CN109264736A - A kind of preparation method of LiBF4 - Google Patents
A kind of preparation method of LiBF4 Download PDFInfo
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- CN109264736A CN109264736A CN201811353418.5A CN201811353418A CN109264736A CN 109264736 A CN109264736 A CN 109264736A CN 201811353418 A CN201811353418 A CN 201811353418A CN 109264736 A CN109264736 A CN 109264736A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation methods of LiBF4.Its technical solution is included the following steps: under 1) normal temperature and pressure, and lithium fluoride is added in esters solvent, lithium fluoride suspension is obtained；2) boron triflouride gas is passed through in lithium fluoride suspension, reacts 1~2h, obtains lithium tetrafluoroborate solution；3) step 2 acquired solution is passed through into millipore filter, filters unreacted micro lithium fluoride；4) liquid after the completion of filtering step 3) is by concentration, degassing；5) solution after the completion of step 4) being concentrated carries out decrease temperature crystalline, filters, dry, and LiBF4 finished product can be obtained.Beneficial effect is: the boron trifluoride that the present invention uses is inexpensive and be easy to get for industrial raw material；Lithium fluoride forms suspension in esters solvent, so that the problems such as reaction is easy to carry out, and easy to operate, safety gets a promotion, the risk of reaction, preparation when avoiding using hydrogen fluoride as solvent, product free acid is excessively high, and ultra-low temperature crystallization energy consumption is high.
Description
Technical field
The present invention relates to a kind of lithium ion battery electrolyte technology of preparing, in particular to a kind of LiBF4
Preparation method.
Background technique
In recent years, as country widelys popularize new-energy automobile, limitation conventional fuel oil car is used, is caused to non-fossil energy
Other energy demands in addition increase substantially, and lithium ion battery explores the environmentally protective cleaning energy developed as 21 century
Source is widelyd popularize and is applied in automotive field.Along with the progress at full speed that power lithium-ion battery is applied, to ring
The different demands in border, temperature and security factor propose rigors to electrolyte system.
Lithium salts used in lithium-ion battery electrolytes be generally divided into lithium perchlorate (LiClO4), LiBF4 (LiBF4),
Hexafluoroarsenate lithium (LiAsF6) and lithium hexafluoro phosphate (LiPF6) etc..LiClO4 has strong oxidizing property, due to the safety of itself
Problem, therefore only used for laboratory research；LiAsF6 is not easily decomposed, but since arsenic has toxicity and price is higher and limited
System；LiPF6 is in current lithium ion battery business application due to ionic conductivity with higher and stable chemical property
Most commonly used electric conducting lithium salt, currently, whether the portable electricity consuming products lithium ion battery of low capacity or large capacity are electronic (certainly
Row) automobile-used lithium ion battery, the basic recipe of electrolyte is LiPF6/EC+ cosolvent, however, LiPF6 is extremely sensitive to water,
Micro moisture, which can react with it, generates HF, while LiPF6 thermal stability is very poor, can also decomposite HF at high temperature, produces
Object HF meeting corroding electrode material and afflux pole, so that undesirable using the battery high-temperature behavior of 6 electrolyte of LiPF.Tetrafluoro
The molecular formula of lithium borate be LiBF4, molecular weight 93.74, moisture, temperature sensitivity and in terms of it is excellent
Gesture, has lower charge-transfer resistance, and addition can make battery have high/low temperature more superior than LiPF6 after part
Performance.
The preparation method of LiBF4 routine has liquid-gas phase contact method, aqua-solution method etc..Liquid-gas phase contact method is with fluorine
Change hydrogen is carrier, and the high requirements on the equipment crosses range request strict control, and reaction, purification process risk are high, product free acid
Height is unfavorable for amplifying on a large scale；And during aqua-solution method synthesizes LiBF4, due to tetrafluoro boric acid in aqueous solution
Lithium occurs in the form of a water object or three water objects, and not only purity is low, and subsequent dry water removal is also extremely difficult, as electrolysis material
Material is used for lithium ion battery, is easy to cause battery to occur under conditions of lower voltage with many side reactions, causes to recycle
Performance decline.
Chinese patent literature Publication No. 104291347A, patent name are " a kind of preparation method of LiBF4 ",
Include the following steps: that lithium fluoride is dissolved in anhydrous hydrogen fluoride under 1) normal temperature and pressure, obtains lithium fluoride solution；It 2) will be borontrifluoride
Boron gas is passed through in lithium fluoride solution obtained by step 1), is reacted 30~60min, is obtained mixed liquor；3) by mixed liquor obtained by step 2
Decrease temperature crystalline is filtered and is dried to get LiBF4.The preparation method of LiBF4 of the invention, boron trifluoride used
It is inexpensive and be easy to get for industrial raw material；Reaction condition is mild, and the reaction time is short, and low energy consumption, reduces production cost.It exists
The problem of be anhydrous hydrogen fluoride for the extremely strong substance of reactivity, can react with various substances, high poison, corrosivity and irritation
It is extremely strong.There is security risk in the industrial production.
Chinese patent literature Publication No. 102826563A, patent name are a kind of " preparation of high-purity lithium tetrafluoroborate
Method ", it is reacted in linear carbonate class organic solvent with high purity lithium fluoride with boron trifluoride complex, through filtering, concentration, extraction
Take crystallization, washing, drying, obtain LiBF4, comprise steps that: high purity lithium fluoride and boron trifluoride complex rub
You than be 1.0~1.5, reaction temperature be 5~60 DEG C, the reaction time be 1~for 24 hours；After the reaction was completed, it is filtered to remove unreacted
Lithium fluoride, the heating concentration filtrate under vacuum or dry inert gas protection, until LiBF4 content is 40~90% in concentrate；
Low polar solvent is added to concentrate, extracts remaining chain carbonate organic solvent, LiBF4 in system is promoted to be precipitated；Extraction
It is filtered after taking crystallization, then residual linear carbonate solvent is removed with organic solvent washing, washing can be selected with organic solvent
One of hexamethylene, pentamethylene, hexane, pentane, carbon tetrachloride, ether, propyl ether, butyl ether, toluene, dimethylbenzene or styrene or
More than one mixture, the wet product obtained after washing is under vacuum or dry inert gas protection no more than LiBF4 points
It is dried at a temperature of solution, obtains high-purity LiBF4 electrolytic salt.Itself the problem is that: use boron trifluoride complex,
Enter to react adding lithium fluoride, adding for solid is difficult to control precisely, is difficult to control so as to cause reaction process, safety is not
It is high；In addition, adding weak polar solvent extractive crystallization using concentration, the quantity of solvent used in this way is big, and solvent extracted is difficult to point
From being difficult recovery.
Summary of the invention
The purpose of the present invention is to drawbacks described above of the existing technology, provide a kind of preparation side of LiBF4
Method, inexpensive, high-purity, low miscellaneous, low water, reaction are easy to carry out, and easy to operate, safety gets a promotion, and effectively reduces
Production cost；Gained LiBF4 product it is high-quality, purity reaches 99.8% or more.
A kind of preparation method for LiBF4 that the present invention mentions, technical solution are to include the following steps:
1) under normal temperature and pressure, lithium fluoride is added in esters solvent, obtains lithium fluoride suspension, the mass fraction of lithium fluoride is 4%
~10%；
2) boron triflouride gas is passed through in lithium fluoride suspension obtained by step 1), the molar ratio of boron trifluoride and lithium fluoride is
0.9~1.2:1 reacts 1~2h, obtains lithium tetrafluoroborate solution；
3) step 2 acquired solution is passed through into millipore filter, filters unreacted micro lithium fluoride；
4) liquid after the completion of filtering step 3) is by concentration, degassing；
5) solution after the completion of step 4) being concentrated carries out decrease temperature crystalline, filters, dry, and LiBF4 finished product can be obtained.
Preferably, lithium fluoride described in step 1) is high purity lithium fluoride, and high-purity is greater than 99.5%.
Preferably, esters solvent described in step 1) is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate or acetic acid second
Ester.
Preferably, for the millipore filter that step 3) uses for PP material, aperture is 0.4 ~ 10um.
Preferably, in concentration, degasification process, N2 aerator is placed in below liquid level of solution liquid in step 4), aeration
5 ~ 100L/min is measured, temperature is 40 ~ 80 DEG C, and vacuum degree is -10kpa ~ -80kpa；Liquid concentration amount is the 10 ~ 40% of solution.
Preferably, decrease temperature crystalline described in step 5) is gradient cooling crystallization, and gradient cooling crystallization refers to: 65~
10 DEG C of range inside gradient decrease temperature crystallines, with the speed decrease temperature crystalline of 3 ~ 6 DEG C/h.
Preferably, at 60 DEG C ~ 40 DEG C, rate of temperature fall control reaches 40 DEG C in 2 ~ 3 DEG C/h, and 1 ~ 3h is stablized in maintenance, 40 ~
10 DEG C, with the speed decrease temperature crystalline of 3 ~ 6 DEG C/h, temperature reaches 10 DEG C, and 3 ~ 6 h are stablized in maintenance.
Preferably, the method for drying described in step 5) is dry for reduced vacuum, and dry temperature is 60~90 DEG C, vacuum degree
For -30kpa ~ -90kpa；4~12h of drying time.
The beneficial effects of the present invention are: the preparation method of LiBF4 of the invention, with high purity lithium fluoride with it is borontrifluoride
It is reacted in esters solvent under boron gas normal-temperature condition of normal pressure, through filtering, concentration, degassing, decrease temperature crystalline, filtering, vacuum drying
Obtain high-purity lithium tetrafluoroborate, boron trifluoride used is industrial raw material, inexpensive and be easy to get；Lithium fluoride is formed in esters solvent
Suspension, so that reaction is easy to carry out, easy to operate, safety gets a promotion, when avoiding using hydrogen fluoride as solvent
The problems such as risk of reaction, preparation, product free acid is excessively high, and ultra-low temperature crystallization energy consumption is high, effectively reduce production cost；
In addition, present invention gained LiBF4 product is high-quality, purity reaches 99.8% or more, moisture control in 20ppm hereinafter,
Free acid control is controlled in 50ppm, insoluble matter in 100ppm or less；Metal cations Fe, Cr, Ni control are in 1ppm hereinafter, completely
Meet the needs of power lithium-ion battery production, there is good economic value and social value；Synthesis technology is simple, is easy to grasp
Make and control, is suitble to large-scale industrial production.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1, a kind of preparation method for LiBF4 that the present invention mentions, including the following steps:
1) the closed addition 2400g dimethyl carbonate into reaction unit, then 100g lithium fluoride is put into, the lithium fluoride is high-purity
Lithium fluoride, high-purity is greater than 99.5%, and under normal temperature and pressure, starting stirring, revolving speed is 10 ~ 40rpm, obtains lithium fluoride suspension,
(mass fraction 4%)；
2) 310g boron triflouride gas is slowly introducing in lithium fluoride suspension obtained by step 1), reaction time 80min must react
Liquid；The mass fraction of LiBF4 is 13.09% in gained reaction solution；
3) reaction solution obtained by step 2 is imported under nitrogen protection in filter device, filtrate imports concentration under nitrogen protection
Device,
4) the resulting filtrate of step 3) is heated up, opens vacuum pump, inspissator temperature is raised to 65 DEG C, carries out in inspissator
Solvent 960g is concentrated out in aeration, N2 flow control 20L/min.
5) cold and hot cycle integration apparatus is opened, starts cooling process, the resulting concentrate of step 4) is crystallized, from
60 DEG C of beginnings carry out gradient cooling to 40 DEG C with the rate of temperature fall of 2 DEG C/h, 2h are maintained, then again with the rate of temperature fall of 4 DEG C/h
10 DEG C are cooled to, constant temperature 4h filters to obtain crystal, and crystal enters in vacuum desiccator under nitrogen protection, and drying temperature control exists
80 DEG C, vacuum degree control is in -80kpa；Drying time 8h is dry to complete to measure to obtain 290g LiBF4, filtered mother liquor
Recycled；
The purity of LiBF4 obtained by the present embodiment is 99.8%, moisture 12ppm, free acid 36ppm, insoluble matter 86ppm,
Fe < 1ppm, Cr < 1ppm, Ni < 1ppm.
Embodiment 2, a kind of preparation method for LiBF4 that the present invention mentions, including the following steps:
1) the closed addition 2500g methyl ethyl carbonate into reaction unit, then 220g lithium fluoride is put into, the lithium fluoride is high-purity
Lithium fluoride, high-purity is greater than 99.5%, and under normal temperature and pressure, starting stirring, revolving speed 30rpm obtains 8.09% lithium fluoride suspension；
2) 590g boron triflouride gas is slowly introducing in lithium fluoride suspension obtained by step 1), reaction time 110min is obtained instead
Answer liquid；The mass fraction of LiBF4 is 24.12% in gained reaction solution；
3) reaction solution obtained by step 2 is imported under nitrogen protection in filter device, filtrate imports concentration under nitrogen protection
Device,
4) the resulting filtrate of step 3) is heated up, opens vacuum pump, inspissator temperature is raised to 68 DEG C, carries out in inspissator
Solvent 1150g is concentrated out in aeration, N2 flow control 30L/min.
5) cold and hot cycle integration apparatus is opened, starts cooling process, the resulting concentrate of step 4) is crystallized, from
60 DEG C of beginnings carry out gradient cooling to 40 DEG C with the rate of temperature fall of 3 DEG C/h, 3h are maintained, then again with the rate of temperature fall of 5 DEG C/h
8 DEG C are cooled to, constant temperature 4h filters to obtain crystal, and crystal enters in vacuum desiccator under nitrogen protection, and drying temperature is controlled 80
DEG C, vacuum degree control is in -90kpa；Drying time 10h packs to obtain product 730g LiBF4.
The purity of LiBF4 obtained by the present embodiment is 99.9%, moisture 7ppm, free acid 32ppm, insoluble matter
98ppm, Fe < 1ppm, Cr < 1ppm, Ni < 1ppm；
Embodiment 3, a kind of preparation method for LiBF4 that the present invention mentions, including the following steps:
1) the filtered mother liquor 1350g in closed addition embodiment 1 into reaction unit, adds 1100g dimethyl carbonate, then
180g lithium fluoride is put into, the lithium fluoride is high purity lithium fluoride, and high-purity is greater than 99.5%, under normal temperature and pressure, starting stirring,
Revolving speed is 40rpm, obtains lithium fluoride suspension；
2) 480g boron triflouride gas is slowly introducing in lithium fluoride suspension obtained by step 1), reaction time 100min is obtained instead
Answer liquid；The mass fraction of LiBF4 is 23.23% in gained reaction solution；
3) reaction solution obtained by step 2 is imported under nitrogen protection in filter device, filtrate imports concentration under nitrogen protection
Device,
4) the resulting filtrate of step 3) is heated up, opens vacuum pump, inspissator temperature is raised to 70 DEG C, carries out in inspissator
Solvent 1000g is concentrated out in aeration, N2 flow control 25L/min.
5) cold and hot cycle integration apparatus is opened, starts cooling process, the resulting concentrate of step 4) is crystallized, from
60 DEG C of beginnings carry out gradient cooling to 40 DEG C with the rate of temperature fall of 2 DEG C/h, 2h are maintained, then again with the rate of temperature fall of 4 DEG C/h
8 DEG C are cooled to, constant temperature 3h filters to obtain crystal, and crystal enters in vacuum desiccator under nitrogen protection, and drying temperature is controlled 90
DEG C, vacuum degree control is in -90kpa；Drying time 8h packs to obtain product 650g LiBF4.
The purity of LiBF4 obtained by the present embodiment is 99.9%, moisture 18ppm, free acid 43ppm, insoluble matter
82ppm, Fe < 1ppm, Cr < 1ppm, Ni < 1ppm；
Embodiment 4, a kind of preparation method for LiBF4 that the present invention mentions, including the following steps:
1) the closed addition 2500g ethyl acetate into reaction unit, then 220g lithium fluoride is put into, the lithium fluoride is high-purity fluorine
Change lithium, high-purity is greater than 99.5%, and under normal temperature and pressure, starting stirring, revolving speed 30rpm obtains 8.09% lithium fluoride suspension；
2) 580g boron triflouride gas is slowly introducing in lithium fluoride suspension obtained by step 1), reaction time 110min is obtained instead
Answer liquid；The mass fraction of LiBF4 is 24.12% in gained reaction solution；
3) reaction solution obtained by step 2 is imported under nitrogen protection in filter device, filtrate imports concentration under nitrogen protection
Device,
4) the resulting filtrate of step 3) is heated up, opens vacuum pump, inspissator temperature is raised to 68 DEG C, carries out in inspissator
Solvent 1150g is concentrated out in aeration, N2 flow control 30L/min.
5) cold and hot cycle integration apparatus is opened, starts cooling process, the resulting concentrate of step 4) is crystallized, from
60 DEG C of beginnings carry out gradient cooling to 40 DEG C with the rate of temperature fall of 3 DEG C/h, 3h are maintained, then again with the rate of temperature fall of 5 DEG C/h
8 DEG C are cooled to, constant temperature 4h filters to obtain crystal, and crystal enters in vacuum desiccator under nitrogen protection, and drying temperature is controlled 80
DEG C, vacuum degree control is in -90kpa；Drying time 10h packs to obtain product 680g LiBF4.
The purity of LiBF4 obtained by the present embodiment is 99.9%, moisture 19ppm, free acid 48ppm, insoluble matter
85ppm, Fe < 1ppm, Cr < 1ppm, Ni < 1ppm.
Embodiment 5, a kind of preparation method for LiBF4 that the present invention mentions, including the following steps:
1) the closed addition 2520g diethyl carbonate into reaction unit, then 280g lithium fluoride is put into, the lithium fluoride is high-purity fluorine
Change lithium, high-purity is greater than 99.5%, and under normal temperature and pressure, starting stirring, revolving speed 30rpm obtains 10% lithium fluoride suspension；
2) 600g boron triflouride gas is slowly introducing in lithium fluoride suspension obtained by step 1), reaction time 110min is obtained instead
Answer liquid；The mass fraction of LiBF4 is 25.12% in gained reaction solution；
3) reaction solution obtained by step 2 is imported under nitrogen protection in filter device, filtrate imports concentration under nitrogen protection
Device,
4) the resulting filtrate of step 3) is heated up, opens vacuum pump, inspissator temperature is raised to 68 DEG C, carries out in inspissator
Solvent 1150g is concentrated out in aeration, N2 flow control 30L/min.
5) cold and hot cycle integration apparatus is opened, starts cooling process, the resulting concentrate of step 4) is crystallized, from
60 DEG C of beginnings carry out gradient cooling to 40 DEG C with the rate of temperature fall of 3 DEG C/h, 3h are maintained, then again with the rate of temperature fall of 5 DEG C/h
8 DEG C are cooled to, constant temperature 4h filters to obtain crystal, and crystal enters in vacuum desiccator under nitrogen protection, and drying temperature is controlled 80
DEG C, vacuum degree control is in -90kpa；Drying time 10h packs to obtain product 735g LiBF4.
The purity of LiBF4 obtained by the present embodiment is 99.8%, moisture 10ppm, free acid 37ppm, insoluble matter
89ppm, Fe < 1ppm, Cr < 1ppm, Ni < 1ppm.
In addition, it is necessary to explanation: the present invention is compared with documents 1, and the present invention uses esters as solution, effectively
It reduces that risk, safety is guaranteed for operation, while reducing finished product free acid value.
Compared with documents 2: documents 2 use boron trifluoride complex, enter to react adding lithium fluoride, solid
Add be difficult to control precisely, so as to cause reaction process be difficult to control, safety is not high, the present invention use gas liquid reaction (three
Boron fluoride and lithium fluoride suspension), the process entirely reacted is controlled using the speed of control boron triflouride gas, very simply
It is convenient.In addition, documents 2 add weak polar solvent extractive crystallization, the quantity of solvent used in this way is big, extracted using concentration
Solvent is difficult to separate, and is difficult recovery, we are using concentration, and then decrease temperature crystalline, can effectively control crystal particle diameter, improves
Product purity, the mother liquor after separation of solid and liquid can be applied directly again, greatly reduce quantity of solvent and improve the receipts of product
Rate.
The above, is only part preferred embodiment of the invention, and anyone skilled in the art may benefit
Equivalent technical solution is modified or is revised as with the technical solution of above-mentioned elaboration.Therefore, technology according to the present invention
Any simple modification or substitute equivalents that scheme is carried out, belong to the greatest extent the scope of protection of present invention.
Claims (8)
1. a kind of preparation method of LiBF4, it is characterized by including the following steps:
Under normal temperature and pressure, lithium fluoride being added in esters solvent, obtains lithium fluoride suspension, the mass fraction of lithium fluoride is 4%~
10%；
2) boron triflouride gas is passed through in lithium fluoride suspension obtained by step 1), the molar ratio of boron trifluoride and lithium fluoride is
0.9~1.2:1 reacts 1~2h, obtains lithium tetrafluoroborate solution；
3) step 2 acquired solution is passed through into millipore filter, filters unreacted micro lithium fluoride；
4) liquid after the completion of filtering step 3) is by concentration, degassing；
5) solution after the completion of step 4) being concentrated carries out decrease temperature crystalline, filters, dry, and LiBF4 finished product can be obtained.
2. the preparation method of LiBF4 according to claim 1, it is characterized in that: lithium fluoride described in step 1) is height
Pure lithium fluoride.
3. the preparation method of LiBF4 according to claim 1, it is characterized in that: esters solvent described in step 1) is
Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate or ethyl acetate.
4. the preparation method of LiBF4 according to claim 1, it is characterized in that: the millipore filter that step 3) uses
For PP material, aperture is 0.4 ~ 10um.
5. the preparation method of LiBF4 according to claim 1, it is characterized in that: liquid is being concentrated, is taking off in step 4)
During gas, N2 aerator is placed in below liquid level of solution, 5 ~ 100L/min of aeration quantity, and temperature is 40 ~ 80 DEG C, and vacuum degree is-
10kpa~-80kpa；Liquid concentration amount is the 10 ~ 40% of solution.
6. the preparation method of LiBF4 according to claim 1, it is characterized in that: decrease temperature crystalline described in step 5) is
Gradient cooling crystallization, the gradient cooling crystallization refer to: in 65~10 DEG C of range inside gradient decrease temperature crystallines, with the speed of 3 ~ 6 DEG C/h
Spend decrease temperature crystalline.
7. the preparation method of LiBF4 according to claim 6, it is characterized in that: at 60 DEG C ~ 40 DEG C, rate of temperature fall
Control reaches 40 DEG C, 1 ~ 3h is stablized in maintenance, and 40 ~ 10 DEG C, with the speed decrease temperature crystalline of 3 ~ 6 DEG C/h, temperature is reached in 2 ~ 3 DEG C/h
10 DEG C, 3 ~ 6 h are stablized in maintenance.
8. the preparation method of LiBF4 according to claim 1, it is characterized in that: the method for drying described in step 5) is
Reduced vacuum is dry, and dry temperature is 60~90 DEG C, and vacuum degree is -30kpa ~ -90kpa；4~12h of drying time.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272056A (en) * | 2019-08-02 | 2019-09-24 | 湖州昆仑动力电池材料有限公司 | Preparation method of lithium tetrafluoroborate |
| CN113912075A (en) * | 2021-11-25 | 2022-01-11 | 山东中顼技术研究有限公司 | Preparation method of lithium tetrafluoroborate |
| 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 |
| CN116102028A (en) * | 2022-12-12 | 2023-05-12 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium tetrafluoroborate |
| CN116715214A (en) * | 2023-07-06 | 2023-09-08 | 中国科学院兰州化学物理研究所 | Method for preparing lithium difluorophosphate and co-producing lithium tetrafluoroborate by ultrasonic promotion |
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| CN110272056A (en) * | 2019-08-02 | 2019-09-24 | 湖州昆仑动力电池材料有限公司 | Preparation method of lithium tetrafluoroborate |
| CN113912075A (en) * | 2021-11-25 | 2022-01-11 | 山东中顼技术研究有限公司 | Preparation method of lithium tetrafluoroborate |
| 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 |
| CN116102028A (en) * | 2022-12-12 | 2023-05-12 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium tetrafluoroborate |
| CN116102028B (en) * | 2022-12-12 | 2023-12-12 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium tetrafluoroborate |
| CN116715214A (en) * | 2023-07-06 | 2023-09-08 | 中国科学院兰州化学物理研究所 | Method for preparing lithium difluorophosphate and co-producing lithium tetrafluoroborate by ultrasonic promotion |
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