CN104030310B - A kind of preparation method of LiBF4 - Google Patents
A kind of preparation method of LiBF4 Download PDFInfo
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- CN104030310B CN104030310B CN201410221765.8A CN201410221765A CN104030310B CN 104030310 B CN104030310 B CN 104030310B CN 201410221765 A CN201410221765 A CN 201410221765A CN 104030310 B CN104030310 B CN 104030310B
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Abstract
A preparation method for LiBF4, feature comprises: select a tetrafluoro borate MBF
4wherein M is Na, K, NH
4, Ag; Or one or more being selected from the ammonium tetrafluoroborate type organic of tetramethyl-ammonium tetrafluoroborate, tetraethyl-ammonium tetrafluoroborate; And with starting halo lithium salts as LiF and product MF, LiBF
4react, utilize the difference of solubleness, utilize ion-exchange techniques to prepare LiBF4; This temperature of reaction is carried out between 0-15 DEG C, filters, and filtrate obtains LiBF after heating concentrated cooling
4crystal, namely obtains LiBF4 product after vacuum rapid drying; Purify with organic solvent again and obtain final LiBF4 product.
Description
Technical field
The present invention relates to lithium ion battery material manufacturing technology field, relate to electrolyte lithium salt production process, be specially a kind of preparation method of LiBF4.
Background technology
Operating voltage is high, energy density is large, self-discharge rate is low because having for lithium ion battery, memory-less effect, have extended cycle life, the advantage such as spry and light convenience and being widely applied in mobile phone, notebook computer, Kamera etc. as compact power.
Ionogen is one of basic material of lithium-ion battery electrolytes, directly affects the serviceability of lithium ion battery.Due to LiPF
6there is higher ionic conductivity and more stable chemical property, and become the widely used electrolyte lithium salt of present stage lithium-ion battery electrolytes, but LiPF
6preparation method is complicated, extremely responsive to moisture, micro-moisture just can with its reaction, generate HF, while LiPF
6poor heat stability, at high temperature, also can decompose and produce HF, thus corrosion target material and collector.And LiBF
4ionogen has good chemical stability and thermostability, has good high-temperature behavior, insensitive to moisture, and it has lower charge transfer resistance, therefore also has and compares LiPF
6more superior low-temperature performance, therefore promises to be and replaces LiPF
6one of electrolyte lithium salt.
At present, LiBF
4preparation method mainly contain solid phase-gas phase contact process, non-aqueous solution method and aqua-solution method.
Solid phase-gas phase contact process is at high temperature, and with basic lithium salts for raw material synthesizes, the method is higher to equipment requirements, and process control requirements is strict, and synthesis difficulty is large, and reaction efficiency is low, is difficult to accomplish scale production.
Non-aqueous solution method is that lithium fluoride is formed suspension liquid in organic solvent, with BF
3reaction generates LiBF
4, but the method is due to an organic solvent, has side reaction to produce, thus affect product quality in reaction process.Meanwhile, the method is owing to using highly toxic BF
3gas, should not realize industrialization.
Aqua-solution method adopts boric acid and HF reactant aqueous solution to prepare Tetrafluoroboric acid, lithium tetrafluoroborate solution is obtained again with carbonate reaction, then product is obtained through concentrated, crystallization, drying, but adopt in the method preparation process, LiBF4 exists with the form of a water or trihydrate, product purity is low, and drying and dehydrating is difficult.
Summary of the invention
For solving in above-mentioned technique Problems existing with not enough, the invention provides a kind of simple and LiBF4 preparation method of practicality.
The present invention is a kind of preparation method of LiBF4, it is characterized in that: the method comprises:
Select a tetrafluoro borate MBF
4wherein M is Na, K, NH4, Ag; Or one or more being selected from the ammonium tetrafluoroborate type organic of tetramethyl-ammonium tetrafluoroborate, tetraethyl-ammonium tetrafluoroborate; And with starting halo lithium salts as LiF and product MF, LiBF
4react, utilize the difference of solubleness in solvent HF, utilize ion-exchange techniques to prepare LiBF4;
Concrete steps get a certain amount of halo lithium salts such as LiF to be placed in the tetrafluoro retort of jacketed and filtration unit, and it is fully dissolved in HF, then add a certain amount of a tetrafluoro borate, the mol ratio of a tetrafluoro borate and halo lithium salts is 1.2-1:1, and generate LiBF
4the quality 20%-38% that accounts for its lithium tetrafluoroborate solution total mass be suitable; The temperature of reaction of this reaction will be carried out between 0-15 DEG C, and fully stir after 2-24 hour, filter, by concentrated through heating for filtration gained filtrate, be concentrated into the 40%-80% of original volume, the HF that steams is reclaimed by condensing mode, and reuses;
Then-20 DEG C are placed in--after the environment of 40 DEG C fully cools, obtain LiBF by filter type
4crystal, at 150 DEG C-200 DEG C, under vacuum condition, rapid drying in 1-3 hour, namely obtains LiBF4 product after drying; But M in this product
+the content of foreign ion reaches more than 1000ppm;
This reaction is carried out in confined conditions, is to ensure product purity, and reaction atmosphere and the anhydrous HF needed for reaction and organic solvent will through except water treatments, and the water content of solvent is less than 10ppm; Rare gas element selects one or more in nitrogen, argon gas, helium;
For by the M in four lithium fluophosphates
+foreign ion removes, and adopts and is dissolved in organic solvent; Ester class is selected from methylcarbonate, diethyl carbonate; Or ethers is selected from ether, dme; Or in nitrile acetonitrile, and removed by foreign ion by the mode of secondary filter, for improving filter effect, the add-on of organic solvent is that LiBF4 can be dissolved in organic solvent completely, according to the difference of solvent, suitably adjusts consumption of organic solvent;
Or employing has certain solubility to MF foreign ion but LiBF4 product is not had to the organic solvent of solubleness; Alkanes is selected from normal hexane; Haloalkane hydro carbons is selected from fluoroalkane hydro carbons, alkyl chloride hydro carbons; Ketone is selected from acetone; The add-on of organic solvent and the mass ratio of LiBF4 product are 5-20:1, obtain the LiBF4 product containing organic solvent after filtering, then obtain required LiBF4 product after four hours 150 DEG C of-200 DEG C of dryings.
According to preparation method of the present invention, the organic solvent used is for high-purity organic solvent and through removing water treatment, organic solvent purity is greater than 99.95%, and water content is less than 10ppm, and the organic solvent used can be reused.
According to preparation method of the present invention, adopt evaporation and crystallization mode to carry out drying to gained LiBF4 product, concrete grammar is: filtration gained lithium tetrafluoroborate solution is placed in 316L stainless steel vessel, utilizes hot N
2carry out drying to product, to obtain high-purity lithium tetrafluoroborate product, concrete grammar is: by cold N
2gas is warming up to 40-60 DEG C, continues to pass into hot N
2gas is after three hours, by N
2gas is warming up to 150-200 DEG C, terminates after dry 4-8 hour.
Advantage of the present invention is to use low-cost a tetrafluoro borate, utilizes replacement(metathesis)reaction to prepare LiBF4, and the method preparation method is simple, overcomes in traditional method preparation process, and reaction is complicated, equipment requirements is high and a large amount of dangerous BF of needs
3gas, thus can cost be saved and substantially increase security.
Embodiment
Embodiment 1:
At ambient temperature, in the tetrafluoro reaction vessel of chuck, add 9.23gLiF, 105.27gHF, and stir a night, LiF is dissolved in HF completely, then adds KBF
444.81g, passes into low-temperature cooling media in chuck, and control temperature is 10 DEG C, stir after 24 hours, fast filtering, after gained filtrate is concentrated into about 50% of original volume, is undertaken freezing by filtrate, freezing temp is-20 DEG C, freezing time is 6 hours, and then filtrate filtered, gained filtrate quality is 49.87g, and LiBF4 product will be obtained carry out drying: filtration gained lithium tetrafluoroborate solution is placed in 316L stainless steel vessel, utilizes hot N
2drying is carried out to product, to obtain high-purity lithium tetrafluoroborate product, by cold N
2gas is warming up to 40 DEG C, continues to pass into hot N
2gas is after three hours, by N
2gas is warming up to 200 DEG C, terminates after dry 4 hours.
Products obtained therefrom quality is 23.77g, LiBF in filtrate
4content is 18.24%, and products obtained therefrom productive rate is 98.58%, and wherein potassium content is 950ppm.Products obtained therefrom is dissolved in DMC, after secondary filter, by evaporative crystallization and after drying, the product purity of products obtained therefrom is 99.96%, and water content is 4.8ppm, and acid content is 12ppm, and potassium content is 4ppm.
Table one
| Project | Index | Analytical procedure |
| Product purity | 99.96％ | NMR, atomic absorption |
| Moisture | 4.8ppm | Fischer coulometry |
| Free acid (in HF) | 12ppm | Acid base titration |
| K +Content | 4 | Atomic absorption |
| LiBF in filtrate 4Content | 18.24％ | Atomic absorption |
Embodiment 2:
At ambient temperature, in the tetrafluoro reaction vessel of chuck, add 4.34gLiF, and embodiment 1 gained filtrate 49.87g is added wherein, stir a night, LiF is dissolved in HF completely, then adds KBF
421.06g, passes into low-temperature cooling media in chuck, and control temperature is 10 DEG C, stir after 24 hours, fast filtering, after gained filtrate is concentrated into about 50% of original volume, is undertaken freezing by gained filtrate, freezing temp is-20 DEG C, freezing time is 4 hours, and then filtrate filtered, gained filtrate quality is 24.55g, LiBF4 product will be obtained and carry out drying: filtration gained lithium tetrafluoroborate solution is placed in 316L stainless steel vessel, utilize hot N
2carry out drying to product, to obtain high-purity lithium tetrafluoroborate product, concrete grammar is: by cold N
2gas is warming up to 60 DEG C, continues to pass into hot N
2gas is after three hours, by N
2gas is warming up to 150 DEG C, terminates after dry 8 hours.
Products obtained therefrom quality is 19.97g, LiBF in filtrate
4content is 18.37%, and products obtained therefrom productive rate is 98.79%, and wherein potassium content is 921ppm.Be dissolved in by products obtained therefrom in DMC, after secondary filter, be 99.32% by the product purity of products obtained therefrom after evaporative crystallization also drying, water content is 7.2ppm, and acid content is 18ppm, and potassium content is 5ppm.
Table two
| Project | Index | Analytical procedure |
| Product purity | 99.23％ | NMR, atomic absorption |
| Moisture | 6.8ppm | Fischer coulometry |
| Free acid (in HF) | 15ppm | Acid base titration |
| K +Content | 5 | Atomic absorption |
| LiBF in filtrate 4Content | 18.37％ | Atomic absorption |
Embodiment 3:
At ambient temperature, in the tetrafluoro reaction vessel of chuck, add 10.51gLiF, 106.23gHF, and stir a night, LiF is fully dissolved in HF, then adds NH
4bF
442.53g, passes into low-temperature cooling media in chuck, and control temperature is 10 DEG C, stir after 24 hours, fast filtering, after gained filtrate is concentrated into about 50% of original volume, gained filtrate is carried out freezing, freezing temp is-20 DEG C, and freezing time is 6 hours, then filtrate is filtered, gained filtrate quality is 46.27g, to obtain after LiBF4 product carries out drying (drying conditions is with embodiment 1), products obtained therefrom quality is 29.52g, LiBF in filtrate
4content is 18.62%, and products obtained therefrom productive rate is 98.66%, and wherein ammonium ion content is 923ppm.Be dissolved in by products obtained therefrom in acetonitrile, after secondary filter, be 99.35% by the product purity of products obtained therefrom after evaporative crystallization also drying, water content is 3.2ppm, NH
4 +content is 6ppm.
Table three
| Project | Index | Analytical procedure |
| Product purity | 99.35％ | NMR, atomic absorption |
| Moisture | 3.2ppm | Fischer coulometry |
| Free acid (in HF) | 14ppm | Acid base titration |
| NH 4 +Content | 6 | Atomic absorption |
| LiBF in filtrate 4Content | 18.62％ | Atomic absorption |
Embodiment 4:
At ambient temperature, in the tetrafluoro reaction vessel of chuck, add 19.39gLiBr, 106.51gHF, and stir a night, LiBr is dissolved in HF completely, then adds KBF
428.53g, low-temperature cooling media is passed in chuck, control temperature is 10 DEG C, stir after 24 hours, fast filtering, after gained filtrate is concentrated into about 50% of original volume, undertaken freezing by gained filtrate, freezing temp is-20 DEG C, freezing time is 6 hours, then filtrate filtered, gained filtrate quality is 50.25g, and will obtain LiBF4 product and carry out drying (drying conditions is with embodiment 2), products obtained therefrom quality is 11.23g, products obtained therefrom productive rate is 97.52%, and wherein potassium content is 953ppm, Br-ion content is 972ppm.For being removed by KBr, KF wherein, be dissolved in by products obtained therefrom in normal hexane, after filtering, after products obtained therefrom drying, the product purity of products obtained therefrom is 99.13%, and water content is 7.8ppm, and acid content is 19ppm, and potassium content is 3ppm, and ionic bromide content is 4ppm.
Table four
| Project | Index | Analytical procedure |
| Product purity | 98.84％ | NMR, atomic absorption |
| Moisture | 7.8ppm | Fischer coulometry |
| Free acid (in HF) | 19ppm | Acid base titration |
| K +Content | 3 | Atomic absorption |
| Br -Content | 4 | Atomic absorption |
| LiBF in filtrate 4Content | 18.27％ | Atomic absorption |
Claims (5)
1. a preparation method for LiBF4, is characterized in that: the method comprises:
Select a tetrafluoro borate MBF
4in solvent HF, product MX, LiBF is obtained by reacting with starting halo lithium salts LiX
4, by the difference of solubleness in solvent HF, utilize ion-exchange techniques to prepare LiBF4; Wherein M is Na, K, NH
4, Ag, tetramethyl-ammonium, one or more in tetraethyl ammonium, X is halogen;
Concrete steps get the tetrafluoro retort that a certain amount of halo lithium salts is placed in jacketed and filtration unit, and it is fully dissolved in HF, then add a certain amount of a tetrafluoro borate, the mol ratio of a tetrafluoro borate and halo lithium salts is 1.2-1:1, and generate LiBF
4the quality 20%-38% that accounts for its lithium tetrafluoroborate solution total mass be suitable; The temperature of reaction of this reaction will be carried out between 0-15 DEG C, and fully stir after 2-24 hour, filter, by concentrated through heating for filtration gained filtrate, be concentrated into the 40%-80% of original volume, the HF that steams is reclaimed by condensing mode, and reuses;
Then-20 DEG C are placed in--after the environment of 40 DEG C fully cools, obtain LiBF by filter type
4crystal, at 150 DEG C-200 DEG C, under vacuum condition, in 1-3 hour after rapid drying, obtains LiBF4 product; But M in this product
+the content of foreign ion reaches more than 1000ppm;
This reaction is carried out in confined conditions, is to ensure product purity, and reaction atmosphere and the anhydrous HF needed for reaction and organic solvent will through except water treatments, and the water content of solvent is less than 10ppm; Rare gas element selects one or more in nitrogen, argon gas, helium;
For by the M in LiBF4
+foreign ion removes, and adopts and is dissolved in organic solvent, and removed by foreign ion by the mode of secondary filter, for improving filter effect, the add-on of organic solvent is that LiBF4 can be dissolved in organic solvent completely, according to the difference of solvent, suitably adjusts consumption of organic solvent; Ester class is selected from methylcarbonate, diethyl carbonate; Or ethers is selected from ether, dme; Or nitrile is selected from acetonitrile;
Obtain the LiBF4 product containing organic solvent after filtering, then obtain required LiBF4 product after four hours 150 DEG C of-200 DEG C of dryings.
2. preparation method according to claim 1, it is characterized in that, the organic solvent used is for high-purity organic solvent and through removing water treatment, organic solvent purity is greater than 99.95%, water content is less than 10ppm, and the organic solvent used can be reused.
3. preparation method according to claim 1, is characterized in that, adopt evaporation and crystallization mode to carry out drying to gained LiBF4 product, concrete grammar is: filtration gained lithium tetrafluoroborate solution is placed in 316L stainless steel vessel, utilizes hot N
2carry out drying to product, to obtain high-purity lithium tetrafluoroborate product, concrete grammar is: by cold N
2be warming up to 40-60 DEG C, continue to pass into hot N
2after three hours, by N
2be warming up to 150-200 DEG C, terminate after dry 4-8 hour.
4. preparation method according to claim 1, is characterized in that, described halo lithium salts is LiF.
5. preparation method according to claim 4, is characterized in that, for by the M in LiBF4
+foreign ion removes, and adopts and has certain solubility to MF foreign ion but LiBF4 product do not had to the organic solvent of solubleness; Alkanes is selected from normal hexane; Haloalkane hydro carbons is selected from fluoroalkane hydro carbons, alkyl chloride hydro carbons; Ketone is selected from acetone; The add-on of organic solvent and the mass ratio of LiBF4 product are 5-20:1.
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Citations (5)
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|---|---|---|---|---|
| JP2000211916A (en) * | 1999-01-20 | 2000-08-02 | Morita Kagaku Kogyo Kk | Treatment of organic solution containing lithium hexafluorophosphate or lithium tetrafluoroborate |
| 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 |
| 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 |
| 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 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000211916A (en) * | 1999-01-20 | 2000-08-02 | Morita Kagaku Kogyo Kk | Treatment of organic solution containing lithium hexafluorophosphate or lithium tetrafluoroborate |
| 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 |
| 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 |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 锂离子二次电池电解质四氟硼酸锂制备技术研究进展;张玥等;《无机盐工业》;20140331;第46卷(第3期);第65页右栏第2段 * |
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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: 20161008 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. |