CN104557995A - Preparation method of lithium oxalyldifluoroborate - Google Patents

Preparation method of lithium oxalyldifluoroborate Download PDF

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CN104557995A
CN104557995A CN201310475552.3A CN201310475552A CN104557995A CN 104557995 A CN104557995 A CN 104557995A CN 201310475552 A CN201310475552 A CN 201310475552A CN 104557995 A CN104557995 A CN 104557995A
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lithium
reaction
oxalate
borate
preparation
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陈琛
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    • 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 System
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages

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

A kind of preparation method of difluorine oxalic acid boracic acid lithium
One, technical field
The present invention relates to the method and this electrolytical lithium ion battery of use of preparing lithium ion battery ionogen difluorine oxalic acid boracic acid lithium LiODFB.
Two, background technology
Lithium ion battery ionogen mainly uses lithium hexafluoro phosphate, and commercial applications exceedes Two decades years.As CN200680042560.7 discloses a kind of method for the preparation of lithium ion battery electrolyte solution.Use phosphorus trichloride, lithium chloride to react in non-aqueous organic solvent time prepared by lithium hexafluoro phosphate, and make the reaction product that formed in a solvent and and hydrogen fluoride reaction.
But lithium hexafluoro phosphate LiPF 6the poor and easy deliquescence of thermostability, thermolysis and deliquescence product all can destroy battery performance and to environment.In addition, it must share and could form stable solid electrolyte interface film (SEI film) on Carbon anode surface with NSC 11801 (EC), and the fusing point of EC is 37 DEG C, seriously limits the low-temperature performance of battery.Boracic lithium salts, because having good thermostability, has higher specific conductivity, and is subject to the extensive concern of researcher in common solvents system.Therefore lithium borate salt is used just to become the heat subject instantly studied as lithium ion battery dielectric medium.The boracic lithium salts studied has tens of kinds, but has LiBF4, LiB (C2O4) 2(that is then mainly of application prospect to be called for short LiBOB) and LiBC2O4F2(abbreviation LiODFB).
What wherein propose at first in lithium borate salt is LiBF4 and di-oxalate lithium borate (LiBOB).With business-like lithium hexafluoro phosphate LiPF 6compare and have some superiority, lithium ion battery applications is subject to very big concern: di-oxalate lithium borate has good thermostability, heat decomposition temperature is Gao Keda 300 DEG C comparatively---enhance the security of battery; Not containing F element, HF corrosion target material and collector can not be produced, improve the cycle life of battery,---reduce the cost of battery; More stable SEI film can be formed on Carbon anode surface, can use in pure PC solvent,---widen battery use temperature scope; Synthesis material is cheap and easy to get, and preparation technology is simple, environmentally friendly.And electrolytic solution prepared by LiBF4 LiBF4 has the lower Charge-transfer resistance major portion of the internal resistance of cell (during the low temperature), institute's assembled battery has the more superior low-temperature performance of relative LiPF6, is industrial application electrolyte lithium salt the most widely except LiPF6.But high-temperature behavior is slightly poor.
Difluorine oxalic acid boracic acid lithium (lithiumoxalyldifluoroborate) is (also known as LiODFB, LiDFOB, LiFOB) be exactly first proposed by American scholar ShengShui Zhang under these conditions, CAS No:409071-16-5, chemical formula LiBC 2o 4f 2molecular weight 143.77g/mol, decomposition temperature 240 DEG C, see An unique lithium saltfor the improved electrolyte of Li-ion battery, ShengShui Zhang ElectrochemistryCommunications8 (2006) 1423-1428.And mention and to react with boron trifluoride and lithium oxalate and to purify through recrystallization.And contemplate because LiODFB is due to the LiBOB of the LiBF4 and half that comprise half in molecular structure, its character also combines the advantage of LiBF4 and LiBOB two kinds of lithium salts very well.Separately can with reference to lithium ion battery electrolyte boracic lithium salts progress such as domestic University Of Tianjin Cui filial piety tinkling of pieces of jade; 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, comprise the steps: (one) by the compound of fluorine-containing compound, boracic, the compound containing lithium and the compound containing oxalate 0 ~ 100 DEG C, reaction pressure reacts in being 0.1 ~ 1Mpa and reaction medium, wherein the mol ratio of elemental lithium, fluorine element, boron and oxalate denominationby is 2 ~ 3: 5 ~ 6: 2: 1; Generate the reaction solution containing difluorine oxalic acid boracic acid lithium and LiBF4; (2) initial gross separation is carried out to the difluorine oxalic acid boracic acid lithium in reaction solution and LiBF4, then carry out further extracting and separating with the organic solvent that can extract difluorine oxalic acid boracic acid lithium or LiBF4; (3) recrystallization is carried out respectively and vacuum-drying obtains difluorine oxalic acid boracic acid lithium and the LiBF4 of cell-grade.But above-mentioned reaction can not obtain the product of wishing smoothly.
Three, summary of the invention
The present invention seeks to propose a kind of method and this electrolytical lithium ion battery of use of preparing lithium ion battery ionogen LiODFB, especially obtain one and be beneficial to industrialization and business-like preparation method, possess the condition and excellent quality that meet lithium dynamical battery use, the quality of reaction conditions and material is easy to control, especially use environment amenable starting material, in preparation process, do not produce pollution.
Technical scheme of the present invention is: a kind of difluoro di-oxalate lithium borate preparation method, it is characterized in that, in non-aqueous solvent, di-oxalate lithium borate and lithium fluoride are uniformly mixed reaction, di-oxalate lithium borate and lithium fluoride and mol ratio be the scope of 1: 1.90 ~ 1: 2.10, reaction times 10-24 hour, reaction generates difluoro di-oxalate lithium borate and lithium oxalate.
Further, in the manufacture method of difluoro di-oxalate lithium borate, non-aqueous solvent is benzene, toluene or dimethylbenzene, and temperature of reaction is from 50-85 DEG C; Reaction times 10-24 hour, especially 12-16 hour.
Further, be especially carry out reflux reaction in benzene, toluene or dimethylbenzene at non-aqueous solvent.
Through the separating-purifying of EC, DMC, DEC, EMC equal solvent after reaction, as being separated di-oxalate lithium borate and lithium oxalate especially by methylcarbonate DMC from mixture difluoro di-oxalate lithium borate and lithium oxalate, make di-oxalate lithium borate lithium fluoride and product mixture dissolve in methylcarbonate DMC; Filter acquisition solution and obtain oxalic acid difluoro lithium tetraborate white solid after concentrated vacuum-drying.Product turns out to be oxalic acid difluoro lithium tetraborate through thermogravimetric analysis and nmr analysis.
The difluoro di-oxalate lithium borate solution manufactured by the method is because the content of chlorine compound, free acid is less, moisture controlled (within 30ppm), thus this ionogen can be used to prepare lithium ion battery---the lithium dynamical battery that especially Large Copacity, high-multiplying power discharge, high temperature and cold condition use properties are all good, and apply this performance as non-aqueous electrolyte lithium ion battery and carry high performance effective additive.
The invention has the beneficial effects as follows: the present invention has unique chemical structure for the preparation of the lithium salts LiODFB of lithium ion battery, makes it combine the advantage of biethyl diacid lithium borate (LiBOB) and LiBF4 (LiBF4).Compared with LiBOB, the viscosity of the solvability of Li ODFB in carbonic ether and solvent has had obvious improvement, thus makes lithium ion battery have better high and low temperature performance and multiplying power discharging property.And compared with LiBF4, LiODFB can promote the formation of stable, solid electrolyte interface (solid electrolyte interface, SEI), improve the high-temperature behavior of lithium ion battery.This kind of new lithium salts also has the following advantages: good with the chemical stability of metallic lithium, aluminium foil can be made well to obtain passivation and improve the ability of lithium ion battery safety performance and anti-over-charging under noble potential.These performances make LiODFB become a kind of lithium salts very likely substituting the commercialization use of LiPF6.In particular for dynamic lithium battery.Process line of the present invention is original, and environmental friendliness, technology controlling and process a wider range, two kinds of resultants of reaction are easy to be separated, and easy preparation quality reaches the electrolytic salt that lithium electricity requires.
Four, accompanying drawing explanation
Fig. 1 is the number of times of battery in 1C charge and discharge cycles and the curve of cell container (capacity of galvanic cell is 20Ah) that under 60 DEG C of conditions, Li ODFB adds the preparation electricity liquid of 3%; Root adopts ODFB above, the circulation of the lithium hexafluoro phosphate of lower curve contrast.
Fig. 2 is the curve of the discharge and recharge of the 1C-1C degree of depth and cell container under 45 DEG C of temperature condition; Go up most one be LIODFB electricity liquid, below three be contrast lithium hexafluoro phosphate electricity liquid circulation.
Five, embodiment
Reaction expression of the present invention is as follows:
LiBC 4O 8+2LiF＝LiBC 2O 4F 2+Li 2C 2O 4
Di-oxalate lithium borate+2 lithium fluoride=difluoro di-oxalate lithium borate+lithium oxalate; Di-oxalate lithium borate and be uniformly mixed and react in non-aqueous solvent, di-oxalate lithium borate and lithium fluoride and mol ratio be the scope of 1: 1.90 ~ 1: 2.10, carry out reaction generation difluoro di-oxalate lithium borate and lithium oxalate.Reflux reaction is carried out in benzene, toluene or dimethylbenzene.Through the separating-purifying of DMC solvent after reaction; Filter acquisition solution and obtain oxalic acid difluoro lithium tetraborate white solid after concentrated vacuum-drying.Product turns out to be oxalic acid difluoro lithium tetraborate through thermogravimetric analysis and nmr analysis.Lithium oxalate can reuse.
Embodiment 1,
193.79g biethyl diacid lithium borate and 51.88g lithium fluoride add in 500ml toluene, stirring heating backflow 16h, filter to obtain oxalic acid difluoro lithium tetraborate and lithium oxalate solid mixture, product mixture dissolves in 500ml diethyl carbonate and stirs 3h, filters acquisition solution and obtain oxalic acid difluoro lithium tetraborate white solid after concentrated vacuum-drying.Product 52g turns out to be oxalic acid difluoro lithium tetraborate (identical with the data of ShengShui Zhang) through thermogravimetric analysis and nmr analysis.In thermogravimetric analysis, product just starts a large amount of decomposition more than 267 DEG C.
Embodiment 2,
203g biethyl diacid lithium borate and 51.88g lithium fluoride add in 500ml dimethylbenzene, stirring heating backflow 12h, filter to obtain oxalic acid difluoro lithium tetraborate and lithium oxalate solid mixture, product mixture dissolves in 500ml methylcarbonate and stirs 3h, filters acquisition solution and obtain oxalic acid difluoro lithium tetraborate white solid after concentrated vacuum-drying.Product 49g turns out to be oxalic acid difluoro lithium tetraborate through thermogravimetric analysis and nmr analysis.
As without reflux, stirring heating is reacted, and under close reaction conditions (reaction times 12-16h, temperature controls at 50 DEG C, 60 DEG C, 70 DEG C, 85 DEG C all without essential distinction), yield is slightly poor.
Main raw material dioxalic acid lithium tetraborate (biethyl diacid lithium borate LiBOB)) adopt the raw material of following technique, CASNo:244761-29; C4BO8.Li molecular weight 193.79.Solid phase synthesis can be adopted, preparation process adopts oxalic acid, lithium hydroxide, boric acid to be raw material, and its amount of substance is than being 2.1:1:1, high-temperature firing after ball milling mixing, firing temperature is 120 DEG C, dehydration temperaturre is 240 DEG C, and namely products obtained therefrom obtains product after ethyl acetate is purified.See the solid phase synthesis of key etc., di-oxalate lithium borate, inorganic chemicals industry 2011-4; The cost of its raw material is not high (its purity more than 99%), and preparation process is without discharge, environmental friendliness.
LiODFB solubleness in common carbonate solvent is greater than LiBOB, but is less than LiBF4.LiODFB electrolytic solution can keep high conductance in wide temperature range: during high temperature, LiODFB electrolytic conductivity close to LiBOB system, and higher than Li BF4.The circulation that the number of times of 1C charge and discharge cycles under 45 DEG C of conditions and cell container LiODFB electrolytic solution are obviously better than lithium hexafluorophosphate electrolyte solution is obtained shown in Fig. 2.
Although the present invention with preferred embodiment disclose as above, so itself and be not used to limit the present invention.Persond having ordinary knowledge in the technical field of the present invention, without departing from the spirit and scope of the present invention, when being used for a variety of modifications and variations.Therefore, protection scope of the present invention is when being as the criterion depending on those as defined in claim.

Claims (4)

1. the preparation method of a difluorine oxalic acid boracic acid lithium, it is characterized in that, in non-aqueous solvent, di-oxalate lithium borate and lithium fluoride are uniformly mixed reaction, di-oxalate lithium borate and lithium fluoride and mol ratio be the scope of 1: 1.90 ~ 1: 2.10, reaction times 10-24 hour, reaction generates difluoro di-oxalate lithium borate and lithium oxalate.
2. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, is characterized in that, in the manufacture method of difluoro di-oxalate lithium borate, non-aqueous solvent is benzene, toluene or dimethylbenzene; Temperature of reaction from 50-85 DEG C, reaction times 12-16 hour.
3. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, is characterized in that, in benzene, toluene or dimethylbenzene, carry out reflux reaction.
4. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, through the separating-purifying of DMC solvent after it is characterized in that reacting, di-oxalate lithium borate lithium fluoride and product mixture dissolve in methylcarbonate DMC; Filter acquisition solution and obtain oxalic acid difluoro lithium tetraborate after concentrated vacuum-drying.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
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
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
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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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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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