CN109053415A - A kind of preparation method of tetrafluoro oxalic acid lithium phosphate - Google Patents
A kind of preparation method of tetrafluoro oxalic acid lithium phosphate Download PDFInfo
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- CN109053415A CN109053415A CN201810737755.8A CN201810737755A CN109053415A CN 109053415 A CN109053415 A CN 109053415A CN 201810737755 A CN201810737755 A CN 201810737755A CN 109053415 A CN109053415 A CN 109053415A
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- C07C51/41—Preparation of salts of carboxylic acids
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Abstract
The invention discloses a kind of preparation methods of tetrafluoro oxalic acid lithium phosphate, it is characterized in that, include the following steps: that lithium hexafluoro phosphate is dissolved in aprotic solvent by (1), oxalic acid or ammonium oxalate, phosphorus pentachloride or phosphorus trichloride is added, reaction obtains tetrafluoro oxalic acid lithium phosphate；(2) poor solvent, which is added, is precipitated the tetrafluoro oxalic acid lithium phosphate generated crystallization；(3) it is filtered, washed, dries to get tetrafluoro oxalic acid lithium phosphate.Method and process of the invention is simple, and advantages of nontoxic raw materials, danger coefficient is low, and the reaction time is short, high income, can be effectively controlled metal ion and anionic impurity content, can prepare high-purity tetrafluoro oxalic acid lithium phosphate target product.
Description
Technical field
The present invention relates to field of lithium ion battery, can be used in non-aqueous electrolyte for lithium ion cell electricity more particularly, to one kind
The preparation method of the tetrafluoro oxalic acid lithium phosphate of pond additive.
Background technique
Tetrafluoro oxalic acid lithium phosphate can be used as the additive of lithium ion battery.The preparation side of known tetrafluoro oxalic acid lithium phosphate
Method the, such as (patent name: the preparation method of tetrafluoro (oxalate conjunction) phosphate solution of patent document one；The patent No.:
CN201380028506.7), method is dissolved in the depositing in silicon tetrachloride reaction promoter of the lithium hexafluoro phosphate in organic solvent
It is reacted lower with oxalic acid.In this method, the solution of the lithium phosphate of oxalic acid containing tetrafluoro can only obtain, organic solvent not can be removed, wherein
Chloride ion, free acid and other soluble impurities are difficult to remove, and product purity is lower, can cause not to lithium ion battery characteristic
Good influence.Meanwhile this method uses highly volatile and virose silicon tetrachloride liquid, therefore reaction is difficult to control and be accompanied by
It is dangerous.
A kind of (the patent name: preparation method of tetrafluoro oxalic acid lithium phosphate of patent document two；The patent No.:
CN201510570831.7 it) is reacted using phosphorus pentachloride with hydrofluoric acid and prepares phosphorus pentafluoride, phosphorus pentafluoride is passed through lithium oxalate
Hydrogen fluoride solution is allowed to reaction and generates tetrafluoro oxalic acid lithium phosphate.This method reaction is complicated, and step is more, and product is associated with hexafluoro phosphorus
Sour lithium is difficult to separate, while using anhydrous hydrofluoric acid in preparation process twice, and reaction consumption is big and with dangerous, unsuitable industry
Metaplasia produces.
Summary of the invention:
It is an object of the invention to overcome the deficiencies of existing technologies, providing one kind can be used in lithium ion battery non-aqueous solution electrolysis
The preparation method of the tetrafluoro oxalic acid lithium phosphate of solution battery additive.
The invention adopts the following technical scheme:
A kind of preparation method of tetrafluoro oxalic acid lithium phosphate, which comprises the steps of:
(1) lithium hexafluoro phosphate is dissolved in aprotic solvent, oxalic acid or ammonium oxalate, phosphorus pentachloride or trichlorine is added
Change phosphorus, reaction obtains tetrafluoro oxalic acid lithium phosphate；
(2) poor solvent, which is added, is precipitated the tetrafluoro oxalic acid lithium phosphate generated crystallization；
(3) it is filtered, washed, dries to get tetrafluoro oxalic acid lithium phosphate.
Preferably, the addition molar ratio of the lithium hexafluoro phosphate, oxalic acid or ammonium oxalate and phosphorus pentachloride is 1:
(0.9~1.1): (0.36~0.44).
Preferably, the addition molar ratio of the lithium hexafluoro phosphate, oxalic acid or ammonium oxalate and phosphorus trichloride is 1:
(0.9~1.1): (0.6~0.73).
Preferably, the addition phosphorus pentachloride is the solution or suspension of phosphorus pentachloride solid or phosphorus pentachloride.
Preferably, the addition phosphorus trichloride is phosphorus trichloride liquid, or the solution containing phosphorus trichloride.
Preferably, the range that the temperature of the reaction is 0~50 DEG C.
Preferably, the aprotic solvent be linear carbonate, cyclic carbonate, cyclic ester, chain ester, cyclic ether,
One of chain ether, nitrile or multiple combinations.
Preferably, the poor solvent is cyclic carbonate, linear carbonate, cyclic ester, chain ester, cyclic ether, chain
One of shape ether, nitrile, petroleum ether, n-hexane, hexamethylene, toluene, ethylbenzene, methylene chloride, chloroform, dichloroethanes or
It is a variety of to be mixed with arbitrary proportion.
Preferably, the mass ratio of the aprotic solvent and poor solvent is 1:5~1:25.
Preferably, the temperature of the crystallization is -25 DEG C~50 DEG C；The drying is vacuum drying, and vacuum degree is -0.01
~-0.1MPa, drying temperature are 40 DEG C~120 DEG C.
In the present invention, when oxalic acid or oxalates encounter lithium hexafluoro phosphate, tetrafluoro oxalic acid lithium phosphate and hydrofluoric acid can be generated
Or the salt of hydrofluoric acid, since hydrofluoric acid has certain solubility in organic solvent, which is a balanced reaction, is added five
The salt of phosphorus chloride or phosphorus trichloride and hydrofluoric acid or hydrofluoric acid generates phosphorus trifluoride or phosphorus pentafluoride gas escapes, so that generating
The reaction of tetrafluoro oxalic acid lithium phosphate constantly carries out.
Aprotic solvent need to dissolve a certain amount of oxalic acid perhaps ammonium oxalate when oxalic acid or ammonium oxalate are almost totally insoluble
When, it reacts very slow, is unfavorable for reaction and carries out.
In the present invention, it is described reaction carried out preferably in closed container, it is described reaction in the environment of inert gas into
Row, the inert gas are selected from one of nitrogen, helium, argon gas and neon.
It is of the present invention reaction preferably be stirred to react, the present invention for stirring concrete mode without limit, ability
Known to field technique personnel.
Preferably, the mass ratio of the aprotic solvent and poor solvent is between 1:5~1:25.It is furthermore preferred that non-
The mass ratio of proton solvent and poor solvent is between 1:8~1:15.
When poor solvent is in shortage, product is precipitated not enough, and product yield is lower；When poor solvent excess, in product
While precipitation, also have impurity precipitation, it is therefore preferable that the mass ratio of aprotic solvent and poor solvent be 1:5~1:25 it
Between, it is highly preferred that the mass ratio of aprotic solvent and poor solvent is 1:8~1:15.
Aprotic solvent in the present invention is linear carbonate, cyclic carbonate, cyclic ester, chain ester, cyclic ether, chain
One of ether and nitrile or multiple combinations, include but are not limited to ethylene carbonate, butylene carbonate, pentylene,
Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, ethylene carbonate, propene carbonate, gamma-butyrolacton,
Methyl formate, Ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, second
Sour isobutyl ester, propyl propionate, isopropyl propionate, dimethyl ether, diethyl ether, dipropyl ether, t-butyl methyl ether, 1,1- dimethyl ethane,
1,2- dimethoxy-ethane, ethylene oxide, tetrahydrofuran, propylene oxide, acetonitrile, propionitrile.It is preferred that dimethyl carbonate, carbonic acid two
Ethyl ester, dipropyl carbonate, methyl ethyl carbonate, ethylene carbonate, propene carbonate, gamma-butyrolacton, methyl formate, Ethyl formate,
Propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, isopropyl propionate, dimethyl ether, diethyl
One of ether, dipropyl ether, 1,1- dimethyl ethane, 1,2- dimethoxy-ethane, tetrahydrofuran, propylene oxide, acetonitrile are more
Kind combination.
Poor solvent in the present invention is cyclic carbonate, linear carbonate, cyclic ester, chain ester, cyclic ether, chain
The mixing of one or more of ether, nitrile, alkanes, substituted benzene, chloralkane arbitrary proportion.Include but are not limited to carbonic acid
Ethyl, butylene carbonate, pentylene, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, carbonic acid
Vinyl acetate, propene carbonate, gamma-butyrolacton, methyl formate, Ethyl formate, propyl formate, butyl formate, ethyl acetate, acetic acid
Propyl ester, isopropyl acetate, butyl acetate, isobutyl acetate, propyl propionate, isopropyl propionate, dimethyl ether, diethyl ether, dipropyl ether,
T-butyl methyl ether, 1,1- dimethyl ethane, 1,2- dimethoxy-ethane, ethylene oxide, tetrahydrofuran, propylene oxide, acetonitrile, third
Nitrile, petroleum ether, n-hexane, hexamethylene, toluene, ethylbenzene, methylene chloride, chloroform, dichloroethanes.It is preferred that tetrahydrofuran, ring
Ethylene Oxide, acetonitrile.It is preferred that ethylene carbonate, dimethyl carbonate, diethyl carbonate, Ethyl formate, propyl formate, propyl propionate,
Dimethyl ether, diethyl ether, ethylene oxide, tetrahydrofuran, acetonitrile, acetonitrile, propionitrile, petroleum ether, n-hexane, hexamethylene, toluene, second
Benzene, methylene chloride, dichloroethanes.
Beneficial effects of the present invention:
1, the present invention provides a kind of methods for preparing tetrafluoro oxalic acid phosphoric acid powder for lithium.
2, method and process of the invention is simple, and the reaction time is short, high income, can be effectively controlled metal ion and anion is miscellaneous
Matter content can prepare high-purity tetrafluoro oxalic acid lithium phosphate target product.
3, advantages of nontoxic raw materials of the present invention, danger coefficient are low.
Detailed description of the invention
The P of the tetrafluoro oxalic acid lithium phosphate prepared in Fig. 1 embodiment 1 composes nuclear-magnetism figure.
Specific embodiment
The present invention will be further described in detail below with reference to specific embodiments.
Embodiment 1:
In dry argon gas glove box, dry methyl ethyl carbonate (EMC) 228g, side stirring are added into three-neck flask
Add lithium hexafluoro phosphate (LiPF in side6) 76.0g (0.5mol), it is dissolved, phosphorus pentachloride 41.6g is then put into flask
(0.2mol), flask are connected with valvular gas conduit, another two mouthfuls of caps flatly.Flask is taken out into glove box, is impregnated
It is stirred in ice-water bath.After half an hour, it is slowly passed through argon gas into flask, opens simultaneously a bottle stopper, makes in flask in argon
The atmosphere of gas shielded is added anhydrous oxalic acid 45.0g (0.5mol) into flask rapidly, is then sufficiently stirred.Slowly increase water-bath
To 10 DEG C or more, reaction starts to carry out temperature, and the gas of generation flows into the solution equipped with sodium hydroxide and absorbs.Continue slowly to increase
Temperature to solid dissolves, solution went clear, and keeps the temperature one hour at 35 DEG C, and reaction is released without gas indicates that reaction terminates.In argon
Under the protection of air-flow, dichloroethanes 800mL is added into flask, slowly stirs at 25 DEG C and is precipitated to crystal, stops stirring, it is brilliant
After body sedimentation, filtering is washed with dichloroethanes, is transferred to vacuum oven drying, and vacuum degree is -0.01~-0.1MPa, dry temperature
Degree is 60 DEG C, obtains white solid 50.4g, yield 80%.
The present invention uses obtained product31P-NMR and19F-NMR is analyzed and identified, and NMR is with deuterated DMSO
For solvent, carried out on the basis of TMS.Fig. 1 is the P spectrum nuclear-magnetism figure that tetrafluoro oxalic acid lithium phosphate is made in the present embodiment,31P-NMP is shown
Product purity is greater than 99.5%.There are the quintet of tetrafluoro oxalic acid lithium phosphate, warp between displacement -134~-150 as seen from the figure
It is accredited as tetrafluoro oxalic acid lithium phosphate.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 2:
In dry argon gas glove box, dry dimethyl carbonate (DMC) 304.0g is added into three-neck flask, while stirring
Mix side addition lithium hexafluoro phosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid is then put into flask
22.5g (0.25mol), takes out glove box for flask, is impregnated in 35 DEG C of stirred in water bath, and constantly stir mixture.Using solid
Body feeder is slowly added into phosphorus pentachloride 20.8 (0.1mol) g, and reaction takes place.The gas of generation, which flows into, is equipped with sodium hydroxide
Solution absorb.It is 1.5 hours time-consuming to add phosphorus pentachloride, then keeps the temperature one hour at 35 DEG C, reaction is released without gas indicates anti-
It should terminate.Under the protection of argon gas stream, hexamethylene 1800mL is added into flask, slowly stirs and is precipitated to crystal.Reduce water-bath
Extremely -10 DEG C of temperature, stop stirring, after crystal sedimentation, filtering is washed with hexamethylene, is transferred to vacuum oven drying, vacuum degree
For -0.01~-0.1MPa, drying temperature is 80 DEG C, obtains white solid 34.6g, yield 69%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 3:
In dry argon gas glove box, dry diethyl carbonate (DEC) 152.0g is added into three-neck flask, while stirring
Mix side addition lithium hexafluoro phosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid ammonium is then put into flask
31.0g (0.25mol), takes out glove box for flask, is impregnated in 40 DEG C of stirred in water bath, and constantly stir mixture.Use perseverance
Phosphorus trichloride 22.9g (0.16mol) is slowly added dropwise in pressure dropping funel, and reaction takes place.The gas of generation, which flows into, is equipped with hydrogen-oxygen
The solution for changing sodium absorbs.It is 1 hour time-consuming that phosphorus trichloride is added dropwise, then keeps the temperature one hour at 40 DEG C, reaction is released without gas and indicated
Reaction terminates.Under the protection of argon gas stream, dichloroethanes 800mL is added into flask, slowly stirs and is precipitated to crystal.Reduce water
Bath temperature stops stirring to 0 DEG C, and after crystal sedimentation, filtering is washed with dichloroethanes, is transferred to vacuum oven drying, vacuum degree
For -0.01~-0.1MPa, drying temperature is 100 DEG C, obtains white solid 36.4g, yield 72%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 4:
In dry argon gas glove box, dry dimethyl carbonate, diethyl carbonate, carbonic acid are added into three-neck flask
The total 304.0g of dipropyl, methyl ethyl carbonate, ethylene carbonate, propene carbonate, gamma-butyrolacton (each component quality is average), side
It stirs side and adds lithium hexafluoro phosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid is then put into flask
20.26g (0.225mol), takes out glove box for flask, is impregnated in 0 DEG C of stirred in water bath, and constantly stir mixture.Using solid
Body feeder is slowly added into the suspension containing phosphorus pentachloride 22.9 (0.11mol) g, and reaction takes place.The gas stream of generation
Enter the solution equipped with sodium hydroxide to absorb.It is 1.5 hours time-consuming to add phosphorus pentachloride, then keeps the temperature one hour at 0 DEG C, reacts without gas
Body, which is released, indicates that reaction terminates.Under the protection of argon gas stream, hexamethylene 1800mL is added into flask, slowly stirs and is analysed to crystal
Out.Bath temperature is reduced to -25 DEG C, stops stirring, after crystal sedimentation, filtering is washed with hexamethylene, and it is dry to be transferred to vacuum oven
Dry, vacuum degree is -0.01~-0.1MPa, and drying temperature is 120 DEG C, obtains white solid 34.6g, yield 69%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 5:
In dry argon gas glove box, dry methyl formate, Ethyl formate, formic acid third are added into three-neck flask
The total 304.0g of ester, butyl formate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate (each component quality is average), while stirring
Mix side addition lithium hexafluoro phosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid ammonium is then put into flask
34.13g (0.275mol), takes out glove box for flask, is impregnated in 15 DEG C of stirred in water bath, and constantly stir mixture.It uses
Feeder for solid materials is slowly added into phosphorus pentachloride solid 18.74 (0.09mol) g, and reaction takes place.The gas inflow of generation is equipped with
The solution of sodium hydroxide absorbs.It is 1.5 hours time-consuming to add phosphorus pentachloride, then keeps the temperature one hour at 15 DEG C, reaction is put without gas
Indicate that reaction terminates out.Under the protection of argon gas stream, hexamethylene 1800mL is added into flask, slowly stirs and is precipitated to crystal.
Bath temperature is reduced to -10 DEG C, stops stirring, after crystal sedimentation, filtering is washed with hexamethylene, and it is dry to be transferred to vacuum oven
Vacuum degree is -0.01~-0.1MPa, and drying temperature is 40 DEG C, obtains white solid 34.6g, yield 69%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 6:
In dry argon gas glove box, added into three-neck flask dry isopropyl propionate, dimethyl ether, diethyl ether,
Dipropyl ether, 1,1- dimethyl ethane, the total 152.0g of 1,2- dimethoxy-ethane (each component quality is average), add six while stirring
Lithium fluophosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid ammonium 34.13g is then put into flask
Flask is taken out glove box by (0.275mol), is impregnated in 40 DEG C of stirred in water bath, and constantly stir mixture.It is dripped using constant pressure
Phosphorus trichloride liquid 24.72g (0.18mol) is slowly added dropwise in liquid funnel, and reaction takes place.The gas of generation, which flows into, is equipped with hydrogen-oxygen
The solution for changing sodium absorbs.It is 1 hour time-consuming that phosphorus trichloride is added dropwise, then keeps the temperature one hour at 40 DEG C, reaction is released without gas and indicated
Reaction terminates.Under the protection of argon gas stream, n-hexane, hexamethylene, toluene, the total 800mL of ethylbenzene are added into flask, and (ratio is appointed
Meaning), it slowly stirs and is precipitated to crystal.Bath temperature is reduced to 0 DEG C, stops stirring, after crystal sedimentation, poor mixing is used in filtering
Solvent washing is transferred to vacuum oven drying, obtains white solid 36.4g, yield 72%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 7:
In dry argon gas glove box, dry tetrahydrofuran 152.0g is added into three-neck flask, is added while stirring
Add lithium hexafluoro phosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid 20.26g is then put into flask
Flask is taken out glove box by (0.225mol), is impregnated in 50 DEG C of stirred in water bath, and constantly stir mixture.It is dripped using constant pressure
The solution containing phosphorus trichloride 20.60g (0.15mol) is slowly added dropwise in liquid funnel, and reaction takes place.The gas of generation flows into dress
There is the solution of sodium hydroxide to absorb.It is 1 hour time-consuming that phosphorus trichloride is added dropwise, then keeps the temperature one hour at 50 DEG C, reaction is put without gas
Indicate that reaction terminates out.Under the protection of argon gas stream, acetonitrile, acetonitrile, propionitrile, the total 800mL (ratio of petroleum ether are added into flask
Arbitrarily), it slowly stirs and is precipitated to crystal.Stop stirring, after crystal sedimentation, filtering is washed with poor mixing solvent, is transferred to vacuum
Drying box is dry, obtains white solid 36.4g, yield 72%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 8:
In dry argon gas glove box, dry dimethyl carbonate (DMC) 304.0g is added into three-neck flask, while stirring
Mix side addition lithium hexafluoro phosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid is then put into flask
20.26g (0.225mol), takes out glove box for flask, is impregnated in 0 DEG C of stirred in water bath, and constantly stir mixture.Using solid
Body feeder is slowly added into the solution containing phosphorus pentachloride 22.9g (0.11mol), and reaction takes place.The gas of generation flows into
Solution equipped with sodium hydroxide absorbs.It is 1.5 hours time-consuming to add phosphorus pentachloride, then keeps the temperature one hour at 0 DEG C, reacts without gas
Releasing indicates that reaction terminates.Under the protection of argon gas stream, dimethyl ether, diethyl ether, ethylene oxide, tetrahydrofuran are added into flask
Total 1800mL (ratio is any) is slowly stirred and is precipitated to crystal.Bath temperature is reduced to -25 DEG C, stops stirring, crystal sedimentation
Afterwards, it filters, is washed with poor mixing solvent, be transferred to vacuum oven drying, vacuum degree is -0.01~-0.1MPa, drying temperature
It is 120 DEG C, obtains white solid 34.6g, yield 69%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 9:
In dry argon gas glove box, dry propylene oxide 304.0g is added into three-neck flask, is added while stirring
Add lithium hexafluoro phosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid ammonium 34.13g is then put into flask
Flask is taken out glove box by (0.275mol), is impregnated in 15 DEG C of stirred in water bath, and constantly stir mixture.Using solid plus
Glassware is slowly added into phosphorus pentachloride solid 18.74 (0.09mol) g, and reaction takes place.The gas of generation, which flows into, is equipped with hydroxide
The solution of sodium absorbs.It is 1.5 hours time-consuming to add phosphorus pentachloride, then keeps the temperature one hour at 15 DEG C, reaction is released without gas and indicated
Reaction terminates.Under the protection of argon gas stream, Ethyl formate, propyl formate, the total 1800mL (ratio of propyl propionate are added into flask
Arbitrarily), it slowly stirs and is precipitated to crystal.Reduction bath temperature stops stirring and filters after crystal sedimentation, use is bad to -10 DEG C
Mixed solvent washing, being transferred to the dry vacuum degree of vacuum oven is -0.01~-0.1MPa, and drying temperature is 40 DEG C, obtains white
Solid 34.6g, yield 69%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Embodiment 10:
In dry argon gas glove box, dry acetonitrile 152.0g is added into three-neck flask, adds six while stirring
Lithium fluophosphate (LiPF6) 38.0g (0.25mol), it is dissolved, anhydrous oxalic acid ammonium 34.13g is then put into flask
Flask is taken out glove box by (0.275mol), is impregnated in 40 DEG C of stirred in water bath, and constantly stir mixture.It is dripped using constant pressure
Phosphorus trichloride liquid 24.72g (0.18mol) is slowly added dropwise in liquid funnel, and reaction takes place.The gas of generation, which flows into, is equipped with hydrogen-oxygen
The solution for changing sodium absorbs.It is 1 hour time-consuming that phosphorus trichloride is added dropwise, then keeps the temperature one hour at 40 DEG C, reaction is released without gas and indicated
Reaction terminates.Under the protection of argon gas stream, ethylene carbonate, dimethyl carbonate, the total 800mL of diethyl carbonate are added into flask
(ratio is any) slowly stirs and is precipitated to crystal.Bath temperature is reduced to 0 DEG C, stops stirring, after crystal sedimentation, filtering, with not
Good mixed solvent washing, is transferred to vacuum oven drying, obtains white solid 36.4g, yield 72%.
The content of chloride ion is analyzed using turbidimetry, specifically: 0.5g solid sample is taken, 8mL deionized water is dissolved in,
After bubble completely disappears, 1mL AgNO is added3/HNO3Solution (AgNO3: HNO3: H2O=1:65:34, mass ratio), then will
Acquired solution is diluted to 25mL with distilled water, compares determining chloride ion range with standard sample turbidity.Chloride ion content is low
In 5ppm.
Above-described embodiment is merely illustrative of the technical solution of the present invention and is not intended to limit it, all without departing from the present invention
Any modification of spirit and scope or equivalent replacement should all cover the range in technical solution of the present invention.
Claims (10)
1. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate, which comprises the steps of:
(1) lithium hexafluoro phosphate is dissolved in aprotic solvent, oxalic acid or ammonium oxalate, phosphorus pentachloride or tri-chlorination is added
Phosphorus, reaction obtain tetrafluoro oxalic acid lithium phosphate；
(2) poor solvent, which is added, is precipitated the tetrafluoro oxalic acid lithium phosphate generated crystallization；
(3) it is filtered, washed, dries to get tetrafluoro oxalic acid lithium phosphate.
2. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the hexafluoro phosphorus
The addition molar ratio of sour lithium, oxalic acid or ammonium oxalate and phosphorus pentachloride is 1:(0.9~1.1): (0.36~0.44).
3. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the hexafluoro phosphorus
The addition molar ratio of sour lithium, oxalic acid or ammonium oxalate and phosphorus trichloride is 1:(0.9~1.1): (0.6~0.73).
4. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the addition five
Phosphorus chloride is the solution or suspension of phosphorus pentachloride solid or phosphorus pentachloride.
5. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the addition three
Phosphorus chloride is phosphorus trichloride liquid, or the solution containing phosphorus trichloride.
6. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the temperature of the reaction
The range that degree is 0~50 DEG C.
7. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that described is non-proton
Solvent is one of linear carbonate, cyclic carbonate, cyclic ester, chain ester, cyclic ether, chain ether, nitrile or a variety of groups
It closes.
8. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that described is bad molten
Agent is cyclic carbonate, linear carbonate, cyclic ester, chain ester, cyclic ether, chain ether, nitrile, petroleum ether, n-hexane, hexamethylene
One of alkane, toluene, ethylbenzene, methylene chloride, chloroform, dichloroethanes a variety of are mixed with arbitrary proportion.
9. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that described is non-proton
The mass ratio of solvent and poor solvent is 1:5~1:25.
10. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the crystallization
Temperature is -25 DEG C~50 DEG C；The drying is vacuum drying, and vacuum degree is -0.01~-0.1MPa, and drying temperature is 40 DEG C
~120 DEG C.
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| CN110240617A (en) * | 2019-06-19 | 2019-09-17 | 上海如鲲新材料有限公司 | A kind of preparation method of difluoro dioxalic acid lithium phosphate |
| CN112442086A (en) * | 2019-09-03 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | Novel preparation method of phosphorus-containing lithium salt |
| CN109850926B (en) * | 2019-01-18 | 2021-08-24 | 武汉海斯普林科技发展有限公司 | Preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate |
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| CN109850926B (en) * | 2019-01-18 | 2021-08-24 | 武汉海斯普林科技发展有限公司 | Preparation method of lithium tetrafluoro oxalate phosphate and lithium difluorobis oxalate phosphate |
| CN110003277A (en) * | 2019-05-05 | 2019-07-12 | 上海如鲲新材料有限公司 | A kind of tetrafluoro oxalic acid lithium phosphate and preparation method thereof |
| CN110240617A (en) * | 2019-06-19 | 2019-09-17 | 上海如鲲新材料有限公司 | A kind of preparation method of difluoro dioxalic acid lithium phosphate |
| CN112442086A (en) * | 2019-09-03 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | Novel preparation method of phosphorus-containing lithium salt |
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