CN103466650A - Method for preparing anhydrous lithium tetrafluoroborate - Google Patents
Method for preparing anhydrous lithium tetrafluoroborate Download PDFInfo
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- CN103466650A CN103466650A CN2013104524069A CN201310452406A CN103466650A CN 103466650 A CN103466650 A CN 103466650A CN 2013104524069 A CN2013104524069 A CN 2013104524069A CN 201310452406 A CN201310452406 A CN 201310452406A CN 103466650 A CN103466650 A CN 103466650A
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Abstract
The invention discloses a method for preparing anhydrous lithium tetrafluoroborate. The method is characterized by including the following processing steps that firstly, water is combined with lithium tetrafluoroborate under the temperature between 170 DEG C and 200 DEG C, and low-moisture lithium tetrafluoroborate powder is obtained in a mechanical stirring dynamic drying manner, a fluidized bed dynamic drying manner and an airflow dynamic drying manner; secondly, the obtained lithium tetrafluoroborate powder is dissolved into lower-carbon alcohol which is ethanol or methanol, the mass ratio of the lower-carbon alcohol and the lithium tetrafluoroborate powder is 1.5:1, insoluble impurities are removed through filtering, and filtered liquid is obtained; thirdly, the filtered liquid is dried to be in the temperature between 120 DEG C and 150 DEG C through vacuum evaporation, and the anhydrous lithium tetrafluoroborate with the moisture content below 0.005% is obtained.
Description
Technical field
The invention belongs to the lithium ion battery material field, relate to a kind of preparation method of waterless lithium terafluoroborate.
Background technology
At present, the ionogen that the production lithium ion battery is used is mainly lithium hexafluoro phosphate (LiPF
6), because lithium hexafluoro phosphate is very sensitive to moisture, be heated and easily decompose and generate the erosion of destroying various materials in battery, cause battery performance to descend, so generally add LiBF4 (LiBF in electrolyte prescription
4) carry out composite improvement.LiBF4 is to thermally-stabilised, poor to the water-sensitive sensitivity, can effectively prevent corrosion, and adds the low-temperature performance of electrolytic solution after appropriate LiBF4 significantly to strengthen.LiBF4 and lithium hexafluoro phosphate are used in conjunction with, make performance of lithium ion battery be improved significantly.
The main method that waterless lithium terafluoroborate is manufactured in industrialization at present is boron trifluoride method and aqua-solution method.The former uses the hypertoxic explosive hazardous substance such as anhydrous hydrogen fluoride and boron trifluoride as raw materials for production, and processing condition are strict, equipment anticorrosion requirement of explosion proof harshness; The latter uses aqueous hydrogen fluoride solution, boric acid and Quilonum Retard for raw materials for production, and the processing condition gentleness does not relate to explosive severe poisonous chemicals, and suitability for industrialized production is safer.But, be heated when dry due to the hydration LiBF4 obtained after aqua-solution method reaction and easily be dissolved in self crystal water and become molten state, cause its dehydration difficulty, especially the moisture of crystalline particle inside is difficult to thoroughly be removed, thereby cause the product moisture and the insolubles content that obtain higher, be difficult to meet the production requirement of high quality electrolytic solution.At present, this technique can only obtain the waterless lithium terafluoroborate of water-content in 0.02% left and right, and insolubles content is higher.
For example, Chinese patent 100593515C has set forth the technique that the ladder-elevating temperature desiccating method prepares waterless lithium terafluoroborate.Adopting aqueous hydrogen fluoride solution, lithium salts is that raw material synthesizes LiBF4 with boric acid, through condensing crystal, obtains a hydration LiBF4, then under vacuum condition in two steps 65～80 ℃ and 90～160 ℃ of dryings, obtain the waterless lithium terafluoroborate product.The method, owing to adopting the ladder-elevating temperature drying, easily is in a liquid state and is improved solving the LiBF4 melted by heating, substantially can keep crystalline powdery to carry out drying operation.But, because the crystalline particle internal moisture is difficult to eliminate through the particle surface melting layer, cause the finished product moisture content generally more than 0.2%.
The low-carbon alcohol solution that the clear 58-190820 of Japanese Patent has introduced a hydration LiBF4 evaporates the method that obtains waterless lithium terafluoroborate.Adopt low-carbon alcohol to dissolve a hydration LiBF4, drying obtains waterless lithium terafluoroborate.Owing in a hydration LiBF4, containing the water more than 16%, a large amount of moisture is difficult to the low-carbon alcohol evaporation totally, and this method can obtain moisture content at 0.02%～0.05% waterless lithium terafluoroborate product.
Chinese patent 102030339A has introduced a water LiBF4 ethanolic soln and has evaporated the method that obtains waterless lithium terafluoroborate.Adopting aqueous hydrogen fluoride solution, lithium salts and boric acid is that raw material prepares LiBF4 solution, irradiate heating through infrared lamp and obtain a hydration LiBF4 under 95 ℃, by the hydration LiBF4 dissolve with ethanol obtained, after filtering, evaporation drying obtains the waterless lithium terafluoroborate sample, and moisture content is lower than 0.02%.It is dry that this method adopts infrared lamp to irradiate, and could not overcome the weakness that the clear 58-190820 of patent exists.
Therefore, although the water legal system is made LiBF4, significant improvement has been arranged, tentatively met the electrolytic solution production requirement, along with the raising of lithium-ion battery electrolytes requirement, wish to use moisture content at the waterless lithium terafluoroborate below 0.005%, the water method still needs to improve.The present invention is improved exactly on existing technical foundation, adopts two-step process, obtains moisture content at the LiBF4 below 0.005%, further meets the service requirements of high performance lithium ion battery electrolytic solution.
Summary of the invention
LiBF4 is heated and easily decomposes, and the lithium fluoride of generation will be brought product into as residual insolubles, affect quality product.Heat the analysis showed that, LiBF4, about 180 ℃ decomposition, decomposes obviously and accelerates more than 200 ℃.When a hydration LiBF4 is heated, because LiBF4 easily is dissolved in self crystal water formation molten state, internal moisture is difficult to migration and goes out, and granule interior is easily decomposed, so the drying of monohydrate need to be upgraded surface at any time, suitable employing is dynamically dry.The drying of monohydrate is carried out at higher temperature, so that reduce moisture is to obtain the more prerequisite of low-water-content product.Rising monohydrate drying temperature also can cause LiBF4 to decompose on a small quantity, but a small amount of insolubles produced is decomposed in filtering after low-carbon alcohol is dissolved, and this filtrate is evaporation drying at a lower temperature, thereby obtains the waterless lithium terafluoroborate product that moisture is lower.
The preparation method that the present invention is a kind of waterless lithium terafluoroborate is characterized in that:
Comprise following processing step:
1) a hydration LiBF4 is at 170～200 ℃; With the dynamic drying mode of mechanical agitation type, fluidized bed type and air-flowing type drying, obtain low moisture Tetrafluoroboric acid powder for lithium;
2) the Tetrafluoroboric acid powder for lithium obtained is dissolved in to low-carbon alcohol: low-carbon alcohol is ethanol or methyl alcohol, and the mass ratio of low-carbon alcohol and Tetrafluoroboric acid powder for lithium is 1.5:1; Remove by filter insoluble impurities, obtain filtrate;
3) filtrate vacuum-evaporation is dried to 120～150 ℃, obtains moisture content at the waterless lithium terafluoroborate below 0.005%.
According to preparation method of the present invention, it is characterized in that:
Comprise following processing step:
1) a hydration LiBF4, at 180～190 ℃, with the dynamic drying mode of mechanical agitation type, fluidized bed type, obtains low moisture Tetrafluoroboric acid powder for lithium;
2) the Tetrafluoroboric acid powder for lithium obtained is dissolved in to low-carbon alcohol: low-carbon alcohol is ethanol;
3) filtrate vacuum-evaporation is dried to 130～140 ℃; Obtain moisture content at the waterless lithium terafluoroborate below 0.005%.
The drying of a hydration LiBF4 of the present invention surface that need to upgrade in time, fixed even integrally fused and affect granule interior moisture and move out to avoid particle surface, so adopt dynamically dry; Dry mode comprises the various ways such as mechanical agitation type, fluidized bed type and air-flowing type drying that can make material constantly move in drying process.
The drying temperature of one hydration LiBF4 is 170～200 ℃, preferably 180～190 ℃.Be due to temperature when too low drying efficiency too low, although can make the sample water ratio lower when temperature surpasses 200 ℃, decomposition amount can strengthen.
There are a small amount of lithium fluoride insolubles and micro-water in above-mentioned dry thing, filtering insolubles after dissolving by low-carbon alcohol.The low-carbon alcohol of dissolving the Tetrafluoroboric acid powder for lithium is ethanol or methyl alcohol, and the mass ratio of low-carbon alcohol and Tetrafluoroboric acid powder for lithium is 1.5:1.This is because ratio hour approaches very much saturation point, easy Crystallization Plugging filtration medium when filtering, and ratio too conference increases cost.
In low-carbon alcohol, the moisture of trace is taken away with evaporation drying, obtains moisture content at the waterless lithium terafluoroborate product below 0.005%.The temperature of filtrate vacuum-evaporation drying is 120～150 ℃, preferably 130～140 ℃.Temperature is low-carbon alcohol and the residual height of minor amount of water during lower than 120 ℃, and temperature easily causes LiBF4 to decompose higher than 150 ℃ and produces undesirable residue.
According to method of the present invention, the drying of one hydration LiBF4 produces a small amount of the decomposition, degradation production can make by condensation absorption process commonly used the hydrogen fluoride that decompose to produce etc. be recycled, and reduces on the impact of ambient air and as the raw material of front synthesis technique and recycles; Low-carbon alcohol is dissolved the raw material that a small amount of lithium fluoride powder leached can be used as other Chemicals of preparation (as lithium hexafluoro phosphate).The preparation of one hydration LiBF4 can adopt known water method technique.
Embodiment
Embodiment 1:
The hydrofluoric acid solution of getting 1400 grams 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, with ice-water bath, cools to below 5 ℃, adds while stirring boric acid 432.6 grams, continues stirring reaction 1 hour; Slowly add Quilonum Retard 258.7 grams in above-mentioned reaction solution, continue stirring reaction 1 hour, evaporate reaction solution and, in 40 ℃ of crystallizations, washing, obtain a hydration LiBF4.One water thing is put into to vibration limit, hot air circulation vibration drying case limit and be warmed up to 185 ℃ and freeze-day with constant temperature 6 hours, take out the Tetrafluoroboric acid lithium powder, with ethanol, fully dissolve, ethanol and LiBF4 mass ratio are 1.5:1, the filtering insolubles, filtrate vacuum-evaporation is dried to 130 ℃, obtains the waterless lithium terafluoroborate that moisture content is 0.003%.
Embodiment 2:
The hydrofluoric acid solution of getting 1400 grams 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, with ice-water bath, cools to below 5 ℃, adds while stirring boric acid 432.6 grams, continues stirring reaction 1 hour; Slowly add Quilonum Retard 258.7 grams in above-mentioned reaction solution, continue stirring reaction 1 hour, evaporate reaction solution and, in 40 ℃ of crystallizations, washing, obtain a hydration LiBF4.One water thing is put into to vibration limit, hot air circulation vibration drying case limit and be warmed up to 200 ℃ and freeze-day with constant temperature 4 hours, take out the Tetrafluoroboric acid lithium powder, with ethanol, fully dissolve, ethanol and LiBF4 mass ratio are 1.5:1, the filtering insolubles, filtrate vacuum-evaporation is dried to 120 ℃, obtains the waterless lithium terafluoroborate that moisture content is 0.002%.
Embodiment 3:
The hydrofluoric acid solution of getting 1400 grams 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, with ice-water bath, cools to below 5 ℃, adds while stirring boric acid 432.6 grams, continues stirring reaction 1 hour; Slowly add Quilonum Retard 258.7 grams in above-mentioned reaction solution, continue stirring reaction 1 hour, evaporate reaction solution and, in 40 ℃ of crystallizations, washing, obtain a hydration LiBF4.One water thing is put into to vibration limit, hot air circulation vibration drying case limit and be warmed up to 170 ℃ and freeze-day with constant temperature 8 hours, take out the Tetrafluoroboric acid lithium powder, with ethanol, fully dissolve, ethanol and LiBF4 mass ratio are 1.5:1, the filtering insolubles, filtrate vacuum-evaporation is dried to 150 ℃, obtains the waterless lithium terafluoroborate that moisture content is 0.0042%.
Embodiment 4:
The hydrofluoric acid solution of getting 1400 grams 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, with ice-water bath, cools to below 5 ℃, adds while stirring boric acid 432.6 grams, continues stirring reaction 1 hour; Slowly add Quilonum Retard 258.7 grams in above-mentioned reaction solution, continue stirring reaction 1 hour, evaporate reaction solution and, in 40 ℃ of crystallizations, washing, obtain a hydration LiBF4.One water thing is put into to vibration limit, hot air circulation vibration drying case limit and be warmed up to 185 ℃ and freeze-day with constant temperature 6 hours, take out the Tetrafluoroboric acid lithium powder, with methyl alcohol, fully dissolve, methyl alcohol and LiBF4 mass ratio are 1.5:1, the filtering insolubles, filtrate vacuum-evaporation is dried to 130 ℃, obtains the waterless lithium terafluoroborate that moisture content is 0.0028%.
Claims (2)
1. the preparation method of a waterless lithium terafluoroborate is characterized in that:
Comprise following processing step:
1) a hydration LiBF4 is at 170～200 ℃; With the dynamic drying mode of mechanical agitation type, fluidized bed type and air-flowing type drying, obtain low moisture Tetrafluoroboric acid powder for lithium;
2) the Tetrafluoroboric acid powder for lithium obtained is dissolved in to low-carbon alcohol: low-carbon alcohol is ethanol or methyl alcohol, and the mass ratio of low-carbon alcohol and Tetrafluoroboric acid powder for lithium is 1.5:1; Remove by filter insoluble impurities, obtain filtrate;
3) filtrate vacuum-evaporation is dried to 120～150 ℃, obtains moisture content at the waterless lithium terafluoroborate below 0.005%.
2. according to preparation method claimed in claim 1, it is characterized in that:
Comprise following processing step:
1) a hydration LiBF4, at 180～190 ℃, with the dynamic drying mode of mechanical agitation type, fluidized bed type, obtains low moisture Tetrafluoroboric acid powder for lithium;
2) the Tetrafluoroboric acid powder for lithium obtained is dissolved in to low-carbon alcohol: low-carbon alcohol is ethanol;
3) filtrate vacuum-evaporation is dried to 130～140 ℃; Obtain moisture content at the waterless lithium terafluoroborate below 0.005%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030310A (en) * | 2014-05-23 | 2014-09-10 | 中国海洋石油总公司 | Method for preparing lithium tetrafluoroborate |
| CN109888269A (en) * | 2018-12-29 | 2019-06-14 | 广东邦普循环科技有限公司 | A kind of pretreated method of ternary material mixing |
| CN110182829A (en) * | 2019-06-11 | 2019-08-30 | 新疆有色金属研究所 | A kind of industrialized process for preparing of cell-grade anhydrous lithium iodide |
| CN112960678A (en) * | 2021-02-06 | 2021-06-15 | 昆明铂生金属材料加工有限公司 | Method for removing crystal water and purifying crude silver tetrafluoroborate |
| CN116462205A (en) * | 2023-03-29 | 2023-07-21 | 宜春国轩电池有限公司 | Synthesis method of lithium tetrafluoroborate |
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| JP2001247307A (en) * | 2000-03-02 | 2001-09-11 | Kanto Denka Kogyo Co Ltd | Method for producing lithium tetrafluoroborate |
| US20020172634A1 (en) * | 2001-03-28 | 2002-11-21 | Council Of Scientific & Industrial Research | Process for the preparation of LiBF4 |
| CN102030339A (en) * | 2011-01-12 | 2011-04-27 | 新疆有色金属研究所 | Preparation method of battery-grade anhydrous lithium tetrafluoroborate |
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2013
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Patent Citations (3)
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| JP2001247307A (en) * | 2000-03-02 | 2001-09-11 | Kanto Denka Kogyo Co Ltd | Method for producing lithium tetrafluoroborate |
| US20020172634A1 (en) * | 2001-03-28 | 2002-11-21 | Council Of Scientific & Industrial Research | Process for the preparation of LiBF4 |
| CN102030339A (en) * | 2011-01-12 | 2011-04-27 | 新疆有色金属研究所 | Preparation method of battery-grade anhydrous lithium tetrafluoroborate |
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| 吴宇平等: "《锂离子二次电池》", 30 November 2002 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030310A (en) * | 2014-05-23 | 2014-09-10 | 中国海洋石油总公司 | Method for preparing lithium tetrafluoroborate |
| CN104030310B (en) * | 2014-05-23 | 2015-11-25 | 中国海洋石油总公司 | A kind of preparation method of LiBF4 |
| CN109888269A (en) * | 2018-12-29 | 2019-06-14 | 广东邦普循环科技有限公司 | A kind of pretreated method of ternary material mixing |
| CN110182829A (en) * | 2019-06-11 | 2019-08-30 | 新疆有色金属研究所 | A kind of industrialized process for preparing of cell-grade anhydrous lithium iodide |
| CN112960678A (en) * | 2021-02-06 | 2021-06-15 | 昆明铂生金属材料加工有限公司 | Method for removing crystal water and purifying crude silver tetrafluoroborate |
| CN116462205A (en) * | 2023-03-29 | 2023-07-21 | 宜春国轩电池有限公司 | Synthesis method of lithium tetrafluoroborate |
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| CN103466650B (en) | 2016-01-20 |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161012 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |