CN103466650B - A kind of preparation method of waterless lithium terafluoroborate - Google Patents
A kind of preparation method of waterless lithium terafluoroborate Download PDFInfo
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Abstract
The present invention is a kind of preparation method of waterless lithium terafluoroborate, it is characterized in that: comprise following processing step: 1) a hydration LiBF4 is at 170 ~ 200 DEG C; 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 low-carbon alcohol: low-carbon alcohol is ethanol or methyl alcohol, the mass ratio of low-carbon alcohol and Tetrafluoroboric acid powder for lithium is 1.5:1; Cross and filter insoluble impurities, obtain filtrate; 3) by filter vacuum evaporation drying to 120 ~ 150 DEG C, obtain the waterless lithium terafluoroborate of moisture content below 0.005%.
Description
Technical field
The invention belongs to field of lithium ion battery material, relate to a kind of preparation method of waterless lithium terafluoroborate.
Background technology
At present, the ionogen mainly lithium hexafluoro phosphate (LiPF of lithium ion battery is produced
6), because lithium hexafluoro phosphate is very sensitive to moisture, be heated and easily decompose and generate the erosion destroying various material in battery, cause battery performance to decline, therefore generally add LiBF4 (LiBF in electrolyte prescription
4) carry out composite improvement.LiBF4 is to thermally-stabilised, poor to water-sensitive sensitivity, effectively can prevent corrosion, and after adding appropriate LiBF4, the low-temperature performance of electrolytic solution significantly strengthens.LiBF4 and lithium hexafluoro phosphate with the use of, make performance of lithium ion battery be improved significantly.
The main method that current industrialization manufactures waterless lithium terafluoroborate 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 require strict, and equipment anticorrosion requirement of explosion proof is harsh; The latter uses aqueous hydrogen fluoride solution, boric acid and Quilonum Retard for raw materials for production, and processing condition are gentle, and do not relate to explosive severe poisonous chemicals, suitability for industrialized production is safer.But, due to the hydration LiBF4 obtained after aqua-solution method reaction dry time be heated and be easily 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, thus cause the product moisture that obtains and insolubles content higher, be difficult to meet the production requirement of high quality electrolytic solution.At present, this technique can only obtain water-content about 0.02% waterless lithium terafluoroborate, and insolubles content is higher.
Such as, Chinese patent 100593515C has set forth the technique that ladder-elevating temperature desiccating method prepares waterless lithium terafluoroborate.Adopt aqueous hydrogen fluoride solution, lithium salts and boric acid to be Material synthesis LiBF4, obtain a hydration LiBF4 through condensing crystal, then under vacuum in two steps 65 ~ 80 DEG C and 90 ~ 160 DEG C of dryings, obtain waterless lithium terafluoroborate product.The method, owing to adopting ladder-elevating temperature dry, is easily in a liquid state to solution LiBF4 melted by heating and is improved, crystalline powdery substantially can be kept to carry out drying operation.But eliminate because crystalline particle internal moisture is difficult to through 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 describes a hydration LiBF4 evaporates the method obtaining waterless lithium terafluoroborate.Adopt low-carbon alcohol to dissolve a hydration LiBF4, drying obtains waterless lithium terafluoroborate.Due in a hydration LiBF4 containing more than 16% water, a large amount of moisture be difficult to low-carbon alcohol evaporation totally, this method can obtain moisture content 0.02% ~ 0.05% waterless lithium terafluoroborate product.
Chinese patent 102030339A describes the method that a water LiBF4 ethanolic soln evaporation obtains waterless lithium terafluoroborate.Aqueous hydrogen fluoride solution, lithium salts and boric acid is adopted to be that lithium tetrafluoroborate solution prepared by raw material, at 95 DEG C, irradiate heating through infrared lamp and obtain a hydration LiBF4, by the hydration LiBF4 dissolve with ethanol obtained, after filtering, evaporation drying obtains 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 Aqueous phase manufactures LiBF4 significant improvement, tentatively meet electrolytic solution production requirement, the raising required along with lithium-ion battery electrolytes, wish to use the waterless lithium terafluoroborate of moisture content below 0.005%, Aqueous phase still needs to improve.The present invention improves exactly in existing technical foundation, adopts two-step process, obtains the LiBF4 of moisture content below 0.005%, meet the service requirements of high performance lithium ion battery electrolytic solution further.
Summary of the invention
LiBF4 is heated and easily decomposes, and the lithium fluoride of generation will bring product into as residual insolubles, affect quality product.Thermal analyses shows, LiBF4 is about 180 DEG C decomposition, and more than 200 DEG C are decomposed obviously quickening.When a hydration LiBF4 is heated, form molten state because LiBF4 is easily dissolved in self crystal water, internal moisture is difficult to migration and goes out, and granule interior is easily decomposed, so the drying of monohydrate needs to upgrade surface at any time, suitable employing is dynamically dry.The drying of monohydrate is carried out at a higher temperature, to reduce moisture as far as possible, is the prerequisite obtaining more low-water-content product.Raising 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, this filtrate evaporation drying at a lower temperature, thus obtains the lower waterless lithium terafluoroborate product of moisture.
The present invention is a kind of preparation method of waterless lithium terafluoroborate, it is characterized in that:
Comprise following processing step:
1) a hydration LiBF4 is at 170 ~ 200 DEG C; 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 low-carbon alcohol: low-carbon alcohol is ethanol or methyl alcohol, the mass ratio of low-carbon alcohol and Tetrafluoroboric acid powder for lithium is 1.5:1; Cross and filter insoluble impurities, obtain filtrate;
3) by filter vacuum evaporation drying to 120 ~ 150 DEG C, obtain the waterless lithium terafluoroborate of moisture content below 0.005%.
According to preparation method of the present invention, it is characterized in that:
Comprise following processing step:
1) a hydration LiBF4 is at 180 ~ 190 DEG C, 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 low-carbon alcohol: low-carbon alcohol is ethanol;
3) by filter vacuum evaporation drying to 130 ~ 140 DEG C; Obtain the waterless lithium terafluoroborate of moisture content below 0.005%.
The drying of a hydration LiBF4 of the present invention needs the surface that upgrades in time, affects granule interior moisture move out to avoid particle surface consolidation even integrally fused, so adopt dynamically dry; Dry mode comprises the various ways such as mechanical agitation type, fluidized bed type and the air-flowing type drying that can make material constantly motion in drying process.
The drying temperature of one hydration LiBF4 is 170 ~ 200 DEG C, preferably 180 ~ 190 DEG C.Be due to temperature too low time drying efficiency too low, although sample water ratio can be made lower when temperature is more than 200 DEG C, decomposition amount can strengthen.
The water of a small amount of lithium fluoride insolubles and trace is there is, filtering insolubles after dissolving by low-carbon alcohol in above-mentioned dry thing.The low-carbon alcohol of dissolving 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 close to saturation point when ratio is too little, the easy Crystallization Plugging filtration medium when filtering, ratio too conference increases cost.
In low-carbon alcohol, the moisture of trace is taken away with evaporation drying, obtains the waterless lithium terafluoroborate product of moisture content below 0.005%.The temperature of filter vacuum evaporation drying is 120 ~ 150 DEG C, preferably 130 ~ 140 DEG C.Temperature is lower than low-carbon alcohol when 120 DEG C and the residual height of minor amount of water, and temperature easily causes LiBF4 to decompose higher than 150 DEG C and produces undesirable residue.
According to method of the present invention, the drying of one hydration LiBF4 produces a small amount of decomposition, the hydrogen fluoride etc. that degradation production can make decomposition produce by conventional condensed absorbent method is recycled, and reduces the impact of ambient air and as the feedstock circulation use of synthesis technique above; Low-carbon alcohol dissolves a small amount of lithium fluoride powder leached can as the raw material of other Chemicals of preparation (as lithium hexafluoro phosphate).The preparation of one hydration LiBF4 can adopt known Aqueous phase technique.
Embodiment
Embodiment 1:
The hydrofluoric acid solution getting 1400 gram 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, cools to less than 5 DEG C, adds boric acid 432.6 grams while stirring, continue stirring reaction 1 hour with ice-water bath; In above-mentioned reaction solution, slowly add Quilonum Retard 258.7 grams, continue stirring reaction 1 hour, evaporation reaction solution also in 40 DEG C of crystallizations, washing, obtains a hydration LiBF4.One water thing is put into vibration limit, hot air circulation vibration drying case limit and be warmed up to 185 DEG C and freeze-day with constant temperature 6 hours, take out Tetrafluoroboric acid lithium powder, fully dissolve with ethanol, ethanol and LiBF4 mass ratio are 1.5:1, filtering insolubles, by filter vacuum evaporation drying to 130 DEG C, obtain the waterless lithium terafluoroborate that moisture content is 0.003%.
Embodiment 2:
The hydrofluoric acid solution getting 1400 gram 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, cools to less than 5 DEG C, adds boric acid 432.6 grams while stirring, continue stirring reaction 1 hour with ice-water bath; In above-mentioned reaction solution, slowly add Quilonum Retard 258.7 grams, continue stirring reaction 1 hour, evaporation reaction solution also in 40 DEG C of crystallizations, washing, obtains a hydration LiBF4.One water thing is put into vibration limit, hot air circulation vibration drying case limit and be warmed up to 200 DEG C and freeze-day with constant temperature 4 hours, take out Tetrafluoroboric acid lithium powder, fully dissolve with ethanol, ethanol and LiBF4 mass ratio are 1.5:1, filtering insolubles, by filter vacuum evaporation drying to 120 DEG C, obtain the waterless lithium terafluoroborate that moisture content is 0.002%.
Embodiment 3:
The hydrofluoric acid solution getting 1400 gram 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, cools to less than 5 DEG C, adds boric acid 432.6 grams while stirring, continue stirring reaction 1 hour with ice-water bath; In above-mentioned reaction solution, slowly add Quilonum Retard 258.7 grams, continue stirring reaction 1 hour, evaporation reaction solution also in 40 DEG C of crystallizations, washing, obtains a hydration LiBF4.One water thing is put into vibration limit, hot air circulation vibration drying case limit and be warmed up to 170 DEG C and freeze-day with constant temperature 8 hours, take out Tetrafluoroboric acid lithium powder, fully dissolve with ethanol, ethanol and LiBF4 mass ratio are 1.5:1, filtering insolubles, by filter vacuum evaporation drying to 150 DEG C, obtain the waterless lithium terafluoroborate that moisture content is 0.0042%.
Embodiment 4:
The hydrofluoric acid solution getting 1400 gram 40% adds in the tetrafluoroethylene reactor of 2000mL band stirring, cools to less than 5 DEG C, adds boric acid 432.6 grams while stirring, continue stirring reaction 1 hour with ice-water bath; In above-mentioned reaction solution, slowly add Quilonum Retard 258.7 grams, continue stirring reaction 1 hour, evaporation reaction solution also in 40 DEG C of crystallizations, washing, obtains a hydration LiBF4.One water thing is put into vibration limit, hot air circulation vibration drying case limit and be warmed up to 185 DEG C and freeze-day with constant temperature 6 hours, take out Tetrafluoroboric acid lithium powder, fully dissolve with methyl alcohol, methyl alcohol and LiBF4 mass ratio are 1.5:1, filtering insolubles, by filter vacuum evaporation drying to 130 DEG C, obtain the waterless lithium terafluoroborate that moisture content is 0.0028%.
Claims (2)
1. a preparation method for waterless lithium terafluoroborate, is characterized in that:
Comprise following processing step:
1) a hydration LiBF4 is at 170 ~ 200 DEG C; 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 low-carbon alcohol: low-carbon alcohol is ethanol or methyl alcohol, the mass ratio of low-carbon alcohol and Tetrafluoroboric acid powder for lithium is 1.5:1; Cross and filter insoluble impurities, obtain filtrate;
3) by filter vacuum evaporation drying to 120 ~ 150 DEG C, obtain the waterless lithium terafluoroborate of moisture content below 0.005%.
2., according to preparation method according to claim 1, it is characterized in that:
Comprise following processing step:
1) a hydration LiBF4 is at 180 ~ 190 DEG C, 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 low-carbon alcohol: low-carbon alcohol is ethanol;
3) by filter vacuum evaporation drying to 130 ~ 140 DEG C; Obtain the waterless lithium terafluoroborate of moisture content below 0.005%.
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| 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 |
| CN110182829B (en) * | 2019-06-11 | 2021-08-13 | 新疆有色金属研究所 | Industrial preparation method of battery-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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| JP2001247307A (en) * | 2000-03-02 | 2001-09-11 | Kanto Denka Kogyo Co Ltd | Method for producing lithium tetrafluoroborate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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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. |