CN109666046A - 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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- CN109666046A CN109666046A CN201710974353.5A CN201710974353A CN109666046A CN 109666046 A CN109666046 A CN 109666046A CN 201710974353 A CN201710974353 A CN 201710974353A CN 109666046 A CN109666046 A CN 109666046A
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- Prior art keywords
- oxalic acid
- preparation
- lithium phosphate
- acid lithium
- phosphorus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
Abstract
The invention discloses a kind of preparation methods of tetrafluoro oxalic acid lithium phosphate, this method specifically comprises the following steps: phosphorus simple substance and the phosphorus pentafluoride of fluorine gas reaction generation by reacting in the reaction kettle of surge tank importing lithium oxalate and organic solvent formation suspension, gas flow rate is controlled in 1~5L/min, it is preferred that 2L/min, the pressure, temperature variation of moment attentive response kettle in reaction process, control temperature, which is maintained between 10 DEG C~40 DEG C, in the process carries out, it is preferred that 30 DEG C, pressure maintains 0~0.5MPa, it is preferred that 0.1MPa, the molar ratio of phosphorus pentafluoride and lithium oxalate obtained is 2.2~2: 1, it is preferred that 2.05: 1, reaction is sufficiently stirred 1~3 hour, it is preferred that 2 hours, after filtering, by the way that crystallization mode is concentrated, through filtering, required product is obtained after drying.The problem of the purpose of the present invention is being directed to prior art and insufficient, the preparation method of improvement tetrafluoro oxalic acid lithium phosphate, so that the preparation cost of tetrafluoro oxalic acid lithium phosphate is reduced, raising product quality.
Description
Technical field
The present invention relates to lithium ion battery material manufacturing technology fields, more particularly to a kind of to be used for lithium-ion electric
The preparation method of pond addition agent of non-aqueous electrolyte tetrafluoro oxalic acid lithium phosphate.
Background technique
Tetrafluoro oxalic acid lithium phosphate is added mainly as the battery with nonaqueous electrolyte of lithium ion battery, lithium-ion capacitor etc.
Agent uses.This kind of additive can form more stable SEI membrane structure on cell positive material surface, effectively improve battery
Cycle performance and high-temperature behavior.The preparation method for this kind of additive being currently known is mainly the following.
US20100267984, which is mentioned, is mixed in lithium hexafluoro phosphate and lithium oxalate in pressure vessel, and be heated to 150 DEG C~
180 DEG C of reactions, then by obtained product, are dissolved in acetonitrile, filtering, decompression removal solvent, the product being recrystallized to give,
Tetrafluoro oxalic acid lithium phosphate product is obtained after being further dried.But not only reaction step is more for this method, consumption of calorie is big, but also not
Economy, and it is insufficient using this method reaction progress, and yield is lower.
EP1308449A2 is using lithium hexafluoro phosphate to be dissolved in organic solvent, in SiCl4As existing for reaction promoter
Under the conditions of react, obtain the solvent containing the product, then by way of vacuum distillation, remove organic solvent, to obtain
Required product.But using the product of this method preparation, lithium phosphate is closed containing difluoro bis- (oxalates) simultaneously, product purity is lower,
And is also contained by product prepared by this method and dysgenic chlorine compound is caused to battery behavior, be not suitable for industry metaplasia
It produces.
CN105218348A obtains phosphorus pentafluoride using phosphorus pentachloride and hydrogen fluoride reaction, with the grass being dissolved in hydrogen fluoride
Sour lithium reaction, the mixture of tetrafluoro oxalic acid lithium phosphate and lithium hexafluoro phosphate is obtained after evaporative crystallization, rapid draing, is then passed through
Means re-crystallization obtains tetrafluoro oxalic acid lithium phosphate.But the chloride ion that certain content is had using the product of this method preparation, is caused
Product quality decline, and then adverse effect is caused to battery performance.
Summary of the invention
In view of this, the problem of the purpose of the present invention is being directed to prior art and insufficient, improvement tetrafluoro oxalic acid phosphorus
The preparation method of sour lithium improves product quality to reduce the preparation cost of tetrafluoro oxalic acid lithium phosphate.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of tetrafluoro oxalic acid lithium phosphate, this method are to react using cheap industrial phosphorus with fluorine gas,
Then phosphorus pentafluoride needed for reaction is made passes through concentration crystallization side to react with the lithium oxalate being suspended in organic solvent
Formula obtains required product.
Its method particularly includes: take a certain amount of lithium oxalate to be placed in the 316L stainless steel Fluorine-lined reaction of jacketed and filter device
It in kettle, and is sufficiently stirred 1~2 hour, to be stirred for, forms uniform suspension, then another with collet and stirring dress
A certain amount of phosphorus simple substance is added in the 316L stainless steel Fluorine-lined reaction kettle set and fluorine gas is reacted, and by phosphorus pentafluoride obtained
Import lithium oxalate and organic solvent by surge tank and formed in the reaction kettle of suspension and reacted, gas flow rate control 1~
5L/min, the pressure, temperature variation of moment attentive response kettle in reaction process control temperature in the process and are maintained at 10 DEG C
It being carried out between~40 DEG C, pressure maintains 0~0.5MPa, and the molar ratio of phosphorus pentafluoride and lithium oxalate obtained is 2.2~2: 1,
Reaction is sufficiently stirred 1~3 hour, after filtering, by be concentrated crystallization mode, filtered, dry after obtain required product.
It is reacted involved in it and includes:
P+F2→PF5
PF5+Li2C2O4→LiC2O4PF4+LiPF6
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, the industrial phosphorus includes white phosphorus, red
One or more of phosphorus, black phosphorus.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, to guarantee that reaction is normally carried out, phosphorus and grass
The molar ratio of sour lithium is 2.2~2: 1, and product quality generated accounts for the 10%~30% of solution gross mass.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, the organic solvent can be completely dissolved
Generated product and hexafluorophosphoric acid in preparation process, and the organic solvent includes any one in esters, ethers or nitrile
Kind.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, the filter type after reaction uses filters pressing
Mode, preferably filter pressure are 2-3 atmospheric pressure.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, when concentration using vacuum distillation mode into
Row concentration, institute this during temperature be maintained between 60 DEG C~80 DEG C and carry out, pressure maintains -0.1MPa, is concentrated into substance
Long-pending 60~80%.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, the crystallization solvent include methylene chloride,
The phenyl ring class such as the saturated alkanes class solvent such as chloroform, tetrachloromethane, dichloroethanes or toluene, dimethylbenzene, chlorobenzene is organic molten
Agent.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, the inert gas includes nitrogen, argon
One of gas, helium are a variety of.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, after the completion of concentration, the addition matter of crystallization agent
Amount is 1~10 times, preferably 5 times of gained gross mass after concentration.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, the major impurity in products obtained therefrom is six
Lithium fluophosphate passes through the dissolubility difference of lithium hexafluoro phosphate and tetrafluoro oxalic acid lithium phosphate in organic solvent, concentrated crystallization side
Formula obtains pure tetrafluoro oxalic acid lithium phosphate product.The mass ratio of gained gross mass is 2 after the addition quality and concentration of crystallization agent
~10: 1.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, used organic solvent is high-purity to have
Solvent is simultaneously passed through except water process, and water content is less than 10ppm.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, the obtained organic solvent of evaporative crystallization
Recycling use can directly be carried out.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, after the completion of crystallization, contain lithium hexafluoro phosphate
Organic solvent can by heat condensation method be recycled, after evaporation gained lithium hexafluoro phosphate can be matched according to recipe requirements
Electrolyte processed.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, resulting tetrafluoro oxalic acid after crystallization is concentrated
Lithium phosphate product will be dried by rapid draing mode, method particularly includes: it is 1 hour dry under vacuum condition, then heat up
It is 2~4 hours dry under vacuum condition to 60-80 DEG C.
Preferably, in a kind of above-mentioned preparation method of tetrafluoro oxalic acid lithium phosphate, tetrafluoro oxalic acid obtained by crystallization is through further
It is dried to obtain required product, specific drying means are as follows: filtering gained tetrafluoro oxalic acid lithium phosphate solid is placed in material and is returned for 316L
Turn in kettle, 80 DEG C~100 DEG C are warming up under vacuum condition, product is dried, terminates after 4~24 hours dry.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of tetrafluoro oxalic acid phosphorus
The preparation method of sour lithium, for the phosphorus pentafluoride generated using phosphorus pentachloride and hydrogen fluoride reaction, the present invention passes through benefit
With the elemental phosphorous phosphorus pentafluoride for reacting generation with fluorine gas, not only the reaction time is short, products obtained therefrom purity is high, and can effectively mention
High reaction efficiency shortens the reaction time；In addition tetrafluoro oxalic acid lithium phosphate, this method preparation side are prepared using cheap raw material
Method is simple, overcomes the disadvantage that the existing reaction consumption of other methods is big, final products impurity is excessive, can substantially save into
This, and improve product quality.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is the preparation flow schematic diagram of tetrafluoro oxalic acid lithium phosphate of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a kind of preparation methods of tetrafluoro oxalic acid lithium phosphate, not only can substantially save cost,
And it can be improved product quality.
Below will by specific embodiment, the present invention is described in detail, but the present invention is not limited to following the description,
Want point range without departing from it, when implementation can arbitrarily change.
Embodiment one
At room temperature, 101.9g lithium oxalate, 800g DMC is added in 2 in the reaction vessel with collet, and stirs
It mixes 1 hour, lithium oxalate and DMC is made to form uniform suspension.65.17g red phosphorus is added in advance in reaction kettle 1, then slowly
It is passed through fluorine gas 200g, is passed through low-temperature cooling media in collet, to control temperature, is then led to the phosphorus pentafluoride generated during this
Enter in reaction vessel 2, it is 2L/Min that gas, which exports rate control, and the moment pays attention to temperature change during being somebody's turn to do, and controls temperature 30
After DEG C hereinafter, gas is passed through, continue stirring 4 hours.After filtering, after concentrated crystallization, crystallization, product 174.43g is obtained,
Wherein theoretical yield is 202g, and product yield reaches 86.35%.The product purity of products obtained therefrom is 99.96%, and water content is
4.8ppm, acid content 28ppm.
Table one
Embodiment two
At room temperature, 110.2g lithium oxalate, 850g DMC is added in 2 in the reaction vessel with collet, and stirs
It mixes 1 hour, lithium oxalate and DMC is made to form uniform suspension.It is passed through 72g red phosphorus in advance in reaction kettle 1, is then slowly introducing
Fluorine gas 200g is passed through low-temperature cooling media in collet, to control temperature, is then passed through the phosphorus pentafluoride generated during this instead
Should hold in kettle 2, it is 2L/Min that gas, which exports rate control, should during the moment pay attention to temperature change, control temperature 30 DEG C with
Under, after gas is passed through, continue stirring 4 hours.After filtering, after concentrated crystallization, crystallization, product 175.23g is obtained, wherein
Theoretical yield is 210g, and product yield reaches 86.74%.The product purity of products obtained therefrom be 99.8%, water content 6.8ppm,
Acid content is 23ppm.
Table two
Embodiment three
At room temperature, 105g lithium oxalate, 820g DMC is added in 2 in the reaction vessel with collet, and stirs 1
Hour, so that lithium oxalate and DMC is formed uniform suspension.68g white phosphorus is added in advance in reaction kettle 1, is then slowly introducing fluorine
Gas 200g is passed through low-temperature cooling media in collet, to control temperature, the phosphorus pentafluoride generated during this is then passed through reaction
In container 2, it is 2L/Min that gas, which exports rate control, should during the moment pay attention to temperature change, control temperature at 30 DEG C hereinafter,
After gas is passed through, continue stirring 4 hours.After filtering, after concentrated crystallization, crystallization, product 174.52g is obtained, wherein managing
It is 205g by yield, product yield reaches 86.4%.The product purity of products obtained therefrom is 99.90%, and water content 5.2ppm contains
Acid amount is 20ppm.
Table three
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (8)
1. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate, which is characterized in that this method comprises:
1. reacting using cheap industrial phosphorus with fluorine gas, phosphorus pentafluoride required for reacting is made；
2. phosphorus pentafluoride is reacted with the lithium oxalate being suspended in organic solvent, needed for being obtained by concentration crystallization, means re-crystallization
Product；
Specifically comprise the following steps: that the phosphorus pentafluoride for generating phosphorus simple substance and fluorine gas reaction imports lithium oxalate by surge tank and has
It is reacted in the reaction kettle of solvent formation suspension, gas flow rate control moment in 1~5L/min, reaction process pays attention to
The pressure, temperature variation of reaction kettle, control temperature, which is maintained between 10 DEG C~40 DEG C, in the process carries out, and pressure maintains 0
~0.5MPa, the molar ratio of phosphorus pentafluoride and lithium oxalate obtained are 2.2~2: 1, reaction are sufficiently stirred 1~3 hour, filter
Afterwards, by be concentrated crystallization mode, filtered, dry after obtain required product.
2. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the industrial phosphorus
Including one or more of white phosphorus, red phosphorus, black phosphorus.
3. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the organic solvent
It can be completely dissolved generated product and hexafluorophosphoric acid in preparation process, and the organic solvent includes esters, ethers or nitrile
Any one in class.
4. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the crystallization solvent
Including the saturated alkanes class solvent such as methylene chloride, chloroform, tetrachloromethane, dichloroethanes or toluene, dimethylbenzene, chlorobenzene etc.
Phenyl ring class organic solvent.
5. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the inert gas
Including one of nitrogen, argon gas, helium or a variety of.
6. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that the present invention is using true
Empty distillation mode is concentrated, institute this during temperature be maintained between 60 DEG C~80 DEG C and carry out, pressure maintains-
0.1MPa is concentrated into the 60~80% of original volume.
7. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 6, which is characterized in that after the completion of concentration,
The addition quality of crystallization agent is 1~10 times, preferably 5 times of gained gross mass after concentration.
8. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, which is characterized in that gained four after crystallization
Fluorine oxalic acid lithium phosphate product is placed in the rotory cauldron that material is 316L stainless steel, 80-100 DEG C is warming up under vacuum condition, drying
Terminate after 4-24 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606952A (en) * | 2020-05-14 | 2020-09-01 | 东莞东阳光科研发有限公司 | Preparation method of lithium tetrafluorooxalate phosphate, nonaqueous electrolyte and battery |
| 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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| CN101417791A (en) * | 2008-11-17 | 2009-04-29 | 袁翔云 | Technique for preparing phosphorus pentafluoride |
| US20100062346A1 (en) * | 2007-03-08 | 2010-03-11 | Board Of Governors For Higher Education, State Of Rhode Island And Providence | Novel electrolyte for lithium ion batteries |
| CN105218348A (en) * | 2015-09-10 | 2016-01-06 | 天津金牛电源材料有限责任公司 | A kind of preparation method of tetrafluoro oxalic acid Trilithium phosphate |
| CN206476750U (en) * | 2017-01-12 | 2017-09-08 | 东营石大胜华新能源有限公司 | One kind production lithium hexafluoro phosphate insulation reaction kettle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317445A (en) * | 2001-06-11 | 2001-10-17 | 山东省肥城市化肥厂 | Process for preparing lithium hexafluorophosphate in large scale by non-water solvent method |
| US20100062346A1 (en) * | 2007-03-08 | 2010-03-11 | Board Of Governors For Higher Education, State Of Rhode Island And Providence | Novel electrolyte for lithium ion batteries |
| CN101417791A (en) * | 2008-11-17 | 2009-04-29 | 袁翔云 | Technique for preparing phosphorus pentafluoride |
| CN105218348A (en) * | 2015-09-10 | 2016-01-06 | 天津金牛电源材料有限责任公司 | A kind of preparation method of tetrafluoro oxalic acid Trilithium phosphate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111606952A (en) * | 2020-05-14 | 2020-09-01 | 东莞东阳光科研发有限公司 | Preparation method of lithium tetrafluorooxalate phosphate, nonaqueous electrolyte and battery |
| CN111606952B (en) * | 2020-05-14 | 2022-04-29 | 东莞东阳光科研发有限公司 | Preparation method of lithium tetrafluorooxalate phosphate, nonaqueous electrolyte and battery |
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