CN103259040B - Organotin fluoride is utilized to prepare the method for high-purity lithium difluorophosphate - Google Patents

Organotin fluoride is utilized to prepare the method for high-purity lithium difluorophosphate Download PDF

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CN103259040B
CN103259040B CN201310097948.9A CN201310097948A CN103259040B CN 103259040 B CN103259040 B CN 103259040B CN 201310097948 A CN201310097948 A CN 201310097948A CN 103259040 B CN103259040 B CN 103259040B
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reaction
organic solvent
difluorophosphate
fluoride
organotin
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CN103259040A (en
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余佩华
余佩娟
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ZHONGSHAN HUAWEI NEW ENERGY TECHNOLOGY Co Ltd
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ZHONGSHAN HUAWEI NEW ENERGY TECHNOLOGY Co Ltd
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Abstract

The invention discloses a kind of method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate, organotin fluoride is utilized to be easy to carry out with the phosphorus compound of chloride, bromine, iodine the feature of halogen exchange reaction, first prepare dichloro lithium phosphate by simple method, then make organotin fluoride and dichloro lithium phosphate haptoreaction generate difluorophosphate.Raw material of the present invention is easy to get, and reaction easily operates; Whole course of reaction mild condition, does not have accessory substance to occur, technical process is simple, low to the requirement of equipment and environmental protection, and avoid the possibility introducing impurity, the difluorophosphate purity that preparation is generated is high, quality better.

Description

Organotin fluoride is utilized to prepare the method for high-purity lithium difluorophosphate
[technical field]
The present invention relates to a kind of method preparing difluorophosphate, relate to a kind of method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate particularly.
[background technology]
In recent years, the basic research of lithium ion battery and application and development be one of focus becoming new energy field, and each flourishing state of the world all it can be used as the break-through point of next new industry to develop and study.Positive electrode, negative material, electrolyte and diaphragm material are the large critical materials of lithium ion battery four, and common electrolyte mainly contains LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiCF 3sO 3, LiN (CF 3sO 2) 2deng, in carbonate based organic solvent, be made into nonaqueous electrolyte by dissolving these electrolyte, wherein LiPF 6it is the most widely used current a kind of electrolyte.
The lithium ion battery adopting nonaqueous electrolyte is significantly different in 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 impact of the durability of lithium ion battery as cyclicity and high-temperature storage characteristics aspect, people have attempted suppressing electrolyte to decompose in active anode compartment or negative terminal surface, to prevent deterioration by adding various additive in electrolyte.
Such as, patent documentation JP-A-11-67270 describes such technology, wherein adopts and comprises at least one and be selected from single lithium fluophosphate Li 2pO 3f and difluorophosphate LiPO 2f 2the nonaqueous electrolytic solution of additive.In the art, described additive and lithium react on interface between a positive electrode and a negative electrode and form film, thus suppress electrolyte to decompose because of contacting with negative electrode active material with positive electrode active material.Therefore, self discharge is inhibited, and the storage characteristic after charging is improved.
In Japan Patent No. 3439085 publications, disclose by via adding film effect that difluorophosphate formed on electrode interface and improve high-temperature cycle in electrolyte.But the synthesis being so used as the difluorophosphate of additive is too difficult, to such an extent as to not yet foundation is suitable for industrial effective ways.Japanese Patent Laid-Open 2005-219994 publication discloses by making lithium hexafluorophosphate electrolyte solution and silicon dioxide react to produce difluorophosphate under 50 ° of C; But until reaction terminates to need extremely for a long time, and when reaction temperature is more than 60 ° of C, lithium hexafluoro phosphate starts to decompose, and cause electrolyte deterioration, this is problematic equally.In addition, by making hexafluorophosphate and water react (J.FluorineChem.126 (2005) in the method for producing difluorophosphate, 27), owing to creating the hydrofluoric acid, difluorophosphoric acid and the single fluorophosphoric acid that are difficult to remove, therefore pure difluorophosphate is not yet obtained.In addition, the difluorophosphate be separated from this solution is unstable among difluorophosphoric acid salt, and due to above-mentioned coexisting of acid 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 raw gas-solid reaction with HF at 140 ° of C, generate difluorophosphate and single lithium fluophosphate and lithium fluoride mixture, be difficult to be separated; Publication WO2012004188A1 proposes another kind of method of producing difluorophosphate, wherein P 2o 5under 300 ° of C, there is solid-solid reaction with LiF, generate the solid solution mixtures of difluorophosphate and lithium phosphate, through long extraction after needs grind, just can isolate a small amount of difluorophosphate; Publication WO2012016924A1 also proposes a kind of method of producing difluorophosphate, wherein PF 5or POF 3with Li 3pO 4issue raw gas-solid reaction at 200 ° of C and 100 ° C respectively, generate difluorophosphate and lithium hexafluoro phosphate and lithium fluoride mixture, not only face a separation difficult problem, and due to raw material PF 5and POF 3be difficult to obtain, not easily implement.
[summary of the invention]
The object of the invention is to overcome prior art that to prepare the production link of difluorophosphate many, no matter be controlled hydrolysis reaction, still gas-solid reaction under the high temperature conditions, product is mostly mixture, extract and separate is difficult, the shortcoming that product purity is not high, there is provided a kind of and technically easily control, process conditions simply utilize organotin fluoride to prepare the method for high-purity lithium difluorophosphate, use the cheap raw material be 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 for achieving the above object, utilizes organotin fluoride R nsnF 4-nbe easy to the feature of carrying out F/Cl (Br, I) halogen exchange reaction with the phosphorus compound of chloride, bromine, iodine, first prepare dichloro lithium phosphate LiPO by simple method 2cl 2, then make organotin fluoride and dichloro lithium phosphate haptoreaction can generate difluorophosphate LiPO 2f 2, technical scheme is particularly:
Utilize organotin fluoride to prepare the method for difluorophosphate, it is characterized in that by by dichloro lithium phosphate and organotin fluoride R nsnF 4-nin dry nitrogen atmosphere, carry out fluorine/chlorine exchange reaction in presence of organic solvent generate difluorophosphate, 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, the one in normal-butyl, isobutyl group, the tert-butyl group, straight or branched alkane, phenyl, benzyl and other substituted aroma alkyl containing 1-10 carbon, n represents 2 or 3;
Wherein said organic solvent is selected from least one in alkane, aromatic hydrocarbons, ether, acetonitrile, organic base, carbonic ester and 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 and the volume ratio (w/v) of organic solvent be 0.1 ~ 0.5:1 ~ 5.
Dichloro lithium phosphate LiPO in the present invention 2cl 2with organotin fluoride R nsnF 4-ngenerate difluorophosphate LiPO 2f 2the reaction temperature of exchange reaction be 20 ~ 200 DEG C, reaction pressure is 0.1 ~ 2.0Mpa, and the reaction time is 5 ~ 10 hours.
Difluorophosphate LiPO is generated in the present invention 2f 2dry atmosphere be the nitrogen gas that water content is less than 10ppm.
Organotin fluoride R nsnF 4-nbe a kind of fluorination reagent efficiently (H.W.Roesky, Chem.Rev.1997, 973425), they can under condition as mild as a dove, there is quantitative F/Cl (Br, I) exchange reaction with nitrogen (N), phosphorus (P), sulphur (S) and soluble metal chloride (Cl) in organic solvent and 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 prepared; The organotin halides R that reaction is remaining nsnX 4-n(X=Cl, Br) can with common fluoride M'F(M'=H after reclaiming +, 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 organotin fluoride to prepare the method for difluorophosphate carries out.
Dichloro lithium phosphate LiPO wherein 2cl 2reaction equation (3) preparation can be passed through:
2POCl 3+Li 3PO 4→3LiPO 2Cl 2（3）；
Its reaction condition is: reaction temperature 20 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0Mpa, 5 ~ 10 hours reaction time, reacts on organic solvent and water content and is less than in the nitrogen atmosphere of 10ppm and carries out, POCl 3and Li 3pO 4the total weight of reactant and the volume ratio (w/v) of organic solvent are 0.1 ~ 0.5:1 ~ 10.
Dichloro lithium phosphate LiPO in the present invention 2cl 2also reaction equation (4) preparation can be passed through:
P 2O 5+POCl 3+3LiCl→3LiPO 2Cl 2（4）；
Its reaction condition is: reaction temperature 20 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0Mpa, 5 ~ 10 hours reaction time, reacts on organic solvent and water content and is less than in the nitrogen atmosphere of 10ppm and carries out, P 2o 5, POCl 3be 0.1 ~ 0.5:1 ~ 10 with the total weight of LiCl reactant and the volume ratio (w/v) of organic solvent.
Dichloro lithium phosphate LiPO in the present invention 2cl 2reaction equation (5) can also be passed through prepare:
LiOH+POCl 3→LiPO 2Cl 2+HCl↑（5）；
Its reaction condition is: reaction temperature 20 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0Mpa, 5 ~ 10 hours reaction time, reacts on organic solvent and water content and is less than in the nitrogen atmosphere of 10ppm and carries out, LiOH and POCl 3the total weight of reactant and the volume ratio (w/v) of organic solvent are 0.1 ~ 0.5:1 ~ 10.
Dichloro lithium phosphate by above-mentioned reaction (3), (4) and (5) preparation, can be formed uniform organic solution after reaction, does not need to isolate LiPO in advance 2cl 2, directly can add organotin fluoride carries out next step F-Cl exchange reaction with it, the LiPO of high-quality after generating difluorophosphate, can be obtained again through purifying 2f 2product.
By above-mentioned can find out of the present inventionly prepare LiPO 2cl 2and LiPO 2f 2process in reaction temperature all control at 20 ~ 200 DEG C, be preferably 40 ~ 120 DEG C, and reaction to be less than in the nitrogen atmosphere of 10ppm at organic solvent and water content and to carry out, reaction pressure is 0.1 ~ 2.0Mpa, be preferably 0.3 ~ 1.0Mpa, the reaction time is 5 ~ 10 hours.
React (3) in the present invention, (4) are identical with the organic solvent at reaction (1) place with the organic solvent at (5) place, alkane wherein and aromatic hydrocarbons are selected from least one in benzinum, n-hexane, cyclohexane, normal heptane, isoheptane, benzene,toluene,xylene; Ether is selected from least one 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 oxolane; Organic base is selected from least one in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine and Methylethyl amine, methyl-propyl amine, ethyl propyl amine; Carbonic ester is selected from least one in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and 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, is all solid or liquid, and reaction easily operates; Organotin fluoride R nsnF 4-nonly with LiPO 2cl 2in chlorine generation exchange reaction, generate LiPO 2f 2and R nsnCl 4-n, wherein R nsnCl 4-nbe easy to isolation andpurification, and easy and M'F(M'=H +, Na +, K +, NH 4 +, Et 4n +, Me 4n +deng) reaction regenerate organotin fluoride R nsnF 4-n; Whole course of reaction mild condition, does not have accessory substance to occur, technical process is simple, low to the requirement of equipment and environmental protection, not only avoids the possibility introducing impurity, makes the LiPO that preparation generates 2f 2purity is high, quality better.
[embodiment]
Below in conjunction with specific embodiment, the invention will be further described:
The present invention is by 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) prepare difluorophosphate LiPO by carrying out halogen exchange reaction formula (1) 2f 2, LiPO wherein 2cl 2can first be prepared by reaction equation mol ratio proportioning by reaction equation (3) or reaction equation (4) or reaction equation (5), then with organotin fluoride R nsnF 4-ndifluorophosphate LiPO is prepared in reaction 2f 2, or dichloro lithium phosphate is generated by reaction in place, need not separate separately, just direct and organotin fluoride R nsnF 4-nnext step reaction (1) is carried out in same reactor; The HCl gas wherein produced in reaction equation (5) can be discharged reactor or directly absorb salify with organic base and be formed precipitation in organic solvent, removes after filtration.
Reaction equation (1), (3), (4) and (5) all need to be less than in the nitrogen atmosphere of 10ppm at organic solvent and water content to carry out, reaction pressure is 0.1 ~ 2.0Mpa, be preferably 0.3 ~ 1.0Mpa, organic solvent all removes water treatment through suitable drying before use, reaction temperature all controls at 20 ~ 200 DEG C, be preferably 40 ~ 120 DEG C, the reaction time is 5 ~ 10 hours.
Dichloro lithium phosphate and organotin fluoride R in reaction equation (1) nsnF 4-nthe molar ratio of reaction is 1:1 ~ 2, described organotin fluoride R nsnF 4-nquality and the volume ratio (w/v) of organic solvent be 0.1 ~ 0.5:1 ~ 5.
The volume ratio (w/v) participating in reactant total weight and the organic solvent reacted in reaction equation (3), (4) and (5) is 0.1 ~ 0.5:1 ~ 10, all LiPO generated in reaction (3) (4) (5) 2cl 2all need not separate in advance from solvent, 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 ethyl acetate, and wherein said alkane and aromatic hydrocarbons are selected from one or more in benzinum, n-hexane, cyclohexane, normal heptane, isoheptane, 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 oxolane; Organic base is selected from one or more in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine and Methylethyl amine, methyl-propyl amine, ethyl propyl amine; Carbonic ester is selected from one or more in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
One, LiPO is prepared by reaction equation of the present invention (3) and (1) 2f 2
Embodiment 1:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 0.5Mpa at water content under, by 30.7g (0.2mol) POCl under normal temperature 3with 11.6g (0.1mol) Li 3pO 4be suspended in the glycol dimethyl ether of 800mL drying, react 5 hours under temperature of reaction kettle being slowly raised under stirring 120 ° of C, then temperature of reaction kettle is dropped to room temperature, by 109.7g (0.6mol) Me 3snF joins in reactor, reacts 7 hours, after being cooled to room temperature, obtaining a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation under stirring under temperature of reaction kettle being slowly raised to 100 ° of C again 3snCl, after the oxolane of remaining solid fresh dried dissolves again, carries out recrystallization, generates crystalline product in the solution, remove mother liquor after filtration under-20 ~ 0 ° of C, collects crystalline solid, obtains 30.4gLiPO under 60 ° of C after vacuumize 2f 2crystalline solid, purity is 99.5%.
Embodiment 2:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 0.8Mpa at water content under, by 30.7g (0.2mol) POCl under normal temperature 3with 11.6g (0.1mol) Li 3pO 4be suspended in the acetonitrile of 800mL drying, react 5 hours under temperature of reaction kettle being slowly raised under stirring 100 ° of C, then temperature of reaction kettle is dropped to room temperature, by 56.1g (0.3mol) Me 2snF 2join in reactor, react 7 hours under again temperature of reaction kettle being slowly raised to 120 ° of C under stirring, after being cooled to room temperature, obtaining a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 2snCl 2, after the acetonitrile of remaining solid fresh dried dissolves again, under-20 ~ 0 ° of C, carry out recrystallization, generate crystalline product in the solution, remove mother liquor after filtration, collect crystalline solid, under 60 ° of C, after vacuumize, obtain 28.1gLiPO 2f 2crystalline solid, purity is 99.7%.
Embodiment 3:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 1.0Mpa at water content under, respectively by 30.7g (0.2mol) POCl under normal temperature 3, 11.6g (0.1mol) Li 3pO 4and 109.7g (0.6mol) Me 3snF joins in reactor in the methyl ethyl carbonate being suspended in 800mL drying, react 10 hours under temperature of reaction kettle being slowly raised under stirring 120 ° of C, then temperature of reaction kettle is dropped to room temperature, obtain a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 3snCl, after the acetonitrile of remaining solid fresh dried dissolves again, carries out recrystallization, generates crystalline product in the solution, remove mother liquor after filtration under-20 ~ 0 ° of C, collects crystalline solid, obtains 30.2gLiPO under 60 ° of C after vacuumize 2f 2crystalline solid, purity is 99.5%.
Embodiment 4:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 0.3Mpa at water content under, respectively by 30.7g (0.2mol) POCl under normal temperature 3, 11.6g (0.1mol) Li 3pO 4and 56.1g (0.3mol) Me 2snF 2join in reactor in the acetonitrile being suspended in 800mL drying, react 10 hours under temperature of reaction kettle being slowly raised under stirring 40 ° of C, then temperature of reaction kettle is dropped to room temperature, obtain a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 2snCl 2, after the acetonitrile of remaining solid fresh dried dissolves again, under-20 ~ 0 ° of C, carry out recrystallization, generate crystalline product in the solution, remove mother liquor after filtration, collect crystalline solid, under 60 ° of C, after vacuumize, obtain 28.3gLiPO 2f 2crystalline solid, purity is 99.6%.
Two, LiPO is prepared by reaction equation of the present invention (4) and (1) 2f 2
Embodiment 5:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 0.1Mpa at water content under, by 15.3g (0.1mol) POCl under normal temperature 3with 14.2g (0.1mol) P 2o 5and 12.7g (0.3mol) LiCl is suspended in the glycol dimethyl ether of 800mL drying, reacts 6 hours under temperature of reaction kettle being slowly raised under stirring 180 ° of C, then temperature of reaction kettle is dropped to room temperature, by 109.7g (0.6mol) Me 3snF joins in reactor, reacts 6 hours, after being cooled to room temperature, obtaining a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation under stirring under temperature of reaction kettle being slowly raised to 110 ° of C again 3snCl, after the ether of remaining solid fresh dried dissolves again, carries out recrystallization, generates crystalline product in the solution, remove mother liquor after filtration under-20 ~ 0 ° of C, collects crystalline solid, obtains 30.1gLiPO under 60 ° of C after vacuumize 2f 2crystalline solid, purity is 99.5%.
Embodiment 6.
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 1.2Mpa at water content under, respectively by 15.3g (0.1mol) POCl under normal temperature 3, 14.2g (0.1mol) P 2o 5, 12.7g (0.3mol) LiCl and 109.7g (0.6mol) Me 3snF joins in reactor in the oxolane being suspended in 800mL drying, under stirring, temperature of reaction kettle is slowly raised to lower 10 hours of 100 ° of C, then temperature of reaction kettle is reduced to room temperature, obtains a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 3snCl, after the oxolane of remaining solid fresh dried dissolves again, carries out recrystallization, generates crystalline product in the solution, remove mother liquor after filtration under-20 ~ 0 ° of C, collects crystalline solid, obtains 30.2gLiPO under 60 ° of C after vacuumize 2f 2crystalline solid, purity is 99.6%.
Embodiment 7:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 1.6Mpa at water content under, respectively by 15.3g (0.1mol) POCl under normal temperature 3, 14.2g (0.1mol) P 2o 5, 12.7g (0.3mol) LiCl and 56.1g (0.3mol) Me 2snF 2join in reactor in the acetonitrile being suspended in 800mL drying, react 5 hours under temperature of reaction kettle being slowly raised under stirring 200 ° of C, then temperature of reaction kettle is dropped to room temperature, obtain a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 2snCl 2, after the acetonitrile of remaining solid fresh dried dissolves again, under-20 ~ 0 ° of C, carry out recrystallization, generate crystalline product in the solution, remove mother liquor after filtration, collect crystalline solid, under 60 ° of C, after vacuumize, obtain 28.0gLiPO 2f 2crystalline solid, purity is 99.5%.
Three, LiPO is prepared by reaction equation of the present invention (5) and (1) 2f 2method comprise the following steps:
Embodiment 8:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 2.0Mpa at water content under, by 15.3g (0.1mol) POCl under normal temperature 3be suspended in the oxolane of 250mL drying with 2.4g (0.1mol) LiOH, add 20mL anhydrous pyridine again, react 7 hours under temperature of reaction kettle being slowly raised under stirring 90 ° of C, then temperature of reaction kettle is dropped to room temperature, by 36.6g (0.2mol) Me 3snF joins in reactor, reacts 7 hour under temperature of reaction kettle being slowly raised to 90 ° of C under stirring again, after being cooled to room temperature, crossing and filters pyridine hydrochloride solid, obtain a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 3snCl, after the oxolane of remaining solid fresh dried dissolves again, carries out recrystallization, generates crystalline product in the solution, remove mother liquor after filtration under-20 ~ 0 ° of C, collects crystalline solid, obtains 9.8gLiPO under 60 ° of C after vacuumize 2f 2crystalline solid, purity is 99.4%.
Embodiment 9:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 0.8Mpa at water content under, by 15.3g (0.1mol) POCl under normal temperature 3with 2.4g (0.1mol) LiOH and 36.6g (0.2mol) Me 3snF is suspended in the methyl ethyl carbonate of 250mL drying, add 20mL anhydrous pyridine again, react 10 hours under temperature of reaction kettle being slowly raised under stirring 90 ° of C, then temperature of reaction kettle is dropped to room temperature, cross and filter pyridine hydrochloride solid, obtain a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 3snCl, after the ether of remaining solid fresh dried dissolves again, carries out recrystallization, generates crystalline product in the solution, remove mother liquor after filtration under-20 ~ 0 ° of C, collects crystalline solid, obtains 9.5gLiPO under 60 ° of C after vacuumize 2f 2crystalline solid, purity is 99.5%.
Embodiment 10:
In airtight reactor, be less than the nitrogen protection of 10ppm, pressure 0.5Mpa at water content under, by 15.3g (0.1mol) POCl under normal temperature 3with 2.4g (0.1mol) LiOH and 18.7g (0.1mol) Me 2snF 2be suspended in the acetonitrile of 250mL drying, add 20mL anhydrous pyridine again, react 12 hours under temperature of reaction kettle being slowly raised under stirring 100 ° of C, then temperature of reaction kettle is dropped to room temperature, cross and filter pyridine hydrochloride solid, obtain a limpid transparent solution, vacuumize the Me of lower removal of solvent under reduced pressure and generation 2snCl 2, after the acetonitrile of remaining solid fresh dried dissolves again, under-20 ~ 0 ° of C, carry out recrystallization, generate crystalline product in the solution, remove mother liquor after filtration, collect crystalline solid, under 60 ° of C, after vacuumize, obtain 9.0gLiPO 2f 2crystalline solid, purity is 99.5%.

Claims (7)

1. utilize organotin fluoride to prepare the method for high-purity lithium difluorophosphate, it is characterized in that by by dichloro lithium phosphate and organotin fluoride R nsnF 4-nin dry nitrogen atmosphere, carry out fluorine/chlorine exchange reaction in presence of organic solvent generate difluorophosphate, 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;
Wherein said organic solvent is selected from least one in alkane, aromatic hydrocarbons, ether, acetonitrile, organic base, carbonic ester and 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-nthe volume ratio (g/ml) of quality and organic solvent is 0.1 ~ 0.5:1 ~ 5.
2. the method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate according to claim 1, it is characterized in that the reaction temperature of the exchange reaction of described generation difluorophosphate is 20 ~ 200 DEG C, reaction pressure is 0.1 ~ 2.0MPa, and the reaction time is 5 ~ 10 hours.
3. the method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate according to claim 1, is characterized in that described dry nitrogen atmosphere is the nitrogen gas that water content is less than 10ppm.
4. the method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate according to claim 1, is characterized in that described alkane and aromatic hydrocarbons are selected from least one in benzinum, n-hexane, cyclohexane, normal heptane, isoheptane, benzene,toluene,xylene; Described ether is selected from least one 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 oxolane; Described organic base is selected from least one in pyridine, Trimethylamine, diethylamide, triethylamine, dipropylamine, tripropylamine, Methylethyl amine, methyl-propyl amine, ethyl propyl amine; Described carbonic ester is selected from least one in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
5. the method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate according to claim 1, is characterized in that described dichloro lithium phosphate is prepared by following reaction:
2POCl 3+Li 3PO 4→3LiPO 2Cl 2；
Its reaction condition is: reaction temperature 20 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0MPa, 5 ~ 10 hours reaction time, react on organic solvent and water content to be less than in the nitrogen atmosphere of 10ppm and to carry out, describedly prepare the total weight of reactant in the reaction equation of dichloro lithium phosphate and the volume ratio (g/ml) of organic solvent is 0.1 ~ 0.5:1 ~ 10.
6. the method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate according to claim 1, is characterized in that described dichloro lithium phosphate is prepared by following reaction:
P 2O 5+POCl 3+3LiCl→3LiPO 2Cl 2；
Its reaction condition is: reaction temperature 20 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0MPa, 5 ~ 10 hours reaction time, react on organic solvent and water content to be less than in the nitrogen atmosphere of 10ppm and to carry out, describedly prepare the total weight of reactant in the reaction equation of dichloro lithium phosphate and the volume ratio (g/ml) of organic solvent is 0.1 ~ 0.5:1 ~ 10.
7. the method utilizing organotin fluoride to prepare high-purity lithium difluorophosphate according to claim 1, is characterized in that described dichloro lithium phosphate is prepared by following reaction:
LiOH+POCl 3→LiPO 2Cl 2+HCl↑；
Its reaction condition is: reaction temperature 20 ~ 200 DEG C, reaction pressure 0.1 ~ 2.0MPa, 5 ~ 10 hours reaction time, react on organic solvent and water content to be less than in the nitrogen atmosphere of 10ppm and to carry out, describedly prepare the total weight of reactant in the reaction equation of dichloro lithium phosphate and the volume ratio (g/ml) of organic solvent is 0.1 ~ 0.5:1 ~ 10.
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