CN104030310A - Method for preparing lithium tetrafluoroborate - Google Patents
Method for preparing lithium tetrafluoroborate Download PDFInfo
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- CN104030310A CN104030310A CN201410221765.8A CN201410221765A CN104030310A CN 104030310 A CN104030310 A CN 104030310A CN 201410221765 A CN201410221765 A CN 201410221765A CN 104030310 A CN104030310 A CN 104030310A
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Abstract
The invention discloses a method for preparing lithium tetrafluoroborate. The method is characterized by comprising the following steps: selecting tetrafluoroborate MBF4, wherein M is Na, K, NH4 or Ag, or selecting one or more of ammonium fluoroborate organic matters of tetramethylammonium tetrafluoroborate and tetraethylammonium tetrafluoroborate, reacting with halogenated lithium materials, for example, LiF, and products MF and LiBF4, and preparing lithium tetrafluoroborate by using an ion exchange method according to different solubilities, wherein the reaction temperature is 0-15 DEG C; filtering, heating, concentrating and cooling filtrate, and then obtaining LiBF4 crystals; quickly drying in vacuum, and then obtaining the lithium tetrafluoroborate product; and purifying by using an organic solvent to obtain the final lithium tetrafluoroborate product.
Description
Technical field
The present invention relates to lithium ion battery material manufacturing technology field, relate to electrolyte lithium salt preparation method, 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 is widely applied at aspects such as mobile phone, notebook computer, Kameras 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, and extremely responsive to moisture, micro-moisture just can react with it, generates HF, simultaneously 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 the LiPF of ratio
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 the basic lithium salts of take synthesizes as raw material, and the method is higher to equipment requirements, and process control requires strict, and synthetic difficulty is large, and reaction efficiency is low, is difficult to accomplish scale production.
Non-aqueous solution method is lithium fluoride to be formed in organic solvent to suspension liquid, with BF
3reaction generates LiBF
4, but the method is due to an organic solvent, has side reaction to produce, thereby 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, obtain LiBF4 solution with carbonate reaction again, then through concentrated, crystallization, the dry product that obtains, yet adopt in the method preparation process, LiBF4 exists with the form of a water or trihydrate, product purity is low, and drying and dehydrating difficulty.
Summary of the invention
For solving the problems and shortcomings that exist in above-mentioned technique, the invention provides a kind of simple and practical LiBF4 preparation method.
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 be selected from one or more in the ammonium tetrafluoroborate type organic of tetramethyl-ammonium tetrafluoroborate, tetraethyl-ammonium tetrafluoroborate; And with raw material 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 are to get a certain amount of halo lithium salts to be placed in the tetrafluoro retort of jacketed and filtration unit as LiF, 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 the LiBF that generates
4the quality 20%-38% that accounts for its LiBF4 solution total mass be suitable; The temperature of reaction of this reaction will be carried out between 0-15 ℃, fully stirs after 2-24 hour, filters, and will filter gained filtrate concentrated through heating, and is concentrated into the 40%-80% of original volume, and the HF that steams reclaims by condensing mode, and reuses;
Then be placed in-20 ℃--after the environment of 40 ℃ is fully cooling, by filter type, obtain LiBF
4crystal, at 150 ℃-200 ℃, under vacuum condition, rapid drying in 1-3 hour, obtains LiBF4 product after being dried; But M in this product
+more than the content of foreign ion has reached 1000ppm;
This reaction is carried out in confined conditions, and for guaranteeing product purity, reaction atmosphere and the anhydrous HF and the organic solvent that react required will be through removing water treatment, and the water content of solvent is less than 10ppm; Rare gas element is selected one or more in nitrogen, argon gas, helium;
For by the M in tetrafluoro Trilithium phosphate
+foreign ion is removed, 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 by the mode of secondary filter, foreign ion is removed, 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 adopt to MF foreign ion is had certain solubility but LiBF4 product be there is no 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 mass ratio of the add-on of organic solvent and LiBF4 product is 5-20:1, obtains after filtering the LiBF4 product containing organic solvent, then obtains needed LiBF4 product at 150 ℃-200 ℃ after dry four hours.
According to preparation method of the present invention, the organic solvent using is for high-purity organic solvent and through removing water treatment, and organic solvent purity is greater than 99.95%, and water content is less than 10ppm, and the organic solvent using can be reused.
According to preparation method of the present invention, adopt evaporation and crystallization mode to be dried gained LiBF4 product, concrete grammar is: filtration gained LiBF4 solution is placed in to 316L stainless steel vessel, utilizes hot N
2product is dried, and to obtain high-purity lithium tetrafluoroborate product, concrete grammar is: by cold N
2gas is warming up to 40-60 ℃, continues to pass into hot N
2after gas three hours, by N
2gas is warming up to 150-200 ℃, dry end after 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, has overcome in traditional method preparation process, and reaction is complicated, equipment requirements is high and need a large amount of dangerous BF
3gas, thus can save cost and greatly improve security.
Embodiment
Embodiment 1:
At ambient temperature, in the tetrafluoro reaction vessel with chuck, add 9.23gLiF, 105.27g HF, and stir a night, LiF is dissolved in HF completely, then add KBF
444.81g, passes into low-temperature cooling media in chuck, controlling temperature is 10 ℃, stir after 24 hours, fast filtering, is concentrated into gained filtrate behind 50% left and right of original volume, and filtrate is carried out freezing, freezing temp is-20 ℃, freezing time is 6 hours, then filtrate is filtered, and gained filtrate quality is 49.87g, and will obtain LiBF4 product and be dried: filtration gained LiBF4 solution is placed in to 316L stainless steel vessel, utilize hot N
2product is dried, to obtain high-purity lithium tetrafluoroborate product, by cold N
2gas is warming up to 40 ℃, continues to pass into hot N
2after gas three hours, by N
2gas is warming up to 200 ℃, dry end after 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, and after secondary filter, by evaporative crystallization and after being dried, 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 with chuck, add 4.34gLiF, and embodiment 1 gained filtrate 49.87g is added wherein, stir a night, LiF is dissolved in HF completely, then add KBF
421.06g, passes into low-temperature cooling media in chuck, controlling temperature is 10 ℃, stir after 24 hours, fast filtering, is concentrated into gained filtrate behind 50% left and right of original volume, and gained filtrate is carried out freezing, freezing temp is-20 ℃, freezing time is 4 hours, then filtrate is filtered, and gained filtrate quality is 24.55g, to obtain LiBF4 product is dried: filtration gained LiBF4 solution is placed in to 316L stainless steel vessel, utilizes hot N
2product is dried, and to obtain high-purity lithium tetrafluoroborate product, concrete grammar is: by cold N
2gas is warming up to 60 ℃, continues to pass into hot N
2after gas three hours, by N
2gas is warming up to 150 ℃, dry end after 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.Products obtained therefrom is dissolved in DMC, and after secondary filter, after being also dried by evaporative crystallization, the product purity of products obtained therefrom is 99.32%, and 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 with chuck, add 10.51gLiF, 106.23g HF, and stir a night, LiF is fully dissolved in HF, then add NH
4bF
442.53g, passes into low-temperature cooling media in chuck, controlling temperature is 10 ℃, stir after 24 hours, fast filtering, is concentrated into gained filtrate behind 50% left and right of original volume, gained filtrate is carried out freezing, freezing temp is-20 ℃, and freezing time is 6 hours, then filtrate is filtered, gained filtrate quality is 46.27g, to obtain LiBF4 product and be dried after (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.Products obtained therefrom is dissolved in acetonitrile, and after secondary filter, after being also dried by evaporative crystallization, the product purity of products obtained therefrom is 99.35%, and 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 with chuck, add 19.39gLiBr, 106.51g HF, and stir a night, LiBr is dissolved in HF completely, then add KBF
428.53g, in chuck, pass into low-temperature cooling media, controlling temperature is 10 ℃, stir after 24 hours, fast filtering, gained filtrate is concentrated into behind 50% left and right of original volume, gained filtrate is carried out freezing, freezing temp is-20 ℃, freezing time is 6 hours, then filtrate is filtered, gained filtrate quality is 50.25g, and will obtain LiBF4 product and be dried (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, and Br-ion content is 972ppm.For KBr wherein, KF are removed, products obtained therefrom is dissolved in normal hexane, after filtering, the product purity of the dry rear products obtained therefrom of products obtained therefrom is 99.13%, and water content is 7.8ppm, and acid content is 19ppm, and potassium content is 3ppm, bromide anion 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 (3)
1. a preparation method for LiBF4, is characterized in that: the method comprises:
Select a tetrafluoro borate MBF
4wherein M is Na, K, NH
4, Ag; Or be selected from one or more in the ammonium tetrafluoroborate type organic of tetramethyl-ammonium tetrafluoroborate, tetraethyl-ammonium tetrafluoroborate; And with raw material 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 are to get a certain amount of halo lithium salts to be placed in the tetrafluoro retort of jacketed and filtration unit as LiF, 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 the LiBF that generates
4the quality 20%-38% that accounts for its LiBF4 solution total mass be suitable; The temperature of reaction of this reaction will be carried out between 0-15 ℃, fully stirs after 2-24 hour, filters, and will filter gained filtrate concentrated through heating, and is concentrated into the 40%-80% of original volume, and the HF that steams reclaims by condensing mode, and reuses;
Then be placed in-20 ℃--after the environment of 40 ℃ is fully cooling, by filter type, obtain LiBF
4crystal at 150 ℃-200 ℃, under vacuum condition, after rapid drying, obtained LiBF4 product in 1-3 hour; But M in this product
+more than the content of foreign ion has reached 1000ppm;
This reaction is carried out in confined conditions, and for guaranteeing product purity, reaction atmosphere and the anhydrous HF and the organic solvent that react required will be through removing water treatment, and the water content of solvent is less than 10ppm; Rare gas element is selected one or more in nitrogen, argon gas, helium;
For by the M in tetrafluoro Trilithium phosphate
+foreign ion is removed, 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 by the mode of secondary filter, foreign ion is removed, 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 adopt to MF foreign ion is had certain solubility but LiBF4 product be there is no 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 mass ratio of the add-on of organic solvent and LiBF4 product is 5-20:1, obtains after filtering the LiBF4 product containing organic solvent, then obtains needed LiBF4 product at 150 ℃-200 ℃ after dry four hours.
2. preparation method according to claim 1, the organic solvent using is for high-purity organic solvent and through except water treatment, and organic solvent purity is greater than 99.95%, and water content is less than 10ppm, and the organic solvent using can be reused.
3. preparation method according to claim 1, adopts evaporation and crystallization mode to be dried gained LiBF4 product, and concrete grammar is: filtration gained LiBF4 solution is placed in to 316L stainless steel vessel, utilizes hot N
2product is dried, and to obtain high-purity lithium tetrafluoroborate product, concrete grammar is: by cold N
2gas is warming up to 40-60 ℃, continues to pass into hot N
2after gas three hours, by N
2gas is warming up to 150-200 ℃, dry end after 4-8 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109836444A (en) * | 2017-11-29 | 2019-06-04 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
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| 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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2014
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Patent 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 |
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Cited By (2)
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| CN109836444A (en) * | 2017-11-29 | 2019-06-04 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
| CN109836444B (en) * | 2017-11-29 | 2021-05-11 | 东莞东阳光科研发有限公司 | Preparation method of lithium difluoroborate |
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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. |