CN104229814A - Cell-grade anhydrous lithium tetrafluoroborate and preparation method thereof - Google Patents
Cell-grade anhydrous lithium tetrafluoroborate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium tetrafluoroborate and a preparation method thereof, and discloses cell-grade anhydrous lithium tetrafluoroborate and a preparation method thereof. Cell-grade anhydrous lithium tetrafluoroborate is prepared by the steps as follows: step one, hydrous lithium tetrafluoroborate is added with an organic solvent and is dissolved to obtain a solution; step two, the solution is filtered to obtain a filtrate and filter residues; step three, the filtrate is distilled to obtain distillate and distillation residues; and step four, the distillation residues are dried to obtain cell-grade anhydrous lithium tetrafluoroborate. The cell-grade anhydrous lithium tetrafluoroborate obtained with the method meets grade requirements of cell-grade anhydrous lithium tetrafluoroborate; according to the preparation method of cell-grade anhydrous lithium tetrafluoroborate, the organic solvent can be recovered, and the recovery rate of the organic solvent in percentage by mass is 70%-95%, so that the environment pollution caused by emission of the organic solvent is reduced; and meanwhile, the preparation cost of anhydrous lithium tetrafluoroborate is reduced.
Description
Technical field
the present invention relates to LiBF4 and preparation method thereof technical field, is a kind of battery-grade anhydrous lithium tetrafluoroborate and preparation method thereof.
Background technology
the ionogen that lithium ion battery uses has multiple, wherein lithium hexafluoro phosphate is the most frequently used electrolyte lithium salt, its anticathode is stablized, have the advantages that loading capacity is large, specific conductivity is high, internal resistance is little and charge/discharge rates is fast, but lithium hexafluoro phosphate to moisture and hydrofluoric acid extremely responsive, non-refractory, and easily there is decomposition reaction.LiBF4 as ionogen, its better heat stability, insensitive to environment moisture content, effectively can prevent corrosion, and in electrolytic solution, add the low-temperature performance that appropriate LiBF4 significantly can strengthen electrolytic solution.LiBF4 and lithium hexafluoro phosphate with the use of can make performance of lithium ion battery be improved significantly, be hopeful to develop into the outstanding electrolyte system that miniature in civilian, military and three boat fields, energy storage and power lithium-ion battery field extensively adopt in extreme circumstances.
the advantage adopting aqua-solution method to prepare LiBF4 is that cheaper starting materials is easy to get, simple to operate and process easily controls, but the LiBF4 that aqua-solution method obtains can occur with the form of crystalline hydrate, make follow-up dry removal process very difficult, LiBF4 containing crystal water can cause electrolyte overall performance to decline, and affects capacity and the cycle life of lithium ion battery.Mention in the periodical literature of a section " moisture is on impact of performance of lithium ion battery " by name: water is as a kind of trace components of electrolytic solution, certain influence is had to the formation of lithium ion battery SEI film and battery performance, main manifestations is that cell container diminishes, discharge time shortens, internal resistance increases, Capacity fading, the phenomenons such as cell expansion, research shows, moisture controlled is within 0.015%, the comprehensive electrochemical of battery is best, therefore, no matter in the making processes of lithium ion battery, must the humidity of strictly controlled environment and positive and negative pole material and electrolytic solution (ionogen, organic solvent, additive) water content (Xiao Shunping, moisture is on the impact of performance of lithium ion battery, applied chemistry, 2005, vol 22 (7)).
publication number be 102030339 Chinese patent literature disclose in the drying process preparing battery-grade anhydrous lithium tetrafluoroborate, adopt glove box to limit the production capacity of this product as dry environment, be not suitable for suitability for industrialized production.Publication number be 103466650 Chinese patent literature disclose a kind of preparation method of waterless lithium terafluoroborate, the LiBF4 of moisture content below 0.005% is obtained by the method, but this method adopts multiple dynamic drying mode in drying products process, make technical process loaded down with trivial details, add the equipment cost in production and energy consumption; In addition, the low-carbon alcohol of introducing is not reclaimed in the method, cause environmental pollution, add the cost preparing waterless lithium terafluoroborate, be unfavorable for realizing suitability for industrialized production.
Summary of the invention
the invention provides a kind of battery-grade anhydrous lithium tetrafluoroborate and preparation method thereof, overcome the deficiency of above-mentioned prior art, efficiently solve the existing problem not reclaiming organic solvent in the process preparing battery-grade anhydrous lithium tetrafluoroborate, the present invention can reduce the production cost of battery-grade anhydrous lithium tetrafluoroborate, and decreases the discharge pollution on the environment of organic solvent.
one of technical scheme of the present invention is realized by following measures: a kind of battery-grade anhydrous lithium tetrafluoroborate, obtain in the steps below: the first step, solution is obtained, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:1 to 1:10 add organic solvent dissolution in hydration LiBF4 after; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 55 DEG C to 95 DEG C, distillation relative vacuum degree be-0.07MPa to 0MPa, the time of distillation is 4h to 8h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 55 DEG C to 250 DEG C, the dry time is 8h to 24h, and dry relative vacuum degree is-0.098MPa to-0.07MPa.
here is the further optimization and/or improvements to one of foregoing invention technical scheme:
above-mentioned organic solvent can be in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, acetonitrile, acetone and methylcarbonate more than one; Or/and in the 3rd step, subsequent disposal is carried out in the steps below: the first step, after molecular sieve is activated 3h to 6h at temperature is 250 DEG C to 550 DEG C, obtain activated molecular sieve; Second step, the percent mass water content of overhead product after activated molecular sieve drying absorption is less than 0.001%, and can reuse, adsorption time is 24 little of 48 hours.
above-mentionedly prepare in battery-grade anhydrous lithium tetrafluoroborate process, the dew-point temperature of environment can be-70 DEG C to-40 DEG C; Or/and pulverized by the battery-grade anhydrous lithium tetrafluoroborate in the 4th step, the particle diameter of the battery-grade anhydrous lithium tetrafluoroborate after pulverizing is 0.15 millimeter to 0.6 millimeter.
above-mentioned hydration LiBF4 can obtain in the steps below: the first step, obtains fluoroboric acid after adding boric acid under cooling bath state in hydrofluoric acid, and the mol ratio of the fluorine in hydrofluoric acid and the boron of boric acid is 4:1, and the temperature of cooling bath is 0 DEG C to 40 DEG C; Second step, adds lithium salts in fluoroboric acid, after lithium salts and fluoroboric acid react completely, obtain lithium tetrafluoroborate solution, and the mol ratio of the lithium in lithium salts and the boron in fluoroboric acid is 1:1; 3rd step, lithium tetrafluoroborate solution is sequentially obtained LiBF4 cooling fluid after evaporation concentration and room temperature naturally cooling, wherein: the temperature of evaporation concentration is 50 DEG C to 150 DEG C, and the quality of LiBF4 cooling fluid is 50% to 80% of the quality of lithium tetrafluoroborate solution; 4th step, obtains hydration LiBF4 and mother liquor, by disposing mother liquor after LiBF4 cooling fluid being filtered.
above-mentioned lithium salts can be Quilonum Retard or lithium hydroxide.
two of technical scheme of the present invention is realized by following measures: a kind of preparation method of battery-grade anhydrous lithium tetrafluoroborate, carry out in the steps below: the first step, solution is obtained, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:1 to 1:10 add organic solvent dissolution in hydration LiBF4 after; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 55 DEG C to 95 DEG C, distillation relative vacuum degree be-0.07MPa to 0MPa, the time of distillation is 4h to 8h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 55 DEG C to 250 DEG C, the dry time is 8h to 24h, and dry relative vacuum degree is-0.098MPa to-0.07MPa.
here is the further optimization and/or improvements to foregoing invention technical scheme two:
above-mentioned organic solvent can be in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, acetonitrile, acetone and methylcarbonate more than one; Or/and in the 3rd step, subsequent disposal is carried out in the steps below: the first step, after molecular sieve is activated 3h to 6h at temperature is 250 DEG C to 550 DEG C, obtain activated molecular sieve; Second step, the percent mass water content of overhead product after activated molecular sieve drying absorption is less than 0.001%, and can reuse, adsorption time is 24 little of 48 hours.
above-mentionedly prepare in battery-grade anhydrous lithium tetrafluoroborate process, the dew-point temperature of environment can be-70 DEG C to-40 DEG C; Or/and pulverized by the battery-grade anhydrous lithium tetrafluoroborate in the 4th step, the particle diameter of the battery-grade anhydrous lithium tetrafluoroborate after pulverizing is 0.15 millimeter to 0.6 millimeter.
above-mentioned hydration LiBF4 can obtain in the steps below: the first step, obtains fluoroboric acid after adding boric acid under cooling bath state in hydrofluoric acid, and the mol ratio of the fluorine in hydrofluoric acid and the boron of boric acid is 4:1, and the temperature of cooling bath is 0 DEG C to 40 DEG C; Second step, adds lithium salts in fluoroboric acid, after lithium salts and fluoroboric acid react completely, obtain lithium tetrafluoroborate solution, and the mol ratio of the lithium in lithium salts and the boron in fluoroboric acid is 1:1; 3rd step, lithium tetrafluoroborate solution is sequentially obtained LiBF4 cooling fluid after evaporation concentration and room temperature naturally cooling, wherein: the temperature of evaporation concentration is 50 DEG C to 150 DEG C, and the quality of LiBF4 cooling fluid is 50% to 80% of the quality of lithium tetrafluoroborate solution; 4th step, obtains hydration LiBF4 and mother liquor, by disposing mother liquor after LiBF4 cooling fluid being filtered.
above-mentioned lithium salts can be Quilonum Retard or lithium hydroxide.
percent mass water content according to the battery-grade anhydrous lithium tetrafluoroborate of the present invention's acquisition is less than 0.01%, reaches the levels necessitate of battery-grade anhydrous lithium tetrafluoroborate; Organic solvent can reclaim by the preparation method according to battery-grade anhydrous lithium tetrafluoroborate of the present invention, the mass percent of the rate of recovery of organic solvent is 70% to 95%, thus decrease the discharge pollution on the environment of organic solvent, meanwhile, the cost preparing waterless lithium terafluoroborate is reduced.
Embodiment
the present invention by the restriction of following embodiment, can not determine concrete embodiment according to technical scheme of the present invention and practical situation.
below in conjunction with embodiment, the invention will be further described:
embodiment 1: this battery-grade anhydrous lithium tetrafluoroborate, obtains by following preparation method: the first step, obtains solution after adding organic solvent dissolution in hydration LiBF4, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:1 to 1:10; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 55 DEG C to 95 DEG C, distillation relative vacuum degree be-0.07MPa to 0MPa, the time of distillation is 4h to 8h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 55 DEG C to 250 DEG C, the dry time is 8h to 24h, and dry relative vacuum degree is-0.098MPa to-0.07MPa.Percent mass water content according to the battery-grade anhydrous lithium tetrafluoroborate of the present embodiment acquisition is less than 0.01%, reaches the levels necessitate of battery-grade anhydrous lithium tetraborate.Organic solvent can be reclaimed according to the present embodiment, the mass percent of the rate of recovery of organic solvent is 70% to 95%, thus decreases the discharge pollution on the environment of organic solvent, reduces the production cost preparing waterless lithium terafluoroborate.
embodiment 2: this battery-grade anhydrous lithium tetrafluoroborate, obtains by following preparation method: the first step, obtains solution after adding organic solvent dissolution in hydration LiBF4, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:1 or 1:10; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 55 DEG C or 95 DEG C, the relative vacuum degree of distillation is-0.07MPa or 0MPa, and the time of distillation is 4h or 8h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 55 DEG C or 250 DEG C, the dry time is 8h or 24h, and dry relative vacuum degree is-0.098MPa or-0.07MPa.
embodiment 3: be with the difference of above-described embodiment, organic solvent is more than one in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, acetonitrile, acetone and methylcarbonate; Or/and in the 3rd step, subsequent disposal is carried out in the steps below: the first step, after molecular sieve is activated 3h to 6h at temperature is 250 DEG C to 550 DEG C, obtain activated molecular sieve; Second step, the percent mass water content of overhead product after activated molecular sieve drying absorption is less than 0.001%, and can reuse, adsorption time is 24 little of 48 hours.
embodiment 4: be with the difference of above-described embodiment, prepares in battery-grade anhydrous lithium tetrafluoroborate process, and the dew-point temperature of environment is-70 DEG C to-40 DEG C; Or/and pulverized by the battery-grade anhydrous lithium tetrafluoroborate in the 4th step, the particle diameter of the battery-grade anhydrous lithium tetrafluoroborate after pulverizing is 0.15 millimeter to 0.6 millimeter.
embodiment 5: be with the difference of above-described embodiment, hydration LiBF4 obtains in the steps below: the first step, obtain fluoroboric acid add boric acid in hydrofluoric acid under cooling bath state after, the mol ratio of the fluorine in hydrofluoric acid and the boron of boric acid is 4:1, and the temperature of cooling bath is 0 DEG C to 40 DEG C; Second step, adds lithium salts in fluoroboric acid, after lithium salts and fluoroboric acid react completely, obtain lithium tetrafluoroborate solution, and the mol ratio of the lithium in lithium salts and the boron in fluoroboric acid is 1:1; 3rd step, lithium tetrafluoroborate solution is sequentially obtained LiBF4 cooling fluid after evaporation concentration and room temperature naturally cooling, wherein: the temperature of evaporation concentration is 50 DEG C to 150 DEG C, and the quality of LiBF4 cooling fluid is 50% to 80% of the quality of lithium tetrafluoroborate solution; 4th step, obtains hydration LiBF4 and mother liquor, by disposing mother liquor after LiBF4 cooling fluid being filtered.
embodiment 6: be with the difference of above-described embodiment, lithium salts is Quilonum Retard or lithium hydroxide.
embodiment 7: this battery-grade anhydrous lithium tetrafluoroborate, obtains by following preparation method:
the first step, obtains solution after adding organic solvent dissolution in hydration LiBF4, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:1; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 55 DEG C, and the relative vacuum degree of distillation is-0.07MPa, the time of distillation is 4h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 55 DEG C, the dry time is 24h, and dry relative vacuum degree is-0.098MPa.Percent mass water content according to the battery-grade anhydrous lithium tetrafluoroborate of the present embodiment acquisition is less than 0.01%, reaches the levels necessitate of battery-grade anhydrous lithium tetrafluoroborate, the mass percent of the rate of recovery of organic solvent can be made according to the present embodiment to be 70%.
embodiment 8: this battery-grade anhydrous lithium tetrafluoroborate, obtains by following preparation method: the first step, obtains solution after adding organic solvent dissolution in hydration LiBF4, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:10; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 95 DEG C, the relative vacuum degree of distillation is 0MPa, and the time of distillation is 8h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 250 DEG C, the dry time is 8h, and dry relative vacuum degree is-0.07MPa.Percent mass water content according to the battery-grade anhydrous lithium tetrafluoroborate of the present embodiment acquisition is less than 0.01%, reaches the levels necessitate of battery-grade anhydrous lithium tetrafluoroborate, the mass percent of the rate of recovery of organic solvent can be made according to the present embodiment to be 95%.
in sum, the percent mass water content according to the battery-grade anhydrous lithium tetrafluoroborate of the present invention's acquisition is less than 0.01%, reaches the levels necessitate of battery-grade anhydrous lithium tetrafluoroborate; Organic solvent can reclaim by the preparation method according to battery-grade anhydrous lithium tetrafluoroborate of the present invention, the mass percent of the rate of recovery of organic solvent is 70% to 95%, thus decrease the discharge pollution on the environment of organic solvent, meanwhile, the cost preparing waterless lithium terafluoroborate is reduced.
above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease non-essential technical characteristic according to actual needs, meet the demand of different situations.
Claims (8)
1.
a kind of battery-grade anhydrous lithium tetrafluoroborate, is characterized in that obtaining in the steps below: the first step, obtains solution after adding organic solvent dissolution in hydration LiBF4, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:1 to 1:10; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 55 DEG C to 95 DEG C, distillation relative vacuum degree be-0.07MPa to 0MPa, the time of distillation is 4h to 8h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 55 DEG C to 250 DEG C, the dry time is 8h to 24h, and dry relative vacuum degree is-0.098MPa to-0.07MPa.
2.
according to the battery-grade anhydrous lithium tetrafluoroborate described in claim 1, it is characterized in that organic solvent is more than one in methyl alcohol, ethanol, Virahol, the trimethyl carbinol, acetonitrile, acetone and methylcarbonate; Or/and in the 3rd step, subsequent disposal is carried out in the steps below: the first step, after molecular sieve is activated 3h to 6h at temperature is 250 DEG C to 550 DEG C, obtain activated molecular sieve; Second step, the percent mass water content of overhead product after activated molecular sieve drying absorption is less than 0.001%, and can reuse, adsorption time is 24 little of 48 hours.
3.
battery-grade anhydrous lithium tetrafluoroborate according to claim 1 and 2, is characterized in that preparing in battery-grade anhydrous lithium tetrafluoroborate process, and the dew-point temperature of environment is-70 DEG C to-40 DEG C; Or/and pulverized by the battery-grade anhydrous lithium tetrafluoroborate in the 4th step, the particle diameter of the battery-grade anhydrous lithium tetrafluoroborate after pulverizing is 0.15 millimeter to 0.6 millimeter.
4.
battery-grade anhydrous lithium tetrafluoroborate according to claim 1 and 2, it is characterized in that hydration LiBF4 obtains in the steps below: the first step, fluoroboric acid is obtained add boric acid in hydrofluoric acid under cooling bath state after, the mol ratio of the fluorine in hydrofluoric acid and the boron of boric acid is 4:1, and the temperature of cooling bath is 0 DEG C to 40 DEG C; Second step, adds lithium salts in fluoroboric acid, after lithium salts and fluoroboric acid react completely, obtain lithium tetrafluoroborate solution, and the mol ratio of the lithium in lithium salts and the boron in fluoroboric acid is 1:1; 3rd step, lithium tetrafluoroborate solution is sequentially obtained LiBF4 cooling fluid after evaporation concentration and room temperature naturally cooling, wherein: the temperature of evaporation concentration is 50 DEG C to 150 DEG C, and the quality of LiBF4 cooling fluid is 50% to 80% of the quality of lithium tetrafluoroborate solution; 4th step, obtains hydration LiBF4 and mother liquor, by disposing mother liquor after LiBF4 cooling fluid being filtered.
5.
battery-grade anhydrous lithium tetrafluoroborate according to claim 3, it is characterized in that hydration LiBF4 obtains in the steps below: the first step, fluoroboric acid is obtained add boric acid in hydrofluoric acid under cooling bath state after, the mol ratio of the fluorine in hydrofluoric acid and the boron of boric acid is 4:1, and the temperature of cooling bath is 0 DEG C to 40 DEG C; Second step, adds lithium salts in fluoroboric acid, after lithium salts and fluoroboric acid react completely, obtain lithium tetrafluoroborate solution, and the mol ratio of the lithium in lithium salts and the boron in fluoroboric acid is 1:1; 3rd step, lithium tetrafluoroborate solution is sequentially obtained LiBF4 cooling fluid after evaporation concentration and room temperature naturally cooling, wherein: the temperature of evaporation concentration is 50 DEG C to 150 DEG C, and the quality of LiBF4 cooling fluid is 50% to 80% of the quality of lithium tetrafluoroborate solution; 4th step, obtains hydration LiBF4 and mother liquor, by disposing mother liquor after LiBF4 cooling fluid being filtered.
6.
battery-grade anhydrous lithium tetrafluoroborate according to claim 4, is characterized in that lithium salts is Quilonum Retard or lithium hydroxide.
7.
battery-grade anhydrous lithium tetrafluoroborate according to claim 5, is characterized in that lithium salts is Quilonum Retard or lithium hydroxide.
8.
a kind of preparation method of the battery-grade anhydrous lithium tetrafluoroborate according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterized in that carrying out in the steps below: the first step, solution is obtained, wherein: the mass ratio of hydration LiBF4 and organic solvent is 1:1 to 1:10 add organic solvent dissolution in hydration LiBF4 after; Second step, obtains filtrate and filter residue by solution after filtering; 3rd step, obtain overhead product after filtrate being distilled and heat up in a steamer excess, overhead product percent mass water content after subsequent disposal is less than 0.001%, can reuse, wherein: the temperature of distillation is 55 DEG C to 95 DEG C, distillation relative vacuum degree be-0.07MPa to 0MPa, the time of distillation is 4h to 8h; 4th step, to heat up in a steamer after excess carries out drying and obtain battery-grade anhydrous lithium tetrafluoroborate, the percent mass water content of battery-grade anhydrous lithium tetrafluoroborate is less than 0.01%, wherein: dry temperature is 55 DEG C to 250 DEG C, the dry time is 8h to 24h, and dry relative vacuum degree is-0.098MPa to-0.07MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN101302014B (en) * | 2008-06-27 | 2011-10-26 | 刘启波 | Production method of superfine boron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302014B (en) * | 2008-06-27 | 2011-10-26 | 刘启波 | Production method of superfine boron phosphate |
| 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 |
| 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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