CN104230970B - Preparation method of lithium difluorooxalatoborate electrolyte - Google Patents
Preparation method of lithium difluorooxalatoborate electrolyte Download PDFInfo
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- CN104230970B CN104230970B CN201310249011.9A CN201310249011A CN104230970B CN 104230970 B CN104230970 B CN 104230970B CN 201310249011 A CN201310249011 A CN 201310249011A CN 104230970 B CN104230970 B CN 104230970B
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Abstract
The invention provides a preparation method of a high-purity lithium difluorooxalatoborate (LiODFB) electrolyte for a lithium ion battery. The preparation method comprises the following steps of firstly adding lithium oxalate and boron trifluoride diethyl ether according to a molar ratio being (1: 1) to (1: 3) into a dried ball-milling tank, carrying out ball-milling at a temperature of 30 DEG C-90 DEG C for 2 hours-24 hours; and then dissolving the ball-milled reaction product in an organic solvent at the temperature of 30-90 DEG C and filtering to remove a solid-phase byproduct and unreacted lithium oxalate to obtain a solution containing LiODFB, crystallizing at a low temperature of -20 DEG C to 10 DEG C to obtain LiODFB crystals and carrying out vacuum drying on the LiODFB crystals at 40 DEG C-100 DEG C for 10 hours-48 hours to obtain the purified LiODFB solid. The preparation method has the advantages of no strict requirements, such as high temperature resistance and high pressure resistance, simple operation and low investment in equipment and has very broad application prospects, and the product of which the purity is above 99.9% can be directly obtained by adopting the preparation method.
Description
Technical field
The present invention relates to the manufacturing technology field of lithium ion battery electrolyte salt, it is a kind of high-purity lithium oxalyldifluoroborate electricity
The preparation method of solution matter salt.
Background technology
At present, the electrolyte of conventional lithium ion battery is mainly lithium hexafluoro phosphate（LiPF6）, di-oxalate lithium borate
（LiBOB）, LiBF4（LiBF4）.LiPF6Heat endurance poor, easy deliquescence, and ethylene carbonate must be coordinated
(EC) use, stable solid electrolyte interface (SEI) film could be formed on Carbon anode surface；And the fusing point of EC is 37
DEG C, cryogenic property can be impacted.LiBF4Charge-transfer resistance as lithium salts is relatively low, makes battery have relative usage
LiPF6When more preferable cryogenic property, but hydrolabil, and be difficult to form SEI film in negative terminal surface, make assembled battery
Cycle performance is poor.The more di-oxalate lithium borate of Recent study (LiBOB), its electrochemical stability window width, high temperature resistant
(heat decomposition temperature is 302 DEG C), even if in pure propene carbonate (PC, fusing point is -49 DEG C), remain on Carbon anode surface
Form stable SEI film, environmentally friendly, but the solubility in the low solvent of dielectric constant (linear carbonate) is low,
The SEI membrane impedance that negative terminal surface is formed is too high, leads to the low temperature capacity conservation rate of battery and high-rate discharge capacity poor.Cause
This, seek a kind of preparation process is simple, easy to operate, and the lithium ion battery electrolyte of excellent combination property seems extremely urgent
Cut.
Attract most attention in industry at present is new lithium salts LiODFB（LiODFB）, its molecular structure bag
Contain half LiBOB and half LiBF4Molecule, dexterously combines LiBOB and LiBF4Advantage.LiODFB has
Higher heat endurance（240 DEG C about）, the high-temperature behavior of existing LiBOB, there is LiBF again4Cryogenic property, the temperature of use
Scope is very wide.The filming performance of LiODFB very well, can participate in being formed stable in the electrolyte with the presence of PC simultaneously
SEI film, has good cycle performance.Meanwhile, the electrode compatibility of LiODFB is fine, particularly with manganese anode material.
At present, there is the report of the more synthetically prepared research with regard to LiODFB both at home and abroad.In european patent number it is
With oxalic acid, LiBF4 as raw material in EP1308449A2, with aluminium chloride or silicon tetrachloride as catalyst, in dimethyl carbonate
Middle reaction is it is achieved that the synthesis of LiODFB.But there is HCl to produce in the reaction of this method, high to equipment requirement, it is unfavorable for industrialization, and
The sample purity that this patent obtains is low, just can be used as lithium ion battery electrolyte after also needing LiODFB is purified.China
Publication " CN101648963A ", " CN101139352A ", the LiODFB sample purity that obtains in " CN2010436A " are all relatively
Low, the accessory substance LiBF of generation4It is difficult to separate, after needing to be purified, just can serve as lithium ion battery electrolyte.
Synthesis technique flow process of the present invention is short, efficiency high, and simple to operate, equipment investment is few, and yield is high, can directly obtain purity
Product more than 99.9%, can be directly used in lithium ion battery without purification, application prospect is very wide.
Content of the invention
The purpose of the present invention is that synthetic sample purity is low in overcoming above-mentioned patent document, and complex operation, to equipment requirement
High defect, provides a kind of ball-milling preparation method of high-purity lithium oxalyldifluoroborate.
The present invention relates to a kind of ball-milling preparation method of high-purity lithium oxalyldifluoroborate, processing step is as follows：
（1）By lithium oxalate and BFEE in molar ratio 1:1～1:3 add in ball grinder, rotational speed of ball-mill 100-
300rpm, ratio of grinding media to material 1:1~10:1, carry out ball milling 2h～24h at 30 DEG C～90 DEG C.
（2）The product that ball milling is obtained is dissolved in organic solvent in 30 DEG C～90 DEG C high temperature, is filtered to remove solid phase byproduct
With unreacted lithium oxalate, obtain the saturated solution containing LiODFB.
（3）- 20 DEG C of the saturated solution constant temperature～10 DEG C low temperature crystallization obtaining, is incubated 1h～24h, separates out LiODFB brilliant
Body.
（4）In -0.05MPa ~ -0.095MPa, 40 DEG C～100 DEG C of constant temperature, it is vacuum dried the crystal 2h～48h separating out,
Obtain highly purified LiODFB solid.
Solvent for use of the present invention is：Dimethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, vinylene carbonate, ethylene
Isopropyl ester, carbonic acid first butyl ester, dibutyl carbonate, ethyl butyl carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate, second
Any one or a few mixture in nitrile, propionitrile, butyronitrile, oxolane, dimethyl-tetrahydrofuran.
The present invention adopts the method for ball milling to prepare LiODFB first, and technological process is short, and simple to operate, efficiency high, to equipment
There is no the rigors such as high temperature resistant, high pressure resistant, highly purified LiODFB product can be directly obtained, be easy to industrialization.
Brief description
The X ray diffracting spectrum of the LiODFB that Fig. 1 obtains for synthesis technique of the present invention.
The nuclear magnetic resonance map of the LiODFB that Fig. 2 obtains for synthesis technique of the present invention.
The FT-IR of the LiODFB that Fig. 3 obtains for synthesis technique of the present invention penetrates figure.
Specific embodiment
Embodiment 1 adds 10.19g lithium oxalate and 12.57mL BFEE in ball grinder, adds the ball of 30g,
Mix, set drum's speed of rotation as 100 rpm, 30 DEG C of ball milling 2h of constant temperature, ball milling product is dissolved under 50 DEG C of high temperature
In 100mL dimethyl carbonate solvent, it is filtered to remove solid phase byproduct and unreacted lithium oxalate, the saturation obtaining containing LiODFB is molten
Liquid.10 DEG C of low temperature crystallization 1h of the solution obtaining, in 80 DEG C, -0.095MPa vacuum drying 2h, have obtained pure LiODFB solid
13.1g, purity 99.9%, yield is 91%.
Embodiment 2 adds 10.19g lithium oxalate and 25.14mL BFEE in ball grinder, adds the ball of 50g,
Mix, set drum's speed of rotation as 150 rpm, 50 DEG C of ball milling 10h of constant temperature, ball milling product is dissolved under 60 DEG C of high temperature
In 80mL acetonitrile solvent, it is filtered to remove solid phase byproduct and unreacted lithium oxalate, obtains the saturated solution containing LiODFB.Obtain
- 20 DEG C of low temperature crystallization 6h of solution, 40 DEG C, -0.095MPa be vacuum dried 10h, obtained pure LiODFB solid
13.8g, purity 99.9%, yield is 96%.
Embodiment 3 adds 10.19g lithium oxalate and 37.71mL BFEE in ball grinder, adds the ball of 75g,
Mix, set drum's speed of rotation as 300 rpm, 90 DEG C of ball milling 24h of constant temperature, ball milling product is dissolved under 80 DEG C of high temperature
In 150mL diethyl carbonate solvent, it is filtered to remove solid phase byproduct and unreacted lithium oxalate, the saturation obtaining containing LiODFB is molten
Liquid.- 10 DEG C of low temperature crystallization 6h of the solution obtaining, in 100 DEG C, -0.095MPa vacuum drying 24h, have obtained pure LiODFB
Solid 13.3g, purity 99.9%, yield is 93%.
Embodiment 4 adds 10.19g lithium oxalate and 18.86mL BFEE in ball grinder, adds the ball of 60g,
Mix, set drum's speed of rotation as 200 rpm, 70 DEG C of ball milling 12h of constant temperature, ball milling product is dissolved under 40 DEG C of high temperature
In 100mL tetrahydrofuran solvent, it is filtered to remove solid phase byproduct and unreacted lithium oxalate, the saturation obtaining containing LiODFB is molten
Liquid.0 DEG C of low temperature crystallization 1h of the solution obtaining, in 60 DEG C, -0.095MPa vacuum drying 2h, has obtained pure LiODFB solid
13.5g, purity 99.9%, yield is 94%.
Comparative example 1 adds 10.19g lithium oxalate and 12.57mL BFEE in ball grinder, mixes, constant temperature
80 DEG C of reaction 24h, product are dissolved in 100mL dimethyl carbonate solvent under 50 DEG C of high temperature, are filtered to remove solid phase by-product
Thing and unreacted lithium oxalate, obtain the saturated solution containing LiODFB.10 DEG C of low temperature crystallization 12h of the solution obtaining, 60 DEG C ,-
0.095MPa is vacuum dried 2h, has obtained pure LiODFB solid 9.2g, purity 67%, and yield is 64%.
Claims (6)
1. a kind of ball-milling preparation method of high-purity lithium oxalyldifluoroborate, its step is：
（1）Lithium oxalate is added in ball grinder with BFEE, places into appropriate ball, carry out ball milling 2h～24h；
（2）The product that ball milling is obtained is dissolved in 30-90 DEG C of organic solvent, is filtered to remove solid phase byproduct and unreacted oxalic acid
Lithium, obtains the solution containing LiODFB；
（3）The solution obtaining, through low temperature crystallization, vacuum drying, obtains high-purity LiODFB solid.
2. the ball-milling preparation method of a kind of high-purity lithium oxalyldifluoroborate according to claim 1, described organic solvent
It is dimethyl carbonate, dipropyl carbonate, ethyl propyl carbonic acid ester, vinylene carbonate, ethylene isopropyl ester, carbonic acid first butyl ester, carbonic acid
Dibutyl ester, ethyl butyl carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate, acetonitrile, propionitrile, butyronitrile, oxolane, two
Any one or a few mixture in methyltetrahydrofuran.
3. a kind of ball-milling preparation method of high-purity lithium oxalyldifluoroborate according to claim 1 is it is characterised in that raw material
Lithium oxalate is 1 with the mol ratio of BFEE:1～1:3, ball milling temperature be 30 DEG C～90 DEG C, Ball-milling Time be 2h～
24h, rotational speed of ball-mill 100-300rpm, ratio of grinding media to material 1:1~10:1.
4. a kind of ball-milling preparation method of high-purity lithium oxalyldifluoroborate according to claim 1 is it is characterised in that added
Solvent is 1 with the mass ratio of theoretical LiODFB yield:10～100:1.
5. a kind of ball-milling preparation method of high-purity lithium oxalyldifluoroborate according to claim 1 is it is characterised in that low temperature
Recrystallization temperature is -20 DEG C～10 DEG C, is incubated 1h～24h.
6. a kind of ball-milling preparation method of high-purity lithium oxalyldifluoroborate according to claim 1 is it is characterised in that vacuum
The vacuum being dried is 0.05MPa～0.095MPa, and baking temperature is 40 DEG C～100 DEG C, drying time 2h～48h.
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| EP3277694B1 (en) * | 2015-03-31 | 2022-10-05 | Bayerische Motoren Werke Aktiengesellschaft | Method of making lithium difluoro (oxalato) borate |
| CN109836444B (en) * | 2017-11-29 | 2021-05-11 | 东莞东阳光科研发有限公司 | Preparation method of lithium difluoroborate |
| CN113968877A (en) * | 2021-10-29 | 2022-01-25 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium difluoroborate |
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| CN102070661B (en) * | 2011-01-25 | 2012-10-17 | 李荐 | Preparation method of high-purity lithium oxalyldifluoroborate |
| CN103319510B (en) * | 2011-06-22 | 2015-09-16 | 重庆广播电视大学 | The preparation method of the lithium oxalyldifluoroborateelectrolyte electrolyte salt of safety and environmental protection |
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Non-Patent Citations (2)
| Title |
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| Crystal structure and physical properties of lithium difluoro(oxalato)borate (LiDFOB or LiBF2Ox);Joshua L. Allen等;《Journal of Power Sources》;20110726;第196卷;第9738页左栏第2.2节 * |
| 锂离子电池电极材料机械化学合成研究进展;伊廷锋等;《现代化工》;20060630;第26卷(第6期);第20-24页 * |
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