CN101139352A - Method for preparing difluorine oxalic acid boracic acid lithium - Google Patents
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Abstract
The present invention discloses a preparation method of the difluoride lithium oxalate borate. The method is characterized in that the compounds containing the fluorin, boron, lithium and oxalate react at a certain temperature and under a certain pressure to produce the crude material of the difluoride lithium oxalate borate; then the organic solvent is used for extracting and purifying; finally, the recrystallization and vacuum drying are done to get the battery-level lithium fluoride oxalate borate. The advantage is that the preparation method of the difluoride lithium oxalate borate can improve the high-temperature and low-temperature performance, the cycle performance, power characteristics and other comprehensive performances of the lithium-ion battery.
Description
Technical field
The present invention relates to the manufacturing technology field of the used electrolytic salt of lithium ion battery, specifically is a kind of preparation method of electrolytic salt difluorine oxalic acid boracic acid lithium.
Background technology
Electrolytic salt is the important component part of lithium-ion electrolyte, to the very big influence of performance generation of lithium ion battery.In recent years, lithium hexafluoro phosphate (LiPF
6) be widely used in the research of lithium ion battery electrolyte salt.LiPF
6Have good ionic conductivity and electrochemical stability, waste battery and handle advantages such as simple, that environmental pollution is little, and good consistency is arranged with the positive and negative electrode of battery.Yet its poor heat stability is easy to resolve into LiF and PF
5, while PF
5Very easily hydrolysis forms HF and POF
3, these two kinds of hydrolysates all have high reaction activity and high for anodal and negative material, thereby cause the cycle performance of lithium ion battery to reduce.Di-oxalate lithium borate (LiBOB) is compared with lithium hexafluoro phosphate, has good cyclical stability under the electrochemical window of broad, higher thermostability and the high temperature, and participate in the formation of SEI film directly, the graphite cathode surface resistivity is increased, prevent the generation that common embedding of solvent and graphite cathode are peeled off phenomenon.The battery that LiBOB forms for the Ni-based composite oxide positive pole of graphite cathode and lithium is also found in research, and circulation time does not have significant capacity attenuation under 60 ℃ or 70 ℃ of comparatively high tempss, particularly spinel manganese oxygen positive electrode material is had very big advantage.Yet also there are some shortcomings in LiBOB, as solubleness is low in the alkyl carbonate solvent, viscosity is high, thereby causes that its electroconductibility is relatively poor, low-temperature performance is bad; In addition, adopt the SEI film of LiBOB salt formation to have bigger resistance, influence the power-performance under the power characteristic of battery, particularly cold condition, therefore limited the extensive application of LiBOB in lithium ion battery to a certain extent.LiBF4 (LiBF
4) as the electrolytic salt of lithium ion battery, can improve the low-temperature performance of lithium ion battery significantly, but have that specific conductivity is lower, poor heat stability and be easy to a series of problems such as hydrolysis.Therefore, make a general survey of the development of lithium-ion battery electrolytes, the electrolytic solution of present commercial use is difficult to take into account simultaneously the high temperature and the low-temperature performance requirement of lithium ion battery.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method that can improve the difluorine oxalic acid boracic acid lithium of over-all propertieies such as lithium ion battery high temperature performance, cycle performance, power characteristic will be provided.
For addressing the above problem, the technical solution used in the present invention is: the preparation method of described difluorine oxalic acid boracic acid lithium is characterized in: fluorochemicals, boron-containing compound, lithium-containing compound and the compound that contains oxalate are reacted under certain temperature and pressure generates the difluorine oxalic acid boracic acid lithium crude product; Carry out purification by liquid extraction with organic solvent then; Obtain the cell-grade difluorine oxalic acid boracic acid lithium carrying out recrystallization and vacuum-drying at last.
Above-mentioned fluorochemicals, boron-containing compound, lithium-containing compound and the compound that contains oxalate are selected from following material: boron trifluoride, boric acid, borax, lithium hydroxide, Quilonum Retard, lithium oxalate, lithium fluoride, fluoroboric acid, oxalic acid.And the mol ratio of control fluorine, boron, lithium and oxalate denominationby is 2～4: 0.9～1.1: 1: 1, temperature of reaction was 0～100 ℃, and reaction pressure is 0.1～1MPa, reaction medium be in air, water, ether, methyl alcohol, the ethanol one or more.
The used organic solvent of above-mentioned extraction is selected from acetonitrile, methylcarbonate, methyl alcohol.
The solvent of above-mentioned recrystallization is selected from water, acetonitrile, methylcarbonate, methyl alcohol, and the temperature of recrystallization is-30 ℃～100 ℃.
Above-mentioned vacuum drying temperature is 60 ℃～250 ℃, and vacuum tightness is-0.1～0.1MPa, and be 0～48 hour time of drying.
The invention has the beneficial effects as follows: resulting target substance is difluorine oxalic acid boracic acid lithium (LiODFB), and its chemical structure is di-oxalate lithium borate (LiBOB) and LiBF4 (LiBF
4) combination of structure, so LiODFB is used in and has LiBOB and LiBF in the lithium ion battery concurrently
4The advantage of two kinds of lithium metal compounds.Compare with LiBOB, LiODFB has higher solubleness, good battery rate capability and cold cycle performance in the alkyl carbonate solvent; With LiBF
4Compare, LiODFB can form more effective SEI film on the graphite cathode surface, improves the high temperature cyclic performance of lithium ion battery.As seen, adopt the electrolytic solution of LiODFB electrolytic salt in very wide temperature range, to use safely, perhaps LiODFB is used as the additive of electrolytic solution, improve the over-all properties of lithium ion battery.
LiODFB has good solubility property in the alkyl carbonate solvent.For example (1: 1: 3wt%) in the mixed solvent, temperature was at the LiODFB of-50 ℃～100 ℃ of equal solubilized 1mol/L, and electrolytic solution has good specific conductivity at propylene carbonate/NSC 11801/Methyl ethyl carbonate.This shows that the LiODFB electrolytic salt can make lithium ion battery work under high temperature and low temperature, the high temperature and the low-temperature performance that solve lithium ion battery are difficult to satisfied simultaneously problem.And can also improve the cyclicity of lithium ion battery under high/low temperature condition, multiplying power etc.
Description of drawings
Fig. 1 is LiMn
2O
4The cycle performance figure of/graphite battery 1C under 60 ℃ and 0 ℃.
Embodiment
The invention will be further described below by specific embodiment; But the present invention should not only limit to these embodiment.
Embodiment 1
Adopting boron trifluoride ether solution and lithium oxalate is the feedstock production difluorine oxalic acid boracic acid lithium.
Step 1, in the dry reactor that electric mixer, thermometer are housed, add 101.9g through 4 hours lithium oxalate of 120 ℃ of dryings, slowly splash into the 158g boron trifluoride ether solution, heating and stirring mix raw material as far as possible, sealed reactor then, be heated to 80 ℃ of constant temperature 48 hours, boron trifluoride and lithium oxalate are fully reacted generate difluorine oxalic acid boracic acid lithium and lithium fluoride, be cooled to room temperature subsequently.
Step 2, post reaction mixture filtered at normal temperatures remove the lithium fluoride solid that unreacted lithium oxalate and reaction back generate, mother liquor carries out concentrating under reduced pressure, crystallisation by cooling after methylcarbonate repeatedly extracts, carry out recrystallization process to remove remaining impurities with methylcarbonate again.
Product behind step 3, the recrystallization in 155 ℃ of dryings 48 hours, finally obtains product 121.7g under vacuum tightness-0.08MPa, be 99.92% through checking its purity.
Products obtained therefrom is analyzed, and the result shows: the purity of product is 99.92%, and moisture content is (with H
2The O meter) be 16ppm.
The difluorine oxalic acid boracic acid lithium of gained is made into electrolytic solution, and (2: 1: 1wt%), recording its specific conductivity by analysis was respectively 7.9mS/cm and 1.2mS/cm when 60 ℃ and-30 ℃ to consist of 1mol/L LiODFB NSC 11801/Methyl ethyl carbonate/methylcarbonate.
Embodiment 2
With lithium hydroxide, oxalic acid and boron trifluoride ether solution is the feedstock production difluorine oxalic acid boracic acid lithium.
Step 1, the 47.9g lithium hydroxide is dissolved in the distilled water, add 140g oxalic acid crystal gradually, start whipping appts simultaneously, treat all slowly to splash into the 173.1g boron trifluoride ether solution after the dissolving, sealed reactor, whole mixed solution is heated to 86 ℃ and constant temperature it was fully reacted in 54 hours, be cooled to room temperature subsequently.
Step 2, post reaction mixture is filtered at normal temperatures, mother liquor carries out concentrating under reduced pressure, crystallisation by cooling after methylcarbonate repeatedly extracts, carry out recrystallization process with acetonitrile solution again, to remove remaining impurities.
Product behind step 3, the recrystallization in 180 ℃ of dryings 48 hours, finally obtains product 129.6g under vacuum tightness-0.08MPa, be 99.94% through checking its purity.
Products obtained therefrom is analyzed, and the result shows: the purity of product is 99.94%, and moisture content is (with H
2The O meter) be 11ppm.
The difluorine oxalic acid boracic acid lithium of gained is made into electrolytic solution, (1: 2: 1wt%), recording its specific conductivity by analysis was respectively 8.10mS/cm and 1.12mS/cm when 60 ℃ and-30 ℃ to consist of 1mol/L LiODFB propylene carbonate/NSC 11801/Methyl ethyl carbonate.
Embodiment 3
With LiMn
2O
4Be positive pole, graphite is that (1: 2: 1wt%) the cycle performance test result was as shown in Figure 1 in the electrolytic solution at 1mol/L LiODFB propylene carbonate/NSC 11801/Methyl ethyl carbonate for the lithium ion battery of negative pole assembling.Show that by analysis lithium ion battery capability retention after 60 ℃ of following 1C circulations 300 times is 90%; Capability retention is 85.4% after 0 ℃ of 1C circulation 300 times.As seen, adopting LiODFB is that the lithium ion battery of electrolytic solution has good high low temperature cycle performance.
Claims (5)
1. the preparation method of difluorine oxalic acid boracic acid lithium is characterized in that: fluorochemicals, boron-containing compound, lithium-containing compound and the compound that contains oxalate are reacted under certain temperature and pressure generates the difluorine oxalic acid boracic acid lithium crude product; Carry out purification by liquid extraction with organic solvent then; Obtain the cell-grade difluorine oxalic acid boracic acid lithium carrying out recrystallization and vacuum-drying at last.
2. preparation method as claimed in claim 1 is characterized in that: described fluorochemicals, boron-containing compound, lithium-containing compound and the compound that contains oxalate are selected from following material: boron trifluoride, boric acid, borax, lithium hydroxide, Quilonum Retard, lithium oxalate, lithium fluoride, fluoroboric acid, oxalic acid.And the mol ratio of control fluorine, boron, lithium and oxalate denominationby is 2～4: 0.9～1.1: 1: 1, temperature of reaction was 0～100 ℃, and reaction pressure is 0.1～1MPa, reaction medium be in air, water, ether, methyl alcohol, the ethanol one or more.
3. preparation method as claimed in claim 1 or 2 is characterized in that: extract used organic solvent and be selected from acetonitrile, methylcarbonate, methyl alcohol.
4. preparation method as claimed in claim 1 or 2 is characterized in that: the solvent of recrystallization is selected from water, acetonitrile, methylcarbonate, methyl alcohol, and the temperature of recrystallization is-30 ℃～100 ℃.
5. preparation method as claimed in claim 1 or 2 is characterized in that: vacuum drying temperature is 60 ℃～250 ℃, and vacuum tightness is-0.1～0.1MPa, and be 0～48 hour time of drying.
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010436A (en) * | 2010-11-10 | 2011-04-13 | 兰州理工大学 | Method for preparing lithium difluoro(oxalato)borate |
| CN101643481B (en) * | 2009-08-28 | 2011-08-17 | 张家港市国泰华荣化工新材料有限公司 | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate |
| CN102260282A (en) * | 2011-06-22 | 2011-11-30 | 常州市国亚新能源科技有限公司 | Preparation method of lithium oxalyldifluoroborate electrolyte salt |
| CN103151561A (en) * | 2013-03-05 | 2013-06-12 | 华南师范大学 | Electrolytic lithium salt and preparation method and applications of electrolyte solution containing lithium salt |
| CN103265569A (en) * | 2013-05-17 | 2013-08-28 | 太原理工大学 | Lithium difluoro(oxalato)borate synthesis method |
| CN103382577A (en) * | 2013-07-29 | 2013-11-06 | 中国科学院青海盐湖研究所 | [(CH3O)2CO]3Li2[C2BF204]2 single crystal and preparation method and application thereof |
| CN103490070A (en) * | 2013-10-24 | 2014-01-01 | 兰州理工大学 | Preparation method of lithium difluoroborate sulfate and lithium difluoroborate sulfite |
| CN103483367A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Preparing method of difluoro oxalic acid boric acid metal salt |
| CN103483368A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Method for preparing lithium oxalyldifluoroborate |
| CN104681301A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super capacitor |
| CN105384761A (en) * | 2015-12-07 | 2016-03-09 | 张家港瀚康化工有限公司 | Preparation method for lithium borane trioxalate |
| CN105399761A (en) * | 2015-10-22 | 2016-03-16 | 中国海洋石油总公司 | Preparation method of lithium difluoro(oxalato)borate |
| CN105481887A (en) * | 2015-12-31 | 2016-04-13 | 苏州润禾化学材料有限公司 | Preparation method of lithium oxalyldifluroborate |
| CN105742703A (en) * | 2016-03-09 | 2016-07-06 | 华南师范大学 | High-voltage functional electrolyte containing LiDFOB additive and preparation and application thereof |
| CN105789611A (en) * | 2016-03-23 | 2016-07-20 | 合肥国轩高科动力能源有限公司 | Electrolyte of considering high temperature cycle performance and low temperature cycle performance of battery and lithium-ion battery |
| 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 |
| CN106946921A (en) * | 2017-04-07 | 2017-07-14 | 上海如鲲新材料有限公司 | The method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate |
| CN109438488A (en) * | 2018-11-13 | 2019-03-08 | 九江天赐高新材料有限公司 | A kind of preparation method of liquid Lithium bis (oxalate) borate salt |
| CN111978339A (en) * | 2020-08-20 | 2020-11-24 | 山东森诺威新能源有限公司 | Preparation method of lithium difluoroborate |
| CN112625055A (en) * | 2019-10-08 | 2021-04-09 | 杉杉新材料（衢州）有限公司 | Method for purifying lithium difluorooxalate borate and lithium tetrafluoroborate mixed lithium salt and application thereof |
| CN116813655A (en) * | 2023-08-28 | 2023-09-29 | 江苏华盛锂电材料股份有限公司 | Preparation process of lithium difluoro oxalate borate |
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2007
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| CN101643481B (en) * | 2009-08-28 | 2011-08-17 | 张家港市国泰华荣化工新材料有限公司 | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate |
| CN102010436A (en) * | 2010-11-10 | 2011-04-13 | 兰州理工大学 | Method for preparing lithium difluoro(oxalato)borate |
| CN102260282B (en) * | 2011-06-22 | 2013-08-21 | 常州市国亚新能源科技有限公司 | Preparation method of lithium oxalyldifluoroborate electrolyte salt |
| CN102260282A (en) * | 2011-06-22 | 2011-11-30 | 常州市国亚新能源科技有限公司 | Preparation method of lithium oxalyldifluoroborate electrolyte salt |
| CN103151561B (en) * | 2013-03-05 | 2015-07-01 | 华南师范大学 | Electrolytic lithium salt and preparation method and applications of electrolyte solution containing lithium salt |
| CN103151561A (en) * | 2013-03-05 | 2013-06-12 | 华南师范大学 | Electrolytic lithium salt and preparation method and applications of electrolyte solution containing lithium salt |
| CN103265569A (en) * | 2013-05-17 | 2013-08-28 | 太原理工大学 | Lithium difluoro(oxalato)borate synthesis method |
| CN103382577A (en) * | 2013-07-29 | 2013-11-06 | 中国科学院青海盐湖研究所 | [(CH3O)2CO]3Li2[C2BF204]2 single crystal and preparation method and application thereof |
| CN103382577B (en) * | 2013-07-29 | 2016-04-06 | 中国科学院青海盐湖研究所 | A kind of [(CH 3o) 2cO] 3li 2[C 2bF 2o 4] 2monocrystalline and preparation method thereof and application |
| CN103483367A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Preparing method of difluoro oxalic acid boric acid metal salt |
| CN103483368A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Method for preparing lithium oxalyldifluoroborate |
| CN103483368B (en) * | 2013-09-17 | 2016-08-17 | 东莞市凯欣电池材料有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
| CN103483367B (en) * | 2013-09-17 | 2016-03-23 | 东莞市凯欣电池材料有限公司 | The preparation method of difluoro oxalic acid boric acid metal salt |
| CN103490070A (en) * | 2013-10-24 | 2014-01-01 | 兰州理工大学 | Preparation method of lithium difluoroborate sulfate and lithium difluoroborate sulfite |
| CN104681301A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super capacitor |
| CN104681301B (en) * | 2013-12-03 | 2018-03-20 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super-capacitor |
| CN105399761A (en) * | 2015-10-22 | 2016-03-16 | 中国海洋石油总公司 | Preparation method of lithium difluoro(oxalato)borate |
| CN105384761A (en) * | 2015-12-07 | 2016-03-09 | 张家港瀚康化工有限公司 | Preparation method for lithium borane trioxalate |
| CN105481887A (en) * | 2015-12-31 | 2016-04-13 | 苏州润禾化学材料有限公司 | Preparation method of lithium oxalyldifluroborate |
| CN105742703A (en) * | 2016-03-09 | 2016-07-06 | 华南师范大学 | High-voltage functional electrolyte containing LiDFOB additive and preparation and application thereof |
| 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 |
| CN105789611A (en) * | 2016-03-23 | 2016-07-20 | 合肥国轩高科动力能源有限公司 | Electrolyte of considering high temperature cycle performance and low temperature cycle performance of battery and lithium-ion battery |
| CN106946921A (en) * | 2017-04-07 | 2017-07-14 | 上海如鲲新材料有限公司 | The method that ethanedioic acid fluorine boron ester prepares difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate |
| CN109438488A (en) * | 2018-11-13 | 2019-03-08 | 九江天赐高新材料有限公司 | A kind of preparation method of liquid Lithium bis (oxalate) borate salt |
| CN112625055A (en) * | 2019-10-08 | 2021-04-09 | 杉杉新材料（衢州）有限公司 | Method for purifying lithium difluorooxalate borate and lithium tetrafluoroborate mixed lithium salt and application thereof |
| CN111978339A (en) * | 2020-08-20 | 2020-11-24 | 山东森诺威新能源有限公司 | Preparation method of lithium difluoroborate |
| CN116813655A (en) * | 2023-08-28 | 2023-09-29 | 江苏华盛锂电材料股份有限公司 | Preparation process of lithium difluoro oxalate borate |
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Application publication date: 20080312 |