CN105503922A - Preparation method and application of lithium bis(oxalato)borate - Google Patents
Preparation method and application of lithium bis(oxalato)borate Download PDFInfo
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- CN105503922A CN105503922A CN201610005565.8A CN201610005565A CN105503922A CN 105503922 A CN105503922 A CN 105503922A CN 201610005565 A CN201610005565 A CN 201610005565A CN 105503922 A CN105503922 A CN 105503922A
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- lithium
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- oxalate
- preparation
- borate
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title abstract 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 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 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 8
- 238000013517 stratification Methods 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- 229940117955 isoamyl acetate Drugs 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 2
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000000859 sublimation Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- -1 aryl boric acid lithium Chemical compound 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010671 solid-state reaction 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 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
- 238000003672 processing method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical class [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of lithium bis(oxalato)borate. The whole synthesis process is conducted in solvent, reaction steps are few, reaction, separation and purification are completed in one step, and product purity is high. The defect that solid-phase reaction oxalic acid is prone to sublimation is overcome, and by-products of the whole process method include H2O and CO2, are harmless to the environment and can not cause secondary pollution. The I-type solvent and the II-type solvent can be used as reaction solvent, can also be used as purification solvent and can be recycled. Lithium bis(oxalato)borate is suitable for being used as lithium ion battery electrolyte salt.
Description
Technical field
The invention belongs to lithium ion battery electrolyte salt field, particularly relate to a kind of preparation method and application thereof of di-oxalate lithium borate.
Background technology
Inside lithium ion cell forms primarily of three parts: positive pole, negative pole and electrolytic solution.Wherein, electrolytic solution is made up of electrolytic salt, solvent and associated additives.At present, the electrolytic salt that the lithium ion battery major part of existing goods uses is lithium hexafluoro phosphate (LiPF
6).LiPF
6there is many premium propertiess, but its synthesis technique is complicated, cost is higher, high temperature and easily decomposing when meeting water.Market wishes to find a kind of excellent property, good stability, synthesis technique simple and lower-cost novel electrolytes salt.
Under normal circumstances, novel electrolytes lithium salts should have more following characteristics: the chemical stability that (1) is good and thermostability; (2) good ionic conductivity can be shown in non-aqueous solution; (3) in non-aqueous solution, have good solubleness, the ion of dissolving has good transport property; (4) negatively charged ion in ionogen and positively charged ion are inertia to the positive and negative pole material of battery and solvent; (5) corrosive nature is not existed to aluminium collector, and ionogen itself is nontoxic.
In the new salt of numerous ionogen, boron series complex salts is with a wide range of applications because of good properties.In lithium-borate complexes, different according to boron atom-linking group, aryl boric acid lithium and alkylboronic acids lithium can be divided into.Aryl boric acid lithium is in the structure containing aromatic group, and because the oxygenolysis voltage of aryl boric acid lithium is all between 3.5 ~ 4V, this makes it be applied to lithium-ion battery system certain gap in addition.Alkylboronic acids lithium comprises two lithium tetraborate (LBPFPB), dimalonic acid lithium tetraborate (LiBMB), di-oxalate lithium borates (LiBOB) etc.The constitutional features of these materials ensure that its higher thermostability, stability to hydrolysis and oxidative stability.Many considerations of the aspects such as the performance of comprehensive above-mentioned electrolytic salt and synthesis technique difficulty, cost, LiBOB is the most possible new salt of ionogen substituting currently available products by market accreditation.
About the synthetic method of LiBOB, CN201010234944 discloses a kind of Rheological Phase Method, by oxalic acid, lithium hydroxide and boric acid in 2: 1: 1 ratio mix the closed reactor of rear loading with pressure relief device, be warming up to 100 ~ 130 DEG C, insulation 5 ~ 10h reaction.Vacuumize 20h at 130 DEG C after synthesis, obtain product.CN102627661A discloses a kind of method for preparing solid phase, and this method is first adding lithium salts and the reaction of oxalic acid Hybrid Heating, then after adding the reaction of boron source, high pressure compressing tablet continuation reacting by heating obtains product.CN101168546A adopts oxalic acid alkyl ester and boron-containing compound and the heating of lithium source to carry out reacting to obtain product.Lithium-containing compound, boron source compound and the solution of compound containing oxalate pressurize reacting by heating in closed container by CN101397305A in organic solvent, obtain the solution containing LiBOB, then separating-purifying.
Above-described synthesis technique has three shortcomings usually: one is that synthesis step is many, and equipment and process cost can be caused to increase; Two is easily volatilize and the control of this process difficult at solid state reaction mesoxalic acid, and cause productive rate to decline, impurity increases; Three relate to multi-solvents, and the cost of separating-purifying can be made to increase; 4th, some technique can produce by product alkyl alcohol, causes secondary pollution.
Summary of the invention
In order to achieve the above object, the invention provides that a kind of preparation process is few, productive rate is high, the preparation method of the di-oxalate lithium borate of by product toxicological harmless and application thereof.
First aspect, the invention provides a kind of preparation method of di-oxalate lithium borate, it comprises the following steps:
Steps A, gets extraction agent and sulfonated kerosene is hybridly prepared into abstraction purification agent, adds alkali lye, and stratification, abandons aqueous phase, adds lithium source solution, abstraction impurity removal, and after concentrated solution, vacuum-drying, obtains high purity lithium source power;
Step B, is dissolved in oxalic acid and boric acid in I kind solvent, obtains solution 1, and high purity lithium source power steps A obtained is dissolved in II kind solvent, obtains solution 2;
Step C, is heated to 50 ~ 80 DEG C by the solution 1 of gained in step B, and drip solution 2, holding temperature is constant, stirs 5 ~ 8h and makes it abundant reaction;
Step D, reaction terminates cooling, and stratification, takes off a layer suspension filtered and obtain settled solution 3, solution 3 is warming up to more than 90 DEG C, steams solvent, obtain di-oxalate lithium borate product after drying.
Second aspect, adopts the di-oxalate lithium borate that described in first aspect present invention prepared by method, and it is used as lithium ion battery electrolyte salt.
The beneficial effect of the preparation method of di-oxalate lithium borate provided by the invention is:
(1) the inventive method building-up process is all carried out in a solvent, and reactions steps is few, and react, be separated, a step of purifying completes, product purity is high;
(2) overcome the shortcoming that solid state reaction oxalic acid easily distils, whole processing method by product is H
2o and CO
2, environmental sound, does not cause secondary pollution;
(3) described I kind solvent and II kind solvent not only can make reaction solvent but also make purification solvent, and can recycle and reuse.
Accompanying drawing explanation
Fig. 1 is the XRD figure that the present invention is based on LiBOB prepared by embodiment 1;
Fig. 2 is the SEM figure that the present invention is based on LiBOB prepared by embodiment 1.
Embodiment
First aspect, the invention provides a kind of preparation method of di-oxalate lithium borate, it comprises the following steps:
Steps A, gets extraction agent and sulfonated kerosene is hybridly prepared into abstraction purification agent, adds alkali lye, and stratification, abandons aqueous phase, adds lithium source solution, abstraction impurity removal, and after concentrated solution, vacuum-drying, obtains high purity lithium source power;
Step B, is dissolved in oxalic acid and boric acid in I kind solvent, obtains solution 1, and high purity lithium source power steps A obtained is dissolved in II kind solvent, obtains solution 2;
Step C, is heated to 50 ~ 80 DEG C by the solution 1 of gained in step B, and drip solution 2, holding temperature is constant, stirs 5 ~ 8h and makes it abundant reaction;
Step D, reaction terminates cooling, and stratification, takes off a layer suspension filtered and obtain settled solution 3, solution 3 is warming up to more than 90 DEG C, steams solvent, obtain di-oxalate lithium borate product after drying.
Concrete, in described steps A, alkali lye can adopt NaOH solution.
Preferably, the extraction agent in described steps A comprises di-(2-ethylhexyl)phosphoric acid ester, i.e. P204, and 2-ethylhexyl phosphonic acid 2-(ethyl hexyl) ester, i.e. P507.
Preferably, in described steps A, lithium source comprises Quilonum Retard, lithium hydroxide, lithium oxalate and lithium acetate.
Preferably, in described step B, I kind solvent comprises acetonitrile, tetrahydrofuran (THF) and alcoholic solvent.
Preferably, in described step B, II kind solvent comprises vinyl acetic monomer, n-Amyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate and methylcarbonate, NSC 11801, propylene carbonate.
Concrete, in step C, the time dripping solution 2 is 0.5 ~ 1h.
Second aspect, adopts the di-oxalate lithium borate that described in first aspect present invention prepared by method, and it is used as lithium ion battery electrolyte salt.
Below in conjunction with specific embodiment, describe the present invention further.Certainly described embodiment is only a part of embodiment of the present invention; instead of whole embodiment; based on the embodiment in the present invention, those skilled in the art, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
Embodiment 1
Get P204 and sulfonated kerosene by volume 3:7 be mixed with abstraction purification agent, be placed in liquid distributing device, add sodium hydroxide solution, after stirring, stratification abandons aqueous phase.By the mass concentration prepared in advance be 30% Lithium carbonate solution pour into wherein, abstraction impurity removal, after concentrated solution, vacuum-drying obtains pure Lithium Carbonate powder.Oxalic acid and boric acid are dissolved in fresh acetonitrile solution, stir and make it fully dissolve, gained solution for standby.Pure Lithium Carbonate after above-mentioned removal of impurities is dissolved in NSC 11801 simultaneously, stirs and make it fully dissolve to obtain solution, this solution is heated to 80 DEG C.Stock solution adds wherein in the mode dripped, and drip 1h, holding temperature is constant, and mechanical stirring 8h makes it abundant reaction.Reaction end is cooled to room temperature, stratification, takes off a layer suspension filtered and obtains settled solution.By this solution warms to 90 DEG C, distilling off solvent under normal temperature, obtains di-oxalate lithium borate product after drying.
Embodiment 2
Get P507 and sulfonated kerosene by volume 3:7 be mixed with abstraction purification agent, be placed in liquid distributing device, add sodium hydroxide solution, after stirring, stratification abandons aqueous phase.By the mass concentration prepared in advance be 30% lithium hydroxide solution pour into wherein, abstraction impurity removal, after concentrated solution, vacuum-drying obtains Lithium hydroxide powder.Oxalic acid and boric acid are dissolved in fresh tetrahydrofuran solution, stir and make it fully dissolve to obtain solution for standby.Lithium hydroxide after above-mentioned removal of impurities is dissolved in vinyl acetic monomer simultaneously, stirs and make it fully dissolve to obtain solution, this solution is heated to 65 DEG C.Stock solution adds wherein in the mode dripped, and drip 0.8h, holding temperature is constant, and mechanical stirring 6.5h makes it abundant reaction.Reaction end is cooled to room temperature, stratification, takes off a layer suspension filtered and obtains settled solution.By this solution warms to 100 DEG C, distilling off solvent under normal temperature, obtains di-oxalate lithium borate product after drying.
Embodiment 3
Get P507 and sulfonated kerosene by volume 3:7 be mixed with abstraction purification agent, be placed in liquid distributing device, add sodium hydroxide solution, after stirring, stratification abandons aqueous phase.By the mass concentration prepared in advance be 30% lithium hydroxide solution pour into wherein, abstraction impurity removal, after concentrated solution, vacuum-drying obtains Lithium hydroxide powder.Oxalic acid and boric acid are dissolved in fresh acetonitrile solution, stir and make it fully dissolve to obtain solution for standby.Lithium hydroxide after above-mentioned removal of impurities is dissolved in vinyl acetic monomer simultaneously, stirs and make it fully dissolve to obtain solution, this solution is heated to 50 DEG C.Stock solution adds wherein in the mode dripped, and drip 0.5h, holding temperature is constant, and mechanical stirring 5h makes it abundant reaction.Reaction end is cooled to room temperature, stratification, takes off a layer suspension filtered and obtains settled solution.By this solution warms to 120 DEG C, distilling off solvent under normal temperature, obtains di-oxalate lithium borate product after drying.
XRD analysis is carried out to di-oxalate lithium borate sample prepared by embodiment 1, obtains the XRD figure spectrum shown in Fig. 1.As shown in Figure 1, this sample peak shape is complete, better crystallinity degree, substantially without assorted peak, illustrates that this sample purity is high.
Scheme as shown in Figure 2 di-oxalate lithium borate sample collecting SEM prepared by embodiment 1, as shown in Figure 2, described di-oxalate lithium borate powder particle size is even, mean sizes little (< 1um), pattern presents sheet, and particle agglomeration is less, stable performance.
Claims (6)
1. a preparation method for di-oxalate lithium borate, it comprises the following steps:
Steps A, gets extraction agent and sulfonated kerosene is hybridly prepared into abstraction purification agent, adds alkali lye, and stratification, abandons aqueous phase, adds lithium source solution, abstraction impurity removal, and after concentrated solution, vacuum-drying, obtains high purity lithium source power;
Step B, is dissolved in oxalic acid and boric acid in I kind solvent, obtains solution 1, and high purity lithium source power steps A obtained is dissolved in II kind solvent, obtains solution 2;
Step C, is heated to 50 ~ 80 DEG C by the solution 1 of gained in step B, and drip solution 2, holding temperature is constant, stirs 5 ~ 8h and makes it abundant reaction;
Step D, reaction terminates cooling, and stratification, takes off a layer suspension filtered and obtain settled solution 3, solution 3 is warming up to more than 90 DEG C, steams solvent, obtain di-oxalate lithium borate product after drying.
2. the preparation method of di-oxalate lithium borate as claimed in claim 1, is characterized in that: the extraction agent in described steps A comprises di-(2-ethylhexyl)phosphoric acid ester and 2-ethylhexyl phosphonic acid 2-(ethyl hexyl) ester.
3. the preparation method of di-oxalate lithium borate as claimed in claim 1, is characterized in that: in described steps A, lithium source comprises Quilonum Retard, lithium hydroxide, lithium oxalate and lithium acetate.
4. the preparation method of di-oxalate lithium borate as claimed in claim 1, is characterized in that: in described step B, I kind solvent comprises acetonitrile, tetrahydrofuran (THF) and alcoholic solvent.
5. the preparation method of di-oxalate lithium borate as claimed in claim 1, is characterized in that: in described step B, II kind solvent comprises vinyl acetic monomer, n-Amyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate and methylcarbonate, NSC 11801, propylene carbonate.
6. adopt the di-oxalate lithium borate that described in claim 1 prepared by method, it is used as lithium ion battery electrolyte salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610005565.8A CN105503922B (en) | 2016-01-06 | 2016-01-06 | The preparation method and applications of di-oxalate lithium borate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610005565.8A CN105503922B (en) | 2016-01-06 | 2016-01-06 | The preparation method and applications of di-oxalate lithium borate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108459141A (en) * | 2018-04-09 | 2018-08-28 | 杉杉新材料（衢州）有限公司 | A kind of analysis method of di-oxalate lithium borate product |
| CN109293691A (en) * | 2018-09-27 | 2019-02-01 | 常熟市常吉化工有限公司 | A kind of new method preparing di-oxalate lithium borate |
| 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 |
| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| KR102070647B1 (en) * | 2018-02-08 | 2020-01-29 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| CN108459141A (en) * | 2018-04-09 | 2018-08-28 | 杉杉新材料（衢州）有限公司 | A kind of analysis method of di-oxalate lithium borate product |
| CN109293691A (en) * | 2018-09-27 | 2019-02-01 | 常熟市常吉化工有限公司 | A kind of new method preparing di-oxalate lithium borate |
| CN109293691B (en) * | 2018-09-27 | 2020-10-16 | 常熟市常吉化工有限公司 | Method for preparing lithium bis (oxalato) borate |
| 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 |
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