CN108808093A - 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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- CN108808093A CN108808093A CN201810841936.5A CN201810841936A CN108808093A CN 108808093 A CN108808093 A CN 108808093A CN 201810841936 A CN201810841936 A CN 201810841936A CN 108808093 A CN108808093 A CN 108808093A
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- oxalic acid
- acid lithium
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- lithium phosphate
- tetrafluoro oxalic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
This application discloses a kind of preparation method of tetrafluoro oxalic acid lithium phosphate, the preparation method includes：(1), phosphorus pentafluoride gas is passed into the reaction kettle for having added lithium oxalate and dimethyl carbonate, fully reaction 5 hours or more is carried out under the conditions of 20~25 DEG C, tetrafluoro oxalic acid lithium phosphate solution is obtained after filtering；(2), dichloromethane is instilled up to no crystal or Precipitation, and tetrafluoro oxalic acid lithium phosphate semifinished product is obtained by filtration；(3), dry.The reaction condition of the present invention is mild, yield is high, process equipment is simple, the tetrafluoro oxalic acid lithium phosphate of high-quality can be made, the DMC condensed during simultaneous reactions is reusable, and by-product lithium hexafluoro phosphate obtained by the reaction is also repeated and utilized, and then saves cost.
Description
Technical field
This application involves technical field of lithium ion, more particularly to a kind of preparation method of tetrafluoro oxalic acid lithium phosphate.
Background technology
Lithium ion battery is since twentieth century end comes out, since it is big with energy density, operating voltage is high, the cycle longevity
The advantages that long is ordered, most popular secondary cell is become.Lithium ion battery is as a kind of environment-protecting clean energy, with fuel cell one
And as the major cell of 21 century electric vehicle, the broad based growth foreground of lithium ion battery is come for lithium ion battery material industrial zone
Huge development space.New century faces two hang-up of energy shortage and environmental pollution, and there is an urgent need to develop high power and great Rong
Lithium ion battery is measured, to meet the requirement of energy saving and environment friendly power vehicle or hybrid vehicle and energy-storage battery.Develop and
Exploitation high-energy-density, cheap, safe and reliable lithium ion battery of new generation are electrochmical power source research fields in recent years
One of focus.By the development of recent two decades, lithium ion battery is portable in mobile phone, laptop, digital camera etc.
It is used widely on formula electronic equipment.
Electrolyte is the indispensable component part of lithium-ion battery electrolytes, is the determinant of performance of lithium ion battery
One of.The major product in current lithium ion battery electrolyte field is LiPF6, and electrolyte system has high conductivity and height
The advantages that electrochemical stability.But another solvent composition necessary to the thermostabilization of LiPF6 base electrolyte is poor and electrolyte
Fusing point (36.4 DEG C) higher cryogenic property for limiting lithium ion battery of EC.Several years of outdoor cycle or higher temperature (>
55 DEG C) under after cycle some months, the capacity of battery significantly reduces, it is difficult to meet the needs of high performance lithium ion battery.This promotes
Numerous cell researchers develop other lithium ion battery electrolyte materials.
Tetrafluoro oxalic acid lithium phosphate (LiPF4C2O4), the temperature range of the carbonic ester electrolyte system of the salt at -40~65 DEG C
With the ionic conductivity similar with LiPF6 and similar charging and discharging coulombic efficiency.Copper foil and aluminum foil current collector are in its carbonic acid
Also there is preferable electrochemical stability, wider electrochemical window in ester electrolyte system.LiPF4C2O4 electrolyte batteries,
Discharge capacity is slightly below LiPF6 base electrolyte batteries to its room temperature for the first time, however the impedance of battery is but than LiPF6 electrolyte battery
It is high.The thermal stability of LiPF6 and LiPF4C2O4 solid samples is suitable, still, the thermal stability of LiPF4C2O4 electrolyte systems
Thermal stability than LiPF6 base electrolyte is significantly improved, and under the high temperature conditions, the battery of LiPF4C2O4 electrolyte is apparent
Keep higher capacity.The negative terminal surface of LiPF4C2O4 electrolyte batteries after storage at high temperatures, the oxalate base substance on surface and
LiF content of material is higher, and positive electrode surface film is relatively thin, the oxalate base substance containing higher concentration, however its LiF material concentration is but very
It is few.The oxalate base substance of positive and negative pole surface is more stable during high temperature storage, this is probably LiPF4C2O4 electrolyte
Battery has the essential reason compared with high discharge capacity after high-temperature storage.Under 85 DEG C of hot conditions, LiPF4C2O4 electrolyte exists
Storage does not decompose after 6 months, is non-discolouring, substantially without Precipitation.
Invention content
The present invention provides a kind of preparation method of tetrafluoro oxalic acid lithium phosphate.
The embodiment of the present application provides a kind of preparation method of tetrafluoro oxalic acid lithium phosphate, and the preparation method includes：
(1), phosphorus pentafluoride gas is passed into the reaction kettle for having added lithium oxalate and dimethyl carbonate, 20~25
Fully reaction 5 hours or more is carried out under the conditions of DEG C, tetrafluoro oxalic acid lithium phosphate solution is obtained after filtering；
(2), dichloromethane is instilled up to no crystal or Precipitation, and tetrafluoro oxalic acid lithium phosphate semifinished product is obtained by filtration；
(3), dry.
Preferably, in the step (2), tetrafluoro oxalic acid lithium phosphate solution is heated to steaming under the conditions of 100~110 DEG C
Hair concentration when 1/3~1/2, instills dichloromethane up to no crystal when tetrafluoro oxalic acid lithium phosphate solution is concentrated into original volumes
Or Precipitation, it is cooled to 20~25 DEG C during instilling.
Preferably, in the step (2), the condensed recycling of dimethyl carbonate of evaporation is repeatable to be utilized.
Preferably, in the step (2), lithium hexafluoro phosphate crude product is obtained after the filtrate decompression drying being obtained by filtration,
It is reusable.
Preferably, in the step (3), tetrafluoro oxalic acid lithium phosphate semifinished product is placed in rotary drier to dry, drying
It is passed through the nitrogen of 10~20L/min in the process, it is 10~15 hours dry under the conditions of 100~120 DEG C.
Preferably, the mass concentration of the lithium oxalate in the step (1) and dimethyl carbonate is 1~3%.
Preferably, the preparation of phosphorus pentafluoride gas includes：Lithium hexafluoro phosphate is warming up to 150~180 DEG C, heat resolve life
At phosphorus pentafluoride gas, which is passed through in reaction kettle by step in (1).
Preferably, the lithium hexafluoro phosphate and lithium oxalate molar ratio are 2.1~2.3:1.
Compared with prior art, the present invention obtains phosphorus pentafluoride by heat resolve lithium hexafluoro phosphate, the same oxalic acid in DMC
Lithium reacts, and the tetrafluoro oxalic acid lithium phosphate of high-quality can be made, and purity reaches 99.9% or more, and moisture is less than 10ppm, and sour part is small
In 5ppm.The DMC condensed during simultaneous reactions is reusable, and by-product lithium hexafluoro phosphate obtained by the reaction also repeats profit
With, and then save cost.
Specific implementation mode
The embodiment of the present application provides a kind of method preparing special specification sodium hexafluoro phosphate, specifically includes following steps：
(1), at 20~25 DEG C, by the lithium oxalate being pre-dried (purity is more than 99.9%) input through except water process
It in DMC, stirs and suspension is made, lithium oxalate mass concentration is 1~3%.
(2), heat resolve lithium hexafluoro phosphate (purity is more than 99.9%), lithium hexafluoro phosphate and oxalic acid at 150~180 DEG C
The molar ratio of lithium is 2.1~2.3:The DMC that the nitrogen of 1, logical 2~5L/min are passed through the phosphorus pentafluoride gas of decomposition lithium oxalate hangs
In turbid, reaction 5 hours or more is sufficiently stirred at 20~25 DEG C.
(3), reaction solution is filtered into away insoluble matter, obtains clear tetrafluoro oxalic acid lithium phosphate and lithium hexafluoro phosphate mixing
DMC solution is evaporated concentration at 100~110 DEG C, reusable after the condensed recycling of DMC of evaporation, surplus when being concentrated into
Remaining 1/3~1/2 when, dichloromethane is added dropwise after cooling, to without crystal or when Precipitation stops that dichloromethane is added dropwise, filter
Obtain tetrafluoro oxalic acid lithium phosphate crude product.Filtrate is dried under reduced pressure to obtain crude product lithium hexafluoro phosphate, is also repeated and is utilized.
(4), the tetrafluoro oxalic acid lithium phosphate crude product of filtering gained is placed in rotary drier, leads to the nitrogen of 10~20L/min
Gas obtains white powder tetrafluoro oxalic acid lithium phosphate in dry 10~15 hours at 100~120 DEG C.
The present invention is described further by the following example：According to following embodiments, the present invention may be better understood.
However, as it will be easily appreciated by one skilled in the art that specific material ratio, process conditions and its result described in embodiment are only used
In illustrating the present invention, without the present invention described in detail in claims should will not be limited.
Embodiment 1
A method of sodium hexafluoro phosphate quickly being prepared, specifically includes following steps：
(1), at 20 DEG C, 51g high-purity oxalic acid lithiums, 2300gDMC are added in the reaction kettle with blender, stirring is made
Suspension, lithium oxalate mass concentration are 2.17%；
(2) 160g lithium hexafluoro phosphates (molar ratio of lithium hexafluoro phosphate and lithium oxalate is 2.105) are put into generator,
Heat resolve at 180 DEG C is passed through the nitrogen of 2L/min, will decompose the phosphorus pentafluoride gas generated and is passed through in reaction kettle, gas is logical
After entering, continue stirring 10 hours.
(3), mother liquor obtained by the reaction is filtered, removes insoluble matter, the filtrate being obtained by filtration is steamed at 110 DEG C
Hair concentration, it is to be concentrated to when also one third take out cooling, after dichloromethane is added dropwise, to without crystal appearance after filter
To 121.93g 1400gDMC is obtained after the condensed recycling of DMC of evaporation.
(4), 15 hours dry at 120 DEG C, while the nitrogen of logical 10L/min, obtain product 90.37g
(5), testing result, product yield 89.48%, purity 99.91%, moisture 4.12ppm, free acid
Content is 3.51ppm.
Embodiment 2:
A method of special specification sodium hexafluoro phosphate is prepared, following steps are specifically included：
(1) at 25 DEG C, 51g high-purity oxalic acid lithiums are added in the reaction kettle with blender, 3400gDMC (contains 1400g
The DMC condensed in embodiment one), it stirs and suspension is made, lithium oxalate mass concentration is 1.48%.
(2), the molar ratio of the input 172g lithium hexafluoro phosphates in generator, lithium hexafluoro phosphate and lithium oxalate is 2.263,
Heat resolve at 160 DEG C is passed through the nitrogen of 4L/min, will decompose the phosphorus pentafluoride gas generated and is passed through in reaction kettle, gas is logical
After entering, continue stirring 6 hours.
(3), mother liquor obtained by the reaction is filtered, removes insoluble matter, the filtrate being obtained by filtration is steamed at 100 DEG C
Hair concentration, it is to be concentrated to when also half take out cooling, after dichloromethane is added dropwise, to without crystal appearance after obtain
118.76g。
(4), 10 hours dry at 110 DEG C, while the nitrogen of logical 15L/min, obtain product 88.14g.
(5), product yield 87.27%, purity 99.93%, moisture 7.68ppm dissociate
Acid content is 2.95ppm.
Each embodiment yield and comparison or purity are as shown in the table：
In conclusion beneficial effects of the present invention：The present invention obtains phosphorus pentafluoride by heat resolve lithium hexafluoro phosphate,
It is reacted with lithium oxalate in DMC, the tetrafluoro oxalic acid lithium phosphate of high-quality can be made, purity reaches 99.9% or more, and moisture is less than
10ppm, sour part are less than 5ppm.The DMC condensed during simultaneous reactions is reusable, by-product hexafluorophosphoric acid obtained by the reaction
Lithium is also repeated and is utilized, and then saves cost.
Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that including a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.
Claims (8)
1. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate, it is characterised in that：The preparation method includes：
(1), phosphorus pentafluoride gas is passed into the reaction kettle for having added lithium oxalate and dimethyl carbonate, in 20~25 DEG C of items
Fully reaction 5 hours or more is carried out under part, tetrafluoro oxalic acid lithium phosphate solution is obtained after filtering；
(2), dichloromethane is instilled up to no crystal or Precipitation, and tetrafluoro oxalic acid lithium phosphate semifinished product is obtained by filtration；
(3), dry.
2. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, it is characterised in that：The step (2)
In, it is heated to tetrafluoro oxalic acid lithium phosphate solution to be evaporated concentration under the conditions of 100~110 DEG C, when tetrafluoro oxalic acid lithium phosphate is molten
Liquid is concentrated into original volumes, when 1/3~1/2, instills dichloromethane until no crystal or Precipitation, cooling during instilling
To 20~25 DEG C.
3. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 3, it is characterised in that：The step (2)
In, the condensed recycling of dimethyl carbonate of evaporation is repeatable to be utilized.
4. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, it is characterised in that：The step (2)
In, lithium hexafluoro phosphate crude product is obtained after the filtrate decompression drying being obtained by filtration, it is reusable.
5. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 1, it is characterised in that：The step (3)
In, tetrafluoro oxalic acid lithium phosphate semifinished product is placed in drying in rotary drier, the nitrogen of 10~20L/min is passed through in drying process
Gas, it is 10~15 hours dry under the conditions of 100~120 DEG C.
6. according to a kind of preparation method of tetrafluoro oxalic acid lithium phosphate described in claim 1, it is characterised in that：In the step (1)
Lithium oxalate and dimethyl carbonate mass concentration be 1~3%.
7. a kind of preparation method of tetrafluoro oxalic acid lithium phosphate according to claim 7, which is characterized in that phosphorus pentafluoride gas
Preparation include：Lithium hexafluoro phosphate is warming up to 150~180 DEG C, heat resolve generates phosphorus pentafluoride gas, will in step (1)
The mixed gas is passed through in reaction kettle.
8. according to a kind of preparation method of tetrafluoro oxalic acid lithium phosphate described in claim 2, it is characterised in that：The lithium hexafluoro phosphate
It is 2.1~2.3 with lithium oxalate molar ratio:1.
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| CN201810841936.5A CN108808093B (en) | 2018-07-27 | 2018-07-27 | Preparation method of lithium tetrafluoro oxalate phosphate |
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| CN201810841936.5A CN108808093B (en) | 2018-07-27 | 2018-07-27 | Preparation method of lithium tetrafluoro oxalate phosphate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678694A (en) * | 2018-12-21 | 2019-04-26 | 东莞东阳光科研发有限公司 | A kind of preparation method of tetrafluoro oxalic 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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| 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 |
| CN105399761A (en) * | 2015-10-22 | 2016-03-16 | 中国海洋石油总公司 | Preparation method of lithium difluoro(oxalato)borate |
| CN105593165A (en) * | 2013-10-04 | 2016-05-18 | 关东电化工业株式会社 | Method for purifying phosphorus pentafluoride |
| CN107973773A (en) * | 2017-11-14 | 2018-05-01 | 石家庄圣泰化工有限公司 | Perfluor substitutes the preparation method of disulfonic acid acid anhydride |
| CN108147436A (en) * | 2018-02-26 | 2018-06-12 | 江苏新泰材料科技有限公司 | Combined coefficient is improved in lithium hexafluoro phosphate production process reduces the synthetic method of unit consumption |
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2018
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105593165A (en) * | 2013-10-04 | 2016-05-18 | 关东电化工业株式会社 | Method for purifying 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 |
| CN105399761A (en) * | 2015-10-22 | 2016-03-16 | 中国海洋石油总公司 | Preparation method of lithium difluoro(oxalato)borate |
| CN107973773A (en) * | 2017-11-14 | 2018-05-01 | 石家庄圣泰化工有限公司 | Perfluor substitutes the preparation method of disulfonic acid acid anhydride |
| CN108147436A (en) * | 2018-02-26 | 2018-06-12 | 江苏新泰材料科技有限公司 | Combined coefficient is improved in lithium hexafluoro phosphate production process reduces the synthetic method of unit consumption |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678694A (en) * | 2018-12-21 | 2019-04-26 | 东莞东阳光科研发有限公司 | A kind of preparation method of tetrafluoro oxalic 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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