CN1275971C - 硼螯合物 - Google Patents
硼螯合物 Download PDFInfo
- Publication number
- CN1275971C CN1275971C CNB028086902A CN02808690A CN1275971C CN 1275971 C CN1275971 C CN 1275971C CN B028086902 A CNB028086902 A CN B028086902A CN 02808690 A CN02808690 A CN 02808690A CN 1275971 C CN1275971 C CN 1275971C
- Authority
- CN
- China
- Prior art keywords
- lithium
- chelate complexes
- boron
- borate
- salt
- 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.)
- Expired - Lifetime
Links
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical class [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 79
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002585 base Substances 0.000 claims description 33
- 235000006408 oxalic acid Nutrition 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- -1 hydrogen Boron chelate complexes Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- JZWFDVDETGFGFC-UHFFFAOYSA-N salacetamide Chemical group CC(=O)NC(=O)C1=CC=CC=C1O JZWFDVDETGFGFC-UHFFFAOYSA-N 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000003930 superacid Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims 2
- QDCCWLMDTJDQLY-UHFFFAOYSA-N [B+3].N Chemical compound [B+3].N QDCCWLMDTJDQLY-UHFFFAOYSA-N 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KEQUMCBPJPVZPP-UHFFFAOYSA-N (2-hydroxyphenyl)methoxyboronic acid Chemical compound OB(O)OCC1=CC=CC=C1O KEQUMCBPJPVZPP-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 238000006264 debenzylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- WAVGXIXQMBSEMK-UHFFFAOYSA-N lithium;phenol Chemical compound [Li].OC1=CC=CC=C1 WAVGXIXQMBSEMK-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride 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
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000005412 pyrazyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical class [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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
-
- 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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
-
- 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
本发明涉及下列通式(I)的硼螯合物,其中X表示-C(R1R2)-或-C(R1R2)-C(=O)-,其中R1和R2,彼此独立,表示H,烷基(具有1-5个碳原子),芳基,甲硅烷基或聚合物,并且烷基R1或R2中的一个可以和另一个螯合硼酸盐基团连接或者X表示在位置3到6(II)具有最高达两个取代基S的1,2-芳基,其中S1和S2,彼此独立,表示烷基(具有1-5个碳原子),氟或聚合物,和M+表示Li+,Na+,K+,Rb+,Cs+或[(R3R4R5R6)N]+或H+,其中R3,R4,R5,R6,彼此独立,表示H或具有优选1-4个碳原子的烷基。
Description
本发明涉及硼螯合物,其生产方法以及其作为电解质和作为催化剂的应用。
移动电子装置日益需要更有效的和再充电式电池以提供独立的电力供应。除了镍-镉和镍-氢化金属电池,特别是再充电式锂电池,其与镍电池相比具有显著高的能量密度,特别适合于此目的。市场上可买到的系统具有大约3V的端电压;这种相对高的电势意味着水基电解质系统不能用于锂电池。相反,非水的,主要是有机电解质(即有机溶剂,例如碳酸酯,醚或酯中的锂盐溶液)被用于液体系统。
在当前主导的电池设计-具有液体电解质的锂离子电池-六氟磷酸锂(LiPF6)实际上唯一地被用作导电盐。这种盐满足了用于高能量电池必需的前提条件,即它在非质子溶剂中易于溶解,导致了具有高电导率的电解质,并具有高水平的电化学稳定性。氧化分解仅在电势值大于大约4.5V的条件下发生。然而LiPF6具有严重缺点,这可以主要归因于热稳定性的缺乏(它在大约130℃以上分解)。并且,一旦受潮,就会释放腐蚀性和有毒的氟化氢,这一方面使处理复杂化,另一方面侵蚀和损坏其它的电池构件,例如阴极。
鉴于这个背景,已经做了深入努力以形成其它的导电盐,特别是已经试验了具有全氟有机基团的锂盐。这些盐包括三氟甲烷磺酸锂(“Li-Triflat”),亚胺基锂(锂-双(全氟烷基磺酰基)二酰亚胺)以及甲基锂(锂-三(全氟烷基磺酰基)甲基化物)。所有这些盐要求相对复杂的生产方法,因此相对昂贵,并且具有其它的缺点,例如考虑到铝时的腐蚀性或差的电导率。
有机硼酸锂作为再充电式锂电池中用作导电盐的进一步的一类化合物已经被研究。然而出于在三有机硼烷的处理中它们的低氧化稳定性和安全性的考虑,它们对于商业系统的应用被排除了。
在EP 698301中提出的用于电解池的ABL2类的锂配合物盐(其中A表示锂或季铵离子,B表示硼,L表示通过两个氧原子与硼原子结合的二齿配位体)表示了相当大的进步。然而提出的盐(其配位体包含至少一个芳基基团)仅具有足够的电化学稳定性,如果芳基基团被吸电子基团取代,典型地氟,或如果在环中它包含至少一个氮原子。这样的螯合物商业上买不到,仅能高成本地生产。因此提出的产品不能打入市场。
在EP 907217中作为在有机电解池中的组分提出了非常相似的硼化合物。作为含硼的导电盐通式提出了LiBXX′的化合物,其中配位体X和X′可以是相同的或不同的,并且每一个配位体包含含氧原子的吸电子基团,该基团与硼原子结合。然而列出的化合物(锂-硼双水杨酸盐和特殊的亚氨基盐)显示了以上已经提到的缺点。
在DE 19829030中第一次描述的化合物锂-双(草酸基)硼酸盐(LOB)是描述的用作电解质的第一个以硼为中心的配合物盐,其使用二羧酸(在这中情况下是草酸)作为螯合物组分。该化合物生产简单,无毒并且电化学稳定性达大约4.5V,这使其可以用于锂离子电池。然而缺点是它几乎不能在具有3V的电池电压的新电池系统内使用。为了这种电化学储存装置,需要具有≥大约5V的稳定性的盐。进一步的缺点是锂-双(草酸基)硼酸盐使没有破坏基本的化学骨架的任何可能的结构变化不可能。
在EP 1035612中添加剂特别是式
Li+B-(OR1)m(OR2)p
被提到,m和p=0,1,2,3或4,其中m+p=4,
并且
R1和R2是相同的或不同的,任选通过单键或双键彼此直接成键,在每一种情况下单独地或共同地表示芳族或脂族羧酸或磺酸,或在每一种情况下单独地或共同地表示选自下列的芳环:苯基,萘基,蒽基或菲基,其可以是未取代的或通过A或Hal被一到四取代,或在每一种情况下单独地或共同地表示选自下列的杂芳环:吡啶基,吡嗪基(pyrazyl)或联吡啶基,其可以是未取代的或通过A或Hal被一到三取代,或每一种情况下单独地或共同地表示选自下列的芳族羟基酸:芳族羟基羧酸或芳族羟基磺酸,其可以是未取代的或通过A或Hal被一到四取代,Hal=F,Cl或Br,并且
A=具有1到6个碳原子的烷基,其可以被1到3卤代。
可以提到的作为特别优选的添加剂有锂-双[1,2-苯二油酸基(2-)O,O′]硼酸盐(1-),锂-双[3-氟-1,2-苯二油酸基(2-)O,O′]硼酸盐(1-),锂-双[2,3-萘二油酸基(2-)O,O′]硼酸盐(1-),锂-双[2,2′-二苯基二油酸基(2-)O,O′]硼酸盐(1-),锂-双[水杨酸基(2-)O,O′]硼酸盐(1-),锂-双[2-油酸基苯磺酸基(2-)O,O′]硼酸盐(1-),锂-双[5-氟-2-油酸基苯磺酸基(2-)O,O′]硼酸盐(1-),苯酚锂和锂-2,2-二苯酚盐。这些全是对称的类Li[BL2]的锂螯合硼酸盐。
锂-双(丙二酸基)硼酸盐,其据说具有最高达5V的电化学窗口(elektrochemisches Fenster),已经通过C.Agell描述,作为电化学特别稳定的简单的锂-(螯合)硼酸盐化合物。然而该化合物具有特别不溶于通常的电池溶剂(例如在碳酸异丙烯酯中仅0.08摩尔)的缺点,这意味着它仅仅在DMSO和相似的限制电池溶剂中溶解和表征(WuXu和C.Austen Angell,Electrochem.Solid-State Lett.4,E1-E4,2001)。
螯合硼酸盐还可以以质子化形式(即H[BL2])存在,其中L是通过两个氧原子与硼原子结合的二齿配位体。这种化合物具有极高的酸强度,因此可以在有机合成中用作所称的超酸,用作环化,氨基化等的催化剂。例如,氢-双(草酸基)硼酸盐已经被建议作为生产生育酚(US 5,886,196)的催化剂。然而这种催化剂的缺点是相对差的水解稳定性。
本发明的目的是消除现有技术的缺点特别是提供对于导电盐的物质,该物质可以从商业上可购买的原料相对简单和不昂贵地生产,该原料具有至少4.5V的足够的氧化稳定性,并且在常规使用的“电池溶剂”中易于溶解。进一步地该物质应该对于通过水或酒精的分解具有相对的抗性。
这个目标通过“混合的”具有下面通式的硼螯合物达到
其中
X是-C(R1R2)-或-C(R1R2)-C(=O),其中
R1,R2彼此独立地表示H,烷基(具有1-5个碳原子),芳基,甲硅烷基或聚合物,烷基R1或R2中的一个可以和进一步的螯合硼酸盐基团连接,
或X表示在位置3到6具有最高达两个取代基S的1,2-芳基,
其中S1,S2彼此独立地表示烷基(具有1-5个碳原子),氟或聚合物,
以及M+表示Li+,Na+,K+,Rb+,Cs+或[(R3R4R5R6)N]+或H+,其中R3,R4,R5,R6彼此独立地表示H或具有优选1-4个碳原子的烷基。
已经惊人地发现上面列出的具有两个不同配位体的硼酸盐(其中之一是草酸基基团)比对称的比较化合物具有显著较好的溶解性。
下面的化合物是优选的:氢-(丙二酸基,草酸基)硼酸盐(HMOB),氢-(乙醇酸基,草酸基)硼酸盐(HGOB),氢-(乳酸基,草酸基)硼酸盐(HLOB),氢-(草酸基,水杨酸基)硼酸盐(HOSB),和双-[氢-(草酸基,酒石酸基)硼酸盐](BHOTB),以及上面提到的酸是锂-,铯-和四烷基铵盐。
通过锂化合物的例子表1中显示了与对称的比较化合物比较混合硼酸盐更好的溶解性。
表1:在室温下各种锂硼酸盐配合物盐(以mol/kg为单位)的溶解性
LOB | LLB | LMB | LOMB | LLOB | LOSB | |
THFPCγ-BL1,2-DME丙酮 | 1.900.881.551.301.82 | <0.01<0.010.02<0.01<0.01 | 0.090.020.130.0030.03 | 0.170.170.620.200.43 | 1.590.170.960.931.38 | 1.211.500.980.430.51 |
LOB=锂-双(草酸基)硼酸盐, THF=四氢呋喃
LLB=锂-双(乳酸基)硼酸盐, PC=碳酸异丙烯酯
LMB=锂-双(丙二酸基)硼酸盐 γ-BL=丁内酯
LOMB=锂-(丙二酸基,草酸基)硼酸盐 1,2-DME=1,2-
二甲氧基乙烷
LLOB=锂-(乳酸基,草酸基)硼酸盐
LOSB=锂-(乳酸基,水杨酸基)硼酸盐
显然没有根据本发明的LOB在大多数情况下具有最好的溶解性。然而与其它对称的化合物(LMB和LLB)比较令人惊奇的是混合螯合硼酸盐显著改进的溶解性。在溶剂碳酸异丙烯酯中混合的LOSB比LOB更显著溶解得多。
表2显示各种螯合硼酸盐的水解能力。
表2:在室温下搅拌2小时后在水中5%的溶液的水解程度
LOB | LMB | LMOB | |
水解程度(%) | >50 | 5 | 15 |
具有混合硼螯合物阴离子的根据本发明的金属盐可以以相对高的浓度溶解于用于高性能电池的典型非质子溶剂中,例如碳酸酯,内酯和醚。表3给出了在室温下测量的电导率。
表3:在室温下在γ-BL,1,2-DME和THF中具有混合螯合硼酸盐的非水电解质的电导率
γ-BL | 1,2-DME | THF | ||||
浓度1) | 电导率2) | 浓度1) | 电导率2) | 浓度1) | 电导率2) | |
LLOBLSOBLMOBLMBLLBLOB | 0.960.540.130.021.04 | 2.613.591.650.016.96 | 0.930.43不溶 | 6.524.170 | 1.591.210.170.009不溶 | 2.913.170.410.010 |
1)以mmol/g为单位 2)以mS/cm为单位
从表3可以看到混合硼酸盐的溶液具有锂电池运转必需的>2mS/cm的电导率。与此形成对照,具有对称取代的盐LMB和LLB的未根据本发明的溶液具有显著较低或几乎为零的电导率。
相应于现有技术例如通过具有高介电常数的至少一种溶剂(例如碳酸亚乙酯,碳酸异丙烯酯)与至少一种减粘剂(例如碳酸二甲酯,乙酸丁酯,1,2-二甲氧基乙烷。2-甲基四氢呋喃)结合可以使电导率最优化。
进一步地具有混合硼螯合物阴离子的盐显示了理想的高度的电化学稳定性。例如,根据本发明的锂-(乳酸基,草酸基)硼酸盐具有大约5V的所称的“电化学窗口(elektrochemisches Fenster)”,即它在0-大约5V(Li/Li+=0)的范围是稳定的,正如在图1中显示的。
以上描述的硼螯合物可以通过已知的技术固定到聚合物化合物上。因此,通过合适的碱把在羰基α-位置上的酸性氢原子除去和把以这种方法获得的碳离子体添加到官能化的(例如卤化的)聚合物上是可能的。
根据本发明的硼螯合物可以任选在氧化金属源(例如Li2CO3,NaOH,K2O)或铵盐存在的条件下,通过硼酸或氧化硼与草酸和其它的螯合物形成剂反应生产,例如根据下列方程式:
或
其中L2表示二羧酸(不是草酸),羟羧酸或水杨酸(其最多可以是二取代的)。
优选使用起始物质的化学计算量,即摩尔比硼/草酸/螯合物形成剂L2/任选氧化金属源或铵盐是大约1∶1∶1∶1。理论化学计量的小的偏差(例如10%上下)是可能的,对于螯合硼酸盐终产品没有显著影响。因此,如果配位体的一种过量存在,相应的对称终产品将会在反应混合物中较大程度上产生。因此例如如果每当量的含硼原料使用>1摩尔的草酸,那么双-(草酸基)硼酸盐将会大量形成。如果反应在氧化锂原料存在的条件下进行,则LOB形成,其与根据本发明的混合螯合硼酸盐混合,没有干扰作为电池电解质的应用。如果另一方面其对称螯合化合物是微溶的的酸L2过量使用,那么副产物M[B(L2)2]可以通过简单的溶解/过滤步骤容易地分离。每当量的硼组分使用大约2摩尔的螯合物形成剂是重要的。如果螯合物形成剂没有以化学计算量使用,未反应的硼组分或不希望的1∶1-加成化合物(HO-B(C2O4)或HO-BL2)将会残留。如果使用了多于2摩尔的螯合物形成剂,那么未反应的螯合物形成剂将会残留,其必须以复杂的步骤分离。
根据上面化学方程式的反应优选用下列方法进行:通过在适合于水的共沸除去的介质(例如甲苯,二甲苯,甲基环己烷,具有多于6个碳原子的全氟烃)中悬浮原料组分进行和通过已知方法共沸除去水。
在水溶液中进行合成也是可能的。在这种情况下组分以任意顺序被添加到水中并在搅拌的同时通过蒸发浓缩,优选在减压条件下。除去大部分水后固态反应产物形成,该产物最后在100-180℃温度和减压条件下(例如10mbar)干燥,这取决于具体的产物性能。除了水,醇和其它的极性有机溶剂,也适合作为反应介质。
最后,产物也可以不添加任何溶剂生产,即商业购买的原料被混合之后,通过供热加热并优选在减压条件下脱水。
以这种方法生产的酸H[BC2O4L2]作为超酸催化剂被用于有机合成,例如对于缩合,氢氨基化或脱苄基作用。混合螯合硼酸盐的锂盐被用作电解池的电解质,优选锂电池。铵和铯盐可以用于电解双层电容器。
附图说明
图1为相对于镍电极的γ-丁内酯中0.5摩尔浓度的锂-(乳酸基,草酸基)硼酸盐(LLOB)溶液的环伏安图
下文在下面的例子的帮助下以更多的细节描述了本发明。
实施例1:通过共沸干燥锂-(乳酸基,草酸基)硼酸盐(LLOB)的生产
100.9g72.0%的乳酸水溶液(801mmol),49.59g硼酸(802mmol)和100.9g草酸二水合物(800mmol)被悬浮于惰性的(即干燥的和用保护性氩气充满的)1l容量的双层夹套反应器中的300ml(大约270g)甲苯中,该反应器安装有冷却器,迪安-斯达克水分离器,搅拌器和温度计。之后总共30.87g(418mmol)的纯碳酸锂被从测量球(Dosierbirne)按比例仔细添加同时良好搅拌。这导致了气体和泡沫的急剧形成。该固体附聚形成粘胶,然而其可以通过急剧搅拌悬浮。
泡沫形成停止后,加热油的温度在大约1小时内被升高到130℃。共沸形成的水按比例除去。总共10小时的回流后,总共96.7g的水被分离。
反应混合物被冷却到40℃并被倒到玻璃料上过滤。用甲苯洗涤无色固体两次,用戊烷洗涤一次。
细粉产物首先在室温下,之后在100℃下在旋转蒸发器上干燥。
产量:150.8g(=理论的97%)
分析:
实际的 | 理论的 | |
LiB | 5.054.9 | 5.165.16 |
δ11B(DMF):8.8ppm;另外在10.1和7.5ppm非常小数量(<5%)的具有硼转移的副产品。
热重量分析法(TGA):分解在大约270℃开始
实施例2:通过共沸干燥锂-(草酸基,水杨酸基)硼酸盐(LOSB)的生产
49.59g硼酸,100.9g草酸二水合物和110.45g水杨酸被悬浮于实施例1中描述的装置中的400ml二甲苯中,30.9g的碳酸锂分批添加,之后被回流6小时。在这段时间内78g水被分离。
反应混合物被冷却到50℃,过滤并且用甲苯洗涤不溶的无色固体之后用己烷洗涤。在室温油泵真空下干燥后获得了无色粉末。
产量:183.5g(=理论的95%)
δ11B(DMF):5.5ppm;(另外在7.4ppm(LOB,大约10%)和3.8(LSB,大约13%) 的杂质)
TGA:分解在大约210℃开始。
粗产物通过在THF/乙醚中重结晶精制。
实施例3:通过在旋转蒸发器上蒸发完全浓缩氢-(水杨酸基,草酸基)硼酸盐(HSOB)的生产
61.8g硼酸,138.1g水杨酸和126.1g草酸二水合物(各自1摩尔)在1l的圆底烧瓶中混合并在旋转蒸发器上在仅仅略微的减压(900mbar)下加热至110-115℃。大约15分钟后反应混合物完全液化,水开始蒸发掉。再过30分钟后压力进一步减小,此时混合物剧烈沸腾。随着趋向水分离结束,(从反应开始算大约2小时后),在20-30mbar的压力和125℃的油浴温度下反应物固化成坚硬的,在一些情况下有色的块。少量(几克)无色的,针形的升华物,其被确定为水杨酸,也可以观察到。
反应物被冷却并通过研杵(Mrser)和研钵(Pistill)研磨。现在白色的,粉末状的反应物在旋转蒸发器上在115-125℃和最终10mbar下再一次被干燥至衡重(2小时)。
产量:216g(92%)几乎无色的粉末
产物在碳酸异丙烯酯,γ-丁内酯,1,2-二甲氧基乙烷,丙酮和二甲基甲酰胺中极易溶解。
δ11B(1,2-DME):5.5ppm(主要产物)
7.6ppm(HOB,大约15%)
3.5ppm(氢-双(水杨酸基)硼酸盐,大约10%)
粗产物通过在丙酮/MTBE中重结晶精制。
Claims (8)
1.下列通式的硼螯合物
其中X是-C(R1R2)-或-C(R1R2)-C(=O)-,其中R1,R2彼此独立地表示H,具有1-5个碳原子的烷基,芳基或甲硅烷基,
或X表示在下列位置3到6具有最多达两个取代基S的1,2-芳基
其中S1,S2彼此独立地表示具有1-5个碳原子的烷基或氟,以及M+表示Li+,Na+,K+,Rb+,Cs+或[(R3R4R5R6)N]+或H+,
其中R3,R4,R5,R6彼此独立地表示H或烷基。
2.根据权利要求1的硼螯合物,特征在于硼螯合物是
锂-(乳酸基,草酸基)硼酸盐,
锂-(草酸基,水杨酸基)硼酸盐,
氢-(水杨酸基,草酸基)硼酸盐。
3.根据权利要求1或2之一的氢硼螯合物的生产方法,特征在于硼酸或硼氧化物与草酸和螯合物形成剂H-O-X-(CO)-O-H反应,其中X如权利要求1中定义。
4.根据权利要求1或2之一的碱金属硼螯合物盐或铵硼螯合物盐的生产方法,特征在于硼酸或硼氧化物与草酸,螯合物形成剂H-O-X-(CO)-O-H和氧化碱金属源或铵盐反应,其中X如权利要求1中定义。
5.根据权利要求1或2之一的氢硼螯合物作为有机合成中的超酸催化剂的应用。
6.根据权利要求1或2之一的锂硼螯合物盐作为电解池中的电解质的应用。
7.根据权利要求1或2之一的锂硼螯合物盐作为锂电池中的电解质的应用。
8.根据权利要求1或2之一的铵和铯硼螯合物盐在电解双层电容器中的应用。
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DE10108592A DE10108592C1 (de) | 2001-02-22 | 2001-02-22 | Borchelatkomplexe, Verfahren zu deren Herstellung sowie deren Verwendung |
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DE10108592C1 (de) * | 2001-02-22 | 2002-08-14 | Chemetall Gmbh | Borchelatkomplexe, Verfahren zu deren Herstellung sowie deren Verwendung |
US20030211383A1 (en) * | 2002-05-09 | 2003-11-13 | Lithium Power Technologies, Inc. | Primary lithium batteries |
US7572554B2 (en) | 2002-09-03 | 2009-08-11 | Quallion Llc | Electrolyte |
US6787268B2 (en) | 2002-09-03 | 2004-09-07 | Quallion Llc | Electrolyte |
US8524397B1 (en) | 2004-11-08 | 2013-09-03 | Quallion Llc | Battery having high rate and high capacity capabilities |
JP4022889B2 (ja) * | 2004-02-12 | 2007-12-19 | ソニー株式会社 | 電解液および電池 |
DE102004011522A1 (de) | 2004-03-08 | 2005-09-29 | Chemetall Gmbh | Leitsalze für Lithiumionenbatterien und deren Herstellung |
US20050274000A1 (en) * | 2004-06-14 | 2005-12-15 | The University Of Chicago | Methods for fabricating lithium rechargeable batteries |
JP5211422B2 (ja) * | 2005-01-24 | 2013-06-12 | セントラル硝子株式会社 | イオン性錯体の合成法 |
WO2008028943A1 (de) * | 2006-09-07 | 2008-03-13 | Chemetall Gmbh | Verwendung von boratsalzen |
JP5120596B2 (ja) * | 2006-11-22 | 2013-01-16 | ソニー株式会社 | 非水電解液、電気化学デバイスおよび非水二次電池 |
CN101796057B (zh) * | 2007-07-04 | 2013-07-17 | 凯密特尔有限责任公司 | 用于制备低酸的锂硼酸盐及由低酸的锂硼酸盐与氢化锂组成的混合物的方法 |
WO2009027541A2 (de) | 2007-08-30 | 2009-03-05 | Chemetall Gmbh | Sauerstoffverbindungen der borgruppe |
US9260456B2 (en) | 2011-11-14 | 2016-02-16 | Rockwood Lithium GmbH | Process for preparing metal difluorochelatoborates and use as battery electrolytes or additives in electrochemical cells |
EP2821408B1 (en) | 2013-07-02 | 2018-02-21 | Samsung SDI Co., Ltd. | Bis(hydroxyacetato)borate as electrolytes for Lithium secondary batteries |
CN104037452B (zh) * | 2014-06-18 | 2016-05-18 | 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 |
US11978597B2 (en) * | 2019-12-09 | 2024-05-07 | Panasonic Intellectual Property Management Co., Ltd. | Liquid component for electrolytic capacitor and electrolytic capacitor |
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US5886196A (en) * | 1996-01-12 | 1999-03-23 | Roche Vitamins Inc. | Method of catalyzing condensation reactions |
DE19829030C1 (de) * | 1998-06-30 | 1999-10-07 | Metallgesellschaft Ag | Lithium-bisoxalatoborat, Verfahren zu dessen Herstellung und dessen Verwendung |
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US7527899B2 (en) * | 2000-06-16 | 2009-05-05 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Electrolytic orthoborate salts for lithium batteries |
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DE50200970D1 (de) | 2004-10-14 |
US20100168476A1 (en) | 2010-07-01 |
DE10108592C1 (de) | 2002-08-14 |
WO2002068432A1 (de) | 2002-09-06 |
US20060142608A1 (en) | 2006-06-29 |
EP1379532B1 (de) | 2004-09-08 |
KR20030077642A (ko) | 2003-10-01 |
TWI316518B (en) | 2009-11-01 |
US20040063986A1 (en) | 2004-04-01 |
JP4076141B2 (ja) | 2008-04-16 |
EP1379532A1 (de) | 2004-01-14 |
CN1516702A (zh) | 2004-07-28 |
KR100902963B1 (ko) | 2009-06-15 |
CA2438611A1 (en) | 2002-09-06 |
JP2004534735A (ja) | 2004-11-18 |
US8168806B2 (en) | 2012-05-01 |
US7709663B2 (en) | 2010-05-04 |
CA2438611C (en) | 2010-01-26 |
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