CN1124975C - Method for preparing lithium hexafluorophosphate - Google Patents
Method for preparing lithium hexafluorophosphate Download PDFInfo
- Publication number
- CN1124975C CN1124975C CN01141437A CN01141437A CN1124975C CN 1124975 C CN1124975 C CN 1124975C CN 01141437 A CN01141437 A CN 01141437A CN 01141437 A CN01141437 A CN 01141437A CN 1124975 C CN1124975 C CN 1124975C
- Authority
- CN
- China
- Prior art keywords
- lithium
- hydrofluoric acid
- hexafluoro phosphate
- phosphorus
- lithium hexafluorophosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y02E60/122—
Landscapes
- Secondary Cells (AREA)
Abstract
The present invention discloses a method for producing lithium hexafluorophosphate (LiPF6) and relates to a technology of preparing lithium hexafluorophosphate of an electrolyte salt used for lithium ion batteries. The technological process of using anhydrous hydrofluoric acid (HF), phosphorus pentachloride (PCl5) and lithium halide as raw material for preparing lithium hexafluorophosphate of high purity comprises: the anhydrous hydrofluoric acid and the phosphorus pentachloride react and generate phosphorus pentafluoride (PF5) required by crystallization in a reactor, the reacting slurry of the phosphorus pentafluoride and the lithium halide is cooled and crystallized at the temperature of-40 to-20 DEGC to prepare LiPF6, vacuum deacidify and high temperature drying are carried out, and mother liquid is returned back for use. The present invention has the advantages of simple technological process, convenient operation and control, low production cost and high production efficiency; the purity of a lithium hexafluorophosphate product reaches more than 99.9%.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, specifically is a kind of preparation method of electrolytic salt lithium hexafluoro phosphate.
Background technology
Lithium ion battery is meant that lithiated intercalation compound is the secondary cell of positive and negative electrode.The anodal lithium compound Li that adopts
xCoO
2, Li
xNiO
2Or LiMn
2O
4, negative pole adopts lithium-carbon intercalation compound LiC
6, ionogen is for being dissolved with lithium salts LiPF
6, LiAsF
6Deng organic solution.At present, organic solvent mainly contains PC (propylene carbonate), EC (NSC 11801), DMC (methylcarbonate), DEC (diethyl carbonate), EMC (Methyl ethyl carbonate) etc.
Ionogen as lithium-ion battery electrolytes must satisfy following performance, and promptly specific conductivity height, chemistry and electrochemical stability are good, but the use temperature wide ranges, security is good, and price is low.Based on these requirements, in design, require will reach more than 99.9% as the purity of electrolytical lithium hexafluoro phosphate, and to various impurity as: extremely strict restriction is all arranged on moisture content, metals content impurity, the free acid content.
Relevant patent relates to several production LiPF
6Production method, all different with preparation process of the present invention and processing condition.As: WO9748709 has proposed by (raw material is LiOH, lithium alkylide etc. and HPF
6) wait organic complex to prepare high purity LiPF
6, vacuum or sulfuric acid are removed organic solvent.CN1210810 has proposed to use PF
5In a tower, contact with LiF in being dissolved in HF with the HCl mixture, in this tower, react PF in this tower
5Substantially absorbed fully.Mention a kind of airflow reaction synthesis method that contains lithium salts in the CN1171368 document, this method is a dry technology for production, and operation repeats, lithium hexafluoro phosphate (LiPF
6) purity reach more than 98%, or the like.
Summary of the invention
For solving the problem and shortage that above-mentioned technology exists, the invention provides a kind of simple its preparation process, reduce effectively or suppressed impurity such as the moisture in the product, free acid.
The present invention prepares the lithium hexafluoro phosphate product by simple crystallization process, is raw material with anhydrous hydrofluoric acid, phosphorus pentachloride and lithium halide, makes the lithium hexafluoro phosphate product through reaction, crystallization, filtration, drying, the filtrated stock Returning utilization.
The present invention prepares as follows: the preparation of intermediate raw material phosphorus pentafluoride does not need special refining, but directly enter reactor and the required phosphorus pentafluoride of hydrofluoric acid reaction acquisition crystallization reaction by cheapness and phosphorus pentachloride that be easy to get, phosphorus pentafluoride reacts with the lithium fluoride that is dissolved in the hydrofluoric acid in advance, by crystallisation by cooling, obtain LiPF at last
6Product.This technology is because process is simple, and raw material sources are abundant, once generally tested by the people.But be considered to exist a series of insoluble problems in the process,, utilize HCl and PF behind the phosphorus pentachloride such as the water content in the hydrofluoric acid
5Separation problem and PCl
5With the heat release problem of HF reaction, problems such as crystallization, separation, drying.The present invention then solves these problems effectively.
At first, in this reaction, not permission system contains moisture, otherwise will produce fluorine oxidation Trilithium phosphate (LiPO
xF
y) byproduct, LiPF
6Also may be broken down into LiF, increase foreign matter content, reduce yield.Therefore system's drying is particularly important.The used hydrofluoric acid of this technology is pure HF, and adopts the form of gasification condensation in transmission course, and adds F
2Or fluorochemical such as KF, thereby reduced moisture among the raw material HF to the utmost.
Secondly, PCl
5With the reaction of HF be an extremely acute process of heat release fast, if can not shift heat rapidly in this process, will cause the excessive evaporation of HF, the lithium salts recrystallization occurs, and device security threatened.In order to overcome this phenomenon, this technology has proposed particular requirement to this conversion unit, and the one, adopt the outer loop cooling to take away the portion of hot amount, the 2nd, the lengthening response path makes to react completely and evenly, make the PF of generation
5Partial reaction liberated heat, PCl are taken away in evaporation with HCl
5Rise in the crystallization reactor with HCl, utilize the temperature distribution of improving control, the employing band stirs, the reactor of register, reacts PF with full hybrid mode
5The HCl that carries secretly need not separate, and directly discharges by reactor, through reclaiming as by-product utilization.And do not adopt tower reactor, do not exist and flow different reinforced operating method such as adverse current.Crystallization reaction carries out under-40～-20 ℃, and the limit coronite is discharged HCl, so the problem that does not exist pressure to raise in the process, operational safety, and technology is simple.
In addition, the crystallization filtration drying of reaction carries out in same specific equipment, drying temperature can carry out under up to 160 ℃ temperature, rather than it is generally acknowledged and under its decomposition starting temperature (70 ℃), to carry out, and vacuum deacidification, so just more effectively reduce the content of moisture and free acid, helped obtaining more highly purified LiPF
6Mother liquor returns and utilizes, and reduces cost, alleviates the burden that spent acid absorbs.This technology once makes product, and purity can reach 99.9%, and does not need to carry out recrystallization again.
Equipment used material of the present invention is the poly-tetrafluoro lining of carbon steel or Hastelloy or Langaloy, and the equipment of so just having stopped is effectively corroded and the metal component introduced, makes that the metals content impurity in the product salt reduces to minimum.
The present invention adopts following technical measures:
The preparation method of lithium hexafluoro phosphate is a raw material with hydrofluoric acid, phosphorus pentachloride and lithium fluoride, and its technological process is:
A. phosphorus pentachloride and anhydrous hydrofluoric acid prepared in reaction phosphorus pentafluoride;
B. the phosphorus pentafluoride of Sheng Chenging reacts under agitation condition with the lithium fluoride that is dissolved in anhydrous hydrofluoric acid or return in the mother liquor, and-40～-20 ℃ of crystallizations, filtration, vacuum-drying obtain lithium hexafluoro phosphate.The present invention can also adopt following technical measures:
The preparation method of above-mentioned lithium hexafluoro phosphate is characterized in what steps A and B carried out simultaneously in two different reactors, phosphorus pentafluoride is direct and lithium fluoride prepared in reaction lithium hexafluoro phosphate while generating.
The preparation method of above-mentioned lithium hexafluoro phosphate is characterized in that the filtration of lithium hexafluoro phosphate, drying process carry out continuously at same equipment, and drying temperature is 100～160 ℃, pressure is 0～-0.1MPa.
Advantage of the present invention and positively effect: the present invention proposes lithium hexafluoro phosphate (LiPF
6) the preparation method, use cheap PCl
5, raw material such as lithium halide, adopted low temperature crystallization, the filtering technological line of vacuum-drying.Therefore, technological process of the present invention is simple, convenient operation and control, low production cost, and the production efficiency height, and reduced foreign matter contents such as the moisture in the product, free acid effectively, the lithium hexafluoro phosphate product purity reaches more than 99.9%.
Embodiment
Below in conjunction with embodiment this technology is further specified, but the present invention is not limited in this
Embodiment.
Embodiment 1
Step 1, the anhydrous hydrogen fluoride that adds 190kg in the reactor (b) of liner PTFE and the lithium fluoride of 10kg stirred about 2 hours, and lithium fluoride is all dissolved, and wherein the concentration of lithium fluoride is about 5%.
Step 2, in the reactor (a) of liner PTFE, add the 80kg phosphorus pentachloride, the temperature that keeps reactor is between-40 ℃～-20 ℃, speed with 10kg per hour adds anhydrous hydrogen fluoride 40kg, make itself and phosphorus pentachloride reaction generate phosphorus pentafluoride and hydrogen chloride gas, phosphorus pentafluoride enters into reactor (b) while generating, generate the lithium hexafluoro phosphate crystallization with the lithium fluoride reaction that is dissolved in the anhydrous hydrogen fluoride under-40～-20 ℃ low temperature.Unabsorbed hydrogen chloride gas can be used as byproduct after water absorbs.
Step 3, lithium hexafluoro phosphate slip are carried out separating of product and mother liquor through the vacuum-drying strainer.Product is through 100～160 ℃ of dryings, and in vacuum tightness is-remove the hydrofluoric acid of deentrainment under the 0.08MPa, finally obtains product 40kg, is 99.95% through check purity.
Products obtained therefrom is analyzed, and the result shows: the purity of product is 99.95%, and free acid content (in HF) is 90ppm, and water content is (with H
2The O meter) be 15ppm.
Adopt the lithium hexafluoro phosphate of gained to be made into electrolytic solution, consist of 1mol LiPF
6EC: DMC=1: 1, recording its specific conductivity by analysis is 10 * 10
3μ S/cm (25 ℃).
Embodiment 2
Step 1, return mother liquor 200kg in the reactor (b) of liner PTFE, add the lithium fluoride of 8kg, stirred about 2 hours, lithium fluoride is all dissolved, the concentration of lithium fluoride is about 5%.
Step 2, in the reactor (a) of liner PTFE, add the 83.4kg phosphorus pentachloride, the temperature that keeps reactor is between-40 ℃～-20 ℃, speed with 10kg per hour adds anhydrous hydrogen fluoride 42kg, make itself and phosphorus pentachloride reaction generate phosphorus pentafluoride and hydrogen chloride gas, phosphorus pentafluoride enters into reactor (b) while generating, generate the lithium hexafluoro phosphate crystallization with the lithium fluoride reaction that is dissolved in the anhydrous hydrogen fluoride under-40～-20 ℃ low temperature. and unabsorbed hydrogen chloride gas can be used as byproduct after water absorbs.
Step 3, lithium hexafluoro phosphate slip are carried out separating of product and mother liquor through the vacuum-drying strainer.Product is through 100～160 ℃ of dryings, and in vacuum tightness is-remove the hydrofluoric acid of deentrainment under the 0.08MPa, finally obtains product 41kg, is 99.98% through check purity.
Products obtained therefrom is analyzed, and the result shows: the purity of product is 99.98%, and free acid content (in HF) is 72ppm, and water content is (with H
2The O meter) be 10ppm.
Adopt the lithium hexafluoro phosphate of gained to be made into electrolytic solution, consist of 1mol LiPF
6EC: DEC=3: 7, recording its specific conductivity by analysis is 8.2 * 10
3μ S/cm (25 ℃).
Claims (3)
1, the preparation method of lithium hexafluoro phosphate is a raw material with anhydrous hydrofluoric acid, phosphorus pentachloride and lithium fluoride, it is characterized in that:
A. the reaction of phosphorus pentachloride and anhydrous hydrofluoric acid generates phosphorus pentafluoride and hydrogenchloride;
B. the phosphorus pentafluoride of Sheng Chenging be dissolved in anhydrous hydrofluoric acid or return lithium fluoride in the mother liquor
React under agitation condition ,-40～-20 ℃ of crystallizations, filtration, vacuum-drying obtain lithium hexafluoro phosphate.
2, method according to claim 1 is characterized in that: steps A is to carry out simultaneously in two different reactors with B, and phosphorus pentafluoride is direct and lithium fluoride prepared in reaction lithium hexafluoro phosphate while generating.
3, method according to claim 1 is characterized in that: the filtration of lithium hexafluoro phosphate, drying process are carried out continuously at same equipment, and drying temperature is 100～160 ℃, and pressure is 0～-0.1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01141437A CN1124975C (en) | 2001-09-25 | 2001-09-25 | Method for preparing lithium hexafluorophosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01141437A CN1124975C (en) | 2001-09-25 | 2001-09-25 | Method for preparing lithium hexafluorophosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339401A CN1339401A (en) | 2002-03-13 |
| CN1124975C true CN1124975C (en) | 2003-10-22 |
Family
ID=4676170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01141437A Expired - Lifetime CN1124975C (en) | 2001-09-25 | 2001-09-25 | Method for preparing lithium hexafluorophosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1124975C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423207B (en) * | 2008-11-17 | 2011-03-16 | 袁翔云 | Synthetic process of lithium hexafluorophosphate |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393609C (en) * | 2006-05-30 | 2008-06-11 | 天津化工研究设计院 | Method for refining solvent of lithium hexafluorophosphate |
| CN101353161B (en) * | 2007-07-27 | 2010-10-06 | 比亚迪股份有限公司 | Methods for preparing phosphorus pentafluoride gas and preparing lithium hexafluorophosphate using the gas |
| KR101069568B1 (en) * | 2008-12-02 | 2011-10-05 | 미쓰비시 가가꾸 가부시키가이샤 | Method for producing difluorophosphate |
| CN101544361B (en) * | 2009-05-07 | 2012-10-03 | 洛阳森蓝化工材料科技有限公司 | Process for continuous preparation of lithium hexafluorophosphate |
| CN101723346B (en) * | 2009-12-11 | 2011-08-31 | 多氟多化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN102583301A (en) * | 2011-01-18 | 2012-07-18 | 孟永 | Preparation method of lithium hexafluorophosphate |
| CN102502565B (en) * | 2011-11-01 | 2013-06-19 | 江苏新泰材料科技有限公司 | Preparation method of lithium hexafluorophate |
| CN102515133A (en) * | 2011-12-31 | 2012-06-27 | 东莞市东骏新能源科技有限公司 | Preparation method of lithium hexafluorophosphate of lithium ion battery electrolyte |
| CN102976298B (en) * | 2012-12-20 | 2014-08-27 | 天津隆尔新材料科技有限公司 | Internal circulation reactor and method for continuously preparing phosphorus pentafluoride |
| CN103466589B (en) * | 2013-08-29 | 2015-12-02 | 中国海洋石油总公司 | A kind of preparation method of high purity lithium hexafluorophosphate |
| CN104211029B (en) * | 2014-07-22 | 2016-09-07 | 浙江东氟塑料科技有限公司 | A kind of preparation method of lithium hexafluoro phosphate |
| CN107244681B (en) * | 2017-03-29 | 2019-07-05 | 东营石大胜华新能源有限公司 | A kind of method and apparatus continuously preparing lithium hexafluoro phosphate |
| CN112340754A (en) * | 2019-08-09 | 2021-02-09 | 惠州比亚迪电池有限公司 | Lithium hexafluorophosphate, crystallization and preparation method thereof, lithium ion battery electrolyte and lithium ion battery |
| CN112678850A (en) * | 2020-12-30 | 2021-04-20 | 徐兴碧 | Production device and method of lithium hexafluorophosphate |
| CN114695952B (en) * | 2022-04-24 | 2023-06-23 | 江西石磊氟材料有限责任公司 | System and method for producing lithium hexafluorophosphate by dynamic constant temperature crystallization method |
| CN115583661B (en) * | 2022-12-12 | 2023-03-10 | 深圳新宙邦科技股份有限公司 | Preparation method of liquid lithium hexafluorophosphate, electrolyte and lithium ion battery |
-
2001
- 2001-09-25 CN CN01141437A patent/CN1124975C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423207B (en) * | 2008-11-17 | 2011-03-16 | 袁翔云 | Synthetic process of lithium hexafluorophosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1339401A (en) | 2002-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1124975C (en) | Method for preparing lithium hexafluorophosphate | |
| CN104445133B (en) | A kind of preparation method of difluorophosphate and non-aqueous electrolyte for lithium ion cell thereof | |
| CN101643481B (en) | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate | |
| CN105731399A (en) | Preparation method of difluoro-sulfonyl imide lithium | |
| CN102702243B (en) | Method for preparation and purifying lithium difluoroborate | |
| CN100365863C (en) | Li-ion battery cathode film forming function electrolyte and its preparing process | |
| CN111224164B (en) | Preparation method of lithium difluorophosphate | |
| CN101645521A (en) | Low temperature functional electrolyte of lithium-ion secondary battery and preparation method thereof | |
| CN103483367B (en) | The preparation method of difluoro oxalic acid boric acid metal salt | |
| JP7429785B2 (en) | LiPF6 production process, production system, mixed crystal containing LiPF6, composition, electrolyte, lithium battery | |
| CN101635379B (en) | Electrolyte for lithium-ion power battery and preparation method thereof | |
| CN114865091A (en) | Preparation method of lithium hexafluorophosphate and lithium ion battery electrolyte containing lithium hexafluorophosphate | |
| CN105236380A (en) | Preparation method of high purity difluorophosphate | |
| Liu et al. | Research progress on preparation and purification of fluorine-containing chemicals in lithium-ion batteries | |
| CN116750780B (en) | Preparation method of hexafluorophosphate, electrolyte and secondary battery | |
| CN102976303A (en) | Method for preparing lithium hexafluorophosphate | |
| JP5286718B2 (en) | Non-aqueous electrolyte for phenyl ester and lithium secondary battery, and lithium secondary battery using the same | |
| CN104211029B (en) | A kind of preparation method of lithium hexafluoro phosphate | |
| EP2581980B1 (en) | Method for producing electrolyte solution for lithium ion battery, and lithium ion battery using the electrolyte solution | |
| CN110683564B (en) | Lithium hexafluorophosphate-containing mixture crystal and application thereof | |
| CN116813671A (en) | Preparation method of pentaerythritol ester compound and application of pentaerythritol ester compound | |
| CN108615942A (en) | Application containing (fluoro) methylene-disulfonic acid lithium salts and preparation method thereof and in nonaqueous electrolytic solution | |
| CN114477122A (en) | Preparation method of lithium difluorophosphate and lithium ion battery electrolyte | |
| CN1189972C (en) | Method for preparing electrolyte solution used for alkali metal cell | |
| CN103214523B (en) | A kind of method of preparation and use and the lithium ion battery comprising this additive of high temp. lithium ion electrolysis additive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190516 Address after: 300400 Shuanghedao South, Beichen Economic Development Zone, Beichen District, Tianjin Patentee after: Tianjin Jinniu Power Sources Material Co.,Ltd. Address before: 300131 No. three, No. 85, Tianjin Road, Hongqiao District, China Patentee before: Tianjin Chemical research &. Design Inst. |
|
| TR01 | Transfer of patent right | ||
| CX01 | Expiry of patent term |
Granted publication date: 20031022 |
|
| CX01 | Expiry of patent term |