CN104557995B - Preparation method of lithium oxalyldifluoroborate - Google Patents
Preparation method of lithium oxalyldifluoroborate Download PDFInfo
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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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Families Citing this family (6)
| 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 |
| 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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| US7820323B1 (en) * | 2006-09-07 | 2010-10-26 | The United States Of America As Represented By The Secretary Of The Army | Metal borate synthesis process |
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Address after: Mochouhu road Jianye District of Nanjing City, Jiangsu Province, No. 48 4-1808 210029 Applicant after: Chen Chen Address before: 210009 No. 301, 19-1, Zuo Gang, Gulou District, Jiangsu, Nanjing Applicant before: Chen Chen |
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