CN106744782A - The preparation method of difluorophosphoric acid salt - Google Patents
The preparation method of difluorophosphoric acid salt Download PDFInfo
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- CN106744782A CN106744782A CN201710004662.XA CN201710004662A CN106744782A CN 106744782 A CN106744782 A CN 106744782A CN 201710004662 A CN201710004662 A CN 201710004662A CN 106744782 A CN106744782 A CN 106744782A
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- acid salt
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- difluorophosphoric acid
- cyclosiloxane
- acetal
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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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
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Abstract
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of efficient difluorophosphoric acid salt, comprise the following steps：Micro passage reaction is passed through after the hexafluorophosphoric acid salting liquid that concentration is 5~50wt% is measured with cyclosiloxane or acetal, 60~900s is reacted under the conditions of 20~150 DEG C, after gained reaction solution is through membrane filtration, then is concentrated, dried, obtain difluorophosphoric acid product salt.The present invention program has the advantages that process route is simple, raw material is easy to get, reaction efficiency is high, energy consumption is low and product purity is high.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of efficient difluorophosphoric acid salt.
Background technology
At present, the support energetically with the commonly used and country of portable electronic mobile device to electric automobile, lithium
The demand of ion battery is continuously increased, especially lightweight, high performance lithium ion battery, and lithium ion battery security
Also more and more higher can be required.Difluorophosphoric acid salt, especially difluorophosphate, as the electrolytic salt additive of lithium ion battery,
Due to causing the broad interest of lithium battery manufacturing enterprise with the excellent properties for improving battery cryogenic property.
The existing synthetic method of difluorophosphoric acid salt is more, and Chinese patent CN102985361 uses P4O10With LiF at 300 DEG C
Synthesis in solid state difluorophosphate under high temperature, because reaction temperature is high, a large amount of lithium phosphates of by-product；Chinese patent CN101626978 is then
Reacted in nonaqueous solvents using halide in addition to fluoride compounds and lithium hexafluoro phosphate and water and prepare the solution containing difluorophosphate；
Japan Patent JP2005219994 is synthesized two using lithium hexafluoro phosphate and silica in carbonic ester or carboxylic acid ester solution
Lithium fluophosphate, accessory substance is ocratation；Japan Patent JP2012051752 is then using difluorophosphoric acid and metal chloride or hydrogen
Lithia reaction prepares difluorophosphoric acid salt.However, synthesize difluorophosphoric acid salt using difluorophosphoric acid, due to being had in building-up process
Substantial amounts of by-product halogen acids or water are generated, and increased subsequent purification difficulty, increase cost；And carried out with phosphorus pentoxide and LiF
Synthesis, high energy consumption, phosphoric acid byproduct lithium is more, and subsequent purification separating difficulty is greatly increased；In addition, traditional still reaction installation period
Long, workload is big, increases manpower and time cost, less efficient.
The content of the invention
For problem above, the present invention provides a kind of preparation method of difluorophosphoric acid salt, using microchannel reaction technology come
The difluorophosphoric acid salt of synthesis of high purity, with efficiency high, energy consumption is low the characteristics of.
To solve problem above, the present invention is achieved through the following technical solutions：
A kind of preparation method of difluorophosphoric acid salt, comprises the following steps：Hexafluorophosphate that concentration is 5~50wt% is molten
Micro passage reaction is passed through after liquid and cyclosiloxane or acetal metering, 60~900s is reacted under the conditions of 20~150 DEG C, gained is anti-
After liquid is answered through membrane filtration, then concentrated, dried, obtained difluorophosphoric acid product salt.
Preferably, the hexafluorophosphate is the alkali metal salt or alkali salt of hexafluorophosphoric acid.
Preferably, the cyclosiloxane be dimethicone, diethyl cyclosiloxane, methyl ethyl cyclosiloxane,
Hexichol cyclosiloxane, methyl phenyl ring siloxane or aryl cyclosiloxane.
Preferably, the acetal is dimethyl methyl acetal, acetal or dimethyl-acetal.
Preferably, the solvent of the hexafluorophosphoric acid salting liquid is at least in carbonic ester, carboxylate, ethers and nitrile
Kind.
It is furthermore preferred that the solvent of the hexafluorophosphoric acid salting liquid be dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate,
Diethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, Ethyl formate, propyl formate, ether, dimethyl ether, dimethoxy
At least one in ethane, diethoxyethane, acetonitrile, propionitrile.
Preferably, the hexafluorophosphate and the raw materials components mole ratio of cyclosiloxane or acetal are 1：2~5；
Preferably, microchannel reaction temperature is 40~100 DEG C；
Preferably, the pore size of filter membrane used by membrane filtration is 0.2~0.45 μm.
Reaction principle of the invention is as follows：
The present invention program is the hexafluorophosphoric acid alkali metal salt soln of 5~50wt% of preparation, then with epoxy silane or acetal
Reaction is obtained difluorophosphoric acid salt, by after filtering, after insoluble matter fluorination alkali metal salt is removed, solution concentrate drying is that can obtain
The anhydrous difluorophosphoric acid salt solid of high-purity.
Reaction equation is：
MPF6+R1CH2-OCHR2-OCH2R3→MPO2F2+R2CHF2+R1CH2F+R3CH2F
Or nMPF6+2[R1R2SiO]n→nMPO2F2+2nR1R2SiF2
Wherein, M is the cation (above-mentioned reaction equation is by taking alkali metal as an example) of alkali metal or alkaline-earth metal, R1、R2、R3It is C1
~C6Alkane or phenyl.
The present invention has following positive beneficial effect：
(1) present invention makes reaction keep homogeneous reaction using 5~50% hexafluorophosphoric acid salting liquid, increases mass-and heat-transfer effect
Really, reaction time, reducing energy consumption are shortened.Cyclosiloxane used of the invention or acetal are industrialization product, easily purchase,
There is no water to produce in course of reaction, solved the problems, such as difluorophosphoric acid salt hydrolysis in the presence of water, filtered after the completion of reaction
The fluoride salt insoluble in system can be removed, then by simple distillation, the dry volatile raw material of removing and solvent, you can obtain
Meet high-purity difluorophosphoric acid product salt of lithium battery additive purity requirement.Acetal or cyclosiloxane and hexafluoro that the present invention is used
Phosphatic mol ratio is 2~5:1, the addition of excessive acetal or cyclosiloxane ensure that hexafluorophosphate reacts completely, after making
The difficulty that continuous purifying obtains high-purity lithium difluorophosphate is substantially reduced.
(2) present invention process route is simple, and raw material is easy to get, and reaction efficiency, yield and purity are high, because excellent mass transfer is passed
Thermal effect, while reducing the loss of the energy, effectively increases efficiency.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of present invention gained difluorophosphoric acid product salt；
Fig. 2 is the nuclear-magnetism fluorine spectrum of present invention gained difluorophosphoric acid product salt；
Fig. 3 is the nuclear-magnetism phosphorus spectrum of present invention gained difluorophosphoric acid product salt.
Specific embodiment
Technical scheme is described further below in conjunction with specific embodiment, but protection scope of the present invention is not
It is limited to this.It is raw materials used in following embodiment, unless otherwise instructed, then it is commercially available.
The preparation method of difluorophosphoric acid salt, comprises the following steps：300g hexafluorophosphoric acid salting liquids are prepared in a reservoir, it is another
A certain amount of cyclosiloxane or acetal are added in container, (setting certain metering ratio with measuring pump) is passed through micro passage reaction, in perseverance
Reacted at fixed temperature, after gained reaction solution is through membrane filtration, then is concentrated, dried, obtain difluorophosphoric acid salt solid, it is specific real
The raw material and parameter for applying example are shown in Table 1.
Product checking：Gained sample structure using U.S.'s Thermo companies IR200 types infrared spectrometer (KBr pressed disc methods) and
Bruker companies Avance 400HD type nuclear magnetic resonance chemical analyser (solvents：Deuterated acetone) infrared spectrum and nuclear-magnetism detection are carried out,
Purity is using the logical 833 type ion chromatographs detection PO of Switzerland ten thousand2F2Anion-content is calculated.
The specific embodiment of table 1 and Contrast on effect
Battery of tests (above counting first row) gained difluorophosphoric acid salt solid is respectively adopted Thermo companies of U.S. IR200 types
Infrared spectrometer (KBr pressed disc methods) and Bruker companies Avance 400HD type nuclear magnetic resonance chemical analyser (solvents：Deuterated acetone)
Infrared spectrum and nuclear-magnetism detection are carried out, as a result as shown in Figures 1 to 3, purity is using the logical 833 type ion chromatographs detection of Switzerland ten thousand
PO2F2Anion-content is calculated, and result of calculation is listed in upper table.
The present invention is described in detail above in conjunction with embodiment, but, person of ordinary skill in the field can
Understand, on the premise of present inventive concept is not departed from, the design parameter of each in above-described embodiment can also be changed, shape
Into multiple specific embodiments, common excursion of the invention is, no longer described in detail one by one herein.
Claims (9)
1. a kind of preparation method of difluorophosphoric acid salt, it is characterised in that comprise the following steps：By the hexafluoro that concentration is 5~50wt%
Micro passage reaction is passed through after phosphate solution and cyclosiloxane or acetal metering, react 60 under the conditions of 20~150 DEG C~
900s, after gained reaction solution is through membrane filtration, then is concentrated, is dried, and obtains difluorophosphoric acid product salt.
2. the preparation method of difluorophosphoric acid salt according to claim 1, it is characterised in that：The hexafluorophosphate is hexafluoro phosphorus
The alkali metal salt or alkali salt of acid.
3. the preparation method of difluorophosphoric acid salt according to claim 1, it is characterised in that：The cyclosiloxane is diformazan basic ring
Siloxanes, diethyl cyclosiloxane, methyl ethyl cyclosiloxane, hexichol cyclosiloxane, methyl phenyl ring siloxane or aryl
Cyclosiloxane.
4. the preparation method of difluorophosphoric acid salt according to claim 1, it is characterised in that：The acetal contracts for dimethyl methyl
Aldehyde, acetal or dimethyl-acetal.
5. according to claim 1 difluorophosphoric acid salt preparation method, it is characterised in that：The hexafluorophosphoric acid salting liquid
Solvent is at least one in carbonic ester, carboxylate, ethers and nitrile.
6. the preparation method of difluorophosphoric acid salt according to claim 5, it is characterised in that：The hexafluorophosphoric acid salting liquid it is molten
Agent is dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, diethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, first
At least one in acetoacetic ester, propyl formate, ether, dimethyl ether, dimethoxy-ethane, diethoxyethane, acetonitrile, propionitrile.
7. according to any one of claim 1~6 difluorophosphoric acid salt preparation method, it is characterised in that：The hexafluorophosphoric acid
Salt is 1 with the raw materials components mole ratio of cyclosiloxane or acetal：2~5.
8. according to any one of claim 1~6 difluorophosphoric acid salt preparation method, it is characterised in that：Reaction temperature is 40
~100 DEG C.
9. according to any one of claim 1~6 difluorophosphoric acid salt preparation method, it is characterised in that：Membrane filtration filter used
The pore size of film is 0.2~0.45 μm.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910846A (en) * | 2018-06-26 | 2018-11-30 | 贵州微化科技有限公司 | A method of low-arsenic yellow phosphorus is prepared using micro passage reaction |
| CN109422257A (en) * | 2017-08-31 | 2019-03-05 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphate |
| CN109455688A (en) * | 2017-09-06 | 2019-03-12 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphoric acid salt |
| CN109867269A (en) * | 2017-12-01 | 2019-06-11 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphate |
| CN110380150A (en) * | 2019-08-02 | 2019-10-25 | 中国科学院宁波材料技术与工程研究所 | A kind of innoxious recovery method of waste and old power battery electrolyte |
| CN111137870A (en) * | 2018-11-06 | 2020-05-12 | 宁波氟创新能源科技有限公司 | Lithium difluorophosphate, preparation method thereof and lithium ion battery electrolyte |
| CN113880066A (en) * | 2021-11-12 | 2022-01-04 | 深圳市研一新材料有限责任公司 | Method for preparing lithium difluorophosphate by flow chemical method |
| CN114634170A (en) * | 2020-12-15 | 2022-06-17 | 江苏国泰超威新材料有限公司 | Preparation method of lithium difluorophosphate |
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| WO2010064637A1 (en) * | 2008-12-02 | 2010-06-10 | ステラケミファ株式会社 | Method for producing difluorophosphate, nonaqueous electrolyte solution, and nonaqueous electrolyte secondary battery |
| CN102064345A (en) * | 2006-08-22 | 2011-05-18 | 三菱化学株式会社 | Nonaqueous electrolytic solution, process for producing nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| CN104487381A (en) * | 2013-06-07 | 2015-04-01 | 斯泰拉化工公司 | Method for producing difluorophosphate |
| CN105800582A (en) * | 2016-03-15 | 2016-07-27 | 衢州氟硅技术研究院 | Method for preparing difluoro-lithium phosphate and lithium-ion battery non-aqueous electrolyte |
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| WO2010064637A1 (en) * | 2008-12-02 | 2010-06-10 | ステラケミファ株式会社 | Method for producing difluorophosphate, nonaqueous electrolyte solution, and nonaqueous electrolyte secondary battery |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109422257A (en) * | 2017-08-31 | 2019-03-05 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphate |
| CN109422257B (en) * | 2017-08-31 | 2022-04-29 | 东莞东阳光科研发有限公司 | Preparation method of lithium difluorophosphate |
| CN109455688A (en) * | 2017-09-06 | 2019-03-12 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphoric acid salt |
| CN109455688B (en) * | 2017-09-06 | 2022-04-29 | 东莞东阳光科研发有限公司 | Preparation method of difluorophosphate |
| CN109867269A (en) * | 2017-12-01 | 2019-06-11 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphate |
| CN109867269B (en) * | 2017-12-01 | 2022-07-08 | 东莞东阳光科研发有限公司 | Preparation method of lithium difluorophosphate |
| CN108910846A (en) * | 2018-06-26 | 2018-11-30 | 贵州微化科技有限公司 | A method of low-arsenic yellow phosphorus is prepared using micro passage reaction |
| CN108910846B (en) * | 2018-06-26 | 2020-10-27 | 贵州微化科技有限公司 | Method for preparing low-arsenic yellow phosphorus by using microchannel reactor |
| CN111137870A (en) * | 2018-11-06 | 2020-05-12 | 宁波氟创新能源科技有限公司 | Lithium difluorophosphate, preparation method thereof and lithium ion battery electrolyte |
| CN110380150A (en) * | 2019-08-02 | 2019-10-25 | 中国科学院宁波材料技术与工程研究所 | A kind of innoxious recovery method of waste and old power battery electrolyte |
| CN114634170A (en) * | 2020-12-15 | 2022-06-17 | 江苏国泰超威新材料有限公司 | Preparation method of lithium difluorophosphate |
| CN113880066A (en) * | 2021-11-12 | 2022-01-04 | 深圳市研一新材料有限责任公司 | Method for preparing lithium difluorophosphate by flow chemical method |
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Application publication date: 20170531 |