CN106829910A - A kind of preparation method of difluorophosphate - Google Patents
A kind of preparation method of difluorophosphate Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
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Abstract
A kind of preparation method of difluorophosphate, comprises the following steps：By LiPF under the first heating-up temperature6It is added in the carbonic ester suspension of carbonate；Reaction obtains difluorophosphate (LiPO under the second heating-up temperature2F2)；Wherein, second heating-up temperature is higher than first heating-up temperature.Preparation method process is simple, low cost and obtained product purity is high that the present invention is provided.
Description
Technical field
The invention belongs to power lithium-ion battery manufacturing technology field, specifically a kind of lithium battery additive difluorophosphate
Preparation method.
Background technology
At present, driven by products such as smart mobile phone, portable power source, panel computers, domestic lithium battery industry production value persistently increases
It is long.At the same time, the application of lithium ion battery has been no longer limited to consumable electronic product, the two new applications of power and energy storage
The direction market space unlimited for lithium battery brings.In the years to come, lithium ion battery by turn into one constantly expand
Global industry.Meanwhile, with the expansion of its suitable application area, to the further requirement for improving battery behavior also more and more higher.
There are some researches show in the electrolytic solution addition difluorophosphate can improve lithium rechargeable battery low-temperature characteristics,
The battery performances such as cycle characteristics, preservation characteristics.The preparation of difluorophosphate is generally adopted with the following method：Such as, using P2O3F4With
Slaine or NH3React to prepare difluorophosphoric acid salt, this method accessory substance is numerous, it is difficult to realize to isolate and purify；By two
The reaction of fluorophosphoric acid and metal chloride prepares difluorophosphoric acid salt, in product can residual fraction chlorion, influence battery performance；
Using LiPF6Mix with LiCl, the method for then passing to vapor obtains difluorophosphate, and the method raw material is cheap, but reaction
It is not easily controlled, accessory substance is numerous, it is difficult to purify, is not suitable for large-scale production；Using LiPF6Difluorophosphoric acid is prepared with water reaction
Lithium, the reaction is not easily controlled, and can produce LiPO4F etc. influences the impurity of battery performance, and is not easily purified, it is difficult to obtain
High purity product.In addition, CN 101847753A disclose a kind of preparation in simple method using general inexpensive materials can use
Make the difluorophosphoric acid salt of secondary cell non-water electrolytic solution additive, the difluorophosphoric acid salt is existed by lithium hexafluoro phosphate and carbonate
React what is prepared in nonaqueous solvents.Difluorophosphoric acid salt prepared by the method is solution, for promoting the use not for difluorophosphoric acid salt
It is very convenient, and has the fluoride salt for being slightly soluble in solvent in the middle of difluorophosphoric acid salting liquid, may to being produced in lithium battery with it
Can negatively affect.
From the above, there is many disadvantages, or complex process, high cost in existing preparation method, it is difficult to industrialized production,
Or yield is low, accessory substance is more, is not easily purified, the difluorophosphoric acid purity salt for preparing is low, influences properties of product.
The content of the invention
Therefore, the technical problems to be solved by the invention are to provide a kind of preparation method of difluorophosphate.The present invention
The preparation method process is simple of offer, low cost and obtained product purity is high.
It is that, up to above-mentioned purpose, the present invention uses following technological means：
A kind of preparation method of difluorophosphate, comprises the following steps：
By LiPF under the first heating-up temperature6It is added in the carbonic ester suspension of carbonate；Under the second heating-up temperature
Reaction obtains difluorophosphate (LiPO2F2)；
Wherein, second heating-up temperature is higher than first heating-up temperature.Preferably, preparation method bag of the invention
Include following steps：
(1) by LiPF under the first heating-up temperature6It is added in the carbonic ester suspension of carbonate, then in the second heating
At a temperature of react, second heating-up temperature be higher than first heating-up temperature；Reaction equation is following：
LiPF6+2Li2CO3=4LiF+2CO2+LiPO2F2
(2) filtration step (1) gained reaction solution；
(3) step (2) gained filter cake is dissolved in organic solvent and is filtered afterwards, filtrate is lithium fluoride；
(4) gained wet product is dried to obtain the difluorophosphate after step (3) being filtered into gained filtrate evaporation.
Preferably, the second heating-up temperature first heating-up temperature is high 5-25 DEG C, for example, 7 DEG C, 9 DEG C, 13
DEG C, 16 DEG C, 20 DEG C, 23 DEG C etc..
Preferably, first heating-up temperature is 45-70 DEG C, for example, 48 DEG C, 52 DEG C, 57 DEG C, 61 DEG C, 66 DEG C etc., excellent
Elect 55-65 DEG C as, second heating-up temperature is 65-85 DEG C, for example, 68 DEG C, 72 DEG C, 75 DEG C, preferably 79 DEG C etc., 68-80
DEG C, more preferably 75 DEG C.
Controlling the first temperature contributes to lithium carbonate to spread in a solvent, is conducive to the reaction of second step.LiPF6It is attached at 80 DEG C
It is near to have begun to thermally decompose generation, when such as reaction is very close to the temperature, has a small amount of catabolite and produce, cause yield meeting partially
It is low.Therefore, setting said temperature can both realize required temperature by setting the design temperature of high temperature and low temperature circulating device.Above-mentioned temperature
Degree setting can obtain higher yields.
Preferably, the preparation of the carbonic ester suspension of carbonate and reaction is carried out in glove box environment.
Preferably, the heating is carried out by high temperature and low temperature circulating device.
Preferably, in the carbonic ester suspension of carbonate lithium carbonate concentration be 1-3mol/L, for example, 1.2mol/L,
1.6mol/L, 1.9mol/L, 2.2mol/L, 2.6mol/L, 2.9mol/L etc., preferably 1.5-2mol/L.
The carbonic ester suspension of carbonate can be completed by the way that carbonate is added in carbonic ester under agitation, stirring
Speed is not particularly limited, such as can be 250r/min.
Preferably, LiPF6It is 1 with the mol ratio of carbonate:0.5-5, for example, 1:0.7、1:0.9、1:1.2、1:1.5、
1:2、1:2.5、1:3.1、1:3.8、1:4.2、1:4.8 etc., preferably 1:1-3, more preferably 1:2.4.
Preferably, by LiPF6It is slowly added into the carbonic ester suspension of carbonate.
Preferably, the time of adition process is more than 5 minutes, more preferably preferably 5-20 minutes, 10 minutes.
Observing response temperature during feeding intake, it is preferable that the temperature control of adition process is below 72 DEG C.
Preferably, the reaction is carried out under agitation.
Preferably, the time of the reaction is more than 1 hour, more preferably preferably 1-6 hours, 6 hours.
Preferably, the carbonate is the carbonate of alkali metal or alkaline-earth metal, preferably lithium carbonate.Can using lithium carbonate
Obtain the product of higher purity.
Preferably, the carbonic ester is diethyl carbonate (DEC).
Preferably, filtered described in step (2) using pressurization closed formula filter, the aperture of preferred filters is 5 μm.
Preferably, filter nitrogen protection during filtering.
Preferably, filtration step (1) gained filter cake evaporation drying, the gas of evaporation drying discharge is condensed by condenser,
Recycle.
Preferably, organic solvent described in step (3) be lithium fluoride indissoluble solvent, preferably glycol dimethyl ether and/
Or acetonitrile, more preferably acetonitrile.
Preferably, filter cake is dissolved in organic solvent is carried out by stirring.
Preferably, the time of the stirring is more than 1 hour, preferably 2 hours.
Preferably, the filtering uses pressurization closed formula filter, and the aperture of preferred filters is 2 μm.
Preferably, drying is carried out in vibrating dryer described in step (4).
Preferably, nitrogen protection when drying.
Preferably, the flow of nitrogen is 5-20L/min, preferably 10L/min.
Preferably, temperature when drying is 70-90 DEG C, and preferably 78-82 DEG C, the dry time is more than 5 hours, preferably
It is 10 hours.
Preferably, after evaporation solution evaporation, condensation are recycled.Evaporimeter outlet is provided with condensing unit, condensed
Liquid can be recycled again.
Preferably, preparation method of the invention comprises the following steps：
(1) in glove box environment, toward the PFA containers of 1L in add 600mL DEC, while open magnetic stirring apparatus, make
Stirrer in PFA containers is started working, and speed of agitator is 250r/min, then adds 1mol lithium carbonates, is formed it into suspended
Liquid；
(2) high temperature and low temperature circulating device is opened, PFA containers is heated, temperature control starts slow throwing at 55~65 DEG C
Plus 0.5mol LiPF6, add the time 10 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C；Feed intake
After the completion of temperature in PFA containers is risen to 72~73 DEG C using high temperature and low temperature circulating device, continue stirring reaction 2 hours.Observation has
Gas overflowing, liquid is suspension；
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using FPA materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers；
(4) toward the glycol dimethyl ether of addition 200mL in the PFA containers of 500mL, magnetic stirring apparatus is opened, makes PFA containers
Interior stirrer is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 2 hours so that LiPO2F2Dissolving
In solvent, LIF is extremely difficult to be dissolved in glycol dimethyl ether；
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PFA Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process2Keep 10L/min, drying temperature to control between 78~82 DEG C, dry
Time 10h is obtained target product.
The present invention with lithium hexafluoro phosphate, lithium carbonate as raw material, using DEC/ lithium fluoride indissoluble solvents as reaction and separate
The solvent of purification prepares difluorophosphate, and various raw material sources enrich, and raw material is easy to get and inexpensively, low production cost, technique
Process is simple, and product yield is high, the advantages of good product quality.Difluorophosphate product purity can obtained in the method for the present invention
More than 99.9% is reached, the actual demand of power lithium-ion battery production is met.Therefore, the method for the present invention has good warp
Ji value and social value, easy popularization and application.
Brief description of the drawings
Fig. 1 is embodiment 619F-NMR collection of illustrative plates；
Fig. 2 is embodiment 619P-NMR collection of illustrative plates.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as to concrete restriction of the invention.
Embodiment 1
(1)LiPO2F2Synthesis：In glove box environment, toward the PFA containers of 1L in add 600mL DEC, while open
Magnetic stirring apparatus, makes the stirrer in PFA containers start working, and speed of agitator is 250r/min, then adds 1mol lithium carbonates,
Form it into suspension.
(2) high temperature and low temperature circulating device is opened, PFA containers is heated, at 62 DEG C, beginning is slowly added temperature control
0.5mol LiPF6, add the time 10 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
Temperature in PFA containers is risen to 72~73 DEG C into rear utilization high temperature and low temperature circulating device, continues stirring reaction 2 hours.Observation has gas
Body overflows, and liquid is suspension.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using FPA materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers.
(4) toward the glycol dimethyl ether of addition 200mL in the PFA containers of 500mL, magnetic stirring apparatus is opened, makes PFA containers
Interior stirrer is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 2 hours so that LiPO2F2Dissolving
In solvent, LIF is extremely difficult to be dissolved in glycol dimethyl ether.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PFA Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process210L/min, drying temperature is kept to control between 80 DEG C, drying time
10h, metering；Finished product 39.6g.
Embodiment 2
(1)LiPO2F2Synthesis：In glove box environment, toward the PFA containers of 1L in add 600mL DEC, while open
Magnetic stirring apparatus, makes the stirrer in PFA containers start working, and speed of agitator is 250r/min, then adds 1.2mol carbonic acid
Lithium, forms it into suspension.
(2) high temperature and low temperature circulating device is opened, PFA containers is heated, temperature control starts slow throwing at 55~65 DEG C
Plus 0.5mol LiPF6, add the time 10 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
After the completion of temperature in PFA containers is risen to 72~73 DEG C using high temperature and low temperature circulating device, continue stirring reaction 2 hours.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using FPA materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers.
(4) toward the glycol dimethyl ether of addition 200mL in the PFA containers of 500mL, magnetic stirring apparatus is opened, makes PFA containers
Interior stirrer is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 2 hours so that LiPO2F2Dissolving
In solvent.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PFA Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process2Keep 10L/min, drying temperature to control between 78~82 DEG C, dry
Time 10h, metering, finished product 40.4g.
Embodiment 3
(1)LiPO2F2Synthesis：In glove box environment, toward the PFA containers of 1L in add 600mL DEC, while open
Magnetic stirring apparatus, makes the stirrer in PFA containers start working, and speed of agitator is 250r/min, then adds 1.2mol carbonic acid
Lithium, forms it into suspension.
(2) high temperature and low temperature circulating device is opened, PFA containers is heated, temperature control starts slow throwing at 55~65 DEG C
Plus 0.5mol LiPF6, add the time 10 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
After the completion of temperature in PFA containers is risen to 75 DEG C using high temperature and low temperature circulating device, continue stirring reaction 2 hours.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using FPA materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers.
(4) toward the glycol dimethyl ether of addition 200mL in the PFA containers of 500mL, magnetic stirring apparatus is opened, makes PFA containers
Interior stirrer is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 2 hours so that LiPO2F2Dissolving
In solvent.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PFA Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process2Keep 10L/min, drying temperature to control between 78~82 DEG C, dry
Time 10h, metering, finished product 40.8g.
Embodiment 4
(1)LiPO2F2Synthesis：In glove box environment, toward the PFA containers of 1L in add 600mL DEC, while open
Magnetic stirring apparatus, makes the stirrer in PFA containers start working, and speed of agitator is 250r/min, then adds 1.2mol carbonic acid
Lithium, forms it into suspension.
(2) high temperature and low temperature circulating device is opened, PFA containers is heated, temperature control starts slow throwing at 55~65 DEG C
Plus 0.5mol LiPF6, add the time 10 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
After the completion of temperature in PFA containers is risen to 70 DEG C using high temperature and low temperature circulating device, continue stirring reaction 6 hours.Solution has a little
Discoloration.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using FPA materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers.
(4) toward the glycol dimethyl ether of addition 200mL in the PFA containers of 500mL, magnetic stirring apparatus is opened, makes PFA containers
Interior stirrer is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 2 hours so that LiPO2F2Dissolving
In solvent.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PFA Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process2Keep 10L/min, drying temperature to control between 78~82 DEG C, dry
Time 10h, metering, finished product 35.6g.
Embodiment 5
(1)LiPO2F2Synthesis：In glove box environment, toward the PFA containers of 1L in add 600mL DEC, while open
Magnetic stirring apparatus, makes the stirrer in PFA containers start working, and speed of agitator is 250r/min, then adds 1.2mol carbonic acid
Lithium, forms it into suspension.
(2) high temperature and low temperature circulating device is opened, PFA containers is heated, temperature control starts slow throwing at 55~65 DEG C
Plus 0.5mol LiPF6, add the time 10 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
After the completion of temperature in PFA containers is risen to 75 DEG C using high temperature and low temperature circulating device, continue stirring reaction 6 hours.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using FPA materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers.
(4) toward the glycol dimethyl ether of addition 200mL in the PFA containers of 500mL, magnetic stirring apparatus is opened, makes PFA containers
Interior stirrer is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 2 hours so that LiPO2F2Dissolving
In solvent.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PFA Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process2Keep 10L/min, drying temperature to control between 78~82 DEG C, dry
Time 10h, metering, finished product 44.8g.
Embodiment 6
(1)LiPO2F2Synthesis：In glove box environment, toward the PFA containers of 1L in add 600mL DEC, while open
Magnetic stirring apparatus, makes the stirrer in PFA containers start working, and speed of agitator is 250r/min, then adds 1.2mol carbonic acid
Lithium, forms it into suspension.
(2) high temperature and low temperature circulating device is opened, PFA containers is heated, temperature control starts slow throwing at 55~65 DEG C
Plus 0.5mol LiPF6, add the time 10 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
After the completion of temperature in PFA containers is risen to 75 DEG C using high temperature and low temperature circulating device, continue stirring reaction 6 hours.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using FPA materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers.
(4) toward the acetonitrile of addition 200mL in the PFA containers of 500mL, magnetic stirring apparatus is opened, makes the stirring in PFA containers
Son is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 2 hours so that LiPO2F2It is dissolved in solvent
In.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PFA Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process2Keep 10L/min, drying temperature to control between 78~82 DEG C, dry
Time 10h, metering, finished product 45.2g.
Embodiment 7
(1)LiPO2F2Synthesis：In glove box environment, toward the PTFE containers of 1L in add 600mL DEC, while opening
Magnetic stirring apparatus is opened, the stirrer in PTFE containers is started working, speed of agitator is 250r/min, then add 0.6mol carbon
Sour lithium, forms it into suspension.
(2) high temperature and low temperature circulating device is opened, PTFE containers is heated, at 45 DEG C, beginning is slowly added temperature control
0.12mol LiPF6, add the time 5 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
Temperature in PTFE containers is risen to 65 DEG C into rear utilization high temperature and low temperature circulating device, continues stirring reaction 5 hours.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using PTFE materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Body is condensed by condenser, is stored into stand-by in A containers.
(4) toward the acetonitrile of addition 200mL in the PTFE containers of 500mL, magnetic stirring apparatus is opened, makes stirring in PFA containers
Sub- start-up operation is mixed, the filter cake obtained by step C is added in glove box environment, stirred 1 hour so that LiPO2F2It is dissolved in solvent
In.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters PTFE Rotary Evaporators
Middle evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation is entered
To enter be dried in vibrating dryer, N in drying process25L/min, drying temperature is kept to control between 70 DEG C, drying time
20h, metering, finished product 4.67g.
Embodiment 8
(1)LiPO2F2Synthesis：In glove box environment, toward the PE containers of 1L in add 600mL DEC, while open
Magnetic stirring apparatus, makes the stirrer in PE containers start working, and speed of agitator is 250r/min, then adds 1.8mol carbonic acid
Lithium, forms it into suspension.
(2) high temperature and low temperature circulating device is opened, PE containers is heated, at 70 DEG C, beginning is slowly added temperature control
3.6mol LiPF6, add the time 20 minutes, observing response temperature during feeding intake, temperature control is below 68 DEG C.Feed intake
Temperature in PE containers is risen to 85 DEG C into rear utilization high temperature and low temperature circulating device, continues stirring reaction 1 hour.
(3) gained suspension is filtered by pressurization closed formula filter, 5 μm of pore size control, and gained filtrate is stored in A containers
Stand-by, filter cake is taken out in the rotary evaporator for entering and being made using PE materials, and drying, the gas of evaporation drying discharge is evaporated under reduced pressure
Condensed by condenser, be stored into stand-by in A containers.
(4) toward the acetonitrile of addition 200mL in the PE containers of 500mL, magnetic stirring apparatus is opened, makes the stirring in PFA containers
Son is started working, and the filter cake obtained by step C is added in glove box environment, is stirred 4 hours so that LiPO2F2It is dissolved in solvent
In.
(5) above-mentioned suspension is again introduced into adding pressure type filter, and aperture is 1 μm, and solution enters in PE Rotary Evaporators
Evaporation, evaporimeter outlet is provided with condensing unit, and it is stand-by that condensed liquid enters B containers.Wet product after rotary evaporation enters
It is dried in vibrating dryer, N in drying process220L/min, drying temperature is kept to control between 90 DEG C, drying time
5h, metering, finished product 13.5g.
Comparative example 1
Carried out according to embodiment 6, except the first heating-up temperature and the second heating-up temperature are 75 DEG C.
Comparative example 2
Carried out according to embodiment 6, except the first heating-up temperature and the second heating-up temperature are 55 DEG C.
NMR is detected
The product that above-described embodiment is obtained is taken into 0.4-0.5g in glove box, is dissolved with D- acetonitriles.After the completion of dissolving, will
Sample is put into 400MHZ nuclear magnetic resonance chemical analysers and carries out9F-NMR、31P-NMR is detected.
19F-NMR is analyzed to the product for obtaining, resonant frequency 376MHZ, chemical shift 79, doublet, two lines, leads to
Cross area normalization method to be calculated, the content of difluorophosphate can be drawn.
31P-NMR is analyzed to the product for obtaining, resonant frequency 162MHZ, chemical shift 127.61, three lines, passes through
Area normalization method is calculated, and can draw the content of difluorophosphate.
With31P-NMR is the product of further confirmatory reaction to sample test, and test wherein whether there is other containing phosphorus impurities.By
F spectrums are sensitive much compared with P spectrums in test process, cause and its micro phosphorus containg substances are composed inspection and do not measured by phosphorus.
Testing result see the table below 1.
The gained sample of embodiment 69F-NMR、31P-NMR detection collection of illustrative plates is shown in Fig. 1 and 2.
Product yield
Difluorophosphate product is carried out to product in above-described embodiment 1-8 and comparative example 1 and 2 according to prior art conventional method
Thing yield and content (product/theoretical product * 100%) detect that testing result see the table below 1.
Table 1
Temperature is heated higher than described first from second heating-up temperature of control that relatively can be seen that of comparative example 1,2 and embodiment 6
Spend and be significantly increased compared to the product yield and purity obtained using the heating of not temperature.
It can be seen that, the method for the invention is attempted with lithium hexafluoro phosphate and lithium carbonate as raw material first, using gradient-heated, with
Glycol dimethyl ether or acetonitrile are used as separating-purifying solvent, it is possible to achieve single sintering, are then peeled off accessory substance lithium fluoride etc. miscellaneous
Thing, purification prepares difluorophosphate, and the whole reaction time is shorter (within 6h), compared to what is mentioned in existing other document reports
Synthesis preparation method, efficiency is improved.Up to more than 83%, product yield is also obtained the product yield of the method for the invention
Lifting is arrived, product purity reaches more than 99.9%, the actual demand of power lithium-ion battery production can have been met completely.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of preparation method of difluorophosphate, it is characterised in that comprise the following steps：
By LiPF under the first heating-up temperature6It is added in the carbonic ester suspension of carbonate；Reacted under the second heating-up temperature
To difluorophosphate；
Wherein, second heating-up temperature is higher than first heating-up temperature.
2. preparation method according to claim 1, it is characterised in that methods described comprises the following steps：
(1) by LiPF under the first heating-up temperature6It is added in the carbonic ester suspension of carbonate, then in the second heating-up temperature
Lower reaction, second heating-up temperature is higher than first heating-up temperature；
(2) filtration step (1) gained reaction solution；
(3) step (2) gained filter cake is dissolved in organic solvent and is filtered afterwards；
(4) gained wet product is dried to obtain the difluorophosphate after step (3) being filtered into gained filtrate evaporation.
3. preparation method according to claim 1 and 2, it is characterised in that second heating-up temperature more described first plus
Hot temperature is high 5-25 DEG C；
Preferably, first heating-up temperature is 45-70 DEG C, and preferably 55-65 DEG C, second heating-up temperature is 65-85 DEG C,
Preferably 68-80 DEG C, more preferably 75 DEG C；
Preferably, the preparation of the carbonic ester suspension of carbonate and reaction is carried out in glove box environment；
Preferably, the heating is carried out by high temperature and low temperature circulating device.
4. the preparation method according to claim any one of 1-3, it is characterised in that carbon in the carbonic ester suspension of carbonate
The concentration of sour lithium is 1-3mol/L, preferably 1.5-2mol/L；
Preferably, LiPF6It is 1 with the mol ratio of carbonate:0.5-5, preferably 1:1-3, more preferably 1:2.4.
5. the preparation method according to claim any one of 1-4, it is characterised in that by LiPF6It is slowly added into carbonate
In carbonic ester suspension；
Preferably, the time of adition process is more than 5 minutes, more preferably preferably 5-20 minutes, 10 minutes；
Preferably, the temperature control of adition process is below 72 DEG C；
Preferably, the carbonate is the carbonate of alkali metal or alkaline-earth metal, preferably lithium carbonate；
Preferably, the carbonic ester is diethyl carbonate.
6. the preparation method according to claim any one of 1-5, it is characterised in that the reaction is carried out under agitation；
Preferably, the time of the reaction is more than 1 hour, more preferably preferably 1-6 hours, 6 hours.
7. the preparation method according to claim any one of 2-6, it is characterised in that filtered described in step (2) using plus
Pressure closed filter, the aperture of preferred filters is 5 μm；
Preferably, filter nitrogen protection during filtering；
Preferably, filtration step (1) gained filter cake evaporation drying, the gas of evaporation drying discharge is condensed by condenser, reclaimed
Utilize.
8. the preparation method according to claim any one of 2-7, it is characterised in that organic solvent is described in step (3)
Lithium fluoride indissoluble solvent, preferably glycol dimethyl ether and/or acetonitrile, more preferably acetonitrile；
Preferably, filter cake is dissolved in organic solvent is carried out by stirring；
Preferably, the time of the stirring is more than 1 hour, preferably 2 hours；
Preferably, the filtering uses pressurization closed formula filter, and the aperture of preferred filters is 2 μm.
9. the preparation method according to claim any one of 2-8, it is characterised in that dried in vibration described in step (4)
Drying machine is carried out；
Preferably, nitrogen protection when drying；
Preferably, the flow of nitrogen is 5-20L/min, preferably 10L/min.
10. the preparation method according to claim any one of 2-9, it is characterised in that temperature when being dried in step (4) is
70-90 DEG C, preferably 78-82 DEG C, the dry time is more than 5 hours, preferably 10 hours；
Preferably, after evaporation solution evaporation, condensation are recycled.
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| CN107226463A (en) * | 2017-07-07 | 2017-10-03 | 上海康鹏科技有限公司 | A kind of combined preparation process of difluorophosphoric acid lithium salts and tetrafluoro boric acid lithium salts |
| CN107381530A (en) * | 2017-08-23 | 2017-11-24 | 中山大学 | A kind of method of purification of difluorophosphate |
| CN107381531A (en) * | 2017-08-23 | 2017-11-24 | 中山大学 | A kind of preparation method of difluorophosphate |
| CN108128764A (en) * | 2017-11-16 | 2018-06-08 | 常州弘正新能源股份有限公司 | A kind of quick method for preparing difluorophosphate |
| CN108178139A (en) * | 2018-02-09 | 2018-06-19 | 天津金牛电源材料有限责任公司 | A kind of method that product yield is improved during difluorophosphate is prepared |
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| CN108751234A (en) * | 2018-06-29 | 2018-11-06 | 惠州市宙邦化工有限公司 | A kind of method of purification of lithium fluoride |
| CN108910857A (en) * | 2018-09-26 | 2018-11-30 | 王静静 | A kind of preparation method of difluorophosphate |
| CN109133023A (en) * | 2017-06-27 | 2019-01-04 | 天津金牛电源材料有限责任公司 | The circulation utilization method of nonaqueous solvents in a kind of difluorophosphate preparation process |
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| CN118164467A (en) * | 2024-05-09 | 2024-06-11 | 江苏创科新材料有限公司 | Lithium difluorophosphate production process and preparation system thereof |
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| CN109133023A (en) * | 2017-06-27 | 2019-01-04 | 天津金牛电源材料有限责任公司 | The circulation utilization method of nonaqueous solvents in a kind of difluorophosphate preparation process |
| CN109133023B (en) * | 2017-06-27 | 2021-12-31 | 天津金牛电源材料有限责任公司 | Method for recycling non-aqueous solvent in lithium difluorophosphate preparation process |
| CN107226463A (en) * | 2017-07-07 | 2017-10-03 | 上海康鹏科技有限公司 | A kind of combined preparation process of difluorophosphoric acid lithium salts and tetrafluoro boric acid lithium salts |
| CN107226463B (en) * | 2017-07-07 | 2019-09-03 | 上海康鹏科技股份有限公司 | A kind of combined preparation process of difluorophosphoric acid lithium salts and tetrafluoro boric acid lithium salts |
| CN107381530A (en) * | 2017-08-23 | 2017-11-24 | 中山大学 | A kind of method of purification of difluorophosphate |
| CN107381531A (en) * | 2017-08-23 | 2017-11-24 | 中山大学 | A kind of preparation method of difluorophosphate |
| CN108128764A (en) * | 2017-11-16 | 2018-06-08 | 常州弘正新能源股份有限公司 | A kind of quick method for preparing difluorophosphate |
| CN108376782A (en) * | 2018-01-23 | 2018-08-07 | 珠海市赛纬电子材料股份有限公司 | A kind of catalysis preparation method of difluorophosphate |
| CN108178139A (en) * | 2018-02-09 | 2018-06-19 | 天津金牛电源材料有限责任公司 | A kind of method that product yield is improved during difluorophosphate is prepared |
| CN108751234A (en) * | 2018-06-29 | 2018-11-06 | 惠州市宙邦化工有限公司 | A kind of method of purification of lithium fluoride |
| CN108910857A (en) * | 2018-09-26 | 2018-11-30 | 王静静 | A kind of preparation method of difluorophosphate |
| CN108910857B (en) * | 2018-09-26 | 2020-10-13 | 深圳市研一新材料有限责任公司 | Preparation method of lithium difluorophosphate |
| CN111924860A (en) * | 2020-09-14 | 2020-11-13 | 湖南博信新能源科技有限公司 | Preparation method of composite lithium salt concentrated solution |
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