CN106946921A - The method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate - Google Patents
The method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate Download PDFInfo
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- lithium
- acid
- oxalate
- oxalic acid
- boron
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 153
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 48
- -1 ethanedioic acid fluorine boron ester Chemical class 0.000 title claims abstract description 38
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 235000010338 boric acid Nutrition 0.000 title claims abstract description 32
- 229960002645 boric acid Drugs 0.000 title claims abstract description 32
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract description 28
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 238000011017 operating method Methods 0.000 claims abstract description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 229910015900 BF3 Inorganic materials 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- OYTBOLVDKAGZLT-UHFFFAOYSA-N methyl hydrogen carbonate trifluoroborane Chemical compound COC(O)=O.B(F)(F)F OYTBOLVDKAGZLT-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- UNWSCLFRWCYCHG-UHFFFAOYSA-N ethyl acetate;trifluoroborane Chemical compound FB(F)F.CCOC(C)=O UNWSCLFRWCYCHG-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- MEMUCXUKCBNISQ-UHFFFAOYSA-N acetonitrile;trifluoroborane Chemical compound CC#N.FB(F)F MEMUCXUKCBNISQ-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 2
- CBVJWBYNOWIOFJ-UHFFFAOYSA-N chloro(trimethoxy)silane Chemical compound CO[Si](Cl)(OC)OC CBVJWBYNOWIOFJ-UHFFFAOYSA-N 0.000 claims description 2
- QEHKWLKYFXJVLL-UHFFFAOYSA-N dichloro(dimethoxy)silane Chemical compound CO[Si](Cl)(Cl)OC QEHKWLKYFXJVLL-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims 1
- HMWVNKJRYWXJGS-UHFFFAOYSA-N C(C)(=O)OC=C.[C] Chemical compound C(C)(=O)OC=C.[C] HMWVNKJRYWXJGS-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- IPBRIJAYQVOWRM-UHFFFAOYSA-N trichloromethylsilicon Chemical compound [Si]C(Cl)(Cl)Cl IPBRIJAYQVOWRM-UHFFFAOYSA-N 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 31
- 239000000047 product Substances 0.000 description 10
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 9
- 229910013188 LiBOB Inorganic materials 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910013075 LiBF Inorganic materials 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 229910003910 SiCl4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 244000025254 Cannabis sativa Species 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910011140 Li2C2 Inorganic materials 0.000 description 1
- 229910010935 LiFOB Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PVAYNUSIECNKJO-UHFFFAOYSA-N [F].OC(=O)C(O)=O Chemical compound [F].OC(=O)C(O)=O PVAYNUSIECNKJO-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- MPDCKIORILZMHV-UHFFFAOYSA-N boric acid;lithium;oxalic acid Chemical compound [Li].OB(O)O.OC(=O)C(O)=O MPDCKIORILZMHV-UHFFFAOYSA-N 0.000 description 1
- RTNXKWDITPWBQM-UHFFFAOYSA-N carbonic acid;trifluoroborane Chemical compound OC(O)=O.FB(F)F RTNXKWDITPWBQM-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000005682 diethyl carbonates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Substances ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, including following operating procedure：(1) fluorochemical, boron-containing compound, radical compound containing oxalic acid, siliceous chlorine compound, solvent are mixed, reaction obtains intermediate；(2) by intermediate crystallizations；(3) after the intermediate, lithium-containing compound, solvent reaction after crystallizing, crystallize, dry, obtain difluorine oxalic acid boracic acid lithium；(4) after intermediate, lithium-containing compound after crystallizing, radical compound containing oxalic acid, solvent reaction, cool, filtering obtains solid and filtrate, solid is dried, obtains di-oxalate lithium borate；Filtrate is cooled, solid is collected by filtration, dries, obtains difluorine oxalic acid boracic acid lithium；In the step (1), boron element, oxalate, fluorine element, element silicon mol ratio are (1~2)：1：(3~9)：(0.5~1.5)；In the step (4), the mol ratio of intermediate, elemental lithium, oxalate after crystallization is (0.5~1)：(2~4)：(0.5~1).
Description
Technical field
The present invention relates to the synthesis technique of the electrolyte lithium salt used by lithium ion battery industry, and in particular to ethanedioic acid fluorine boron
The method that ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate.
Background technology
Electrolytic salt is the important component of lithium ion battery, performance of its research and development to lithium rechargeable battery
It is extremely important with developing.At present, the electrolyte for commonly using lithium ion battery is mainly lithium hexafluoro phosphate (LiPF6), double oxalic acid boric acid
Lithium (LiBOB), LiBF4 (LiBF4) etc..
LiPF6Heat endurance it is poor, easy deliquescence, and ethylene carbonate (EC) must be coordinated to use could be in Carbon anode
Surface forms stable solid electrolyte interface (SEI) film；And EC fusing point is 37 DEG C, cryogenic property can be impacted.
LiBF4It is relatively low as the charge-transfer resistance of lithium salts, make battery that there is relative usage LiPF6When more preferable cryogenic property, but to water
It is unstable, and be difficult to, in negative terminal surface formation SEI films, make the cycle performance of assembled battery poor.
The more di-oxalate lithium borate of Recent study (LiBOB), its electrochemical stability window is wide, high temperature resistant (thermal decomposition
Temperature is 302 DEG C), in pure propene carbonate (PC, fusing point is -49 DEG C), remain to form stabilization on Carbon anode surface
SEI films, it is environmentally friendly, but the solubility in the low solvent of dielectric constant (linear carbonate) is low, is formed in negative terminal surface
SEI membrane impedances it is too high, cause the low temperature capacity conservation rate and high-rate discharge capacity of battery poor.
The structure of di-oxalate lithium borate is as follows：
Difluorine oxalic acid boracic acid lithium (lithiumoxalyldifluoroborate) (also known as LiODFB, LiDFOB, LiFOB)
Proposed first by American scholar ShengShui Zhang, CAS No：409071-16-5, chemical formula LiBC2O4F2, molecular weight
143.77g/mol, 240 DEG C of decomposition temperature, referring to An unique lithium salt for the improved
electrolyte of Li-ion battery,ShengShui Zhang Electrochemistry
Communications8(2006)1423-1428.And refer to boron trifluoride and lithium oxalate reaction and purified through recrystallization.And
Contemplate the LiBF due to including half in molecular structure because of LiODFB4With the LiBOB of half, its property is also combined very well
LiBF4With the advantage of two kinds of lithium salts of LiBOB.Difluorine oxalic acid boracic acid lithium (LiODFB) has excellent high temperature performance, at -20 DEG C and
60 DEG C all have good chemical property；Copper foil of affluxion body and aluminium foil can be supported well；With good filming performance, energy
Enough help to form stabilization, low-impedance SEI films in the electrolytic solution, effectively inhibit PC that reduction, altogether insertion occur on graphite.
Because with above advantage, difluorine oxalic acid boracic acid lithium (LiODFB) has good application prospect in lithium ion battery.It is tied
Structure is as follows：
The typical preparation method of difluorine oxalic acid boracic acid lithium, mainly has Tsujioka.S et al. in European patent
With LiBF in EP1195834A24、CH(CF3)2OLi、H2C2O4, reaction medium is that carbonic ester or acetonitrile polar aprotic are molten
Agent is synthesized, unreacted LiBF4Up to more than 15%；Tsujioka.S et al. in European patent EP 1308449A2 with
H2C2O4、LiBF4And AlCl3Or SiCl4The synthesis of difluorine oxalic acid boracic acid lithium is carried out in dimethyl carbonate；HerzigT,
ShchreinerC,GerhardD,etal.JFluorineChem,2007,128:612-618 uses H2C2O4And LiBF4In carbon
In AlCl in acid esters or acetonitrile3Or SiCl4Synthesized under promoter effect, the above method, which exists, requires consersion unit high, anti-
Substantial amounts of HCl gas and silicon tetrafluoride gas are sent in answering, and is also easy to produce the accessory substance being not readily separated or reaction mixture not
The characteristics of molten thing filtering hardly possible.To overcome disadvantages mentioned above, ZhangSS.Electrochem.Commun, 2006,8:1423-1428；
Uno AKIRA, UchiyamaHatsuo, KawaswaYoshio.JP59-50018,1984) use BF3(CH2CH3)2With
Li2C2O4Synthesis difluorine oxalic acid boracic acid lithium product is carried out in DMC, technique is simple, with low cost, but has accessory substance LiBF4 simultaneously
Generate and be difficult to separate, cause reaction yield low.In recent years, Chinese publication " CN101643481A ",
The publication such as " CN102260282A ", " CN1031113396A ", " CN105399761A " is all similar with above-mentioned patent, obtains
LiODFB sample purities it is all relatively low, the accessory substance LiBF of generation4It is difficult to separate, it is necessary to just can serve as lithium ion after being purified
Electrolyte for batteries.Therefore find that a kind of cost is lower, to be more suitable for industrialized synthetic route aobvious particularly to produce LiODFB
It is important.
The preparation method of di-oxalate lithium borate mainly has WO2002068433 boric acid, lithium carbonate, oxalic acid under solvent-free
High temperature dehydration reacts, and temperature is higher, and the requirement to equipment is also higher, and WO1308449 proposes to use oxalic acid, LiBF4,
SiCl4The lower generation product of catalysis, has the disadvantage to produce substantial amounts of corrosive gas, CN1687081A by boric acid, lithium hydroxide, grass
Acid carries out ball milling mixing, has the disadvantage that mixing is uneven, CN101397305A is by diboron trioxide, oxalic acid hydrogen lithium, oxalic acid in toluene
Microwave reaction is carried out inside solution, having the disadvantage can not industrialized production.
The content of the invention
In order to solve prior art problem, the present invention provides a kind of ethanedioic acid fluorine boron ester and prepares difluorine oxalic acid boracic acid lithium and double
The method of Lithium bis (oxalate) borate, it is characterised in that including following operating procedure：
(1) fluorochemical, boron-containing compound, radical compound containing oxalic acid, siliceous chlorine compound, solvent are mixed, 0~
1~3h is reacted at 90 DEG C, intermediate ethanedioic acid fluorine boron ester is obtained, with following structure：
(2) by intermediate crystallizations；
(3) intermediate, lithium-containing compound after crystallizing, solvent react 1~3h at 30~60 DEG C, crystallize, and dry, obtain
Difluorine oxalic acid boracic acid lithium；
(4) intermediate, lithium-containing compound after crystallizing, radical compound containing oxalic acid, solvent react 5 at 85~95 DEG C~
7h, is cooled to 30~40 DEG C, filtering obtains solid and filtrate, solid is dried, obtains di-oxalate lithium borate；Filtrate is cooled
To -5~5 DEG C, solid is collected by filtration, dries, obtains difluorine oxalic acid boracic acid lithium；
In the step (1), boron element, oxalate, fluorine element, element silicon mol ratio are (1~2)：1：(3~9)：(0.5
~1.5)；In the step (4), the mol ratio of intermediate, elemental lithium, oxalate after crystallization is (0.5~1)：(2~4)：
(0.5~1).
In some embodiments, the radical compound containing oxalic acid is selected from oxalic acid hydrogen lithium, lithium oxalate, oxalic acid, double (trimethyls
Silicon) any one in oxalate.
In some embodiments, the fluorochemical is selected from fluoboric acid, lithium fluoride, boron trifluoride, boron trifluoride second
Nitrile, BFEE, boron trifluoride methylcarbonate, boron trifluoride ethyl acetate, boron trifluoride tetrahydrofuran, boron trifluoride
Any one in methyl ether complex compound.
In some embodiments, the boron-containing compound is selected from fluoboric acid, diboron trioxide, boron trifluoride, borax, three
Boron fluoride acetonitrile, boric acid, BFEE, boron trifluoride methylcarbonate, boron trifluoride ethyl acetate, boron trifluoride tetrahydrochysene
Any one in furans complex compound.
In some embodiments, the siliceous chlorine compound is selected from trichlorine silicon hydrogen, trim,ethylchlorosilane, dimethyl dichloro
Silane, trichloromethyl silane, silicon tetrachloride, methoxy base trichlorosilane, dimethoxy dichlorosilane, trimethoxy chlorosilane, four
Any one in methoxy silane.
In some embodiments, the solvent is selected from diethyl carbonate, dimethyl carbonate, propene carbonate, ethylene
Alkene ester, methyl ethyl carbonate, tetrahydrofuran, toluene, ethyl acetate, methyl acetate, acetonitrile, glycol dimethyl ether, diethylene glycol two
Any one in methyl ether, acetone, ether, Isosorbide-5-Nitrae-dioxane, dichloromethane, gamma-butyrolacton.
In some embodiments, lithium-containing compound is selected from lithium carbonate, lithium oxalate, lithium chloride, oxalic acid hydrogen lithium, hydroxide
Any one in lithium, lithium sulfate, lithium dihydrogen phosphate, lithium fluoride, lithia, lithium bromide, lithium amide, lithium diisopropylamine.
In some embodiments, in the step (2), the solvent of the crystallization is selected from diethyl carbonate, carbonic acid diformazan
Ester, propene carbonate, ethylene carbonate, methyl ethyl carbonate, tetrahydrofuran, toluene, ethyl acetate, methyl acetate, acetonitrile, second two
At least one in diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, ether, Isosorbide-5-Nitrae-dioxane, dichloromethane, gamma-butyrolacton
Kind.
In some embodiments, in the step (2), the temperature of the crystallization is -50-120 DEG C.
In some embodiments, the drying is vacuum drying, and vacuum drying time is 0-72h, and temperature is 30-230
DEG C, vacuum be -0.1-0.1MPa.
The present invention positive effect be：The present invention can obtain the difluoro grass of higher degree using step synthesis
Sour lithium borate and di-oxalate lithium borate, it is all the electric electrolyte lithium salt of lithium of superior performance, with larger implementary value and society
Can economic benefit.
Embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, the definition in this specification is defined.
Quality, concentration, temperature, time or other values or parameter are preferred with scope, preferred scope or a series of upper limits
During the Range Representation that value and lower preferable values are limited, this, which is appreciated that, specifically discloses by any range limit or preferred value
All scopes that any pairing with any range lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.
For example, 1-50 scope is understood to include selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,
19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、
44th, 45,46,47,48,49 or 50 any numeral, number combinatorics on words or subrange and all between above-mentioned integer
Fractional value, for example, 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8 and 1.9.It is specific to consider from scope on subrange
Interior any end points starts " the nested subrange " of extension.For example, exemplary range 1-50 nested subrange can include
1-10,1-20,1-30 and 1-40 on one direction, or 50-40,50-30,50-20 and 50-10 on other direction.
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification is selected.
Embodiment 1
Ethanedioic acid fluorine boron ester (OFB) is prepared using boron trifluoride methylcarbonate, oxalic acid and silicon tetrachloride reaction.
(1) dimethyl carbonate 300g (3.33mol) and boron trifluoride carbonic acid under stirring are added in 1000ml four-hole bottle
Dimethyl ester complex 290g (1.84mol), is warming up to 40 DEG C, adds oxalic acid 150g (1.66mol) after system is entirely molten, then
Insulation reaction 2 hours at 45 DEG C, cooling are added dropwise after 155g silicon tetrachlorides, completion of dropping；
(2) system is cooled to 25 DEG C of beginning crystallizations, continues to be cooled to 15 DEG C of precipitation mass crystallization solids, 15 DEG C of insulations 1 are small
When, filtering is rinsed with reaction dissolvent, is then dried in vacuo 2 hours at 30 DEG C, is obtained intermediate ethanedioic acid fluorine boron ester 320g,
Yield 92.4%；Ethanedioic acid fluorine boron ester has following structure：
Embodiment 2
Difluorine oxalic acid boracic acid lithium is prepared using ethanedioic acid fluorine boron ester (OFB) carbonic acid dimethyl ester complex and lithium fluoride reaction
(LiODFB)。
(1) the ethanedioic acid fluorine boron added in 500ml four-hole bottle in dimethyl carbonate 200g (2.2mol), embodiment 1
Ester 150g (0.72mol) and lithium fluoride 17.8g (0.68mol), stirring is warming up to 50 DEG C, reacts 2 hours, cooling；
(2) 40 DEG C are cooled to, a large amount of solids are separated out, continues to be cooled to 15 DEG C, is incubated 1 hour, filtering obtains LiODFB wet
Product；
(3) LiODFB wet products are dried in vacuo 8 hours at 150 DEG C, obtain LiODFB dry product 84g, and content 99.86% is received
Rate 85%, water content 54ppm, each metal ion in addition to lithium is less than or equal to 3ppm, reaches LITHIUM BATTERY quality.
Embodiment 3
Di-oxalate lithium borate is prepared using ethanedioic acid fluorine boron ester (OFB) carbonic acid dimethyl ester complex and lithium oxalate reaction
And difluorine oxalic acid boracic acid lithium (LiODFB) (LiBOB).
(1) the ethanedioic acid fluorine added in 1000ml four-hole bottle in 300g diethyl carbonates (2.53mol), embodiment 1
Boron ester 160g (0.77mol) and lithium oxalate 76.8g (0.75mol), stirring is warming up to 90 DEG C, reacts 6 hours, cooling；
(2) 35 DEG C are cooled to, LiBOB wet products and filtrate is filtrated to get；
(3) LiBOB wet products are dried in vacuo 8 hours at 150 DEG C, obtain LiBOB dry product 78.2g, and content 99.37% is received
Rate 53%, water content 35ppm, each metal ion in addition to lithium is less than or equal to 3ppm, reaches LITHIUM BATTERY quality；
(4) filtrate in step (2) is cooled to 0 DEG C after de- partial solvent, separates out solid LiODFB, then through filtering, drift
Wash, depressurize, in being dried in vacuo 8 hours at 150 DEG C, obtain LiODFB dry product 41.3g, content 99.45%, yield 38%, water contains
67ppm is measured, each metal ion in addition to lithium is less than or equal to 3ppm, reaches LITHIUM BATTERY quality.
Foregoing example is merely illustrative, some features for explaining the present invention.Appended claim is intended to
The scope as wide as possible being contemplated that is sought, and embodiments as presented herein is only the combination according to all possible embodiment
Selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the feature of the explanation present invention
Example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and it is not current
The possible equivalent or son considered is replaced, and these changes should also be interpreted to be wanted by appended right in the conceived case
Ask covering.
Claims (10)
1. the method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, it is characterised in that including following
Operating procedure：
(1) fluorochemical, boron-containing compound, radical compound containing oxalic acid, siliceous chlorine compound, solvent are mixed, at 0~90 DEG C
1~3h of lower reaction, obtains intermediate ethanedioic acid fluorine boron ester, with following structure：
(2) by intermediate crystallizations；
(3) intermediate, lithium-containing compound after crystallizing, solvent react 1~3h at 30~60 DEG C, crystallize, and dry, obtain difluoro
Lithium bis (oxalate) borate；
(4) intermediate, lithium-containing compound after crystallizing, radical compound containing oxalic acid, solvent react 5~7h at 85~95 DEG C, drop
Temperature is to 30~40 DEG C, and filtering obtains solid and filtrate, solid is dried, obtains di-oxalate lithium borate；Cool the filtrate to -5~
5 DEG C, solid is collected by filtration, dries, obtains difluorine oxalic acid boracic acid lithium；
In the step (1), boron element, oxalate, fluorine element, element silicon mol ratio are (1~2)：1：(3~9)：(0.5~
1.5)；In the step (4), the mol ratio of intermediate, elemental lithium, oxalate after crystallization is (0.5~1)：(2~4)：(0.5
~1).
2. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
It is characterised by, the radical compound containing oxalic acid is selected from appointing in oxalic acid hydrogen lithium, lithium oxalate, oxalic acid, double (trimethyl silicane) oxalates
Meaning is a kind of.
3. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
It is characterised by, the fluorochemical is selected from fluoboric acid, lithium fluoride, boron trifluoride, boron trifluoride acetonitrile, BFEE,
Appointing in boron trifluoride methylcarbonate, boron trifluoride ethyl acetate, boron trifluoride tetrahydrofuran, boron trifluoride methyl ether complex compound
Meaning is a kind of.
4. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
Be characterised by, the boron-containing compound be selected from fluoboric acid, diboron trioxide, boron trifluoride, borax, boron trifluoride acetonitrile, boric acid,
Appointing in BFEE, boron trifluoride methylcarbonate, boron trifluoride ethyl acetate, boron trifluoride tetrahydrofuran complex compound
Meaning is a kind of.
5. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
It is characterised by, the siliceous chlorine compound is selected from trichlorine silicon hydrogen, trim,ethylchlorosilane, dimethyldichlorosilane, trichloromethyl silicon
Appointing in alkane, silicon tetrachloride, methoxy base trichlorosilane, dimethoxy dichlorosilane, trimethoxy chlorosilane, tetramethoxy-silicane
Meaning is a kind of.
6. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
Be characterised by, the solvent be selected from diethyl carbonate, dimethyl carbonate, propene carbonate, ethylene carbonate, methyl ethyl carbonate,
Tetrahydrofuran, toluene, ethyl acetate, methyl acetate, acetonitrile, glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, ether, 1,
Any one in 4- dioxane, dichloromethane, gamma-butyrolacton.
7. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
It is characterised by, lithium-containing compound is selected from lithium carbonate, lithium oxalate, lithium chloride, oxalic acid hydrogen lithium, lithium hydroxide, lithium sulfate, biphosphate
Any one in lithium, lithium fluoride, lithia, lithium bromide, lithium amide, lithium diisopropylamine.
8. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
It is characterised by, in the step (2), the solvent of the crystallization is selected from diethyl carbonate, dimethyl carbonate, propene carbonate, carbon
Vinyl acetate, methyl ethyl carbonate, tetrahydrofuran, toluene, ethyl acetate, methyl acetate, acetonitrile, glycol dimethyl ether, diethyl two
At least one in diethylene glycol dimethyl ether, acetone, ether, Isosorbide-5-Nitrae-dioxane, dichloromethane, gamma-butyrolacton.
9. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
It is characterised by, in the step (2), the temperature of the crystallization is -50-120 DEG C.
10. the method that ethanedioic acid fluorine boron ester as claimed in claim 1 prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, its
It is characterised by, the drying is vacuum drying, vacuum drying time is 0-72h, temperature is 30-230 DEG C, vacuum is -0.1-
0.1MPa。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698611A (en) * | 2017-09-06 | 2018-02-16 | 浙江圣持新材料科技有限公司 | A kind of synthetic method of electrolyte lithium salt difluorine oxalic acid boracic acid lithium |
| CN108912155A (en) * | 2018-08-29 | 2018-11-30 | 苏州松湖新能源材料有限公司 | A kind of preparation method of difluoro oxalate borate |
| CN108912156A (en) * | 2018-09-20 | 2018-11-30 | 武汉海斯普林科技发展有限公司 | A kind of preparation method of di-oxalate lithium borate |
| CN109734735A (en) * | 2019-01-18 | 2019-05-10 | 武汉海斯普林科技发展有限公司 | A kind of purification process of difluorine oxalic acid boracic acid lithium |
| CN109796482A (en) * | 2019-01-30 | 2019-05-24 | 江苏长园华盛新能源材料有限公司 | The preparation method of di-oxalate lithium borate and LiBF4 |
| CN111393464A (en) * | 2020-05-09 | 2020-07-10 | 洛阳和梦科技有限公司 | Method for optimizing production of lithium bis (fluorooxalate) borate |
| CN112625055A (en) * | 2019-10-08 | 2021-04-09 | 杉杉新材料（衢州）有限公司 | Method for purifying lithium difluorooxalate borate and lithium tetrafluoroborate mixed lithium salt and application thereof |
| CN113549095A (en) * | 2021-07-13 | 2021-10-26 | 河北津宏化工有限公司 | Preparation process of lithium bis (oxalato) borate |
| CN114349775A (en) * | 2022-01-12 | 2022-04-15 | 王怀英 | Method for joint production of lithium bis (oxalato) borate and lithium difluoro (oxalato) borate |
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1308449A2 (en) * | 2001-11-05 | 2003-05-07 | Central Glass Company, Limited | Process for synthesizing ionic metal complex |
| CN101139352A (en) * | 2007-09-29 | 2008-03-12 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing difluorine oxalic acid boracic acid lithium |
| CN101643481A (en) * | 2009-08-28 | 2010-02-10 | 张家港市国泰华荣化工新材料有限公司 | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate |
| CN102070661A (en) * | 2011-01-25 | 2011-05-25 | 李荐 | Preparation method of high-purity lithium oxalyldifluoroborate |
| CN102702243A (en) * | 2012-06-12 | 2012-10-03 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
| CN102826563A (en) * | 2012-09-07 | 2012-12-19 | 广州天赐高新材料股份有限公司 | Preparation method of high-purity lithium tetrafluoroborate |
| CN103733416A (en) * | 2011-08-03 | 2014-04-16 | 中央硝子株式会社 | Method for producing lithium tetrafluoroborate solution |
| TW201434849A (en) * | 2012-12-21 | 2014-09-16 | Central Glass Co Ltd | Production method for ionic metal complex salt using organic compound as ligand |
| CN104291347A (en) * | 2014-02-17 | 2015-01-21 | 多氟多化工股份有限公司 | Preparation method of lithium tetrafluoroborate |
| CN104334564A (en) * | 2012-05-30 | 2015-02-04 | 中央硝子株式会社 | Purified metal complex having oxalic acid as ligand, and method for producing purified solution of said metal complex in non-aqueous solvent |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
| CN104628754A (en) * | 2015-02-01 | 2015-05-20 | 湖南省正源储能材料与器件研究所 | Preparation method of lithium ion battery electrolyte salt LiODFB (lithium oxalyldifluroborate) |
| CN105293512A (en) * | 2014-11-11 | 2016-02-03 | 汕头市金光高科有限公司 | Direct synthesis method of lithium tetrafluoroborate |
-
2017
- 2017-04-07 CN CN201710225619.6A patent/CN106946921A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1308449A2 (en) * | 2001-11-05 | 2003-05-07 | Central Glass Company, Limited | Process for synthesizing ionic metal complex |
| CN101139352A (en) * | 2007-09-29 | 2008-03-12 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing difluorine oxalic acid boracic acid lithium |
| CN101643481A (en) * | 2009-08-28 | 2010-02-10 | 张家港市国泰华荣化工新材料有限公司 | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate |
| CN102070661A (en) * | 2011-01-25 | 2011-05-25 | 李荐 | Preparation method of high-purity lithium oxalyldifluoroborate |
| CN103733416A (en) * | 2011-08-03 | 2014-04-16 | 中央硝子株式会社 | Method for producing lithium tetrafluoroborate solution |
| CN104334564A (en) * | 2012-05-30 | 2015-02-04 | 中央硝子株式会社 | Purified metal complex having oxalic acid as ligand, and method for producing purified solution of said metal complex in non-aqueous solvent |
| CN102702243A (en) * | 2012-06-12 | 2012-10-03 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
| CN102826563A (en) * | 2012-09-07 | 2012-12-19 | 广州天赐高新材料股份有限公司 | Preparation method of high-purity lithium tetrafluoroborate |
| TW201434849A (en) * | 2012-12-21 | 2014-09-16 | Central Glass Co Ltd | Production method for ionic metal complex salt using organic compound as ligand |
| CN104291347A (en) * | 2014-02-17 | 2015-01-21 | 多氟多化工股份有限公司 | Preparation method of lithium tetrafluoroborate |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
| CN105293512A (en) * | 2014-11-11 | 2016-02-03 | 汕头市金光高科有限公司 | Direct synthesis method of lithium tetrafluoroborate |
| CN104628754A (en) * | 2015-02-01 | 2015-05-20 | 湖南省正源储能材料与器件研究所 | Preparation method of lithium ion battery electrolyte salt LiODFB (lithium oxalyldifluroborate) |
Non-Patent Citations (2)
| Title |
|---|
| JIA GUO-FENG ET AL.: ""Synthesis and Structural Characterizations of a New Lithium Salt for Lithium-ion Batteries"", 《CHINESE J. STRUCT. CHEM》 * |
| V ARAVINDAN ET AL.: ""Effect of aging on the ionic conductivity of polyvinylidenefluoride–hexafluoropropylene (PVdF–HFP) membrane impregnated with different lithium salts"", 《INDIAN J PHYS》 * |
Cited By (10)
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| CN112625055A (en) * | 2019-10-08 | 2021-04-09 | 杉杉新材料（衢州）有限公司 | Method for purifying lithium difluorooxalate borate and lithium tetrafluoroborate mixed lithium salt and application thereof |
| CN111393464A (en) * | 2020-05-09 | 2020-07-10 | 洛阳和梦科技有限公司 | Method for optimizing production of lithium bis (fluorooxalate) borate |
| CN113549095A (en) * | 2021-07-13 | 2021-10-26 | 河北津宏化工有限公司 | Preparation process of lithium bis (oxalato) borate |
| CN114349775A (en) * | 2022-01-12 | 2022-04-15 | 王怀英 | Method for joint production of lithium bis (oxalato) borate and lithium difluoro (oxalato) borate |
| CN116813655A (en) * | 2023-08-28 | 2023-09-29 | 江苏华盛锂电材料股份有限公司 | Preparation process of lithium difluoro oxalate borate |
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Application publication date: 20170714 |