CN107720717A - A kind of preparation method of difluorophosphate - Google Patents
A kind of preparation method of difluorophosphate Download PDFInfo
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Abstract
A kind of preparation method of difluorophosphate, composition principle include difluorophosphoric acid and lithium hydroxide haptoreaction or difluorophosphoric acid and lithium carbonate haptoreaction in nonaqueous solvents in nonaqueous solvents；Specific reaction equation includes：HPO2F2+ LiOH=LiPO2F2+H2O；Or 2HPO2F2+Li2CO3=2LiPO2F2+H2O+CO2.The application, without using lithium hexafluoro phosphate commonly used in the prior art, it is low can to reduce reaction cost using difluorophosphoric acid and lithium carbonate or lithium hydroxide as primary raw material；And it is easily controlled in preparation process without using the pernicious gases such as fluorine gas, course of reaction, safety coefficient is high, and equipment cost is low；Course of reaction is solid-liquid reaction, and raw material among purpose product with being free of gas, therefore the purity of raw material and product is easily controllable, convenience in transport, and raw material availability is high, so as to reduce cost.
Description
Technical field
The present invention relates to a kind of preparation method of difluorophosphoric acid salt, specially a kind of preparation method of difluorophosphate.
Background technology
In the last few years, lithium-ion-power cell and energy-storage battery had become one of new energy field study hotspot.Currently,
For lithium ion power battery cathode material mainly based on LiFePO 4 and nickel-cobalt-manganese ternary material, electrolyte is with hexafluorophosphoric acid
Lithium (LiPF6) collocation carbonate based organic solvent liquid electrolytic liquid system based on.
And in tertiary cathode material system, difluorophosphate (LiPO is added in right amount2F2) it can reduce the internal resistance of cell, and
Anode forms diaphragm so that the cycle performance of battery is obviously improved；Meanwhile in the ferrous phosphate of high compacted density
In lithium positive pole system, difluorophosphate is added in electrolyte as electrolytic salt so that the cryogenic property of battery is substantially carried
It is high.In addition, difluorophosphate is higher to moisture tolerance, therefore it is less demanding to production environment, easily carries out industrial metaplasia
Production；And reduce it and the possibility of adverse reaction occurs in applied to cell process.Difluorophosphate is due to above-mentioned
Clear advantage and receive much concern.
Preparation on difluorophosphate in the prior art, a part are the decomposition generation unstripped gas using lithium hexafluoro phosphate
Body prepares difluorophosphate.As disclosed in patent document CN200580043400.X by including carbonate and/or phosphate
Raw material salt contacted with the unstrpped gas being made up of P and F and the O optionally contained and carry out reaction be made, unstrpped gas can
Be by lithium hexafluoro phosphate decompose be made.But there is the defects of obvious in the method.Firstly, since using lithium hexafluoro phosphate as
Reaction raw materials, and the price of lithium hexafluoro phosphate is higher so that its production cost is higher, is not suitable for producing in enormous quantities；Secondly
It is the haptoreaction by unstrpped gas and raw material salt in course of reaction, due to being related to gas in reaction raw materials, and gas is joined
With reaction so that the yield of reaction reduces, and practical operation is also more complicated, and adverse effect is brought to actual production.
Another part is to prepare difluorophosphate using the electrolyte of lithium hexafluoro phosphate.Such as patent document
Recorded in CN200880007432.8 former by reaction of the halide such as lithium hexafluorophosphate electrolyte solution and lithium chloride, lithium bromide
Material, and add a small amount of moisture with provide reaction needed for oxygen atom, prepare difluorophosphate.This method is intrinsic scarce there is also some
Fall into.First, also due to being used as reaction raw materials using lithium hexafluoro phosphate so that production cost is higher；Secondly, six in electrolyte
Lithium fluophosphate, which decomposes, to be difficult to control, and reaction temperature is too high to cause lithium hexafluoro phosphate to resolve into the excessive phosphorous oxide of high activity five,
Side reaction product is caused to increase.
Some is to prepare difluorophosphate by hazardous gases such as fluorine gas.Including：Patent document
React to obtain the gaseous mixture containing single fluorodioxy phosphorus by pyrophosphate and fluorine gas disclosed in CN201410537713.1, then should
Gaseous mixture, which is passed into react in the anhydrous hydrogen fluoride solution of lithium fluoride, is made difluorophosphate product；Patent document
Lithium fluoride is set to be in contact with phosphorus pentafluoride gas disclosed in CN201380050491.4, and under the conditions of existing for a small amount of moisture
Difluorophosphate is made in reaction.Due to having used the hazardous gases such as fluorine gas, five phosphorous oxides in these methods, production danger coefficient compared with
It is high；And in order to ensure production safety, it is necessary to the use to gas is accurately controlled, prevent gases did escape so that raw
Production. art is increasingly complex；Further, since gas participates in reaction, it is also difficult to ensures higher raw material availability.
Due to drawbacks described above in the prior art be present, it is therefore desirable to a kind of synthetic method of new difluorophosphate is provided,
It can solve the problem that the problem of prior art is present.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation method of difluorophosphate, it is solid-liquid reaction, raw
It is low to produce cost, it is simple to operate, and the yield of product is high.
A kind of preparation method of difluorophosphate, it is characterised in that composition principle includes difluorophosphoric acid and existed with lithium hydroxide
Haptoreaction or difluorophosphoric acid and lithium carbonate haptoreaction in nonaqueous solvents in nonaqueous solvents；The nonaqueous solvents includes two
The bad nonaqueous solvents of the benign nonaqueous solvents or difluorophosphate of lithium fluophosphate；Reaction equation includes：
HPO2F2+ LiOH=LiPO2F2+H2O；
Or 2HPO2F2+Li2CO3=2LiPO2F2+H2O+CO2。
Preferably, the purity of the difluorophosphoric acid is more than 96%, and the purity of the lithium carbonate is more than 98%, the hydrogen
The purity of lithia is more than 98%.
Preferably, the purity of the difluorophosphoric acid is more than 99%, and the purity of the lithium carbonate is more than 99%, the hydrogen
The purity of lithia is more than 99%.
A kind of preparation method of difluorophosphate, reaction dissolvent include the benign nonaqueous solvents of difluorophosphate, specific step
Suddenly include：
(1), back flow reaction
A, lithium hydroxide and difluorophosphoric acid are weighed in proportion or weigh lithium carbonate and difluorophosphoric acid in proportion, it is standby；
B, above-mentioned load weighted lithium hydroxide or lithium carbonate are added in the benign nonaqueous solvents of difluorophosphate, stirred
Mix, obtain uniform mixture；
C, at the reaction temperatures, the difluorophosphoric acid of above-mentioned weighing is slowly added dropwise to said mixture；
D, keep at the reaction temperatures, at the uniform velocity stirring 2-10 hours, obtaining reaction product；
(2), mother liquid disposal
A, by the filtered processing of above-mentioned reaction product, filtrate is obtained；
B, deicer is added into above-mentioned filtrate, uniform stirring 0.5-2 hours, obtains the filtrate of dewater treatment；
C, by the concentrating filter liquor of above-mentioned dewater treatment, crystallization, drying process, final product difluorophosphate is obtained.
Preferably, the benign nonaqueous solvents of the difluorophosphate includes glycol dimethyl ether, ethylene glycol diethyl ether, contracting two
Glycol dimethyl ether, triethylene Glycol dimethyl ether, four condensed ethandiol dimethyl ether, tetrahydrofuran, oxinane, 2- methyl tetrahydrochysene furans
Mutter, the one or more in alkylol or alkyl ketone.
Preferably, the mol ratio of the lithium carbonate and difluorophosphoric acid is more than 0.5.
Preferably, the mol ratio of the lithium carbonate and difluorophosphoric acid is 0.5-1.
Preferably, the mol ratio of the lithium carbonate and difluorophosphoric acid is 0.5-0.6.
Preferably, the mol ratio of the lithium hydroxide and difluorophosphoric acid is more than 1.
Preferably, the mol ratio of the lithium hydroxide and difluorophosphoric acid is 1-1.5.
Preferably, the mol ratio of the lithium hydroxide and difluorophosphoric acid is 1-1.2.
Preferably, the deicer includes：Lithium metal silk or phosphorus pentoxide.
Preferably, the method for the concentration includes rotary evaporation or falling film evaporation；The method of the crystallization includes dissolved knot
Brilliant or crystallisation by cooling；The method of the drying includes vacuum drying or fluidized drying；The reaction temperature only ensures that reaction is normal
Occur.
Preferably, reaction temperature is 20-120 DEG C.
A kind of preparation method of difluorophosphate, reaction dissolvent be difluorophosphate bad nonaqueous solvents, specific steps
Including：
(1) crystallization reacts
A, lithium hydroxide and difluorophosphoric acid are weighed in proportion or weigh lithium carbonate and difluorophosphoric acid in proportion, it is standby；
B, above-mentioned load weighted lithium hydroxide or lithium carbonate are added in the bad nonaqueous solvents of difluorophosphate, stirred
Mix, obtain uniform mixture；
C, above-mentioned load weighted difluorophosphoric acid is well mixed with the bad nonaqueous solvents of the difluorophosphate, reacted
At a temperature of, it is slowly dropped in said mixture；
D, keep at the reaction temperatures, at the uniform velocity stirring, obtaining reaction product；
(2), product separates
A, by the filtered processing of above-mentioned product, solid product is obtained；
B, above-mentioned solid product is obtained into final product after drying process.
Preferably, the bad nonaqueous solvents of the difluorophosphate include chain type carbonic ester, ring type carbonic ester, chain type ester or
Ring type ester one or more therein.
Preferably, the bad nonaqueous solvents of the difluorophosphate is including dimethyl carbonate, diethyl carbonate, carbonic acid two just
Propyl ester, diisopropyl carbonate, dibutyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, carbonic acid first isopropyl ester, carbonic acid first butyl ester, carbon
Sour second propyl ester, ethylene isopropyl ester, vinyl carbonate, propylene carbonate, butylene carbonic ester, methyl formate, Ethyl formate, acetic acid
Methyl esters, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolacton or gamma-valerolactone are therein
It is one or more.
Preferably, the bad nonaqueous solvents of the difluorophosphate includes carbonate-based solvent.
Preferably, the bad nonaqueous solvents of the difluorophosphate includes low boiling chain type carbonic ester.
Preferably, the mol ratio of the lithium carbonate and difluorophosphoric acid is below 0.5.
Preferably, the mol ratio of the lithium carbonate and difluorophosphoric acid is 0.25-0.5.
Preferably, the mol ratio of the lithium carbonate and difluorophosphoric acid is 0.4-0.5.
Preferably, the mol ratio of the lithium hydroxide and difluorophosphoric acid is below 1.
Preferably, the mol ratio of the lithium hydroxide and difluorophosphoric acid is 0.5-1.
Preferably, the mol ratio of the lithium hydroxide and difluorophosphoric acid is 0.8-1.
Preferably, reaction temperature is less than 200 DEG C；Reaction time is 2-10h.
Preferably, reaction temperature is 30-120 DEG C.
Preferably, the dosage of the solvent should meet that solid-to-liquid ratio is 5%-50%.
Preferably, the difluorophosphoric acid is prepared through chemical reaction, and the chemical equation of reaction includes：
KH2PO4+2HSO3F=HPO2F2+KHSO4+H2SO4；
H3PO4+2SO3+2CaF2=HPO2F2+2HF+2CaSO4；
H3PO4+2POF3=3HPO2F2；
POF3+HNO3=HPO2F2+NO2F；
P2O3F4+H2O=2HPO2F2；
Or POF3+H2O=HPO2F2+HF。
Preferably, the preparation method of the difluorophosphoric acid is：Fluosulfonic acid is weighed under ar gas environment protection, in 5 DEG C of constant temperature bars
Potassium dihydrogen phosphate is slowly added under part while stirring, continues stirring 2 hours；It is evaporated under reduced pressure after the completion of reaction and produces colourless liquid two
Fluorophosphoric acid.
Beneficial effect：
First, the application is using difluorophosphoric acid and lithium carbonate or lithium hydroxide as primary raw material, without using in the prior art
Conventional lithium hexafluoro phosphate, it is low production cost can be reduced.And without using the pernicious gases such as fluorine gas, reaction in preparation process
Process is easily controlled, and safety coefficient is high, and equipment cost is low；Course of reaction is solid-liquid reaction, among raw material and purpose product not
Containing gas, the purity of raw material and product is easily controllable, raw material and product all convenience in transport, and raw material availability is high, so as to reduce into
This.
Reaction product difluorophosphate can be completely dissolved in the benign nonaqueous solvents of difluorophosphate, and reaction raw materials
Lithium carbonate or lithium hydroxide are almost insoluble wherein, are liquid condition under difluorophosphoric acid normal temperature, lithium carbonate is controlled in course of reaction
Or lithium hydroxide is excessive, unique solute is reaction product difluorophosphate in the benign nonaqueous solvents of difluorophosphate, reaction
Unreacted lithium carbonate or lithium hydroxide are removed after end, it is possible to realize the separation of product and raw material.During back flow reaction,
By constantly stirring reactant can be made sufficiently to contact, accelerate reaction speed, save the reaction time；Constantly stir and may be used also
With the carbon dioxide of discharge reaction generation, raw material availability is improved, reduces and wastes, reduce cost.Reaction passes through filtering after terminating
Unreacted lithium carbonate or lithium hydroxide can be removed, then solution is concentrated, crystallized and drying process, you can is reacted
Product difluorophosphate, obtained product purity are high.Whole preparation method is simple to operate, and safety coefficient is high, and yield is high, before development
Scape is good.
Reactant difluorophosphate and reaction raw materials lithium carbonate or hydrogen in the bad nonaqueous solvents of difluorophosphate
Lithia not readily dissolves, and reaction raw materials difluorophosphoric acid is liquid, need to only control difluorophosphoric acid excessive in course of reaction, ensure
Lithium carbonate or difluorophosphate reaction are complete, react after terminating through being filtrated to get filter residue, just very easily realize product and raw material
Separation.Difluorophosphoric acid is slowly added dropwise into reaction solution in crystallization course of reaction, increases raw material availability, reduces and wastes, section
About cost；Persistently stirred after being added dropwise to complete, reactant is fully contacted, accelerate reaction rate；Lasting stirring can also discharge anti-
The carbon dioxide that should be generated, raw material availability is improved, save cost.React after terminating through being filtrated to get filter residue, enter to filter residue
Row dries purification and can obtain final product difluorophosphate, and the purity of product is high, and the yield of this method is high.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1-4
Reaction principle is that lithium carbonate and difluorophosphoric acid react in the benign nonaqueous solvents of difluorophosphate, reaction equation
For：2HPO2F2+Li2CO3=2LiPO2F2+H2O+CO2。
Specific steps include：
(1), back flow reaction
1., weigh lithium carbonate and difluorophosphoric acid in proportion, it is standby；Ensure that lithium carbonate is excessive, to avoid obtaining after the completion of reaction
To solution in contain unreacted difluorophosphoric acid, so as to cause the purity of product to reduce, yield reduce；
2., above-mentioned load weighted lithium carbonate is added in the benign nonaqueous solvents of appropriate difluorophosphate, stir, obtain
To uniform mixture；Stable system can be made by obtaining uniform mixture, and lithium carbonate can be dispersed in a solvent；Solvent
Usage amount to ensure that reaction product difluorophosphate can be completely dissolved；
3., the difluorophosphoric acid of above-mentioned weighing is slowly added dropwise under reaction temperature to said mixture；Keep at the reaction temperatures
Dropwise addition can be such that compound is reacted during dropwise addition, can save the reaction time, improve efficiency；
4., keep at the reaction temperatures, at the uniform velocity stir 2-10 hours, obtain reaction product；Reaction time and reaction temperature
Influence each other, reaction temperature is high, and reaction rate is fast, and short the time required to reaction, reaction temperature is low, and yield is high, but the reaction time is grown；
Quickening reaction rate is continuously agitated, saves the reaction time；The carbon dioxide that reaction can simultaneously generated is discharged faster.
(2), mother liquid disposal
A, by the filtered processing of above-mentioned reaction product, filtrate is obtained；Filtering includes pressure filtration or vacuum filtration；
B, deicer is added into above-mentioned filtrate, uniform stirring 0.5-2 hours, obtains the filtrate of dewater treatment；Uniformly stir
Mixing makes deicer dispersed in system, can make the moisture in deicer fully contact system, reach the effect being fully dehydrated
Fruit, be advantageous to improve the purity of product；Deicer includes lithium metal silk or phosphorus pentoxide；
C, by the concentrating filter liquor of above-mentioned dewater treatment, crystallization, drying process, final product difluorophosphate is obtained；It is dense
Contracting includes rotary evaporation or falling film evaporation；Crystallization includes dilution crystallization or crystallisation by cooling；Dry to include being dried in vacuo or seethe with excitement and do
It is dry.
The experiment parameter and the yield of final product that embodiment 1-4 is related in experimentation are specifically as shown in table 1：
Table 1
From the above results, the mol ratio of lithium carbonate and difluorophosphoric acid is 0.55, wherein lithium carbonate mistake in embodiment 4
Amount, is prepared difluorophosphate, the yield of final product is up to 94.12% by it.
Embodiment 5-8
Reaction principle is that lithium hydroxide and difluorophosphoric acid react in the benign nonaqueous solvents of difluorophosphate, reactional equation
Formula is：HPO2F2+ LiOH=LiPO2F2+H2O；
Specific steps include：
(1), back flow reaction
1., weigh lithium hydroxide and difluorophosphoric acid in proportion, it is standby；Ensure that lithium hydroxide is excessive, to avoid reaction from completing
Contain unreacted difluorophosphoric acid in the solution obtained afterwards, so as to cause the purity of product to reduce, yield reduces；
2., above-mentioned load weighted lithium hydroxide is added in the benign nonaqueous solvents of appropriate difluorophosphate, stir,
Obtain uniform mixture；Stable system can be made by obtaining uniform mixture, and lithium hydroxide can be dispersed in a solvent；
The usage amount of solvent will ensure that reaction product difluorophosphate can be completely dissolved；
3., the difluorophosphoric acid of above-mentioned weighing is slowly added dropwise to said mixture at the reaction temperatures；It is maintained at reaction temperature
Lower dropwise addition can be such that compound is reacted during dropwise addition, can save the reaction time, improve efficiency；
4., keep at the reaction temperatures, at the uniform velocity stir 2-10 hours, obtain reaction product；Reaction time and reaction temperature
Influence each other, reaction temperature is high, and reaction rate is fast, and short the time required to reaction, reaction temperature is low, and yield is high, but the reaction time is grown；
Quickening reaction rate is continuously agitated, saves the reaction time.
(2), mother liquid disposal
A, by the filtered processing of above-mentioned reaction product, filtrate is obtained；Filtering includes pressure filtration or vacuum filtration；
B, deicer is added into above-mentioned filtrate, uniform stirring 0.5-2 hours, obtains the filtrate of dewater treatment；Uniformly stir
Mixing makes deicer dispersed in system, can make the moisture in deicer fully contact system, reach the effect being fully dehydrated
Fruit, be advantageous to improve the purity of product；Deicer includes lithium metal silk or phosphorus pentoxide；
C, by the concentrating filter liquor of above-mentioned dewater treatment, crystallization, drying process, final product difluorophosphate is obtained；It is dense
Contracting includes rotary evaporation or falling film evaporation；Crystallization includes dilution crystallization or crystallisation by cooling；Dry to include being dried in vacuo or seethe with excitement and do
It is dry.
The experiment parameter and the yield of final product that embodiment 5-8 is related in experimentation are specifically as shown in table 2：
Table 2
From the above results, the mol ratio of lithium hydroxide and difluorophosphoric acid is 1.1, wherein lithium hydroxide in embodiment 8
It is excessive, difluorophosphate is prepared by it, the yield of final product is up to 88.24%.
Embodiment 9-12
Reaction principle is that lithium carbonate and difluorophosphoric acid react in the bad nonaqueous solvents of difluorophosphate, reaction equation
For：2HPO2F2+Li2CO3=2LiPO2F2+H2O+CO2。
Specific steps include：
(1) crystallization reacts
1., weigh lithium carbonate and difluorophosphoric acid in proportion, it is standby；Control difluorophosphoric acid excessive, make the lithium carbonate in system
Reaction is complete, so that all difluorophosphates of solid insoluble in end reaction system, to ensure the purity of product；
2., above-mentioned load weighted lithium carbonate is added in the bad nonaqueous solvents of difluorophosphate, stir, obtain uniformly
Mixture；The usage amount of bad aqueous solvent will meet lithium carbonate dispersed requirement wherein；Simultaneously because reaction terminates
Some unreacted difluorophosphoric acid can be dissolved in solvent afterwards, and the boiling point of difluorophosphoric acid not easily passs through drying at 115.9 DEG C
Remove, so should try one's best the solubility of reduction difluorophosphoric acid to improve the purity of product, i.e. the usage amount of solvent should try one's best more；
3., above-mentioned load weighted difluorophosphoric acid is well mixed with the bad nonaqueous solvents of the difluorophosphate, 30-
At 120 DEG C, it is slowly dropped in said mixture；First difluorophosphoric acid is well mixed with bad aqueous solvent, then is added dropwise to reaction
System, system can be made to be rapidly achieved balance, accelerate reaction rate；
4., under same temperature, at the uniform velocity stir 2-10 hours, obtain reaction product；Reaction time and the mutual shadow of reaction temperature
Ring, reaction temperature is high, and reaction rate is fast, and short the time required to reaction, reaction temperature is low, and yield is high, but the reaction time is grown；Ceaselessly
Reaction rate is accelerated in stirring, saves the reaction time.
(2), product separates
A, by the filtered processing of above-mentioned product, filter residue is obtained；Filter residue main component is reaction product difluorophosphate, and two
There is a small amount of solvent on lithium fluophosphate surface, it is necessary to be purified by drying process；Filtering includes vacuum filtration or pressure filtration；
B, above-mentioned solid product is obtained into final product after drying process；Difluorophosphate can be removed through drying process
The solvent on surface, and the boiling point of solvent is lower, is more removed easily by drying process；Drying includes fluidized drying or vacuum is done
It is dry.
The experiment parameter and the yield of final product that embodiment 9-12 is related in experimentation are specific such as the institute of table 3
Show：
Table 3
From the above results, the mol ratio of lithium carbonate and difluorophosphoric acid is 0.45, wherein difluorophosphoric acid in embodiment 12
It is excessive, difluorophosphate is prepared by it, the yield of final product is up to 84.54%.
Embodiment 13-16
Reaction principle is that lithium hydroxide and difluorophosphoric acid react in the bad nonaqueous solvents of difluorophosphate, reactional equation
Formula is：HPO2F2+ LiOH=LiPO2F2+H2O。
Specific steps include：
(1) crystallization reacts
1., weigh lithium hydroxide and difluorophosphoric acid in proportion, it is standby；Control difluorophosphoric acid excessive, control difluorophosphoric acid mistake
Amount, the lithium hydroxide in system is set to react complete, so that all difluorophosphates of solid insoluble in end reaction system,
To ensure the purity of product；
2., above-mentioned load weighted lithium hydroxide is added in the bad nonaqueous solvents of difluorophosphate, stir, obtain
Even mixture；The usage amount of bad aqueous solvent will meet lithium hydroxide dispersed requirement wherein；Simultaneously because reaction
Some unreacted difluorophosphoric acid can be dissolved after end in solvent, and the boiling point of difluorophosphoric acid not easily passs through at 115.9 DEG C
Dry and remove, so should try one's best the solubility of reduction difluorophosphoric acid to improve the purity of product, i.e. the usage amount of solvent should use up
Amount is more；
3., above-mentioned load weighted difluorophosphoric acid is well mixed with the bad nonaqueous solvents of the difluorophosphate, 30-
At 120 DEG C, it is slowly dropped in said mixture；First difluorophosphoric acid is well mixed with bad aqueous solvent, then is added dropwise such as reaction
System, the system that makes that can be quickly reach balance, accelerate reaction rate；
4., under same temperature, at the uniform velocity stir 2-10 hours, obtain reaction product；Reaction time and the mutual shadow of reaction temperature
Ring, reaction temperature is high, and reaction rate is fast, and short the time required to reaction, reaction temperature is low, and yield is high, but the reaction time is grown；Ceaselessly
Reaction rate is accelerated in stirring, saves the reaction time.
(2), product separates
A, by the filtered processing of above-mentioned product, filter residue is obtained；Filter residue main component is reaction product difluorophosphate, and two
There is a small amount of solvent on lithium fluophosphate surface, it is necessary to be purified by drying process；
B, above-mentioned solid product is obtained into final product after drying process；Difluorophosphate can be removed through drying process
The solvent on surface, and the boiling point of solvent is lower, is more removed easily by drying process.
The experiment parameter and the yield of final product that embodiment 13-16 is related in experimentation are specific such as the institute of table 4
Show：
Table 4
From the above results, the mol ratio of lithium hydroxide and difluorophosphoric acid is 0.9, wherein difluorophosphoric acid in embodiment 16
It is excessive, difluorophosphate is prepared by it, the yield of final product is up to 82.15%.
Embodiment 17
Fluosulfonic acid 98.17g is weighed under ar gas environment protection, is at the uniform velocity stirred under 5 DEG C of constant temperatures and is slowly added into di(2-ethylhexyl)phosphate
Hydrogen potassium 70.06g, it is further continued for stirring 2 hours；After the completion of reaction, it is evaporated under reduced pressure, obtains under 50 DEG C and 8mm Hg post vacuum
Bright colorless fraction, yield are about 86.16%.
It the above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited to reality shown in this article
Example is applied, all technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that led for this technology
For the those of ordinary skill in domain, some modifications and retouching without departing from the principles of the present invention also should be regarded as the present invention's
Protection domain.
Claims (10)
1. a kind of preparation method of difluorophosphate, it is characterised in that composition principle includes difluorophosphoric acid with lithium hydroxide non-
Haptoreaction or difluorophosphoric acid and lithium carbonate haptoreaction in nonaqueous solvents in aqueous solvent；The nonaqueous solvents includes difluoro
The bad nonaqueous solvents of the benign nonaqueous solvents or difluorophosphate of lithium phosphate；Reaction equation includes：
HPO2F2+ LiOH=LiPO2F2+H2O；
Or 2HPO2F2+Li2CO3=2LiPO2F2+H2O+CO2。
A kind of 2. preparation method of difluorophosphate according to claim 1, it is characterised in that the difluorophosphoric acid it is pure
Degree is more than 96%, and the purity of the lithium carbonate is more than 98%, and the purity of the lithium hydroxide is more than 98%.
A kind of 3. preparation method of difluorophosphate according to claim 1 or 2, it is characterised in that reaction dissolvent two
The benign nonaqueous solvents of lithium fluophosphate, specific steps include：
(1), back flow reaction
1., weigh lithium hydroxide and difluorophosphoric acid in proportion or weigh lithium carbonate and difluorophosphoric acid in proportion, it is standby；
2., above-mentioned load weighted lithium hydroxide or lithium carbonate be added in the benign nonaqueous solvents of difluorophosphate, stir, obtain
To uniform mixture；
3., at the reaction temperatures, the difluorophosphoric acid of above-mentioned weighing is slowly added dropwise to said mixture；
4., keep at the reaction temperatures, at the uniform velocity stir 2-10 hours, obtain reaction product；
(2), mother liquid disposal
A, by the filtered processing of above-mentioned reaction product, filtrate is obtained；
B, deicer is added into above-mentioned filtrate, uniform stirring 0.5-2 hours, obtains the filtrate of dewater treatment；
C, by the concentrating filter liquor of above-mentioned dewater treatment, crystallization, drying process, final product difluorophosphate is obtained.
4. the preparation method of a kind of difluorophosphate according to claim 3, it is characterised in that the difluorophosphate
Benign nonaqueous solvents include glycol dimethyl ether, ethylene glycol diethyl ether, diglycol ethylene dimethyl ether, triethylene Glycol dimethyl ether,
Four condensed ethandiol dimethyl ether, tetrahydrofuran, oxinane, 2- methyltetrahydrofurans, alkylol or one kind or more in alkyl ketone
Kind.
5. the preparation method of a kind of difluorophosphate according to claim 3, it is characterised in that the lithium carbonate and difluoro
The mol ratio of phosphoric acid is more than 0.5.
6. the preparation method of a kind of difluorophosphate according to claim 3, it is characterised in that the lithium hydroxide and two
The mol ratio of fluorophosphoric acid is more than 1.
A kind of 7. preparation method of difluorophosphate according to claim 1 or 2, it is characterised in that reaction dissolvent two
The bad nonaqueous solvents of lithium fluophosphate, specific steps include：
(1) crystallization reacts
1., weigh lithium hydroxide and difluorophosphoric acid in proportion or weigh lithium carbonate and difluorophosphoric acid in proportion, it is standby；
2., above-mentioned load weighted lithium hydroxide or lithium carbonate be added in the bad nonaqueous solvents of difluorophosphate, stir, obtain
To uniform mixture；
3., above-mentioned load weighted difluorophosphoric acid is well mixed with the bad nonaqueous solvents of the difluorophosphate, in reaction temperature
Under degree, it is slowly dropped in said mixture；
4., keep at the reaction temperatures, at the uniform velocity stir, obtain reaction product；
(2), product separates
A, by the filtered processing of above-mentioned product, solid product is obtained；
B, above-mentioned solid product is obtained into final product after drying process.
8. the preparation method of a kind of difluorophosphate according to claim 7, it is characterised in that the difluorophosphate
Bad nonaqueous solvents includes chain type carbonic ester, ring type carbonic ester, chain type ester or ring type ester.
9. the preparation method of a kind of difluorophosphate according to claim 7, it is characterised in that the lithium carbonate and difluoro
The mol ratio of phosphoric acid is below 0.5.
A kind of 10. preparation method of difluorophosphate according to claim 7, it is characterised in that the lithium hydroxide with
The mol ratio of difluorophosphoric acid should be below 1.
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| CN108423651A (en) * | 2018-05-23 | 2018-08-21 | 上海如鲲新材料有限公司 | A method of preparing difluorophosphate |
| CN108910857A (en) * | 2018-09-26 | 2018-11-30 | 王静静 | A kind of preparation method of difluorophosphate |
| CN112158816A (en) * | 2020-09-24 | 2021-01-01 | 湖南博信新能源科技有限公司 | Method for simultaneously preparing high-purity difluorophosphoric acid and high-purity lithium difluorophosphate |
| CN112320782A (en) * | 2020-11-13 | 2021-02-05 | 临沂小篆新材料科技有限公司 | Process for preparing lithium difluorophosphate |
| KR102219684B1 (en) * | 2020-04-20 | 2021-02-24 | (주)부흥산업사 | A method for preparing litium difluorophosphate |
| CN113336214A (en) * | 2021-07-15 | 2021-09-03 | 西安荣岩科技发展有限公司 | Preparation method of lithium difluorophosphate |
| CN115215316A (en) * | 2021-04-15 | 2022-10-21 | 浙江省化工研究院有限公司 | Preparation method of lithium difluorophosphate |
| WO2024002386A1 (en) * | 2022-10-18 | 2024-01-04 | 山东海科创新研究院有限公司 | Preparation method for lithium difluorophosphate and product obtained therefrom |
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