CN106749361A - A kind of high efficiency preparation method of high-purity difluorine oxalic acid boracic acid lithium - Google Patents
A kind of high efficiency preparation method of high-purity difluorine oxalic acid boracic acid lithium Download PDFInfo
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- CN106749361A CN106749361A CN201611116619.4A CN201611116619A CN106749361A CN 106749361 A CN106749361 A CN 106749361A CN 201611116619 A CN201611116619 A CN 201611116619A CN 106749361 A CN106749361 A CN 106749361A
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- boron trifluoride
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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 132
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229960002645 boric acid Drugs 0.000 title claims abstract description 15
- 235000010338 boric acid Nutrition 0.000 title claims abstract description 15
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 claims abstract description 8
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002288 cocrystallisation Methods 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 14
- -1 oxalic acid hydrogen Chemical class 0.000 claims description 10
- 229910015900 BF3 Inorganic materials 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- 210000003298 dental enamel Anatomy 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910015844 BCl3 Inorganic materials 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 229910006109 GeBr4 Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910003676 SiBr4 Inorganic materials 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 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
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- FZUIUHFZKOQKHQ-UHFFFAOYSA-N diethyl carbonate;trifluoroborane Chemical compound FB(F)F.CCOC(=O)OCC FZUIUHFZKOQKHQ-UHFFFAOYSA-N 0.000 claims description 3
- UNWSCLFRWCYCHG-UHFFFAOYSA-N ethyl acetate;trifluoroborane Chemical compound FB(F)F.CCOC(C)=O UNWSCLFRWCYCHG-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- VJHDVMPJLLGYBL-UHFFFAOYSA-N tetrabromogermane Chemical compound Br[Ge](Br)(Br)Br VJHDVMPJLLGYBL-UHFFFAOYSA-N 0.000 claims description 3
- ZFCQDZKQFPEDJE-UHFFFAOYSA-N thiolane 1,1-dioxide trifluoroborane Chemical compound S1(=O)(=O)CCCC1.B(F)(F)F ZFCQDZKQFPEDJE-UHFFFAOYSA-N 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 229910015446 B(OCH3)3 Inorganic materials 0.000 claims description 2
- 229910015845 BBr3 Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910006113 GeCl4 Inorganic materials 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- VWCIBMAHWVHJJM-UHFFFAOYSA-N butyl acetate trifluoroborane Chemical compound C(C)(=O)OCCCC.B(F)(F)F VWCIBMAHWVHJJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012611 container material Substances 0.000 claims description 2
- OYTBOLVDKAGZLT-UHFFFAOYSA-N methyl hydrogen carbonate trifluoroborane Chemical compound COC(O)=O.B(F)(F)F OYTBOLVDKAGZLT-UHFFFAOYSA-N 0.000 claims description 2
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 claims description 2
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 claims description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- 230000005311 nuclear magnetism Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 238000013019 agitation Methods 0.000 description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 9
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 9
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000002913 oxalic acids Chemical class 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 229910011140 Li2C2 Inorganic materials 0.000 description 3
- 229910013075 LiBF Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MMBNZCXOOIYEQW-UHFFFAOYSA-L C(C(=O)[O-])(=O)[O-].[F].[F].[Li+].[Li+] Chemical compound C(C(=O)[O-])(=O)[O-].[F].[F].[Li+].[Li+] MMBNZCXOOIYEQW-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KWGASIUWELSTHP-UHFFFAOYSA-N boron;phenol Chemical class [B].OC1=CC=CC=C1 KWGASIUWELSTHP-UHFFFAOYSA-N 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000008096 xylene Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of high-purity difluorine oxalic acid boracic acid lithium（LiODFB）High efficiency preparation method.First with Li2CO3And H2C2O4·2H2O is raw material, synthesizes a kind of high-crystallinity, high activity with lithium oxalate and oxalic acid hydrogen lithium as the needle-like mixed crystal A of principal phase cocrystallization；Mixed crystal A is added in the closed container equipped with organic solvent, BF is then added3X complex compounds, at least one in oxamides, oxamic acid, anhydrous oxalic acid, ammonium oxalate, and a certain amount of initiator, persistently stirring obtain milky solution B in 30 minutes, are filtrated to get clear transparent solutions C；Solution C is removed into solvent under uniform temperature and pressure, the LiODFB products of purity more than 99% are obtained.Recrystallized by organic solvent and once remove impurity, obtain more than 99.9% high-purity LiODFB products.The preparation method, the LiODFB products of purity more than 99% can be directly obtained by synthetic reaction.Avoid low yield caused by repeated recrystallize, high cost, cycle shortcoming long.And the preparation method is simple, easy to operate, cycle is short, it is easy to industrialization production, with very strong application prospect.
Description
Technical field
The present invention relates to a kind of lithium ion battery electrolyte lithium salt difluorine oxalic acid boracic acid lithium（LiODFB）Preparation newly side
Method, belongs to new energy materialses and preparing technical field.
Background technology
Difluorine oxalic acid boracic acid lithium（LiODFB）As new lithium salts by since reporting first, because its combination property is superior,
Causing the extensive concern of researcher nearly ten years, reported by numerous studies, be considered as always most possibly to replace LiPF6's
New lithium salts.Existing research is concentrated mainly in the stability and chemical property of LiODFB, and the preparation on LiODFB
And the report of purifying is less, the research of particularly industrialized scale has no relevant report.Although the excellent performance of LiODFB, so
And for various reasons, including：Cost of material is high, and synthesis technique complexity is difficult to control to, accessory substance LiBF4Influence be difficult to disappear
Remove, separating-purifying difficulty is big, causes yield more low, causes the scale of LiODFB, and industrialization process is hindered.Wherein most
Main reasons is that in building-up process, accessory substance LiBF4Amount it is more, it is difficult to eliminate, need to can just obtain pure through repeated recrystallize
Spend satisfactory product.
Report in terms of LiODFB synthesis, 2002, patent US6485868B1 reported the synthesis side of LiODFB
Method, with LiBF4、CH(CF3)2OLi and H2C2O4It is raw material, is situated between as reaction with carbonic ester or acetonitrile (AN) polar aprotic solution
Matter, but products therefrom purity is relatively low, LiBF4Content is more than 15%.2006, Zhang, C, C etc. were in document
Reported with BFEE and oxalic acid in Electrochemistry Communications 8 (2006) 1423-1428
Lithium (mol ratio 1:1) it is raw material, in dimethyl carbonate（DMC）Middle reaction, is prepared for LiODFB crude products, using DMC or other
Aprotic solvent carries out repeated recrystallize to LiODFB crude products can be obtained compared with net product, but this method yield is relatively low and is also easy to produce not
Molten impurity, production cost is higher.2007, Herzig etc. was in document Journal of Fluorine Chemistry 128
Report uses LiBF in (2007) 612-6184Reacted in DMC or AN with anhydrous oxalic acid, add AlCl3Or SiCl4Catalysis is anti-
Should, LiODFB crude products are obtained, yield is 86.3%.But because the reaction need to be carried out at low temperature, the raw material Li BF for using4Valency
Lattice are higher, and still need to carry out repeated recrystallize just to obtain purer LiODFB products, so application value is little.2013,
Li etc. reports the synthetic method of LiODFB in document Electrochimica Acta 91 (2013) 282-292, with three
Fluorination borate ether, lithium oxalate and diethyl carbonate（DEC）(mol ratio 2:1:4) for raw material carries out compound experiment, equimolar is obtained
The LiODFB and LiBF of ratio4, repeated recrystallize is carried out by DMC（More than 7 times）Obtain purity LiODFB products higher, but this
The yield of method is relatively low, and direct yield only has 10%, with high costs, it is difficult to large-scale promotion application.
Existing disclosure is reported in that raw material lithium salts selection aspect is main to use lithium oxalate, the LiBF4 to be carried out instead for raw material
Should synthesize, there is larger defect.The present invention bases oneself upon actual conditions prepared by existing LiODFB, starts with from synthesis material, closes
It is the needle-like mixed crystal of principal phase cocrystallization into a kind of lithium oxalate and oxalic acid hydrogen lithium, effectively reduces by-product in building-up process
Thing LiBF4Growing amount, make it below 1% level, it is to avoid LiODFB and LiBF4Difficulty in terms of separating-purifying.Obtain
LiODFB crude products only need once to recrystallize the purity that can reach more than 99.9%.
The content of the invention
It is an object of the invention to provide a kind of preparation method that can be prepared high-purity and LiODFB in high yield can be kept.
To achieve the above object, the high efficiency preparation method of a kind of high-purity difluorine oxalic acid boracic acid lithium of the invention, including it is as follows
Step：
The first step:Li is used first2CO3And H2C2O4·2H2O is raw material, synthesize a kind of high-crystallinity, high activity with lithium oxalate and
Oxalic acid hydrogen lithium is the needle-like mixed crystal A of principal phase cocrystallization；
Second step：Mixed crystal A is added in the closed container equipped with organic solvent, BF is then added3X complex compounds, grass
At least one in acid amides, oxamic acid, anhydrous oxalic acid, ammonium oxalate, and a certain amount of initiator, persistently stir 30 minutes, obtain
To milky solution B, clear transparent solutions C is filtrated to get；
3rd step：By solution C at 60 to 150 DEG C, solvent is removed under -0.05 to -0.1MPa, obtain purity 99% or so
LiODFB products.Removal of impurities is recrystallized by organic solvent, you can obtain more than 99.9% high-purity LiODFB products.
The use Li mentioned in the first step in a kind of high efficiency preparation method of above-mentioned high-purity difluorine oxalic acid boracic acid lithium2CO3With
H2C2O4·2H2O carries out synthetic reaction for raw material, its mol ratio n=(Li2CO3Molal quantity)/(H2C2O4·2H2O molal quantitys),
0.4 < n < 1.2。
The BF mentioned in second step in a kind of high efficiency preparation method of above-mentioned high-purity difluorine oxalic acid boracic acid lithium3X is complexed
Thing is boron trifluoride diethyl carbonate, boron trifluoride acetonitrile, boron trifluoride tetrahydrofuran, boron trifluoride methylcarbonate, trifluoro
Change boron gamma-butyrolacton, boron trifluoride ethyl acetate, BFEE, boron trifluoride methyl ether, boron trifluoride sulfolane, trifluoro
Change any one in boron butyl acetate, boron trifluoride glycol dimethyl ether, boron trifluoride phenol.
Mentioned in second step in a kind of high efficiency preparation method of above-mentioned high-purity difluorine oxalic acid boracic acid lithium use it is closed
Container material quality is stainless steel, polypropylene, glass, titanium alloy, any one in enamel and polytetrafluoroethylene (PTFE).
The initiation of the addition mentioned in second step in a kind of high efficiency preparation method of above-mentioned high-purity difluorine oxalic acid boracic acid lithium
Agent, is AlCl3、FeCl3、LiCl、CuCl、SnCl4、CCl4、AlBr3、SiBr4、GeBr4、TiCl4、BCl3、SiCl4、GeCl4、
TiBr4、 BBr3、B(OCH3)3In at least one.
The present invention has advantages below：The preparation method, first by Li2CO3And H2C2O4Synthesis includes Li2C2O4With
LiHC2O4Mixing presoma crystalline solid, the mixed crystallization body has well-regulated acicular texture, than traditional use Li2C2O4Powder
End, LiHC2O4Powder or the mix powder of the two do that raw material is more beneficial, and main cause should be and hybrid mode and crystallization
Degree is relevant, and LiBF can be particularly greatly reduced4Growing amount.Can directly be obtained by the synthetic reaction purity 99% with
On LiODFB products, accessory substance LiBF4Can be controlled in the level less than 1%, it is only necessary to once recrystallization can obtain 99.9% with
On high-purity LiODFB products.Avoid because of repeated recrystallize purification ＆ isolation LiODFB and LiBF4The yield for causing is low, cost
Height, cycle shortcoming long.And the preparation method is simple, easy to operate, cycle is short, it is easy to industrialization production, with very strong application
Prospect.
Brief description of the drawings
Fig. 1 is with Li2CO3And H2C2O4·2H2O is the XRD of the mixed crystal A of Material synthesis
The crystal shape photo of the mixed crystal A of Fig. 2 synthesis
The nuclear-magnetism of the LiODFB products that Fig. 3 is directly prepared by synthetic reaction11B is composed
The nuclear-magnetism of the LiODFB products that Fig. 4 is once obtained afterwards using dimethyl carbonate recrystallization11B is composed.
Specific embodiment
Make one to the present invention below to describe in detail, it is described to be explanation of the invention and non-limiting.
Embodiment 1：
50g Li are weighed first2CO3With 103g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid hydrogen radical
Mixed crystal A, its XRD as shown in figure 1, through material phase analysis mixed crystal A mainly include Li2C2O4And LiHC2O4Two kinds of things
Phase structure, corresponds respectively to standard card number：24-0646 and 49-1209.Fig. 2 shows the pattern after mixed crystal A crystallizations
Photo, has well-regulated acicular texture.Mixed crystal A is added in the glass container equipped with solvent dimethyl carbonate, then
Addition 230g boric carbonic acid dimethyl ester complex trifluorides, 66 g anhydrous oxalic acids and 64 g AlCl3, magnetic agitation obtains for 30 minutes
Milky solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 120 DEG C, solvent is removed under -0.1MPa, obtained
To LiODFB products, tested through nuclear-magnetism, it is 99% to calculate its purity, as shown in Figure 2.One is recrystallized by solvent dimethyl carbonate
After secondary, high-purity LiODFB products are obtained, tested through nuclear-magnetism, it is more than 99.9% to calculate its purity, as shown in Figure 3.Taken by karr
Not water tester carries out moisture content test, measures its water content for 60 ppm.
Embodiment 2：
110g Li are weighed first2CO3With 243g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid hydrogen
The mixed crystal A of root；Mixed crystal A is added in the polytetrafluoroethylcontainer container equipped with diethyl carbonate solvent, then addition
496 g boron trifluoride diethyl carbonate complex compounds, 152 g anhydrous oxalic acids and 142 g SiCl4, magnetic agitation obtains for 30 minutes
Milky solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 100 DEG C, solvent is removed under -0.05MPa,
LiODFB products are obtained, is tested through nuclear-magnetism, it is 99% to calculate its purity.After being recrystallized once by solvent diethyl carbonate, obtain
High-purity LiODFB products, test through nuclear-magnetism, and it is more than 99.9% to calculate its purity.Water-filling is entered by karl Fischer moisture tester
Part test, measures its water content for 108 ppm.
Embodiment 3：
100g Li are weighed first2CO3With 346g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid hydrogen
The mixed crystal A of root；Mixed crystal A is added in the stainless steel closed container equipped with tetrahydrofuran solvent, 347 are then added
G boron trifluoride tetrahydrofuran complex compounds, 104 g anhydrous oxalic acids and 161 g TiCl4, it is molten that magnetic agitation obtains emulsus in 30 minutes
Liquid B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 105 DEG C, solvent is removed under -0.07MPa, obtained
LiODFB products, test through nuclear-magnetism, and it is 96.8% to calculate its purity.After being recrystallized once by solvent ethyl acetate, obtain high-purity
LiODFB products, test through nuclear-magnetism, and it is more than 99.5% to calculate its purity.Moisture content survey is carried out by karl Fischer moisture tester
Examination, measures its water content for 300 ppm.
Embodiment 4：
73.8g Li are weighed first2CO3With 132.2g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid
The mixed crystal A of hydrogen radical；Mixed crystal A is added in the enamel closed container equipped with butyl acetate solvent, then addition
364.7 g boron trifluoride butyl acetate complex compounds, 99 g anhydrous oxalic acids, 38.5 g BCl3With 53g AlBr3, magnetic agitation 30
Minute obtains milky solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 65 DEG C, removed under -0.08MPa
Solvent is removed, LiODFB products are obtained, tested through nuclear-magnetism, it is 98.5% to calculate its purity.Recrystallized once by solvent ethyl acetate
Afterwards, high-purity LiODFB products are obtained, is tested through nuclear-magnetism, it is more than 99.9% to calculate its purity.By karl Fischer moisture tester
Moisture content test is carried out, its water content is measured for 80 ppm.
Embodiment 5：
40g Li are weighed first2CO3With 162g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid hydrogen radical
Mixed crystal A；Mixed crystal A is added in the polypropylene closed container equipped with glycol dinitrate ether solvents, then addition
425g boron trifluoride glycol dinitrate ether complexes, 83 g anhydrous oxalic acids and 80 g trimethylborate B (OCH3)3, magnetic agitation 30
Minute obtains milky solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 75 DEG C, removed under -0.06MPa
Solvent is removed, LiODFB products are obtained, tested through nuclear-magnetism, it is 98.9% to calculate its purity.Recrystallized once by solvent ethyl acetate
Afterwards, high-purity LiODFB products are obtained, is tested through nuclear-magnetism, it is more than 99.9% to calculate its purity.By karl Fischer moisture tester
Moisture content test is carried out, its water content is measured for 85 ppm.
Embodiment 6：
150g Li are weighed first2CO3With 256g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid hydrogen
The mixed crystal A of root；Mixed crystal A is added in the titanium alloy closed container equipped with ethyl acetate solvent, then addition
570g boron trifluoride ethyl acetate complex compounds, 164 g anhydrous oxalic acids and 135 g trimethylborates, magnetic agitation are obtained for 30 minutes
Milky solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 135 DEG C, solvent is removed under -0.9MPa, obtained
To LiODFB products, tested through nuclear-magnetism, it is 98.8% to calculate its purity.After being recrystallized once by solvent ethyl acetate, obtain high
Pure LiODFB products, test through nuclear-magnetism, and it is more than 99.9% to calculate its purity.Moisture content is carried out by karl Fischer moisture tester
Test, measures its water content for 110 ppm.
Embodiment 7：
150g Li are weighed first2CO3With 256g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid hydrogen
The mixed crystal A of root；Mixed crystal A is added in the glass closed container equipped with phenolic solvent, then addition 680g trifluoros
Change boron phenol complexes, 132g oxamides, 270 g SiBr4With 39.5g CuCl, magnetic agitation obtains milky solution in 30 minutes
B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 95 DEG C, solvent is removed under -0.1MPa, obtain LiODFB products
Product, test through nuclear-magnetism, and it is 94.1% to calculate its purity.After being recrystallized once by solvent toluene, high-purity LiODFB products are obtained,
Tested through nuclear-magnetism, it is more than 99.5% to calculate its purity.Moisture content test is carried out by karl Fischer moisture tester, its water is measured
Part content is 420 ppm.
Embodiment 8：
73.8g Li are weighed first2CO3With 150 g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid
The mixed crystal A of hydrogen radical；Mixed crystal A is added in the polytetrafluoroethylene (PTFE) closed container equipped with acetonitrile solvent, then addition
336g boron trifluoride acetonitrile complex compounds, 88 g ammonium oxalate, 140 g AlBr3With 20g LiCl, magnetic agitation obtains breast in 30 minutes
Shape solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 85 DEG C, solvent is removed under -0.85MPa, obtained
LiODFB products, test through nuclear-magnetism, and it is 98.5% to calculate its purity.After being recrystallized once by solvent acetonitrile, obtain high-purity
LiODFB products, test through nuclear-magnetism, and it is more than 99.9% to calculate its purity.Moisture content survey is carried out by karl Fischer moisture tester
Examination, measures its water content for 110 ppm.
Embodiment 9：
73.8 g Li are weighed first2CO3With 189 g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid
The mixed crystal A of hydrogen radical；Mixed crystal A is added in the polypropylene closed container equipped with sulfolane solvent, then addition
346g boron trifluoride sulfolane complex compounds, 121 g oxamic acid, 195 g TiBr4With 69.3g FeCl3, magnetic agitation 30 minutes must
To milky solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 110 DEG C, removed under -0.65MPa molten
Agent, obtains LiODFB products, is tested through nuclear-magnetism, and it is 98.5% to calculate its purity.After being recrystallized once by solvent ethyl acetate,
High-purity LiODFB products are obtained, is tested through nuclear-magnetism, it is more than 99.7% to calculate its purity.Entered by karl Fischer moisture tester
Water-filling part test, measures its water content for 110 ppm.
Embodiment 10：
73.8 g Li are weighed first2CO3With 251g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid
The mixed crystal A of hydrogen radical；Mixed crystal A is added in the enamel closed container equipped with methyl ether solvent, then 218 g tri- of addition
Boron fluoride methyl ether complex compound, 105 g anhydrous oxalic acids and 390 g GeBr4, magnetic agitation obtains milky solution B in 30 minutes；Filtering
Fall insoluble matter, obtain clear transparent solutions C；By solution C at 115 DEG C, solvent is removed under -0.75MPa, obtains LiODFB products,
Tested through nuclear-magnetism, it is 96.9% to calculate its purity.After being recrystallized once by solvent dimethyl carbonate, obtain high-purity LiODFB and produce
Product, test through nuclear-magnetism, and it is more than 99.0% to calculate its purity.Moisture content test is carried out by karl Fischer moisture tester, it is measured
Water content is 330 ppm.
Embodiment 11：
73.8 g Li are weighed first2CO3With 220g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid
The mixed crystal A of hydrogen radical；Mixed crystal A is added in the stainless steel closed container equipped with gamma-butyrolacton solvent, then addition
278 g boron trifluoride gamma-butyrolacton complex compounds, 135 g ammonium oxalate, 158 g BBr3、52g SnCl4With 8.5g LiCl, magnetic force
Stirring obtains milky solution B in 30 minutes；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 125 DEG C ,-
Solvent is removed under 0.55MPa, LiODFB products are obtained, tested through nuclear-magnetism, it is 98.9% to calculate its purity.By solvent γ-Ding Nei
After ester is recrystallized once, high-purity LiODFB products are obtained, tested through nuclear-magnetism, it is more than 99.9% to calculate its purity.Taken by karr
Not water tester carries out moisture content test, measures its water content for 190 ppm.
Embodiment 12：
73.8 g Li are weighed first2CO3With 110 g H2C2O4·2H2O is raw material, and synthesis includes Li ions, oxalate and oxalic acid
The mixed crystal A of hydrogen radical；Mixed crystal A is added in the titanium alloy closed container equipped with ether solvent, then 215 g of addition
Boron trifluoride etherate, 68 g anhydrous oxalic acids, 80 g CCl4With 52.6g SiCl4, magnetic agitation obtains emulsus in 30 minutes
Solution B；Insoluble matter is filtered out, clear transparent solutions C is obtained；By solution C at 145 DEG C, solvent is removed under -0.5MPa, obtained
LiODFB products, test through nuclear-magnetism, and it is 95% to calculate its purity.After being recrystallized once by solvent xylene, obtain high-purity
LiODFB products, test through nuclear-magnetism, and it is more than 98.9% to calculate its purity.Moisture content survey is carried out by karl Fischer moisture tester
Examination, measures its water content for 230 ppm.
Claims (5)
1. a kind of high efficiency preparation method of high-purity difluorine oxalic acid boracic acid lithium, comprises the steps:
The first step:With Li2CO3And H2C2O4·2H2O is raw material, synthesizes a kind of high-crystallinity, high activity with lithium oxalate and oxalic acid hydrogen
Lithium is the needle-like mixed crystal A of principal phase cocrystallization；
Second step：Mixed crystal A is added in the closed container equipped with organic solvent, BF is then added3X complex compounds, grass
At least one in acid amides, oxamic acid, anhydrous oxalic acid, ammonium oxalate, and a certain amount of initiator, persistently stir 30 minutes, obtain
To milky solution B, clear transparent solutions C is filtrated to get；
3rd step：By solution C at 60 DEG C to 150 DEG C, solvent is removed under -0.05 to -0.1MPa, obtain purity 99% or so
LiODFB products；Recrystallized by organic solvent and once remove impurity, you can obtain more than 99.9% high-purity LiODFB products.
2. the high efficiency preparation method of a kind of high-purity difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that：Institute
The use Li mentioned in the first step stated2CO3And H2C2O4·2H2O carries out synthetic reaction for raw material, its mol ratio n=(Li2CO3Rub
That number)/(H2C2O4·2H2O molal quantitys), 0.4< n < 1.2.
3. the high efficiency preparation method of a kind of high-purity difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that：Institute
The BF mentioned in the second step stated3X complex compounds, are boron trifluoride diethyl carbonate, boron trifluoride acetonitrile, boron trifluoride tetrahydrochysene
Furans, boron trifluoride methylcarbonate, boron trifluoride gamma-butyrolacton, boron trifluoride ethyl acetate, BFEE, trifluoro
In change boron methyl ether, boron trifluoride sulfolane, boron trifluoride butyl acetate, boron trifluoride glycol dimethyl ether and boron trifluoride phenol
Any one.
4. the high efficiency preparation method of a kind of high-purity difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that：Institute
The closed container material for using mentioned in the second step stated is stainless steel, polypropylene, titanium alloy, glass, enamel and polytetrafluoro
Any one in ethene.
5. the high efficiency preparation method of a kind of high-purity difluorine oxalic acid boracic acid lithium according to claim 1, it is characterised in that：Institute
The initiator of the addition mentioned in the second step stated, is AlCl3、FeCl3、LiCl、CuCl、SnCl4、CCl4、AlBr3、SiBr4、
GeBr4、TiCl4、BCl3、SiCl4、GeCl4、TiBr4、 BBr3、B(OCH3)3In at least one.
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| 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 |
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| CN107226821A (en) * | 2017-06-12 | 2017-10-03 | 上海如鲲新材料有限公司 | A kind of synthesis technique that difluorine oxalic acid boracic acid lithium is prepared with di-oxalate lithium borate |
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| CN112479871A (en) * | 2020-11-24 | 2021-03-12 | 万华化学集团股份有限公司 | Method for synthesizing geranic acid from methyl heptenone |
| CN112479871B (en) * | 2020-11-24 | 2023-07-14 | 万华化学集团股份有限公司 | Method for synthesizing fragrant folic acid from methyl heptenone |
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