CN104557995B - Preparation method of lithium oxalyldifluoroborate - Google Patents
Preparation method of lithium oxalyldifluoroborate Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 229960002645 boric acid Drugs 0.000 claims description 12
- 235000010338 boric acid Nutrition 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 10
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 4
- -1 difluoro lithium Chemical compound 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 4
- 239000003125 aqueous solvent Substances 0.000 abstract 2
- 230000035484 reaction time Effects 0.000 abstract 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 229910003002 lithium salt Inorganic materials 0.000 description 10
- 159000000002 lithium salts Chemical class 0.000 description 10
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 9
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 9
- 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 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- WROINEBQQPMAQU-UHFFFAOYSA-N B([O-])(O)O.[Li+].C(C(=O)O)(=O)OF.C(C(=O)O)(=O)OF Chemical compound B([O-])(O)O.[Li+].C(C(=O)O)(=O)OF.C(C(=O)O)(=O)OF WROINEBQQPMAQU-UHFFFAOYSA-N 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910011140 Li2C2 Inorganic materials 0.000 description 1
- 229910010935 LiFOB Inorganic materials 0.000 description 1
- GNCVXLOOEYOACU-UHFFFAOYSA-N [B](F)F.C(C(=O)O)(=O)O Chemical compound [B](F)F.C(C(=O)O)(=O)O GNCVXLOOEYOACU-UHFFFAOYSA-N 0.000 description 1
- INFPCZDTSUZKKR-UHFFFAOYSA-M [F-].[Li+].B([O-])(O)O.[Li+].C(C(=O)O)(=O)O.C(C(=O)O)(=O)O Chemical compound [F-].[Li+].B([O-])(O)O.[Li+].C(C(=O)O)(=O)O.C(C(=O)O)(=O)O INFPCZDTSUZKKR-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a preparation method of lithium oxalyldifluoroborate. The preparation method comprises the steps that lithium bis(oxalato)borate and lithium fluoride are stirred to perform hybrid reaction in a non-aqueous solvent, wherein the molar ratio of the lithium bis(oxalato)borate to the lithium fluoride is within the range of (1:1.90)-(1:2.10), the reaction time lasts for 10-24 hours, and difluoro lithium bis(oxalato)borate and lithium oxalate are generated in the reaction, wherein the non-aqueous solvent is benzene, toluene or xylene, the reaction temperature is within the range of 50-85 DEG C, and the reaction time lasts for 12-16 hours. According to the invention, a technology line is unique, the lithium oxalyldifluoroborate is environment-friendly, the technology control range is wider, two resultants of the reaction are easy to separate, and electrolyte salt of which the quality satisfies the requirements of lithium batteries is easy to prepare. Because the content of chlorine compounds and the content of free acids are lower, the moisture content of the difluoro lithium bis(oxalato)borate solution prepared by the preparation method is controllable.
Description
First, technical field
The present invention relates to preparing the method for lithium ion battery electrolyte difluorine oxalic acid boracic acid lithium LiODFB and using this electricity
The lithium ion battery of solution matter.
2nd, background technology
, mainly using lithium hexafluoro phosphate, commercial applications were more than 20 years for lithium ion battery electrolyte.As
CN200680042560.7 discloses a kind of method for preparing lithium ion battery electrolyte solution.Prepared by lithium hexafluoro phosphate
When reacted in non-aqueous organic solvent using Phosphorous chloride., lithium chloride, and make the product that formed in a solvent and with fluorination
Hydrogen reacts.
But lithium hexafluoro phosphate LiPF6Heat stability is poor and easy deliquescence, thermal decomposition and deliquescence product all can destroy battery
Performance to environment.Additionally, it must be with ethylene carbonate（EC）Share to be formed on Carbon anode surface and stablize
Solid electrolyte interface film（SEI film）, and the fusing point of EC is 37 DEG C, seriously limits the cryogenic property of battery.Boracic lithium salts
Because having preferable heat stability, in common solvents system, there is higher electrical conductivity, and be subject to the extensive of researcher
Concern.Therefore it is used lithium borate salt just to become, as lithium ion battery electrolyte, the heat subject instantly studied.Studied
Existing tens of kinds of boracic lithium salts, but have then predominantly LiBF4, LiB (C2O4) 2 of application prospect（Abbreviation LiBOB）And
LiBC2O4F2（Abbreviation LiODFB）.
Wherein propose at first in lithium borate salt is LiBF4 and di-oxalate lithium borate (LiBOB).With business-like
Lithium hexafluoro phosphate LiPF6Compare with some superiority, of great interest in lithium ion battery applications：Di-oxalate lithium borate has
There is good heat stability, the higher safety enhancing battery up to 300 DEG C of heat decomposition temperature；Do not contain F element, no
HF corrosion electrode material and collector can be produced, improve the cycle life of battery, reduce the cost of battery；Can be
Carbon anode surface forms more stable SEI film, can use, widened battery and used temperature range in pure PC solvent；
Synthesis material is cheap and easy to get, preparation process is simple, environmentally friendly.And the electrolyte of LiBF4 LiBF4 preparation has relatively
Low Charge-transfer resistance（The major part of internal resistance of cell during low temperature）, institute's assembled battery has more superior low of relative LiPF6
Warm nature energy, is the most commonly used electrolyte lithium salt of commercial Application in addition to LiPF6.But high-temperature behavior is slightly poor.
Difluorine oxalic acid boracic acid lithium (lithiumoxalyldifluoroborate) (also known as LiODFB, LiDFOB, LiFOB)
It is exactly under these conditions by American scholar ShengShui Zhang proposition first, 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 reacted with lithium oxalate with boron trifluoride and through recrystallization purification.And
Contemplate and also combine very well due to comprising the LiBF4 of the half and LiBOB of half, its property in molecular structure because of LiODFB
LiBF4 and the advantage of two kinds of lithium salts of LiBOB.Separately refer to the lithium ion battery electrolyte boracics such as domestic University Of Tianjin Cui filial piety tinkling of pieces of jade
Lithium salts progress；Xie Hui etc., can be used for the new lithium salts of lithium ion battery:LiODFB etc..
LiODFB structural formula is as follows：
CN101648963 discloses a kind of synthesis technique obtaining difluorine oxalic acid boracic acid lithium and LiBF4, including such as
Lower step：(1) by fluorine-containing compound, the compound of boracic, the compound containing lithium and the compound containing oxalate 0～
100 DEG C, reaction pressure be to react in 0.1～1Mpa and reaction medium, wherein elemental lithium, fluorine element, boron element and oxalate from
The mol ratio of son is 2～3: 5～6: 2: 1；Generate the reactant liquor containing difluorine oxalic acid boracic acid lithium and LiBF4；(2) to anti-
The difluorine oxalic acid boracic acid lithium in liquid is answered to carry out initial gross separation with LiBF4, then use can extract difluorine oxalic acid boracic acid lithium or four
The organic solvent of lithium fluoroborate carries out further extract and separate；(3) carry out recrystallization respectively and be vacuum dried and obtain LITHIUM BATTERY
Difluorine oxalic acid boracic acid lithium and LiBF4.But above-mentioned reaction can not smoothly obtain desired product.
3rd, content of the invention
The present invention seeks to proposition is a kind of and preparing the method for lithium ion battery electrolyte LiODFB and uses this electrolyte
Lithium ion battery, especially obtain a kind of be beneficial to industrialization and business-like preparation method, possess and meet lithium dynamical battery and make
Condition and excellent quality, the quality of reaction condition and material is easily controllable, especially with environment amenable former material
Material, does not produce pollution in preparation process.
The technical scheme is that：A kind of difluoro di-oxalate lithium borate preparation method is it is characterised in that in nonaqueous solvent
Middle di-oxalate lithium borate and lithium fluoride stirring hybrid reaction, di-oxalate lithium borate and lithium fluoride and mol ratio be 1: 1.90～1:
2.10 scope, response time 10-24 hour, reaction generates difluoro di-oxalate lithium borate and lithium oxalate.
Further, in the manufacture method of difluoro di-oxalate lithium borate, nonaqueous solvent is benzene, toluene or dimethylbenzene, reaction temperature
Degree is from 50-85 DEG C；Response time 10-24 hour, especially 12-16 hour.
Further, especially it is benzene, carries out being heated at reflux reaction in toluene or dimethylbenzene in nonaqueous solvent.
Separating-purifying through EC, DMC, DEC, EMC equal solvent after reaction, such as from mixture difluoro di-oxalate lithium borate and grass
Di-oxalate lithium borate and lithium oxalate is separated especially by dimethyl carbonate DMC so that di-oxalate lithium borate lithium fluoride in sour lithium
With product mixture dissolve in dimethyl carbonate DMC；Filter and obtain ethanedioic acid boron difluoride after obtaining the concentrated vacuum drying of solution
Sour lithium white solid.Product turns out to be ethanedioic acid difluoro Lithium biborate through thermogravimetric analysiss and nmr analysis.
The difluoro di-oxalate lithium borate solution being manufactured by the method is because the content of chlorine compound, free acid is less, water
Divide controlled（Within 30ppm）, thus lithium ion battery especially Large Copacity, high magnification can be prepared using this electrolyte and put
Electricity, high temperature and all good lithium dynamical battery of cryogenic conditions serviceability, and apply this as non-aqueous electrolyte lithium ion battery
Performance carries high performance effective additive.
The invention has the beneficial effects as follows：The lithium salts LiODFB that the present invention is prepared for lithium ion battery has the chemistry of uniqueness
Structure is so as to combine biethyl diacid lithium borate (LiBOB) and the advantage of LiBF4 (LiBF4).Compared with LiBOB, Li
The viscosity of dissolubility in carbonic ester for the ODFB and solvent has and is obviously improved so that lithium ion battery have more preferable high,
Cryogenic property and multiplying power discharging property.And compared with LiBF4, LiODFB can promote stable, solid electrolyte interface (solid
Electrolyte interface, SEI) formation, improve the high-temperature behavior of lithium ion battery.This kind of new lithium salts also have
Have the advantage that:Good with the chemical stability of lithium metal, aluminium foil can be made well to be passivated under high potential and improve lithium
Ion battery security performance and the ability of anti-over-charging.These performances make Li ODFB become a kind of and very likely substitute LiPF6's
Commercially use lithium salts.In particular for dynamic lithium battery.The process line of the present invention is original, and environmental friendliness, technique control
Wider range processed, two kinds of products of reaction are easily isolated, and easily preparation quality reaches the electrolytic salt that lithium electricity requires.
4th, brief description
Fig. 1 be 60 DEG C under the conditions of Li ODFB add 3% prepare electro-hydraulic battery 1C charge and discharge cycles number of times with electric
Tankage（The capacity of galvanic element is 20Ah）Curve；Root is to adopt ODFB above, the lithium hexafluoro phosphate of lower curve contrast
Circulation.
Fig. 2 is the curve of 1C-1C depth discharge and recharge and battery capacity under 45 DEG C of temperature conditionss；Going up one most is LIODFB
Electro-hydraulic, below three be contrast the electro-hydraulic circulation of lithium hexafluoro phosphate.
5th, specific embodiment
The reaction expression of the present invention is as follows：
LiBC4O8+ 2LiF=LiBC2O4F2+Li2C2O4
Di-oxalate lithium borate+2 lithium fluoride=difluoro di-oxalate lithium borate+lithium oxalate；Di-oxalate lithium borate in nonaqueous solvent
Mix with stirring and react, di-oxalate lithium borate and lithium fluoride and mol ratio be 1: 1.90～1: 2.10 scope, carry out anti-
Difluoro di-oxalate lithium borate and lithium oxalate should be generated.Benzene, toluene or dimethylbenzene are carried out be heated at reflux reaction.Warp after reaction
The separating-purifying of DMC solvent；Filter and obtain ethanedioic acid difluoro Lithium biborate white solid after obtaining the concentrated vacuum drying of solution.Produce
Thing turns out to be ethanedioic acid difluoro Lithium biborate through thermogravimetric analysiss and nmr analysis.Lithium oxalate can be with reuse.
Embodiment 1,
193.79g biethyl diacid lithium borate and 51.88g lithium fluoride add in 500ml toluene, agitating heating backflow 16h, mistake
Filter to obtain ethanedioic acid difluoro Lithium biborate and lithium oxalate solid mixture, product mixture dissolves in 500ml diethyl carbonate stirring 3h,
Filter and obtain ethanedioic acid difluoro Lithium biborate white solid after obtaining the concentrated vacuum drying of solution.Product 52g through thermogravimetric analysiss and
Nmr analysis turn out to be ethanedioic acid difluoro Lithium biborate（Identical with the data of ShengShui Zhang）.In thermogravimetric analysiss
Product just starts to decompose in a large number more than 267 DEG C.
Embodiment 2,
203g biethyl diacid lithium borate and 51.88g lithium fluoride add in 500ml dimethylbenzene, agitating heating backflow 12h, mistake
Filter to obtain ethanedioic acid difluoro Lithium biborate and lithium oxalate solid mixture, product mixture dissolves in 500ml dimethyl carbonate stirring 3h, mistake
Filter obtains ethanedioic acid difluoro Lithium biborate white solid after obtaining the concentrated vacuum drying of solution.Product 49g is through thermogravimetric analysiss and core
Magnetic resonance spectroscopy turns out to be ethanedioic acid difluoro Lithium biborate.
As without being heated at reflux, agitating heating is reacted, under close reaction condition（Response time 12-16h, temperature
Control in 50 DEG C, 60 DEG C, 70 DEG C, 85 DEG C of all no essential distinctions）, yield is slightly worse.
Primary raw material dioxalic acid lithium borate（Biethyl diacid lithium borate LiBOB)）Using the raw material of following techniques, CAS No：
244761-29；C4BO8.Li molecular weight 193.79.Solid phase synthesis can be adopted, preparation process adopts oxalic acid, Lithium hydrate, boron
Acid is raw material, and the amount of its material ratio is for 2.1：1：1, high-temperature firing after ball milling mixing, firing temperature is 120 DEG C, dehydration temperaturre
For 240 DEG C, products obtained therefrom obtains final product product after ethyl acetate purification.Referring to the solid phase synthesis of key etc., di-oxalate lithium borate, no
Machine salt industrial 2011-4；The cost of its raw material is not high（Its purity more than 99%）, and preparation process is no discharged, environmental friendliness.
LiODFB dissolubility in common carbonate solvent is more than LiBOB, but is less than LiBF4.LiODFB electrolyte can be
High conductance is kept in wide temperature range：During high temperature, LiODFB electrolytic conductivity is close to LiBOB system, and is higher than Li
BF4.Obtain the number of times of 1C charge and discharge cycles and battery capacity LiODFB electrolyte under the conditions of 45 DEG C shown in Fig. 2 and be substantially better than hexafluoro
The circulation of lithium phosphate electrolyte.
Although the present invention is disclosed above with preferred embodiment, so it is not limited to the present invention.The affiliated skill of the present invention
Has usually intellectual, without departing from the spirit and scope of the present invention, when can be used for a variety of modifications and variations in art field.Cause
This, protection scope of the present invention ought be defined depending on those as defined in claim.
Claims (2)
1. a kind of preparation method of difluorine oxalic acid boracic acid lithium is it is characterised in that di-oxalate lithium borate and fluorination in nonaqueous solvent
Lithium stirs hybrid reaction, di-oxalate lithium borate and lithium fluoride and mol ratio be 1: 1.90～1: 2.10 scope,
Reaction generates difluorine oxalic acid boracic acid lithium and lithium oxalate；Nonaqueous solvent is benzene, toluene or dimethylbenzene；Response time 12-16 hour；And
Benzene, toluene or dimethylbenzene are carried out be heated at reflux reaction.
2. the difluorine oxalic acid boracic acid lithium according to claim 1 preparation method it is characterised in that reaction after through carbonic acid two
The separating-purifying of methyl ester DMC solvent, the product mixing with di-oxalate lithium borate and lithium fluoride dissolves in dimethyl carbonate DMC；Filter
Difluorine oxalic acid boracic acid lithium is obtained after obtaining the concentrated vacuum drying of solution.
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| CN105859760A (en) * | 2016-03-18 | 2016-08-17 | 汕头市金光高科有限公司 | A synthetic method of electronic grade lithium difluoro(oxalato)borate |
| CN107226821B (en) * | 2017-06-12 | 2019-06-21 | 上海如鲲新材料有限公司 | A kind of synthesis technology preparing difluorine oxalic acid boracic acid lithium with di-oxalate lithium borate |
| CN109053787A (en) * | 2018-09-18 | 2018-12-21 | 天津金牛电源材料有限责任公司 | A kind of preparation method 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 |
| CN114891031A (en) * | 2022-04-15 | 2022-08-12 | 石家庄圣泰化工有限公司 | Preparation method of lithium difluoro (oxalato) borate |
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