接或间接地连接,所述基团分别独立地或一起代表选自苯基、萘基、蒽基或菲基的芳香环,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~六元取代,
或分别独立地或一起代表选自吡啶基、吡唑基(pyrazyl)或嘧啶基的芳香杂环,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~四元取代,
或分别独立地或一起代表选自羟基苯羧基、羟基萘羧基、羟基苯磺酰基和羟基萘磺酰基的芳香环,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~四元取代,
R3-R6分别独立地或成对地通过一个单键或双键彼此直接或间接地连接,所述基团具有下列定义:
1.烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)
2.选自下列基团的芳环:
苯基、萘基、蒽基或菲基,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~六元取代,
吡啶基、吡唑基或嘧啶基,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~四元取代,
其特征在于:
a)将合适溶剂中的3-、4-、5-、6-取代苯酚(Ⅲ)与氯磺酸混合,
b)将a)中形成的中间体(Ⅳ)与三甲基氯硅烷进行反应,过滤产物并进行分馏,
c)将b)中形成的中间体(Ⅱ)与适当溶剂中的四甲氧基硼酸(1-)锂进行反应,从中离析目的产物(Ⅰ)。
R3-R6分别独立地或成对地通过一个单键或双键彼此直接或间接地连接,所述基团具有下列定义:
1.烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)
2.选自下列基团的芳环:
苯基、萘基、蒽基或菲基,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~六元取代,
吡啶基、吡唑基或嘧啶基,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~四元取代。
R1和R2分别独立地或一起代表下列基团:
R1、R2为H、具有1-6个碳原子的烷基和三烷基甲硅烷基(包括C1-C6烷基),
R3-R6分别独立地或成对地通过一个单键或双键彼此直接或间接地连接,所述基团具有下列定义:
1.烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)
2.选自下列基团的芳环:
苯基、萘基、蒽基或菲基,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~六元取代,
吡啶基、吡唑基或嘧啶基,它们可以未经取代或被烷基(C1-C6)、烷氧基(C1-C6)或卤素(F、Cl、Br)一~四元取代。
通式(Ⅰ)的目的产物可在锂电池的电解质中单独使用或与其它锂盐和/或硼酸盐配合物混合使用。这样做时,重要的是确保含钠杂质含量极低。对于指定的电化学特性来说(钠比锂差),那么钠离子会被嵌入阴极的结构中。其结果必然毁坏电池。本发明的方法则无需使用钠。
因此,按本发明方法制备的硼酸锂配合物特别适合在电化学电池中使用。在二次锂电池的电解质中既可以将硼酸锂配合物与其它锂盐一起使用,也可以与硼酸盐配合物一起使用。
另外,在含常规导电盐的电解质中也可使用硼酸锂配合物。例如,合适的电解质含有选自LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2或LiC(CF3SO2)3及其混合物的导电盐。为降低水含量,电解质还可含有有机异氰酸盐(DE19944603)。同样,电解质可含有有机碱金属盐(DE19910968)添加剂。合适的添加剂实例是下列通式的碱金属硼酸盐:
Li+B-(OR1)m(OR2)p其中:
m和p代表0、1、2、3或4,并且m+p=4,和
R1和R2相同或不同,通过一个单键或双键彼此直接或间接地连接,
分别独立地或一起代表芳香或脂族羧基、二元羧基或磺酸基团,或
分别独立地或一起代表选自苯基、萘基、蒽基或菲基的芳环,它们可以未经取代或被A或卤素一~四元取代,或
分别独立地或一起代表选自吡啶基、吡唑基或双吡啶基的芳香杂环,它们可以未经取代或被A或卤素一~三元取代,或
分别独立地或一起代表选自芳香羟基羧酸或芳香羟基磺酸的芳香羟基酸,它们可以未经取代或被A或卤素一~四元取代,和
卤素代表F、Cl或Br,和
A代表具有1-6个碳原子的烷基并且可以被一~三元卤代。同样合适的是下列通式的碱金属醇化物
Li+OR-其中:
R代表芳香或脂族羧基、二元羧基或磺酸基团,或
代表选自苯基、萘基、蒽基或菲基的芳环,它们可以未经取代或被A或卤素一~四元取代,或
代表选自吡啶基、吡唑基或双吡啶基的芳香杂环,它们可以未经取代或被A或卤素一~三元取代,或
代表选自芳香羟基羧酸或芳香羟基磺酸的芳香羟基酸,它们可以未经取代或被A或卤素一~四元取代,和
卤素代表F、Cl或Br,和
A代表具有1-6个碳原子的烷基并且可以被一~三元卤代。
电解质同样可含有下式的化合物(DE19941566)
[([R1(CR2R3)k]lAx)yKt]+ -N(CF3)2其中
Kt=N、P、As、Sb、S、Se
A=N、P、P(O)、O、S、S(O)、SO2、As、As(O)、Sb、Sb(O)
R1、R2和R3相同或不同,代表H、卤素、取代和/或未取代的烷基CnH2n+1、取代和/或未取代的具有1-18个碳原子和一个或多个双键的链烯基、取代和/或未取代的具有1-18个碳原子和一个或多个三键的炔基、取代和/或未取代的环烷基CmH2m-1、单-或多取代和/或未取代的苯基、取代和/或未取代的杂芳基,
A可被包含在R1、R2和/或R3的各个位置上,
Kt可被包含在环或杂环上,
与Kt连接的基团可相同或不同,其中:
n=1-18
m=3-7
k=0,1-6
l=1或2(在x=1的情况下),l=1(在x=0的情况下)
x=0,1
y=1-4。
这些化合物的制备方法的特征在于:将通式(Ⅱ)的碱金属盐
D+ -N(CF3)2 (Ⅱ)
D+选自碱金属,在极性有机溶剂中与通式(Ⅲ)的盐进行反应
[([R1(CR2R3)k]lAx)yKt]+ -E (Ⅲ)
其中
Kt、A、R1、R2、R3、k、l、x和y具有上述定义,和
-E代表F-、Cl-、Br-、I-、BF4 -、ClO4 -、AsF6 -、SbF6 -或PF6 -。但是,同样可使用含下列通式化合物的电解质(DE19953638)
X-(CYZ)m-SO2N(CR1R2R3)2其中:
X代表H、F、Cl、CnF2n+1、CnF2n-1、(SO2)kN(CR1R2R3)2
Y代表H、F、Cl
Z代表H、F、Cl
R1、R2、R3代表H和/或烷基、氟烷基、环烷基
m代表0-9和如果X=H,m≠0
n代表1-9
k代表0,如果m=0,和k=1,如果m=1-9,
上述化合物通过使部分氟化或全氟化烷基磺酰氟与二甲胺在有机溶剂中进行反应制备,该电解质中还含有下列通式配盐(DE19951804)
Mx+[EZ]y- x/y其中:
x、y代表1、2、3、4、5、6
Mx+代表金属离子
E代表选自BR1R2R3、Al R1R2R3、P R1R2R3R4R5、As R1R2R3R4R5、VR1R2R3R4R5的路易斯酸,
R1-R5相同或不同,通过一个单键或双键彼此直接或间接连接,所述基团分别独立地或一起代表下列基团:
卤素(F、Cl、Br),
可以部分或完全被F、Cl、Br取代的烷基或烷氧基(C1-C8),
通过氧连接或未连接的芳香环选自苯基、萘基、蒽基或菲基,它们可以未经取代或被烷基(C1-C8)或F、Cl、Br一~六元取代,
通过氧连接或未连接的芳香杂环选自吡啶基、吡唑基或嘧啶基,它们可以未经取代或被烷基(C1-C8)或F、Cl、Br一~四元取代和
Z代表OR6、NR6R7、CR6R7R8、OSO2R6、N(SO2R6)(SO2R7)、C(SO2R6)(SO2R7)(SO2R8)、OCOR6,其中:R6-R8相同或不同,通过一个单键或双键彼此直接或间接地连接,并且所述基团分别独立地或一起代表下列基团:
氢或定义与R1-R5相同的基团,
上述配盐通过使适当的硼或磷路易斯酸溶剂加成物与锂或四烷基铵酰亚胺、methanide或三氟甲磺酸盐进行反应制备。
也可有下列通式的硼酸盐(DE19959722)存在其中:
M代表金属离子或四烷基铵离子,
x、y代表1、2、3、4、5或6,
R1-R4相同或不同,代表烷氧基或羧基(C1-C8),它们通过一个单键或双键彼此直接或间接地连接。这些硼酸盐通过使四烷氧基硼酸锂或1∶1烷氧基锂与硼酸酯的混合物在非质子传递溶剂中与合适的羟基或羧基化合物按2∶1或4∶1的比例进行反应制备。
在含通式(Ⅰ)氟烷基磷酸锂的电解质中也可使用添加剂,
Li+[PFx(CyF2y+1-zHz)6-x]-(Ⅰ)其中:
1≤x≤5
3≤y≤8
0≤z≤2y+1
和配位体(CyF2y+1-zHz)可以相同或不同,通式(Ⅰ′)的化合物除外,
Li+[PFa(CHbFc(CF3)d)e]-(Ⅰ′)其中:a代表2-5的整数,b=0或1,c=0或1,d=2和e代表1-4的整数,条件是b或c不同时为O、a+e=6并且配位体(CHbFc(CF3)d)相同或不同(DE10008955)。通式(Ⅰ)氟烷基磷酸锂的制备方法的特征在于:使下列通式的至少一种化合物HmP(CnH2n+1)3-m(Ⅲ),OP(CnH2n+1)3 (Ⅳ),ClmP(CnH2n+1)3-m(Ⅴ),FmP(CnH2n+1)3-m(Ⅵ),CloP(CnH2n+1)5-o(Ⅶ),FoP(CnH2n+1)5-o(Ⅷ),其中:0≤m≤2,3≤n≤8和0≤o≤4,在氟化氢中电解氟化,由此获得的氟化产物混合物经萃取、相分离和/或蒸馏分离,并使由此获得的氟化烷基正膦与氟化锂在非质子传递溶剂或溶剂混合物存在下,在无水分条件下进行反应,按照常规步骤提纯和离析由此获得的通式(Ⅰ)的盐。
在含阳极材料的电化学电池的电解质中可使用添加剂,所述阳极材料由选自Sb、Bi、Cd、In、Pb、Ga和锡或其合金的涂覆金属芯组成(DE10016024)。所述阳极材料的制备方法的特征在于:
a)在六亚甲基四胺中制备金属芯或合金芯的溶胶的悬浮液,
b)用C5-C12烃乳化该悬浮液,
c)将乳液沉积在金属芯或合金芯上,和
d)通过退火该体系将金属氢氧化物或羟基氧化物转变成相应的氧化物。
在含普通锂夹杂和嵌入化合物阴极或含阴极材料的电化学电池的电解质中也可使用添加剂,所述阴极材料由锂混合氧化物颗粒组成,所述颗粒被一种或多种金属氧化物涂覆(DE19922522),该涂覆过程包括将颗粒悬浮在有机溶剂中,将悬浮液与可水解金属化合物溶液和水解溶液混合,然后过滤出涂覆颗粒,进行干燥,必要时进行煅烧。另外,它们可由锂混合氧化物颗粒组成,所述颗粒被一种或多种聚合物涂覆(DE19946066),它们是按下列方法制备的:将颗粒悬浮在溶剂中,然后过滤出涂覆颗粒,干燥,必要时进行煅烧。同样在含阴极的系统中可使用本发明的添加剂,所述阴极由锂混合氧化物颗粒组成,可用碱金属化合物和金属氧化物对它们进行一次或多次涂覆(DE10014884)。这些材料的制备方法的特征在于:将颗粒悬浮在有机溶剂中,添加悬浮在有机溶剂中的碱金属盐化合物,添加溶解在有机溶剂中的金属氧化物,将悬浮液与水解溶液混合,然后过滤出涂覆颗粒,进行干燥和煅烧。
在惰性气氛(氩或氮)下,将3-、4-、5-、6-取代的苯酚(Ⅲ)溶解在合适的溶剂中。在30分钟至2小时内,将该溶液与5-20%过量氯磺酸混合,混合温度为10-30℃,优选为室温。在反应进行20-40小时后,一般进行24小时后,在惰性气氛下通过吸滤过滤出沉淀的产物(Ⅳ),用合适的溶剂洗涤并真空干燥。
在惰性气氛下将中间体(Ⅳ)与1.5-4倍超出化学计量的三甲基氯硅烷混合并加热至沸腾。在释放HCl的剧烈程度逐渐减缓后,再加入相同量三甲基氯硅烷,回流加热溶液50-100小时。在惰性气氛下冷却后,过滤出沉淀的起始原料。在轻度减压下除去过量三甲基氯硅烷,经分馏离析出通式(Ⅱ)的中间体。转变成锂配盐的过程:
为制备锂配盐(Ⅰ),在惰性气氛下将四烷氧基硼酸锂作为初始进料引入到极性非质子传递溶剂中。所使用的溶剂可以是选自乙腈、丙酮、硝基甲烷、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、碳酸二甲酯、碳酸二乙酯、碳酸异丙烯酯、碳酸丁烯酯和碳酸甲·乙酯的溶剂。在添加化学计量中间体(Ⅱ)后,在40-70℃的温度下搅拌混合物30分钟至5小时,优选45-90分钟。在轻度减压下除去形成的硅烷和溶剂,真空干燥粗产物至恒重。用合适的溶剂或溶剂混合物重结晶粗产物,然后真空干燥至恒重。
下面的实施例旨在更详细地说明本发明,而不是对其进行限制。
实施例
实施例15-氟-2-羟基苯磺酸
在氮气氛下,将200克(1.78摩尔)4-氟苯酚溶解在1300毫升CHCl3中(蒸馏,在氯化钙上干燥)。在室温下,在1小时内向搅拌的溶液中滴加131毫升(229克=1.96摩尔)氯磺酸,开始时观察到有HCl急剧释放,在反应完成30分钟后,HCl的释放逐渐减弱,再过3小时完全停止。反应进行24小时后,在室温和惰性气氛下通过吸滤过滤出沉淀的产物,每次用200毫升CHCl3洗涤两次,在1333Pa的真空和室温下干燥3小时。
产物是灰白色、高吸湿性粉末。
产率:302克(88%)
熔点:110-114℃(密封的毛细管)
1H-NMR(250MHz,[D6]DMSO):
δ=6.77(dd,3JH3-H4=8.9Hz,4JH3-F=4.6Hz,1H,H-3),
7.04(dt,3JH4-H3=8.9Hz,4JH4-H6=3.3Hz,3JH4-F=8.9Hz,1H,H-4),
7.16(dd,3JH6-F=8.4Hz,4JH6-H4=3.3Hz,1H,H-6),
12.32(宽单峰,2H,OH,SO3H)
13C-NMR(62.9MHz,[D6]DMSO):
δ=113.46(+,d,2JC-F=24.0Hz,C-6),
118.47(+,d,3JC-F=7.4Hz,C-3),
118.53(+,d,2JC-F=23.0Hz,C-4),
131.79(C四重峰,d,3JC-F=5.8Hz,C-1),
150.22(C四重峰,d,4JC-F=1.8Hz,C-2),
155.10(C四重峰,d,1JC-F=236.3Hz,C-5),
MS(70eV,El),m/z(%):
194(2)[M++2],193(3)[M++1],192(54)[M+],174(44),126(23),110(65),98(15),82(100),63(16),57(20)
C6H5O4FS:观察值191.9892(校正HRMS)
实施例25-氟-2-三甲基甲硅烷氧基-苯磺酸三甲基甲硅烷基酯
在惰性气氛和室温下将302克(1.57摩尔)5-氟-2-羟基苯磺酸与794毫升(683克,6.28摩尔)三甲基氯硅烷搅拌混合,加热混合物至沸腾。在HCl的急剧释放逐渐减弱后,再加入794毫升三甲基氯硅烷,加热回流浑浊溶液96小时。冷却后,在惰性气氛下过滤出沉淀物,在40-50℃、稍微减压下(约4000Pa)除去过量三甲基氯硅烷,通过真空分馏获得产物。
产物是无色、粘稠、易水解的液体。
产率:496克(93%)
熔点:93-96℃/1.333Pa
1H-NMR(250MHz,CDCl3):
δ=0.32(s,9H,OTMS),
0.36(s,9H,OTMS),
6.87(dd,3JH3-H4=9.0Hz,4JH3-F=4.3Hz,1H、H-3),
7.16(ddd,3JH4-H3=9.0Hz,4JH4-H6=3.2Hz,3JH4-F=7.6Hz,1H,H-4),
7.57(dd,4JH6-H4=3.2Hz,3JH6-F=8.0Hz,1H、H-6),
13C-NMR(62.9MHz,CDCl3):
δ=0.38(+,OTMS),
0.43(+,OTMS),
116.23(+,d,2JC-F=26.4Hz,C-6),
121.08(+,d,2JC-F=23.0Hz,C-4),
121.70(+,d,3JC-F=7.4Hz,C-3),
130.99(C四重峰,d,3JC-F=7.3Hz,C-1),
149.82(C四重峰,d,4JC-F=2.6Hz,C-2),
155.77(C四重峰,d,1JC-F=243.2Hz,C-5),
MS(70eV,El),m/z(%):336(3)[M+],321(33),264(43),249(60),233(96),169(39),147(59),75(100),73(76),45(18)C12H21O4FSSi2:观察值336.0683(校正HRMS)元素分析: %C %H计算值: 42.82 6.29观测值: 42.57 6.30
实施例3双[5-氟-2-羟连-苯磺化(2-)O,O′]-硼酸(1-)锂
在惰性气氛下,将2.81克(19.8毫摩尔)四甲氧基硼酸(1-)锂悬浮在100毫升碳酸二甲酯(DMC)中。添加13.35克(39.7毫摩尔)5-氟-2-三甲基甲硅烷氧基-苯磺酸三甲基甲硅烷基酯形成透明溶液。在45-50℃下保温1小时,在该步骤中溶液变得轻度浑浊。在50℃和轻度减压下将形成的硅烷与溶剂一起汽提,在70℃和油泵真空下干燥获得的粗产物24小时。用甲苯/DMC重结晶粗产物四次。通过烧结玻璃滤除开始的两个纯化步骤中观测到的云状物。在1-10Pa,70℃和真空下干燥锂盐至恒重。
获得无色针状结晶产物。
1H-NMR(250MHz,[D6]DMSO):
δ=7.08(dd,3JH3-H4=8.9Hz,4JH3-F=4.4Hz,2H,H-3,H-3′),
7.40(dt,3JH4-H3=8.9Hz,4JH4-H6=3.2Hz,3JH4-F=8.9Hz,2H,H-4,H-4′),
7.50(dd,4JH6-H4=3.2Hz,3JH6-F=8.9Hz,2H,H-6,H-6′),
13C-NMR(62.9MHz,[D6 DMSO]):
δ=110.6(+,d,2JC-F=25.7Hz,C-6),
121.3(+,d,2JC-F=22.9Hz,C-4),
121.4(+,d,3JC-F=7.9Hz,C-3),
125.3(C四重峰,3JC-F=7.6Hz,C-1),
148.9(C四重峰,4JC-F=2.2Hz,C-2),
155.2(C四重峰,1JC-F=240.0Hz,C-5),AAS:锂含量:计算值: 1.74% 观测值: 1.75%
实施例4双[5-氟-2-羟连-苯磺化(2-)O,O′]硼酸(1-)锂的抗氧化性
用含有铂工作电极、锂对电极和锂参比电极的测试电池连续5次记录每种情况下循环伏安图。为了进行该测试,对Li/Li+来说,首先以10mV/s的速率将电势由静止电位增加至5V,接着返回到静止电位。电解质:0.42mol/kgLm双[5-氟-2-羟连-苯磺化(2-)O,O′]硼酸(1-)锂EC/DMC(1∶1)氧化电位测定值为4.5V Li/Li+。
Claims (6)
1.通式(Ⅰ)锂配盐的制备方法其中:
R1和R2相同或不同,通过一个单键或双键彼此直接或间接地连接,所述基团分别独立地或一起代表选自苯基、萘基、蒽基或菲基的芳环,它们可以未经取代或被C1~6烷基、C1~6烷氧基或卤素F、Cl、Br一~六元取代,
或分别独立地或一起代表吡啶基、吡唑基或嘧啶基的芳香杂环,它们可以未经取代或被C1~6烷基、C1~6烷氧基或卤素F、Cl、Br一~四元取代,
或分别独立地或一起代表选自羟基苯羧基、羟基萘羧基、羟基苯磺酰基和羟基萘磺酰基的芳环,它们可以未经取代或被C1~6烷基、C1~6烷氧基或卤素F、Cl、Br一~四元取代,
R3-R6分别独立地或成对地通过一个单键或双键彼此直接或间接地连接,所述基团具有下列定义:
1.C1~6烷基、C1~6烷氧基或卤素F、Cl、Br
2.选自下列基团的芳环:
苯基、萘基、蒽基或菲基,它们可以未经取代或被C1~6烷基、C1~6烷氧基或卤素F、Cl、Br一~六元取代,
吡啶基、吡唑基或嘧啶基,它们可以未经取代或被C1~6烷基、C1~6烷氧基或卤素F、Cl、Br一~四元取代,
其特征在于:
a)将合适溶剂中的3-、4-、5-、6-取代的苯酚(Ⅲ)与氯磺酸混合,
b)将a)中形成的中间体(Ⅳ)与三甲基氯硅烷进行反应,过滤产物并进行分馏,
c)将b)中形成的中间体(Ⅱ)与适当溶剂中的四甲氧基硼酸(1-)锂进行反应,从中离析目的产物(Ⅰ)。
3.根据权利要求1的方法,其特征在于:将步骤c)的中间体(Ⅱ)悬浮在极性非质子传递溶剂中。
4.通式(Ⅱ)化合物在通式(Ⅰ)化合物的制备过程中的用途。
5.权利要求1的方法制备的通式(Ⅰ)锂配盐作为电化学电池中的电解质的用途。
6.权利要求1的方法制备的通式(Ⅰ)锂配盐与其它锂盐和/或硼酸盐配合物一起作为二次锂电池的电解质的用途。
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CN1957498B (zh) * | 2004-03-08 | 2010-05-05 | 坎梅陶尔股份有限公司 | 用于原电池的导电盐、其制备及应用 |
CN104037452A (zh) * | 2014-06-18 | 2014-09-10 | 厦门首能科技有限公司 | 一种锂离子二次电池及含有该电解液的锂离子电池 |
CN110627742A (zh) * | 2018-10-31 | 2019-12-31 | 苏州固锂新能源科技有限公司 | 一种含有至少一种环状配体结构的化合物的制备方法和纯化方法 |
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DE19932317A1 (de) * | 1999-07-10 | 2001-01-11 | Merck Patent Gmbh | Verfahren zur Herstellung von Lithiumkomplexsalzen zur Anwendung in elektrochemischen Zellen |
DE19959722A1 (de) * | 1999-12-10 | 2001-06-13 | Merck Patent Gmbh | Alkylspiroboratsalze zur Anwendung in elektrochemischen Zellen |
DE10055811A1 (de) | 2000-11-10 | 2002-05-29 | Merck Patent Gmbh | Tetrakisfluoroalkylborat-Salze und deren Verwendung als Leitsalze |
DE10108592C1 (de) * | 2001-02-22 | 2002-08-14 | Chemetall Gmbh | Borchelatkomplexe, Verfahren zu deren Herstellung sowie deren Verwendung |
JP4895335B2 (ja) * | 2001-03-23 | 2012-03-14 | 日立マクセルエナジー株式会社 | 非水電池 |
JP5242315B2 (ja) * | 2008-09-25 | 2013-07-24 | 株式会社東芝 | 非水電解質二次電池 |
WO2014129972A1 (en) * | 2013-02-25 | 2014-08-28 | National University Of Singapore | Sp3 boron-based single-ion conducting polymer electrolytes |
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US2877191A (en) * | 1954-07-14 | 1959-03-10 | Graydon William Frederick | Cation exchange resin membranes by hydrolysis of styrene sulfonic ester or amide copolymers |
US3401222A (en) * | 1965-07-29 | 1968-09-10 | Shell Oil Co | Nematocidal 2, 4-dihalophenyl esters of ethanesulfonic acid ethers and alcohols |
US5318769A (en) * | 1993-03-31 | 1994-06-07 | Sterling Winthrop Inc. | Compositions of iodophenyl esters for X-ray visualization of the gastrointestinal tract |
US5670691A (en) * | 1994-10-18 | 1997-09-23 | Rohm And Haas Company | Method for making a substituted benzene compound |
DE19633027A1 (de) * | 1996-08-16 | 1998-02-19 | Merck Patent Gmbh | Verfahren zur Herstellung von neuen Lithium-Borat-Komplexen |
US6599664B2 (en) * | 1997-08-22 | 2003-07-29 | Yardney Technical Products, Inc. | Inorganic gel-polymer electrolyte |
US6203949B1 (en) * | 1997-08-22 | 2001-03-20 | Yardney Technical Products, Inc. | Solid electrolyte for an electrochemical cell composed of an inorganic metal oxide network encapsulating a liquid electrolyte |
DE19757126A1 (de) * | 1997-12-20 | 1999-06-24 | Merck Patent Gmbh | Nichtwäßrige Elektrolytzusammensetzungen |
DE19910968A1 (de) * | 1999-03-12 | 2000-11-09 | Merck Patent Gmbh | Anwendung von Additiven in Elektrolyten für elektrochemische Zellen |
DE19932317A1 (de) | 1999-07-10 | 2001-01-11 | Merck Patent Gmbh | Verfahren zur Herstellung von Lithiumkomplexsalzen zur Anwendung in elektrochemischen Zellen |
US20010033964A1 (en) | 1999-12-10 | 2001-10-25 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Alkylspiroborate salts for use in electrochemical cells |
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CN1957498B (zh) * | 2004-03-08 | 2010-05-05 | 坎梅陶尔股份有限公司 | 用于原电池的导电盐、其制备及应用 |
CN104037452A (zh) * | 2014-06-18 | 2014-09-10 | 厦门首能科技有限公司 | 一种锂离子二次电池及含有该电解液的锂离子电池 |
CN110627742A (zh) * | 2018-10-31 | 2019-12-31 | 苏州固锂新能源科技有限公司 | 一种含有至少一种环状配体结构的化合物的制备方法和纯化方法 |
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US6441216B1 (en) | 2002-08-27 |
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DE50008571D1 (de) | 2004-12-16 |
US20030028023A1 (en) | 2003-02-06 |
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