CN103259040A - Method for preparing high-purity lithium difluorophosphate by utilization of organo tin fluoride - Google Patents
Method for preparing high-purity lithium difluorophosphate by utilization of organo tin fluoride Download PDFInfo
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- CN103259040A CN103259040A CN2013100979489A CN201310097948A CN103259040A CN 103259040 A CN103259040 A CN 103259040A CN 2013100979489 A CN2013100979489 A CN 2013100979489A CN 201310097948 A CN201310097948 A CN 201310097948A CN 103259040 A CN103259040 A CN 103259040A
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Abstract
The invention discloses a method for preparing high-purity lithium difluorophosphate by the utilization of organo tin fluoride. By the utilization of the characteristic that organo tin fluoride is easily subjected to a halogen exchange reaction with a phosphorus compound containing chlorine, bromine and iodine, lithium dichlorophosphate is firstly prepared by a simple method, and then organo tin fluoride and lithium dichlorophosphate undergo a contact reaction so as to generate lithium difluorophosphate. The raw materials provided by the invention are easily available and the reactions are easy to operate. Conditions of the whole reaction process are mild; no by-products appear; the process is simple; requirements on equipment and environmental protection are low; and the possibility of impurity introduction is avoided. Thus, the lithium difluorophosphate generated by the preparation method has high purity and good quality.
Description
[technical field]
The present invention relates to a kind of method for preparing difluorophosphate, relate to a kind of method of utilizing the organotin fluoride to prepare the high-purity difluorophosphate particularly.
[background technology]
In recent years, the basic research of lithium ion battery and application and development have become one of focus of new energy field, and each flourishing state of the world all develops its break-through point as next new industry and study.Positive electrode, negative material, electrolyte and diaphragm material are lithium ion battery four big critical materials, and common electrolyte mainly contains LiPF
6, LiBF
4, LiClO
4, LiAsF
6, LiCF
3SO
3, LiN (CF
3SO
2)
2Deng, in the carbonates organic solvent, be made into nonaqueous electrolyte by dissolving these electrolyte, wherein LiPF
6It is the most widely used a kind of electrolyte at present.
The lithium ion battery that adopts nonaqueous electrolyte is significantly different aspect battery behavior, because the reactivity of electrode surface changes with the composition of nonaqueous electrolytic solution.Particularly, the decomposition of electrolyte and side reaction become problem to the durability of lithium ion battery such as the influence of cyclicity and high-temperature storage characteristics aspect, people have attempted suppressing electrolyte in active anode compartment or negative terminal surface decomposition, to prevent deterioration by add various additives in electrolyte.
For example, patent documentation JP-A-11-67270 has put down in writing such technology, wherein adopts to comprise at least a single lithium fluophosphate Li that is selected from
2PO
3F and difluorophosphate LiPO
2F
2The nonaqueous electrolytic solution of additive.In this technology, described additive and lithium are reflected to form on the interface between positive pole and the negative pole and film, thereby suppress electrolyte because contact with negative electrode active material with positive electrode active material and decompose.Therefore, self discharge is inhibited, and the storage characteristic after the charging is improved.
In No. 3439085 communiques of Japan Patent, disclose by improving high-temperature cycle via in electrolyte, adding difluorophosphate in the film effect that electrode interface forms.Yet, so as the synthetic too difficulty of the difluorophosphate of additive, be not suitable for industrial effective ways to such an extent as to set up as yet.The Japan Patent spy opens the 2005-219994 communique and discloses by lithium hexafluoro phosphate electrolyte and silicon dioxide are reacted under 50 ° of C and produce difluorophosphate; Yet finishing until reaction need be extremely long-time, and when reaction temperature surpassed 60 ° of C, lithium hexafluoro phosphate began to decompose, and causes the electrolyte deterioration, and this is problematic equally.In addition, (J.Fluorine Chem.126 (2005) in by the method that makes hexafluorophosphate and water reaction production difluorophosphate, 27), owing to produced hydrofluoric acid, difluorophosphoric acid and the single fluorophosphoric acid that is difficult to remove, therefore do not obtain pure difluorophosphate as yet.In addition, the difluorophosphate that separates from this solution is unstable among difluorophosphoric acid salt, and because the coexistence of above-mentioned acid and accelerated decomposition, to such an extent as to never really isolate difluorophosphate.
Publication WO2012004187A2 proposes a kind of method of producing difluorophosphate, wherein LiHPO
4Issue living gas-solid reaction with HF at 140 ° of C, generate difluorophosphate and single lithium fluophosphate and lithium fluoride mixture, be difficult to separate; Publication WO2012004188A1 proposes another kind of method of producing difluorophosphate, wherein P
2O
5Under 300 ° of C solid-solid reaction taking place with LiF, generate the solid solution mixtures of difluorophosphate and lithium phosphate, through long extraction, just can isolate a spot of difluorophosphate after need grinding; Publication WO2012016924A1 also proposes a kind of method of producing difluorophosphate, wherein PF
5Perhaps POF
3With Li
3PO
4Issue living gas-solid reaction at 200 ° of C and 100 ° of C respectively, generate difluorophosphate and lithium hexafluoro phosphate and lithium fluoride mixture, not only face a separation difficult problem, and because raw material PF
5And POF
3Be difficult to obtain, be difficult for implementing.
[summary of the invention]
The production link that the objective of the invention is in order to overcome the prior art for preparing difluorophosphate is many, no matter be the control hydrolysis, or the gas-solid reaction under hot conditions, product mostly is mixture, the extract and separate difficulty, the shortcoming that product purity is not high, provide a kind of technical easy control, process conditions simply to utilize the organotin fluoride to prepare the method for high-purity difluorophosphate, use the cheap raw material that is easy to get at low cost suitability for industrialized production can be used for improving the additive difluorophosphate of battery with nonaqueous electrolyte performance.
The present invention utilizes organotin fluoride R for achieving the above object
nSnF
4-nBe easy to carry out with the phosphorus compound of chloride, bromine, iodine the characteristics of F/Cl (Br, I) halogen exchange reaction, prepare dichloro lithium phosphate LiPO with simple method earlier
2Cl
2, make organotin fluoride and dichloro lithium phosphate haptoreaction can generate difluorophosphate LiPO then
2F
2, technical scheme is particularly:
Utilize the organotin fluoride to prepare the method for difluorophosphate, it is characterized in that by with dichloro lithium phosphate and organotin fluoride R
nSnF
4-nCarry out fluorine/chlorine exchange reaction and generate difluorophosphate in the presence of organic solvent in dry nitrogen atmosphere, reaction equation is:
LiPO
2Cl
2+R
nSnF
4-n→LiPO
2F
2+R
nSnCl
4-n （1）；
Wherein said organotin fluoride R
nSnF
4-nIn R represent methyl, ethyl, propyl group, isopropyl, a kind of in normal-butyl, isobutyl group, the tert-butyl group, the straight or branched alkane that contains 1-10 carbon, phenyl, benzyl and other substituted aroma alkyl, n represents 2 or 3;
Wherein said organic solvent is selected from least a in alkane, aromatic hydrocarbons, ether, acetonitrile, organic base, carbonic ester and the ethyl acetate;
Wherein said dichloro lithium phosphate and organotin fluoride R
nSnF
4-nThe molar ratio of reaction is 1:1～2, described organotin fluoride R
nSnF
4-nQuality be 0.1～0.5:1～5 with volume of organic solvent than (w/v).
Dichloro lithium phosphate LiPO among the present invention
2Cl
2With organotin fluoride R
nSnF
4-nGenerate difluorophosphate LiPO
2F
2The reaction temperature of exchange reaction be 20～200 ℃, reaction pressure is 0.1～2.0Mpa, the reaction time is 5～10 hours.
Generate difluorophosphate LiPO among the present invention
2F
2Dry atmosphere be that water content is less than the nitrogen gas of 10ppm.
Organotin fluoride R
nSnF
4-nBe a kind of fluorination reagent efficiently (H.W.Roesky, Chem.Rev.1997,
973425), they can be under condition as mild as a dove, with nitrogen (N), phosphorus (P), sulphur (S) and easily be dissolved in metal chloride (Cl) in the organic solvent and quantitative F/Cl (Br, I) exchange reaction takes place for bromide (Br) or iodide (I), generate some and adopt conventional methods to be difficult to nitrogen (N), phosphorus (P), sulphur (S) and the metal fluoride of preparation; The organotin halide R that reaction is remaining
nSnX
4-n(X=Cl, Br) reclaim after can with common fluoride M'F(M'=H
+, Na
+, K
+, NH
4 +, Et
4N
+, Me
4N
+Deng) become corresponding organotin fluoride R by equation (2) reaction regeneration
nSnF
4-n, can be recycled, be a kind of very economical fluorine chemical technology.
R
nSnX
4-n+M'F→R
nSnF
4-n+M'X （2）
The reaction equation (1) that the present invention utilizes the organotin fluoride to prepare the method for difluorophosphate carries out.
Dichloro lithium phosphate LiPO wherein
2Cl
2Can pass through reaction equation (3) preparation:
2POCl
3+Li
3PO
4→3LiPO
2Cl
2 （3）；
Its reaction condition is: 20～200 ℃ of reaction temperatures, reaction pressure 0.1～2.0Mpa in 5～10 hours reaction time, reacts on organic solvent and water content less than carrying out POCl in the nitrogen atmosphere of 10ppm
3And Li
3PO
4The total weight of reactant and volume of organic solvent are 0.1～0.5:1～10 than (w/v).
Dichloro lithium phosphate LiPO among the present invention
2Cl
2Also can pass through reaction equation (4) preparation:
P
2O
5+POCl
3+3LiCl→3LiPO
2Cl
2 （4）；
Its reaction condition is: 20～200 ℃ of reaction temperatures, reaction pressure 0.1～2.0Mpa in 5～10 hours reaction time, reacts on organic solvent and water content less than carrying out P in the nitrogen atmosphere of 10ppm
2O
5, POCl
3With total weight and the volume of organic solvent of LiCl reactant be 0.1～0.5:1～10 than (w/v).
Dichloro lithium phosphate LiPO among the present invention
2Cl
2Can also prepare by reaction equation (5):
LiOH+POCl
3→LiPO
2Cl
2+HCl↑ （5）；
Its reaction condition is: 20～200 ℃ of reaction temperatures, reaction pressure 0.1～2.0Mpa in 5～10 hours reaction time, reacts on organic solvent and water content less than carrying out LiOH and POCl in the nitrogen atmosphere of 10ppm
3The total weight of reactant and volume of organic solvent are 0.1～0.5:1～10 than (w/v).
The dichloro lithium phosphate can be by above-mentioned reaction (3), (4) and (5) preparation, and the reaction back forms uniform organic solution, does not need to isolate in advance LiPO
2Cl
2, can directly add the organotin fluoride and carry out next step F-Cl exchange reaction with it, can obtain high-quality LiPO through purifying again behind the generation difluorophosphate
2F
2Product.
By the above-mentioned LiPO for preparing of the present invention as can be seen
2Cl
2And LiPO
2F
2Process in reaction temperature all control at 20～200 ℃, be preferably 40～120 ℃, and be reflected at organic solvent and water content less than carrying out in the nitrogen atmosphere of 10ppm, reaction pressure is 0.1～2.0Mpa, be preferably 0.3～1.0Mpa, the reaction time is 5～10 hours.
The organic solvent at reaction (3), (4) and (5) place is identical with the organic solvent at reaction (1) place among the present invention, and alkane wherein and aromatic hydrocarbons are selected from least a in benzinum, n-hexane, cyclohexane, normal heptane, isoheptane, the benzene,toluene,xylene; Ether is selected from least a in methyl ether, ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether, methyl phenyl ethers anisole, phenetole and the oxolane; Organic base is selected from least a in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine and Methylethyl amine, methyl-propyl amine, the ethyl propyl amine; Carbonic ester is selected from least a in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the ethylene carbonate.
The present invention compared with prior art has following advantage:
The present invention prepares raw material Li Cl, the POCl of dichloro lithium phosphate
3, P
2O
5And Li
3PO
4Being easy to get, all is solid or liquid, and reaction is operation easily; Organotin fluoride R
nSnF
4-nOnly with LiPO
2Cl
2In chlorine generation exchange reaction, generate LiPO
2F
2And R
nSnCl
4-n, R wherein
nSnCl
4-nBe easy to separate and purify, and easy and M'F(M'=H
+, Na
+, K
+, NH
4 +, Et
4N
+, Me
4N
+Deng) reaction regenerates organotin fluoride R
nSnF
4-nThe entire reaction course mild condition does not have accessory substance to occur, and technical process is simple, and is low to equipment and environmental protection requirement, has not only avoided introducing the possibility of impurity, the LiPO that preparation is generated
2F
2The purity height, quality better.
[embodiment]
Below in conjunction with specific embodiment the present invention is further described:
The present invention is with dichloro lithium phosphate LiPO
2Cl
2With organotin fluoride R
nSnF
4-n(R=Me, Et, Pr, i-Pr, n-Bu, i-Bu, t-Bu etc. contain the straight or branched alkane of 1-10 carbon, phenyl Ph, benzyl Bn and other substituted aroma alkyl; N=2,3) by carrying out halogen exchange reaction formula (1) preparation difluorophosphate LiPO
2F
2, LiPO wherein
2Cl
2Can be earlier prepare by reaction equation mol ratio proportioning by reaction equation (3) or reaction equation (4) or reaction equation (5), again with organotin fluoride R
nSnF
4-nPrepared in reaction difluorophosphate LiPO
2F
2, perhaps the dichloro lithium phosphate is generated by reaction in place, needn't separate separately, just direct and organotin fluoride R
nSnF
4-nIn same reactor, carry out next step reaction (1); Wherein the HCl gas that produces in the reaction equation (5) can be discharged reactor or directly absorb salify with organic base and form precipitation in organic solvent, removes after filtration.
Reaction equation (1), (3), (4) and (5) all need be carried out in less than the nitrogen atmosphere of 10ppm at organic solvent and water content, reaction pressure is 0.1～2.0Mpa, be preferably 0.3～1.0Mpa, organic solvent all passes through suitable drying before use except water treatment, reaction temperature is all controlled at 20～200 ℃, be preferably 40～120 ℃, the reaction time is 5～10 hours.
Dichloro lithium phosphate and organotin fluoride R in the reaction equation (1)
nSnF
4-nThe molar ratio of reaction is 1:1～2, described organotin fluoride R
nSnF
4-nQuality be 0.1～0.5:1～5 with volume of organic solvent than (w/v).
The reactant total weight and the volume of organic solvent that participate in reaction in reaction equation (3), (4) and (5) are 0.1～0.5:1～10 than (w/v), the LiPO that all generate in reaction (3) (4) (5)
2Cl
2All needn't from solvent, separate in advance, directly carry out next step fluoro-chlorine exchange reaction, generate difluorophosphate LiPO
2F
2
Organic solvent can be selected from one or more in alkane, aromatic hydrocarbons, ether, acetonitrile, organic base, carbonic ester and the ethyl acetate, and wherein said alkane and aromatic hydrocarbons are selected from one or more in benzinum, n-hexane, cyclohexane, normal heptane, isoheptane, the benzene,toluene,xylene; Ether is selected from one or more in methyl ether, ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether, methyl phenyl ethers anisole, phenetole and the oxolane; Organic base is selected from one or more in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine and Methylethyl amine, methyl-propyl amine, the ethyl propyl amine; Carbonic ester is selected from one or more in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the ethylene carbonate.
One, by reaction equation of the present invention (3) and (1) preparation LiPO
2F
2
Embodiment 1:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 0.5Mpa, under the normal temperature with 30.7g (0.2mol) POCl
3And 11.6g (0.1mol) Li
3PO
4Be suspended in the glycol dimethyl ether of 800mL drying, stir down temperature of reaction kettle slowly to be raised under 120 ° of C and reacted 5 hours, then temperature of reaction kettle is dropped to room temperature, with 109.7g (0.6mol) Me
3SnF joins in the reactor, stirs temperature of reaction kettle slowly to be raised under 100 ° of C reaction down 7 hours again, be cooled to room temperature after, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
3SnCl, remaining solid carry out recrystallization after dissolving again with the oxolane of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, remove mother liquor after filtration, collect the crystalloid solid, obtain 30.4gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.5%.
Embodiment 2:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 0.8Mpa, under the normal temperature with 30.7g (0.2mol) POCl
3And 11.6g (0.1mol) Li
3PO
4Be suspended in the acetonitrile of 800mL drying, stir down temperature of reaction kettle slowly to be raised under 100 ° of C and reacted 5 hours, then temperature of reaction kettle is dropped to room temperature, with 56.1g (0.3mol) Me
2SnF
2Join in the reactor, stir and again temperature of reaction kettle slowly to be raised under 120 ° of C reaction down 7 hours, be cooled to room temperature after, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
2SnCl
2, remaining solid carries out recrystallization after dissolving again with the acetonitrile of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, removes mother liquor after filtration, and collection crystalloid solid obtains 28.1gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.7%.
Embodiment 3:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 1.0Mpa, under the normal temperature respectively with 30.7g (0.2mol) POCl
3, 11.6g (0.1mol) Li
3PO
4And 109.7g (0.6mol) Me
3SnF joins in the methyl ethyl carbonate that is suspended in the 800mL drying in the reactor, stir down temperature of reaction kettle slowly to be raised under 120 ° of C and reacted 10 hours, then temperature of reaction kettle is dropped to room temperature, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
3SnCl, remaining solid carry out recrystallization after dissolving again with the acetonitrile of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, remove mother liquor after filtration, collect the crystalloid solid, obtain 30.2gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.5%.
Embodiment 4:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 0.3Mpa, under the normal temperature respectively with 30.7g (0.2mol) POCl
3, 11.6g (0.1mol) Li
3PO
4And 56.1g (0.3mol) Me
2SnF
2Join in the acetonitrile that is suspended in the 800mL drying in the reactor, stir down temperature of reaction kettle slowly to be raised under 40 ° of C and reacted 10 hours, then temperature of reaction kettle is dropped to room temperature, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
2SnCl
2, remaining solid carries out recrystallization after dissolving again with the acetonitrile of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, removes mother liquor after filtration, and collection crystalloid solid obtains 28.3gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.6%.
Two, by reaction equation of the present invention (4) and (1) preparation LiPO
2F
2
Embodiment 5:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 0.1Mpa, under the normal temperature with 15.3g (0.1mol) POCl
3And 14.2g (0.1mol) P
2O
5And 12.7g (0.3mol) LiCl is suspended in the glycol dimethyl ether of 800mL drying, stirs down temperature of reaction kettle slowly to be raised under 180 ° of C reaction 6 hours, then temperature of reaction kettle dropped to room temperature, with 109.7g (0.6mol) Me
3SnF joins in the reactor, stirs temperature of reaction kettle slowly to be raised under 110 ° of C reaction down 6 hours again, be cooled to room temperature after, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
3SnCl, remaining solid carry out recrystallization after dissolving again with the ether of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, remove mother liquor after filtration, collect the crystalloid solid, obtain 30.1gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.5%.
Embodiment 6.
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 1.2Mpa, under the normal temperature respectively with 15.3g (0.1mol) POCl
3, 14.2g (0.1mol) P
2O
5, 12.7g (0.3mol) LiCl and 109.7g (0.6mol) Me
3SnF joins in the oxolane that is suspended in the 800mL drying in the reactor, stir down temperature of reaction kettle slowly is raised to following 10 hours of 100 ° of C, then temperature of reaction kettle is reduced to room temperature, obtains a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
3SnCl, remaining solid carry out recrystallization after dissolving again with the oxolane of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, remove mother liquor after filtration, collect the crystalloid solid, obtain 30.2gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.6%.
Embodiment 7:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 1.6Mpa, under the normal temperature respectively with 15.3g (0.1mol) POCl
3, 14.2g (0.1mol) P
2O
5, 12.7g (0.3mol) LiCl and 56.1g (0.3mol) Me
2SnF
2Join in the acetonitrile that is suspended in the 800mL drying in the reactor, stir down temperature of reaction kettle slowly to be raised under 200 ° of C and reacted 5 hours, then temperature of reaction kettle is dropped to room temperature, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
2SnCl
2, remaining solid carries out recrystallization after dissolving again with the acetonitrile of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, removes mother liquor after filtration, and collection crystalloid solid obtains 28.0gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.5%.
Three, by reaction equation of the present invention (5) and (1) preparation LiPO
2F
2Method may further comprise the steps:
Embodiment 8:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 2.0Mpa, under the normal temperature with 15.3g (0.1mol) POCl
3And 2.4g (0.1mol) LiOH is suspended in the oxolane of 250mL drying, adds the 20mL anhydrous pyridine again, stirs down temperature of reaction kettle slowly to be raised under 90 ° of C reaction 7 hours, then temperature of reaction kettle dropped to room temperature, with 36.6g (0.2mol) Me
3SnF joins in the reactor, stirs temperature of reaction kettle slowly to be raised under 90 ° of C reaction down 7 hours again, be cooled to room temperature after, remove by filter the pyridine hydrochloride solid, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
3SnCl, remaining solid carry out recrystallization after dissolving again with the oxolane of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, remove mother liquor after filtration, collect the crystalloid solid, obtain 9.8gLiPO under 60 ° of C after vacuumize
2F
2Are crystalloid solid, purity 99.4%?
Embodiment 9:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 0.8Mpa, under the normal temperature with 15.3g (0.1mol) POCl
3And 2.4g (0.1mol) LiOH and 36.6g (0.2mol) Me
3SnF is suspended in the methyl ethyl carbonate of 250mL drying, add the 20mL anhydrous pyridine again, stir down temperature of reaction kettle slowly to be raised under 90 ° of C and reacted 10 hours, then temperature of reaction kettle is dropped to room temperature, remove by filter the pyridine hydrochloride solid, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
3SnCl, remaining solid carry out recrystallization after dissolving again with the ether of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, remove mother liquor after filtration, collect the crystalloid solid, obtain 9.5gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.5%.
Embodiment 10:
In closed reaction kettle, under the nitrogen protection of water content less than 10ppm, pressure 0.5Mpa, under the normal temperature with 15.3g (0.1mol) POCl
3And 2.4g (0.1mol) LiOH and 18.7g (0.1mol) Me
2SnF
2Be suspended in the acetonitrile of 250mL drying, add the 20mL anhydrous pyridine again, stir down temperature of reaction kettle slowly to be raised under 100 ° of C and reacted 12 hours, then temperature of reaction kettle is dropped to room temperature, remove by filter the pyridine hydrochloride solid, obtain a limpid transparent solution, vacuumize down the Me of removal of solvent under reduced pressure and generation
2SnCl
2, remaining solid carries out recrystallization after dissolving again with the acetonitrile of fresh dried under-20～0 ° of C, generate the crystalloid product in solution, removes mother liquor after filtration, and collection crystalloid solid obtains 9.0gLiPO under 60 ° of C after vacuumize
2F
2Crystalloid solid, purity are 99.5%.
Claims (7)
1. utilize the organotin fluoride to prepare the method for high-purity difluorophosphate, it is characterized in that by with dichloro lithium phosphate and organotin fluoride R
nSnF
4-nCarry out fluorine/chlorine exchange reaction and generate difluorophosphate in the presence of organic solvent in dry nitrogen atmosphere, reaction equation is:
LiPO
2Cl
2+R
nSnF
4-n→LiPO
2F
2+R
nSnCl
4-n；
Wherein said organotin fluoride R
nSnF
4-nIn R represent methyl, ethyl, propyl group, isopropyl, a kind of in normal-butyl, isobutyl group, the tert-butyl group, the straight or branched alkane that contains 1-10 carbon, phenyl, benzyl and other substituted aroma alkyl, n represents 2 or 3;
Wherein said organic solvent is selected from least a in alkane, aromatic hydrocarbons, ether, acetonitrile, organic base, carbonic ester and the ethyl acetate;
Wherein said dichloro lithium phosphate and organotin fluoride R
nSnF
4-nThe molar ratio of reaction is 1:1～2, described organotin fluoride R
nSnF
4-nQuality is 0.1～0.5:1～5 with volume of organic solvent than (w/v).
2. the method for utilizing the organotin fluoride to prepare the high-purity difluorophosphate according to claim 1, the reaction temperature that it is characterized in that the exchange reaction of described generation difluorophosphate is 20～200 ℃, reaction pressure is 0.1～2.0Mpa, and the reaction time is 5～10 hours.
3. the method for utilizing the organotin fluoride to prepare the high-purity difluorophosphate according to claim 1 is characterized in that described dry nitrogen atmosphere is that water content is less than the nitrogen gas of 10ppm.
4. the method for utilizing the organotin fluoride to prepare the high-purity difluorophosphate according to claim 1 is characterized in that described alkane and aromatic hydrocarbons are selected from least a in benzinum, n-hexane, cyclohexane, normal heptane, isoheptane, the benzene,toluene,xylene; Described ether is selected from least a in methyl ether, ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether, methyl phenyl ethers anisole, phenetole and the oxolane; Described organic base is selected from least a in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine and Methylethyl amine, methyl-propyl amine, the ethyl propyl amine; Described carbonic ester is selected from least a in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the ethylene carbonate.
5. the method for utilizing the organotin fluoride to prepare the high-purity difluorophosphate according to claim 1 is characterized in that described dichloro lithium phosphate is by following prepared in reaction:
2POCl
3+Li
3PO
4→3LiPO
2Cl
2；
Its reaction condition is: 20～200 ℃ of reaction temperatures, reaction pressure 0.1～2.0Mpa, 5～10 hours reaction time, react on organic solvent and water content less than carrying out in the nitrogen atmosphere of 10ppm, the total weight of reactant and volume of organic solvent are 0.1～0.5:1～10 than (w/v) in the described reaction equation.
6. the method for utilizing the organotin fluoride to prepare the high-purity difluorophosphate according to claim 1 is characterized in that described dichloro lithium phosphate is by following prepared in reaction:
P
2O
5+POCl
3+3LiCl→3LiPO
2Cl
2；
Its reaction condition is: 20～200 ℃ of reaction temperatures, reaction pressure 0.1～2.0Mpa, 5～10 hours reaction time, react on organic solvent and water content less than carrying out in the nitrogen atmosphere of 10ppm, the total weight of reactant and volume of organic solvent are 0.1～0.5:1～10 than (w/v) in the described reaction equation.
7. the method for utilizing the organotin fluoride to prepare the high-purity difluorophosphate according to claim 1 is characterized in that described dichloro lithium phosphate is by following prepared in reaction:
LiOH+POCl
3→LiPO
2Cl
2+HCl↑；
Its reaction condition is: 20～200 ℃ of reaction temperatures, reaction pressure 0.1～2.0Mpa, 5～10 hours reaction time, react on organic solvent and water content less than carrying out in the nitrogen atmosphere of 10ppm, the total weight of reactant and volume of organic solvent are 0.1～0.5:1～10 than (w/v) in the described reaction equation.
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