CN104692405A - Preparation method of lithium tetrafluoroborate - Google Patents
Preparation method of lithium tetrafluoroborate Download PDFInfo
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- CN104692405A CN104692405A CN201510057912.7A CN201510057912A CN104692405A CN 104692405 A CN104692405 A CN 104692405A CN 201510057912 A CN201510057912 A CN 201510057912A CN 104692405 A CN104692405 A CN 104692405A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/063—Tetrafluoboric acid; Salts thereof
- C01B35/066—Alkali metal tetrafluoborates
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Abstract
The invention discloses a preparation method of lithium tetrafluoroborate. The preparation method comprises the following steps: 1) adding boric acid into hydrofluoric acid and reacting to obtain a fluoboric acid solution; 2) adding a lithium compound into the fluoboric acid solution and reacting to obtain a lithium tetrafluoroborate solution; 3) concentrating the lithium tetrafluoroborate solution, cooling, crystallizing and filtering to obtain lithium tetrafluoroborate crystals; 4) drying the lithium tetrafluoroborate crystals to obtain a lithium tetrafluoroborate crude product; and 5) putting the lithium tetrafluoroborate crude product into a reactor, introducing fluorine gas or fluorine-nitrogen mixed gas and reacting to obtain lithium tetrafluoroborate. According to the preparation method of lithium tetrafluoroborate disclosed by the invention, the deficiencies of the existing preparation method are made up, the process is simple to operate, no organic solvent is introduced, and the obtained lithium tetrafluoroborate product is high in purity and low in water content; and the whole preparation process is strong in operability and high in utilization rate of raw materials, has no emission of three wastes, and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to lithium ion battery electrolyte lithium salt technical field, be specifically related to a kind of preparation method of LiBF4.
Background technology
Electrolyte solution is the important component part of lithium ion battery, plays a part to carry ionic conduction current between positive and negative electrode, has been the indispensable part of electrochemical reaction.Select suitable ionogen to be also the key obtaining high-energy-density and the good lithium ion battery of power density, long circulation life and safety performance, electrolytical performance directly affects optimization and the raising of performance of lithium ion battery.At present, the ionogen of commercial lithium-ion batteries is mainly lithium hexafluoro phosphate (LiBF
6).Due to lithium hexafluoro phosphate there is good specific conductivity, stable solid electrolyte film can be formed, the advantage such as the little and charge/discharge rates of internal resistance is fast, be the first-selected ionogen of current lithium-ion battery electrolytes.But, this ionogen exist too responsive to moisture, by thermally labile, and easily discharge PF after being heated
5etc. problem; The SEI membrane impedance that low temperature generates is excessive, easily decomposes, and then cause solvolysis when electrolyte temperature rises to more than 80 DEG C.
In contrast, LiBF4 (LiBF
4) there is good chemical stability and thermostability, responsive to ambient water distribution, be hopeful to develop into the outstanding electrolyte system that energy storage and power lithium-ion battery field extensively adopt.At present, LiBF
4mainly as LiBF
6base electrolyte system additive, for improving cycle life, improves performance of lithium ion battery; As film for additive, LiBF
4be widely used in current electrolytic solution, added LiBF
4the operating temperature range of lithium ion battery can be widened afterwards, improve the high/low temperature discharge performance of battery.
At present, the preparation method of LiBF4 comprises aqua-solution method, gas-solid reaction method and non-aqueous solution method.Aqua-solution method adopts hydrofluoric acid, boric acid and Quilonum Retard to be raw material, and processing condition are gentle, do not relate to explosive chemicals, synthesize simple and safe; But the product one hydration LiBF4 obtained after aqua-solution method reaction is heated when drying and is easily dissolved in self crystal water and becomes molten state, cause its dehydration difficulty, and insolubles content is higher.
Patent CN100593515C discloses the technique that ladder-elevating temperature desiccating method prepares waterless lithium terafluoroborate, aqueous hydrogen fluoride solution, lithium salts and boric acid is adopted to be Material synthesis LiBF4, a hydration LiBF4 is obtained through condensing crystal, then under vacuum in two steps 65 ~ 80 DEG C and 90 ~ 160 DEG C of dryings, waterless lithium terafluoroborate product is obtained.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 the moisture due to crystalline particle inside is difficult to through particle surface melting layer, and therefore moisture is difficult to eliminate, the LiBF4 product moisture content finally obtained is generally more than 0.2%.
Patent CN1171368A discloses a kind of airflow reaction synthesis method of fluorine-containing lithium salts, this method synthesis LiBF
4need to carry out under the conditions such as high temperature, high pressure, vacuum, require higher to the stopping property, resistance to pressure, erosion resistance etc. of equipment; The LiBF that reaction generates
4be wrapped in the surface of solid material LiF, be unfavorable for deeply carrying out of reaction, repeatedly operation is loaded down with trivial details; Reaction is thorough, causes LiF foreign matter content many, and washing need consume a large amount of organic solvents, and steams to desolventize and can cause severe contamination and high energy consumption.
Non-aqueous solvent method is that lithium fluoride or other lithium salts are suspended in some and can form title complex with boron trifluoride and in the LiBF4 organic solvent that solubleness is large, obtain high-pure anhydrous LiBF4 with boron trifluoride reaction wherein.Patent CN102803142A discloses a kind of LiBF4 preparation method, in the organic solvent being dissolved with boron triflouride gas in advance, add fluorochemical make the two reaction, obtain the Tetrafluoroboric acid salts solution of not residual fluorinated thing, this solution circulated uses, dissolve boron triflouride gas and react with fluorochemical, manufacturing high purity a tetrafluoro borate continuously.Patent CN102826563A discloses a kind of preparation method of high-purity lithium tetrafluoroborate, and high purity lithium fluoride and boron trifluoride complex react in linear carbonate class organic solvent, after filtration, concentrated, extractive crystallization, washing, drying, obtain LiBF4.Carbonate based organic solvent residual in this reaction product need use other solvent washs, can select one or more mixtures in hexanaphthene, pentamethylene, hexane, pentane, tetracol phenixin, ether, propyl ether, butyl ether, toluene, dimethylbenzene or vinylbenzene.Non-aqueous solvent method have employed a large amount of organic solvents as extraction agent, and have certain pollution to environment, production cost is higher.Therefore, be badly in need of that a kind of technological operation of exploitation is simple, the preparation method of environmental friendliness, high-purity lithium tetrafluoroborate that products obtained therefrom water content is low.
Summary of the invention
The object of this invention is to provide that a kind of technological operation is simple, the preparation method of environmental friendliness, LiBF4 that products obtained therefrom water content is low, solve the problem of existing LiBF4 product except shipwreck.
In order to realize above object, the technical solution adopted in the present invention is:
A preparation method for LiBF4, comprises the following steps:
1) according to H
3bO
3be the ratio of 1:4 ~ 6 with the mol ratio of HF, boric acid added in hydrofluoric acid and reacts, obtain fluoborate solution;
2) be the ratio of 1.05 ~ 1.5:1 according to the mol ratio of Li and B, get lithium compound and add step 1) react in gained fluoborate solution, obtain lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrate, crystallisation by cooling, filter, obtain Tetrafluoroboric acid crystalline lithium;
4) by step 3) drying of gained Tetrafluoroboric acid crystalline lithium, obtain LiBF4 crude product;
5) by step 4) gained LiBF4 crude product is placed in reactor, passes into fluorine gas or fluorine nitrogen mixed gas reacts, and obtains described LiBF4.
Step 1) in, the temperature of described reaction is-10 ~ 10 DEG C, and the reaction times is 0.5 ~ 5h.
Step 1) in, in described hydrofluoric acid, the mass percent concentration of HF is 10% ~ 60%.
Step 2) in, described lithium compound is Quilonum Retard, lithium hydroxide or lithium bicarbonate.
Step 2) in, the temperature of described reaction is 50 ~ 100 DEG C, and the time of reaction is 0.5 ~ 5h.
Step 3) in, described concentrated be by step 2) gained lithium tetrafluoroborate solution is concentrated into 1/3 ~ 1/8 of original volume.
Step 3) in, described concentrating concentrates under-0.05 ~-0.09MPa, 50 ~ 90 DEG C of conditions.
Step 3) in, described crystallisation by cooling refers to that cooling the temperature to room temperature 20 DEG C carries out crystallization.
Step 4) in, described drying is by Tetrafluoroboric acid crystalline lithium under 30 ~ 60 DEG C of conditions after preliminarily dried 2 ~ 8h, then at 50 ~ 100 DEG C of vacuum-drying 2 ~ 8h.
Step 4) in, the water content of gained LiBF4 crude product is 3500 ~ 4500ppm.
Step 5) in, the amount passing into fluorine gas or fluorine nitrogen mixed gas is: in fluorine gas and LiBF4 crude product, the mol ratio of crystal water is 1.5 ~ 10:1.
Step 5) in, in described fluorine nitrogen mixed gas, the mass percentage content of fluorine gas is 5% ~ 20%.
Step 5) in, the temperature of described reaction is 20 ~ 80 DEG C, and the time is 3 ~ 10h.
Step 5) in, the tail gas solid chlorine calcium absorption that reactor is discharged.
The preparation method of LiBF4 of the present invention, boric acid, hydrofluoric acid and lithium compound is adopted to be raw material, after obtained LiBF4 crude product, pass into fluorine gas or fluorine nitrogen mixed gas carries out purification removal of impurities to LiBF4 crude product, crystal water in fluorine gas and LiBF4 crude product reacts, generate hydrofluoric acid and oxygen, can effective elimination moisture wherein, products obtained therefrom purity is high, water content is low; This preparation method compensate for the deficiency of existing preparation method, and technological operation is simple, and organic solvent-free is introduced, and gained LiBF4 product purity is high, water content is low; Whole preparation process is workable, and raw material availability is high, three-waste free discharge, is applicable to large-scale industrial production.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The preparation method of the LiBF4 of the present embodiment, comprises the following steps:
1) under-10 DEG C of conditions, according to H
3bO
3be the ratio of 1:4 with the mol ratio of HF, boric acid slowly being added mass percent concentration is in the hydrofluoric acid of 10%, Keep agitation afterwards, and reaction 2h, obtains fluoborate solution;
2) being the ratio of 1.05:1 according to the mol ratio of Li and B, Quilonum Retard added step 1) in gained fluoborate solution, under 100 DEG C of conditions, stirring reaction 0.5h, obtains lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrates, is concentrated into 1/8 of lithium tetrafluoroborate solution original volume, carries out crystallization at being down to room temperature 20 DEG C afterwards under-0.05MPa, 90 DEG C of conditions, and filter, gained solid is Tetrafluoroboric acid crystalline lithium;
4) by step 3) gained Tetrafluoroboric acid crystalline lithium preliminarily dried 8h under 60 DEG C of conditions, afterwards vacuum-drying 2h under 100 DEG C of conditions again, obtain the LiBF4 crude product that water content is 3800ppm;
5) by 200g step 4) gained LiBF4 crude product is placed in reactor, slowly pass into 23.9g fluorine nitrogen mixed gas (mass content of fluorine gas is 10%), the mol ratio of crystal water in fluorine gas and LiBF4 crude product is made to be 1.5:1, under 20 DEG C of conditions, react 10h, obtain the LiBF4 product that water content is 92ppm.
Embodiment 2
The preparation method of the LiBF4 of the present embodiment, comprises the following steps:
1) under-5 DEG C of conditions, according to H
3bO
3be the ratio of 1:5 with the mol ratio of HF, boric acid slowly being added mass percent concentration is in the hydrofluoric acid of 40%, Keep agitation afterwards, and reaction 1h, obtains fluoborate solution;
2) being the ratio of 1.10:1 according to the mol ratio of Li and B, lithium hydroxide added step 1) in gained fluoborate solution, under 90 DEG C of conditions, stirring reaction 2h, obtains lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrates, is concentrated into 1/6 of lithium tetrafluoroborate solution original volume, carries out crystallization at being down to room temperature 20 DEG C afterwards under-0.09MPa, 50 DEG C of conditions, and filter, gained solid is Tetrafluoroboric acid crystalline lithium;
4) by step 3) gained Tetrafluoroboric acid crystalline lithium preliminarily dried 2h under 60 DEG C of conditions, afterwards vacuum-drying 4h under 90 DEG C of conditions again, obtain the LiBF4 crude product that water content is 4000ppm;
5) by 200g step 4) gained LiBF4 crude product is placed in reactor, slowly pass into 39.9g fluorine nitrogen mixed gas (mass content of fluorine gas is 10%), the mol ratio of crystal water in fluorine gas and LiBF4 crude product is made to be 2.5:1, under 40 DEG C of conditions, react 7h, obtain the LiBF4 product that water content is 90ppm.
Embodiment 3
The preparation method of the LiBF4 of the present embodiment, comprises the following steps:
1) under 0 DEG C of condition, according to H
3bO
3be the ratio of 1:6 with the mol ratio of HF, boric acid slowly being added mass percent concentration is in the hydrofluoric acid of 30%, Keep agitation afterwards, and reaction 3h, obtains fluoborate solution;
2) being the ratio of 1.20:1 according to the mol ratio of Li and B, lithium bicarbonate added step 1) in gained fluoborate solution, under 80 DEG C of conditions, stirring reaction 3h, obtains lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrates, is concentrated into 1/7 of lithium tetrafluoroborate solution original volume, carries out crystallization at being down to room temperature 20 DEG C afterwards under-0.06MPa, 80 DEG C of conditions, and filter, gained solid is Tetrafluoroboric acid crystalline lithium;
4) by step 3) gained Tetrafluoroboric acid crystalline lithium preliminarily dried 8h under 40 DEG C of conditions, afterwards vacuum-drying 8h under 50 DEG C of conditions again, obtain the LiBF4 crude product that water content is 3800ppm;
5) by 200g step 4) gained LiBF4 crude product is placed in reactor, slowly pass into 71.8g fluorine nitrogen mixed gas (mass content of fluorine gas is 10%), the mol ratio of crystal water in fluorine gas and LiBF4 crude product is made to be 4.5:1, under 70 DEG C of conditions, react 4h, obtain the LiBF4 product that water content is 89ppm.
Embodiment 4
The preparation method of the LiBF4 of the present embodiment, comprises the following steps:
1) under 5 DEG C of conditions, according to H
3bO
3be the ratio of 1:4 with the mol ratio of HF, boric acid slowly being added mass percent concentration is in the hydrofluoric acid of 50%, Keep agitation afterwards, and reaction 4h, obtains fluoborate solution;
2) being the ratio of 1.50:1 according to the mol ratio of Li and B, Quilonum Retard added step 1) in gained fluoborate solution, under 60 DEG C of conditions, stirring reaction 4h, obtains lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrates, is concentrated into 1/3 of lithium tetrafluoroborate solution original volume, carries out crystallization at being down to room temperature 20 DEG C afterwards under-0.08MPa, 60 DEG C of conditions, and filter, gained solid is Tetrafluoroboric acid crystalline lithium;
4) by step 3) gained Tetrafluoroboric acid crystalline lithium preliminarily dried 5h under 50 DEG C of conditions, afterwards vacuum-drying 5h under 70 DEG C of conditions again, obtain the LiBF4 crude product that water content is 3800ppm;
5) by 200g step 4) gained LiBF4 crude product is placed in reactor, slowly pass into 103.7g fluorine nitrogen mixed gas (mass content of fluorine gas is 10%), the mol ratio of crystal water in fluorine gas and LiBF4 crude product is made to be 6.5:1, under 50 DEG C of conditions, react 6h, obtain the LiBF4 product that water content is 63ppm.
Embodiment 5
The preparation method of the LiBF4 of the present embodiment, comprises the following steps:
1) under 10 DEG C of conditions, according to H
3bO
3be the ratio of 1:5 with the mol ratio of HF, boric acid slowly being added mass percent concentration is in the hydrofluoric acid of 20%, Keep agitation afterwards, and reaction 5h, obtains fluoborate solution;
2) being the ratio of 1.40:1 according to the mol ratio of Li and B, lithium hydroxide added step 1) in gained fluoborate solution, under 70 DEG C of conditions, stirring reaction 2h, obtains lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrates, is concentrated into 1/4 of lithium tetrafluoroborate solution original volume, carries out crystallization at being down to room temperature 20 DEG C afterwards under-0.07MPa, 70 DEG C of conditions, and filter, gained solid is Tetrafluoroboric acid crystalline lithium;
4) by step 3) gained Tetrafluoroboric acid crystalline lithium preliminarily dried 8h under 30 DEG C of conditions, afterwards vacuum-drying 6h under 60 DEG C of conditions again, obtain the LiBF4 crude product that water content is 3800ppm;
5) by 200g step 4) gained LiBF4 crude product is placed in reactor, slowly pass into 135.7g fluorine nitrogen mixed gas (mass content of fluorine gas is 10%), the mol ratio of crystal water in fluorine gas and LiBF4 crude product is made to be 8.5:1, under 60 DEG C of conditions, react 5h, obtain the LiBF4 product that water content is 79ppm.
Embodiment 6
The preparation method of the LiBF4 of the present embodiment, comprises the following steps:
1) under-10 DEG C of conditions, according to H
3bO
3be the ratio of 1:6 with the mol ratio of HF, boric acid slowly being added mass percent concentration is in the hydrofluoric acid of 60%, Keep agitation afterwards, and reaction 0.5h, obtains fluoborate solution;
2) being the ratio of 1.30:1 according to the mol ratio of Li and B, lithium bicarbonate added step 1) in gained fluoborate solution, under 50 DEG C of conditions, stirring reaction 5h, obtains lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrates, is concentrated into 1/5 of lithium tetrafluoroborate solution original volume, carries out crystallization at being down to room temperature 20 DEG C afterwards under-0.75MPa, 65 DEG C of conditions, and filter, gained solid is Tetrafluoroboric acid crystalline lithium;
4) by step 3) gained Tetrafluoroboric acid crystalline lithium preliminarily dried 4h under 55 DEG C of conditions, afterwards vacuum-drying 3h under 80 DEG C of conditions again, obtain the LiBF4 crude product that water content is 3800ppm;
5) by 200g step 4) gained LiBF4 crude product is placed in reactor, slowly pass into 159.6g fluorine nitrogen mixed gas (mass content of fluorine gas is 10%), the mol ratio of crystal water in fluorine gas and LiBF4 crude product is made to be 10:1, under 80 DEG C of conditions, react 3h, obtain the LiBF4 product that water content is 83ppm.
Experimental example
This experimental example carries out foreign ion analysis to embodiment 1-6 gained LiBF4 product, and result is as shown in table 1.
Table 1 embodiment 1-6 gained LiBF4 product foreign ion analytical results
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Main content/% | 99.983 | 99.983 | 99.983 | 99.986 | 99.985 | 99.984 |
| HF/ppm | 32 | 35 | 42 | 38 | 29 | 38 |
| H 2O/ppm | 92 | 90 | 89 | 63 | 79 | 83 |
| K/ppm | 2.6 | 2.5 | 2.5 | 2.4 | 2.5 | 2.6 |
| Ca/ppm | 4.5 | 4.6 | 3.9 | 4.3 | 5.0 | 4.8 |
| Na/ppm | 8.2 | 8.3 | 7.9 | 7.5 | 8.5 | 8.0 |
| Fe/ppm | 12.3 | 10.9 | 13.0 | 12.0 | 11.9 | 12.5 |
| Pb/ppm | 2.2 | 2.3 | 2.0 | 2.1 | 2.2 | 2.2 |
| SO 4/ppm | 8.9 | 9.5 | 9.6 | 8.7 | 9.0 | 9.3 |
| Cl/ppm | 5.0 | 4.9 | 3.9 | 4.2 | 5.2 | 4.5 |
As can be seen from Table 1, in embodiment 1-6 gained LiBF4 product, the content of LiBF4 is up to more than 98.983%, and foreign matter content is extremely low.Experimental result shows, the preparation method of LiBF4 of the present invention, pass into fluorine gas or fluorine nitrogen mixed gas carries out purification removal of impurities to LiBF4 crude product, can effective elimination moisture wherein, gained LiBF4 product purity is high, especially water content is low for foreign matter content, has broad application prospects.
Claims (10)
1. a preparation method for LiBF4, is characterized in that: comprise the following steps:
1) according to H
3bO
3be the ratio of 1:4 ~ 6 with the mol ratio of HF, boric acid added in hydrofluoric acid and reacts, obtain fluoborate solution;
2) be the ratio of 1.05 ~ 1.5:1 according to the mol ratio of Li and B, get lithium compound and add step 1) react in gained fluoborate solution, obtain lithium tetrafluoroborate solution;
3) by step 2) gained lithium tetrafluoroborate solution concentrate, crystallisation by cooling, filter, obtain Tetrafluoroboric acid crystalline lithium;
4) by step 3) drying of gained Tetrafluoroboric acid crystalline lithium, obtain LiBF4 crude product;
5) by step 4) gained LiBF4 crude product is placed in reactor, passes into fluorine gas or fluorine nitrogen mixed gas reacts, and obtains described LiBF4.
2. the preparation method of LiBF4 according to claim 1, is characterized in that: step 1) in, the temperature of described reaction is-10 ~ 10 DEG C, and the reaction times is 0.5 ~ 5h.
3. the preparation method of LiBF4 according to claim 1 and 2, is characterized in that: step 2) in, described lithium compound is Quilonum Retard, lithium hydroxide or lithium bicarbonate.
4. the preparation method of LiBF4 according to claim 1, is characterized in that: step 2) in, the temperature of described reaction is 50 ~ 100 DEG C, and the time of reaction is 0.5 ~ 5h.
5. the preparation method of LiBF4 according to claim 1, is characterized in that: step 3) in, described concentrated be by step 2) gained lithium tetrafluoroborate solution is concentrated into 1/3 ~ 1/8 of original volume.
6. the preparation method of LiBF4 according to claim 1 or 5, is characterized in that: step 3) in, described concentrated be concentrate under-0.05 ~-0.09MPa, 50 ~ 90 DEG C of conditions.
7. the preparation method of LiBF4 according to claim 1, is characterized in that: step 4) in, described drying is by Tetrafluoroboric acid crystalline lithium under 30 ~ 60 DEG C of conditions after preliminarily dried 2 ~ 8h, then at 50 ~ 100 DEG C of vacuum-drying 2 ~ 8h.
8. the preparation method of the LiBF4 according to claim 1 or 7, is characterized in that: step 4) in, the water content of gained LiBF4 crude product is 3500 ~ 4500ppm.
9. the preparation method of LiBF4 according to claim 1, is characterized in that: step 5) in, the amount passing into fluorine gas or fluorine nitrogen mixed gas is: in fluorine gas and LiBF4 crude product, the mol ratio of crystal water is 1.5 ~ 10:1.
10. the preparation method of LiBF4 according to claim 1, is characterized in that: step 5) in, the temperature of described reaction is 20 ~ 80 DEG C, and the time is 3 ~ 10h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106335907A (en) * | 2016-08-27 | 2017-01-18 | 洛阳和梦科技有限公司 | Catalytic synthesis method of lithium tetrafluoroborate |
| 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 |
| CN112758904A (en) * | 2019-11-22 | 2021-05-07 | 多氟多化工股份有限公司 | Preparation method of lithium difluorophosphate |
| CN115196646A (en) * | 2022-08-23 | 2022-10-18 | 江苏瀚康电子材料有限公司 | Method for synthesizing lithium tetrafluoroborate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310421A (en) * | 2014-10-20 | 2015-01-28 | 多氟多化工股份有限公司 | Preparation method of high-purity lithium tetrafluoroborate |
-
2015
- 2015-02-04 CN CN201510057912.7A patent/CN104692405A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310421A (en) * | 2014-10-20 | 2015-01-28 | 多氟多化工股份有限公司 | Preparation method of high-purity lithium tetrafluoroborate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106335907A (en) * | 2016-08-27 | 2017-01-18 | 洛阳和梦科技有限公司 | Catalytic synthesis method of lithium tetrafluoroborate |
| 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 |
| CN112758904A (en) * | 2019-11-22 | 2021-05-07 | 多氟多化工股份有限公司 | Preparation method of lithium difluorophosphate |
| CN115196646A (en) * | 2022-08-23 | 2022-10-18 | 江苏瀚康电子材料有限公司 | Method for synthesizing lithium tetrafluoroborate |
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Application publication date: 20150610 |