CN102030339A - Preparation method of battery-grade anhydrous lithium tetrafluoroborate - Google Patents
Preparation method of battery-grade anhydrous lithium tetrafluoroborate Download PDFInfo
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Abstract
The invention discloses a preparation method of battery-grade anhydrous lithium tetrafluoroborate. The preparation method comprises the following steps of: making hydrofluoric acid and boric acid react and adding lithium carbonate or lithium hydroxide to obtain a lithium tetrafluoroborate solution; then, filtering, evaporating, concentrating, crystallizing, separating and drying; and adding absolute ethanol to dissolve in a glove box and evaporating the ethanol to obtain a lithium tetrafluoroborate product. The invention improves an aqueous solution method, synthesizes in an inorganic medium, extracts with an organic solvent, further dries to obtain an anhydrous product, overcomes the difficulties in dehydration, extraction and separation because of the inorganic medium and has low cost and convenient operation.
Description
Technical field
The present invention relates to a kind of preparation method of battery-grade anhydrous LiBF4.
Background technology
Lithium ion battery because have operating voltage height, energy density height, advantage such as memory effect is little, self-discharge rate is low, spry and light convenience and being used widely at aspects such as mobile phone, notebook computer, Kameras as compact power, and future high specific energy, high-power energy-storage battery market demonstrate obvious competitive edge.
Ionogen is the indispensable integral part of lithium-ion battery electrolytes, is one of determinative of lithium ion battery performance.Therefore electrolyte system being improved is to improve the electrical property of lithium ion battery and the importance of security.
LiBF4 base (LiBF
4) electrolytical better heat stability, insensitive to environment moisture content, be hopeful to develop into outstanding electrolyte system civilian, military, that three boat fields are miniature, extensively adopt in energy storage and power lithium-ion battery field.
Synthetic LiBF4 method mainly contains at present: solid phase-vapor phase process, non-aqueous solution method and aqua-solution method.
Solid phase-vapor phase process is at high temperature, is that raw material generates with basic salt, and purifying with organic solvent obtains product again, needs first synthetic intermediate, and synthetic difficulty is big, and the equipment requirements height is difficult to obtain purer product, needs further to purify.
The non-aqueous solution method is to form suspension liquid in organic solvent, the generation product that reacts again, and it adopts organic solvent, and the generation of side reaction is arranged, and produces compact intermediate compound simultaneously, separation difficulty.
Aqua-solution method adopts acids and the reaction of basic lithium salts, concentrated, crystallization, filtration, drying, and recrystallization obtains comparatively purified product again.
Summary of the invention
The technical issues that need to address of the present invention just are to overcome the higher defective of prior art moisture content, a kind of preparation method of battery-grade anhydrous LiBF4 is provided, the present invention is improved on the basis of aqua-solution method, in inorganic medium, synthesize, obtain anhydrous product with organic solvent purification and further drying, the present invention has overcome dehydration, purification, isolating difficulty that inorganic medium is purified and brought, and cost is low, easy to operate.
The invention provides a kind of preparation method of battery-grade anhydrous LiBF4, comprise the following steps:
With hydrofluoric acid and acid reaction, add Quilonum Retard or lithium hydroxide again and obtain LiBF4 solution, then by filtration, evaporation concentration, crystallization, drying, in glove box, add anhydrous alcohol solution, ethanol evaporation obtains the waterless lithium terafluoroborate product.
Concrete steps are:
1), in cooling bath, stir and slowly boric acid added in the hydrofluoric acid, obtain Tetrafluoroboric acid solution; The mol ratio of described boric acid and hydrofluoric acid is 1:1.01;
2), Quilonum Retard or lithium hydroxide are slowly added in the above-mentioned solution, control pH be a neutrality, adds in 1 hour; Obtain LiBF4 solution;
3), filter LiBF4 solution, filtrate evaporation concentration to Tetrafluoroboric acid lithium content under infrared lamp is about 70%; Cooling is separated out the crystal after-filtration and is separated crystallization liquid, reclaims mother liquor, and crystallization continues under infrared lamp dry, and the temperature that the control infrared lamp is radiated at the material surface is not higher than 95 ℃, obtains the hydration LiBF4;
4), with the hydration LiBF4 put into the circulation dry air glove box, use a small amount of anhydrous alcohol solution, the continuation under infrared lamp, be dried to ethanol fully by evaporate to dryness, obtain the battery-grade anhydrous LiBF4 of white powder.
The mixed solution that described filtrated stock is back to Tetrafluoroboric acid solution and Quilonum Retard or lithium hydroxide reuses.
The present invention is improved on the basis of aqua-solution method, synthesizes in inorganic medium, obtains waterless lithium terafluoroborate with organic solvent purification and further drying, and it has overcome dehydration, purification, isolating difficulty that inorganic medium is purified and brought.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the product of embodiment of the invention preparation.
Fig. 2 is assembled into electrochemistry loop test figure behind the secondary cell for the present invention.
Embodiment
Embodiment 1
Taking by weighing massfraction is 40% hydrofluoric acid 427.4g, stirs slowly to add boric acid 130.0g in cooling bath, adds in 1 hour.Continue to stir 1 hour, the 78.8g Quilonum Retard is slowly added in the above-mentioned solution, regulator solution pH is neutral, adds in 1 hour.Filter, filtrate evaporation concentration to Tetrafluoroboric acid lithium content under infrared lamp is about 70%.Cooling is separated out the crystal after-filtration and is separated crystallization liquid, and mother liquor reclaims, and crystallization continued under infrared lamp dry about 4 hours, obtained white powder.
White powder is put into the glove box of circulation dry air, use a small amount of anhydrous alcohol solution, continued under infrared lamp dry 48 hours, ethanol is obtained white powder LiBF4 product by complete evaporate to dryness.
The mixed solution that described filtrated stock is back to Tetrafluoroboric acid solution and Quilonum Retard or lithium hydroxide reuses.
Embodiment 2
Taking by weighing massfraction is 40% hydrofluoric acid 427.4g, stirs slowly to add boric acid 130.0g in cooling bath, adds in 1 hour.Continue to stir 1 hour, about 89.6g one hydronium(ion) oxidation lithium is slowly added in the above-mentioned solution, regulator solution pH is neutral, adds in 1 hour.Filter, filtrate evaporation concentration to Tetrafluoroboric acid lithium content under infrared lamp is about 70%.Filter, mother liquor reclaims, and solid continued under infrared lamp dry about 4 hours, obtained white powder.
White powder is dissolved in dehydrated alcohol, once more filtering and impurity removing.Filtrate was evaporated 12 hours under infrared lamp, obtained white Tetrafluoroboric acid lithium powder.
White powder is put into the glove box of circulation dry air, use a small amount of anhydrous alcohol solution, continued under infrared lamp drying 48 hours, ethanol obtains white powder LiBF4 product fully by evaporate to dryness.
The mixed solution that described filtrated stock is back to Tetrafluoroboric acid solution and Quilonum Retard or lithium hydroxide reuses.
As shown in Figure 1, the cell-grade LiBF4 of the embodiment of the invention 1 preparation is measured through X ray diffracting spectrum, and its diffraction approach is clear sharp-pointed, and is corresponding fully with standard card, illustrates that the product of the present invention's preparation is a waterless lithium terafluoroborate, and complete in crystal formation.
As shown in Figure 2, the battery-grade anhydrous LiBF4 of the embodiment of the invention 1 preparation is made into 1.0M LiBF
4(1:1, electrolytic solution v/v) is assembled into LiCoO to-EC/DEC
2/ Li secondary cell carries out the electrochemistry loop test, and loading capacity is 148.9mAh/g first, and capacity attenuation only 1.54% after the charge and discharge cycles 50 times.
Measure through Ka Er-Fei Xiu moisture content tester, the battery-grade anhydrous LiBF4 moisture content of the embodiment of the invention 1 preparation is lower than 0.02%, reaches battery-grade anhydrous LiBF4 rank.
It should be noted that at last: obviously, the foregoing description only is for example of the present invention clearly is described, and is not the qualification to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being amplified out thus or change still are among protection scope of the present invention.
Claims (3)
1. the preparation method of a battery-grade anhydrous LiBF4 is characterized in that, described preparation method comprises the following steps:
With hydrofluoric acid and acid reaction, add Quilonum Retard or lithium hydroxide again and obtain LiBF4 solution, then by filtration, evaporation concentration, crystallization, separation, drying, in glove box, add anhydrous alcohol solution, ethanol evaporation obtains the LiBF4 product.
2. the preparation method of battery-grade anhydrous LiBF4 as claimed in claim 1 is characterized in that, described preparation method's concrete steps are:
1), in cooling bath, stir and slowly boric acid added in the hydrofluoric acid, obtain Tetrafluoroboric acid solution; The mol ratio of described boric acid and hydrofluoric acid is 1:1.01;
2), Quilonum Retard or lithium hydroxide are slowly added in the above-mentioned solution, control pH be a neutrality, adds in 1 hour; Obtain LiBF4 solution;
3), filter LiBF4 solution, filtrate evaporation concentration to Tetrafluoroboric acid lithium content under infrared lamp is about 70%; Cooling is separated out the crystal after-filtration and is separated crystallization liquid, reclaims mother liquor, and crystallization continues under infrared lamp dry, and the temperature that the control infrared lamp is radiated at the material surface is not higher than 95 ℃, obtains the hydration LiBF4;
4), with the hydration LiBF4 put into the circulation dry air glove box, use a small amount of anhydrous alcohol solution, the continuation under infrared lamp, be dried to ethanol fully by evaporate to dryness, obtain the battery-grade anhydrous LiBF4 of white powder.
3. the preparation method of battery-grade anhydrous LiBF4 as claimed in claim 2, it is characterized in that: the mixed solution that described filtrated stock is back to Tetrafluoroboric acid solution and Quilonum Retard or lithium hydroxide reuses.
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| CN 201110005133 CN102030339A (en) | 2011-01-12 | 2011-01-12 | Preparation method of battery-grade anhydrous lithium tetrafluoroborate |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073014A (en) * | 2012-10-25 | 2013-05-01 | 中国电子科技集团公司第十八研究所 | Preparation method of high-purity lithium tetrafluoroborate with low water content |
| CN103236562A (en) * | 2013-04-11 | 2013-08-07 | 多氟多化工股份有限公司 | Preparation method for lithium tetrafluoroborate |
| CN103342372A (en) * | 2013-07-23 | 2013-10-09 | 森田化工(张家港)有限公司 | Method for preparing lithium tetrafluoroborate |
| CN103466650A (en) * | 2013-09-27 | 2013-12-25 | 中国海洋石油总公司 | Method for preparing anhydrous lithium tetrafluoroborate |
| CN104030310A (en) * | 2014-05-23 | 2014-09-10 | 中国海洋石油总公司 | Method for preparing lithium tetrafluoroborate |
| CN104229814A (en) * | 2014-09-18 | 2014-12-24 | 新疆有色金属研究所 | Cell-grade anhydrous lithium tetrafluoroborate and preparation method thereof |
| CN106082251A (en) * | 2016-06-12 | 2016-11-09 | 兰州理工大学 | A kind of preparation method of LiBF4 |
| CN108046233A (en) * | 2017-11-16 | 2018-05-18 | 常州弘正新能源股份有限公司 | A kind of preparation method of LiBF4 |
| CN109110773A (en) * | 2018-09-07 | 2019-01-01 | 昆山市富乐化工有限公司 | The production and processing method of fluoboric acid |
| CN109110774A (en) * | 2018-10-25 | 2019-01-01 | 河南省法恩莱特新能源科技有限公司 | 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 |
| CN115304074A (en) * | 2022-08-25 | 2022-11-08 | 江西赣锋锂业股份有限公司 | Preparation method of anhydrous lithium tetraborate |
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| JPS56145113A (en) * | 1980-04-09 | 1981-11-11 | Morita Kagaku Kogyo Kk | Synthesis of anhydrous lithium borofluoride |
| CN101318664A (en) * | 2008-05-09 | 2008-12-10 | 中国科学院青海盐湖研究所 | Method of preparing waterless lithium terafluoroborate |
| CN101863489A (en) * | 2010-06-11 | 2010-10-20 | 中国海洋石油总公司 | Method for preparing anhydrous high-purity lithium tetrafluoroborate |
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2011
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| JPS56145113A (en) * | 1980-04-09 | 1981-11-11 | Morita Kagaku Kogyo Kk | Synthesis of anhydrous lithium borofluoride |
| CN101318664A (en) * | 2008-05-09 | 2008-12-10 | 中国科学院青海盐湖研究所 | Method of preparing waterless lithium terafluoroborate |
| CN101863489A (en) * | 2010-06-11 | 2010-10-20 | 中国海洋石油总公司 | Method for preparing anhydrous high-purity lithium tetrafluoroborate |
Non-Patent Citations (1)
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073014A (en) * | 2012-10-25 | 2013-05-01 | 中国电子科技集团公司第十八研究所 | Preparation method of high-purity lithium tetrafluoroborate with low water content |
| CN103073014B (en) * | 2012-10-25 | 2016-01-13 | 中国电子科技集团公司第十八研究所 | The preparation method of high-purity lithium tetrafluoroborate with low water content |
| CN103236562A (en) * | 2013-04-11 | 2013-08-07 | 多氟多化工股份有限公司 | Preparation method for lithium tetrafluoroborate |
| CN103236562B (en) * | 2013-04-11 | 2015-03-25 | 多氟多化工股份有限公司 | Preparation method for lithium tetrafluoroborate |
| CN103342372A (en) * | 2013-07-23 | 2013-10-09 | 森田化工(张家港)有限公司 | Method for preparing lithium tetrafluoroborate |
| CN103342372B (en) * | 2013-07-23 | 2015-03-25 | 森田化工(张家港)有限公司 | Method for preparing lithium tetrafluoroborate |
| CN103466650B (en) * | 2013-09-27 | 2016-01-20 | 中国海洋石油总公司 | A kind of preparation method of waterless lithium terafluoroborate |
| CN103466650A (en) * | 2013-09-27 | 2013-12-25 | 中国海洋石油总公司 | Method for preparing anhydrous lithium tetrafluoroborate |
| 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 |
| CN104229814A (en) * | 2014-09-18 | 2014-12-24 | 新疆有色金属研究所 | Cell-grade anhydrous lithium tetrafluoroborate and preparation method thereof |
| CN104229814B (en) * | 2014-09-18 | 2019-05-10 | 新疆有色金属研究所 | The preparation method of battery-grade anhydrous lithium tetrafluoroborate |
| CN106082251A (en) * | 2016-06-12 | 2016-11-09 | 兰州理工大学 | A kind of preparation method of LiBF4 |
| CN106082251B (en) * | 2016-06-12 | 2018-01-30 | 兰州理工大学 | A kind of preparation method of LiBF4 |
| CN108046233A (en) * | 2017-11-16 | 2018-05-18 | 常州弘正新能源股份有限公司 | A kind of preparation method of LiBF4 |
| CN109110773A (en) * | 2018-09-07 | 2019-01-01 | 昆山市富乐化工有限公司 | The production and processing method of fluoboric acid |
| CN109110774A (en) * | 2018-10-25 | 2019-01-01 | 河南省法恩莱特新能源科技有限公司 | A kind of preparation method of LiBF4 |
| CN109110774B (en) * | 2018-10-25 | 2022-02-01 | 河南省法恩莱特新能源科技有限公司 | Preparation method of 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 |
| CN115304074A (en) * | 2022-08-25 | 2022-11-08 | 江西赣锋锂业股份有限公司 | Preparation method of anhydrous lithium tetraborate |
| CN115304074B (en) * | 2022-08-25 | 2023-05-12 | 江西赣锋锂业股份有限公司 | Preparation method of anhydrous lithium tetraborate |
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Application publication date: 20110427 |