CN110395750A - The preparation method of trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte - Google Patents
The preparation method of trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte Download PDFInfo
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- CN110395750A CN110395750A CN201910733843.5A CN201910733843A CN110395750A CN 110395750 A CN110395750 A CN 110395750A CN 201910733843 A CN201910733843 A CN 201910733843A CN 110395750 A CN110395750 A CN 110395750A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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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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- 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
The invention discloses a kind of preparation methods of trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte, belong to technical field of lithium ion.The preparation method include take sulfan reacted under atmosphere of inert gases with fluoroform gas be made include trifluoromethane sulfonic acid reaction solution, wherein exhaust gas processing device is sequentially connected sodium hydroxide solution, the first organic solvent；By include trifluoromethane sulfonic acid reaction solution be added lithium carbonate aqueous suspension in fully reacting, it filters, be evaporated mother liquor, obtain trifluoromethyl sulfonic acid lithium crude product, continue to recrystallize trifluoromethyl sulfonic acid lithium crude product using the second organic solvent, is dried to obtain the trifluoromethyl sulfonic acid lithium that purity is greater than 99.9%.The preparation method does not introduce alkali metal ion, and purifying process is simple.
Description
Technical field
The present invention relates to a kind of lithium ion battery electrolyte salt, belong to technical field of lithium ion, more particularly to one
Kind is used as the preparation method of the trifluoromethyl sulfonic acid lithium of lithium ion battery electrolyte.
Background technique
With the fast development of lithium ion battery, the demand that lithium ion battery corresponds to electrolyte is also increasing sharply.For
Meet the needs of lithium ion battery industry future development, it is necessary to develop the power battery of high security, high environmental suitability
Electrolyte material.Although LiPF6Being recognized is ideal lithium-ion battery electrolytes, but its synthesis technology is complicated, is decomposed
Temperature is low, just there is a small amount of decomposition since 60 °, and under higher temperature or rugged environment, the ratio of decomposition is greatly increased, and generates
The free acids such as HF eventually lead to the damage of electrode material and the sharply deterioration of battery performance so that electrolyte be made to be acidified.
CF3SO3The conductivity and electrochemical stability of Li is not so good as LiPF6, but its thermal stability, absorb water decomposability, cyclicity
Equal it can all be higher than LiPF6, when it is applied to solid electrolyte, since its stable anion can make electrolyte and negative electrode material
Passivation layer structure and composition between interface are improved, and the stabilization of electrolyte, passivating film, electrode is conducive to.
Currently, the production technology of trifluoromethyl sulfonic acid lithium is mainly controlled by Japan and the U.S., there is day in external manufacturing enterprise
This center nitre, Minnesota Mining and Manufacturing Company etc..
It is proposed in Japanese Laid-Open Patent JP2005-232040: methyl being generated by methylsufonyl chloride and fluorination nak response first
Methanesulfonyl fluoride and liquid hydrogen fluoride are added in electrolytic cell carry out a solution, the trimethyl fluoride sulfonyl fluorine of generation later by sulfuryl fluoride
It is reacted with lithium carbonate aqueous solution or lithium carbonate suspension, generates crude product trifluoromethyl sulfonic acid lithium solution.The patent document also mentions
Contain lithium fluoride, lithium carbonate, lithium sulfate in due to crude product trifluoromethyl sulfonic acid lithium solution；Firstly, passing through the mistake being separated by solid-liquid separation
Lithium fluoride and lithium carbonate, can be removed that (20 DEG C, trifluoromethyl sulfonic acid lithium meltage in 100g water is by filter form from aqueous solution
283g), then by obtained trifluoromethyl sulfonic acid lithium and acetone, acetonitrile and 1,2- dimethoxy-ethane or these mixed solvents
Dissolution, is modulated into lysate, lysate is filtered, and removes contained lithium sulfate, finally under vacuum conditions by obtained filtrate
It is concentrated and dried recycling powder, obtains product trifluoromethyl sulfonic acid lithium.
Document trifluoromethyl sulfonic acid lithium preparation research, author Li Hui have studied and use methylsufonyl chloride as raw material, with electrolysis
Method prepares trifluoromethane sulfonic acid fluorine and prepares trifluoromethyl sulphur in turn by washing and with saturation LiOH solution absorption method
Sour lithium, then purifies it.
However the purifying process of above-mentioned preparation method is comparatively laborious.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of trifluoromethane sulfonic acids as lithium ion battery electrolyte
The preparation method of lithium, which does not introduce alkali metal ion, and purifying process is simple.
To achieve the above object, the invention discloses a kind of trifluoromethyl sulfonic acid lithiums as lithium ion battery electrolyte
Preparation method, it includes trifluoro including taking sulfan to react obtained under atmosphere of inert gases with fluoroform gas
The reaction solution of methane sulfonic acid, wherein exhaust gas processing device is sequentially connected sodium hydroxide solution, the first organic solvent；By the packet
Fully reacting in the aqueous suspension of lithium carbonate is added in reaction solution containing trifluoromethane sulfonic acid, filters, is evaporated mother liquor, obtains three
Methyl fluoride Sulfonic Lithium crude product continues to dissolve the trifluoromethyl sulfonic acid lithium crude product using the second organic solvent, filter, recrystallized
And be dried, obtain the trifluoromethyl sulfonic acid lithium that purity is greater than 99.9%.
Specific chemical reaction process is as follows:
Further, second organic solvent is at least one of dimethyl carbonate or methyl ethyl carbonate.Wherein, carbon
Sour lithium solubility in second organic solvent is lower, and trifluoromethyl sulfonic acid lithium solubility is higher, therefore may be selected first to filter out
The complete lithium carbonate of unreacted, and trifluoromethyl sulfonic acid lithium obtained is recrystallized to improve product purity.
Further, the molar ratio between the sulfan and fluoroform gas is (1.5~2.0): 1.This hair
Bright selection fluoroform gas excessive 50% or more, excessive fluoroform gas is rectangular at saturated vapor on the reaction vessel,
As concentration reduces, reaction also becomes slow, and the complete sulfur trioxide of last unreacted and fluoroform will be recycled.
Specifically, first using sodium hydroxide solution absorb sulfur trioxide, to sulfur trioxide absorption after, remaining fluoroform gas
Body is absorbed by the first organic solvent, to reduce the outlet of gas as far as possible.
Further, the reaction temperature of the sulfan and fluoroform gas is 20 DEG C~35 DEG C.
Specific reaction process includes that sulfan is taken to seal stirring a period of time under the conditions of 20~30 DEG C of constant temperature, so
After be passed through fluoroform gas, constant temperature persistently stirs 2~3 hours, be to slowly warm up to 50~70 DEG C, recycling unreacted it is complete three
Fluoromethane and sulfur trioxide gas.
Further, first organic solvent is one or more of acetone, methanol or n-butanol.This is first organic molten
Agent can effectively absorb the complete fluoroform gas of unreacted.
Further, in the aqueous suspension of the lithium carbonate lithium carbonate and the mass ratio of deionized water be 1:(10~
14).To ensure fully reacting, lithium carbonate is using excessive.
It includes that the reaction solution of trifluoromethane sulfonic acid is added dropwise to the aqueous suspension of lithium carbonate that specific reaction process, which includes described,
In liquid, rate of addition is controlled, while dropwise addition, reaction vessel and ambient atmosphere holding is made mutually to pass to discharge tail gas carbon dioxide,
After being added dropwise, control reaction temperature is 40 DEG C~60 DEG C, reacts 3~4 hours, obtains trifluoromethyl sulfonic acid lithium crude product, described
Trifluoromethyl sulfonic acid lithium crude product using at least one of dimethyl carbonate or methyl ethyl carbonate recrystallization through being handled and through drying
The trifluoromethyl sulfonic acid lithium that purity is greater than 99.9% is made.
The beneficial effects are mainly reflected as follows following aspects:
1, for the synthetic method that the present invention designs without pyroreaction, products material is from a wealth of sources, subsequent purification technique letter
It is single, and the target product prepared does not introduce Cl-、Br-、Na+、K+Equal foreign ions；
2, when the target product that present invention design obtains is added in solid electrolyte, the circulation of lithium battery can be effectively improved
Stability.
Detailed description of the invention
The battery that Fig. 1 designs for embodiment of the present invention cycle performance test chart at normal temperature；
The battery that Fig. 2 designs for embodiment of the present invention cycle performance test chart at high temperature.
Specific embodiment
The invention discloses a kind of preparation methods of trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte, it includes
It takes sulfan to seal stirring a period of time under the conditions of 20~30 DEG C of constant temperature, then passes to fluoroform gas, constant temperature
Persistently stir 2~3 hours, be to slowly warm up to 50~70 DEG C, recycle obtain after tail gas include trifluoromethane sulfonic acid reaction solution,
Wherein, exhaust gas processing device is sequentially connected sodium hydroxide solution, the first organic solvent；Described includes the anti-of trifluoromethane sulfonic acid
It answers drop to add in the aqueous suspension of lithium carbonate, controls rate of addition, while dropwise addition, protect reaction vessel and ambient atmosphere
It holds and mutually passes to discharge tail gas carbon dioxide, after being added dropwise, control reaction temperature is 40 DEG C~60 DEG C, reacts 3~4 hours, obtains
To trifluoromethyl sulfonic acid lithium crude product, the trifluoromethyl sulfonic acid lithium crude product is through using in dimethyl carbonate or methyl ethyl carbonate extremely
Simultaneously trifluoromethyl sulfonic acid lithium of the purity greater than 99.9% is made through dry in a kind of few recrystallization processing.
In order to better explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
The contents of the present invention are not limited solely to following embodiment.
Embodiment 1
Liquid SO is added in the reaction vessel380.06g, constant temperature are stirred at 25 DEG C, are slowly persistently filled in 2 hours
CHF3Gas 112g is persistently stirred 1 hour；Liquid in reaction vessel is warming up to 60 DEG C, with NaOH solution and organic solvent third
Ketone absorbs tail gas and it is spare that liquid in reaction vessel is cooled to room temperature after emission-free discharge；It is added in new reaction vessel
Lithium carbonate 45.0g is added 450g deionized water and stirs evenly, above-mentioned reaction solution after cooling is slowly added dropwise, opens emptying and drop
Temperature, at 45 DEG C, time for adding is controlled at 1 hour or so control temperature, continues isothermal reaction 3 hours after being added dropwise to complete；Filtering is anti-
Liquid is answered, mother liquor is evaporated and obtains the white powder containing trifluoromethyl sulfonic acid lithium and a small amount of lithium carbonate.By powder 800g carbon
Dimethyl phthalate dissolution obtains the white powder trifluoromethyl sulphur that purity is 99.93% by processes such as filtering, recrystallization, dryings
Sour lithium 126g, whole yield are 80.7%.
Embodiment 2
Liquid SO is added in the reaction vessel380.06g, constant temperature are stirred at 30 DEG C, are slowly persistently filled in 2.5 hours
CHF3Gas 140g is persistently stirred 1 hour；Liquid in reaction vessel is warming up to 65 DEG C, with NaOH solution and organic solvent third
Ketone absorbs tail gas and it is spare that liquid in reaction vessel is cooled to room temperature after emission-free discharge；It is added in new reaction vessel
Lithium carbonate 59.0g is added 600g deionized water and stirs evenly, above-mentioned reaction solution after cooling is slowly added dropwise, opens emptying and drop
Temperature, at 55 DEG C, time for adding is controlled at 2 hours or so control temperature, continues isothermal reaction 4 hours after being added dropwise to complete；Filtering is anti-
Liquid is answered, mother liquor is evaporated and obtains the white powder containing trifluoromethyl sulfonic acid lithium and a small amount of lithium carbonate.By powder 800g carbon
Dimethyl phthalate dissolution obtains the white powder trifluoromethyl sulphur that purity is 99.92% by processes such as filtering, recrystallization, dryings
Sour lithium 128g, whole yield are 82.1%.
Wherein, the purity of target product trifluoromethyl sulfonic acid lithium and impurity content made from above-described embodiment are listed as follows:
1 purity of table and impurity content list
The trifluoromethyl sulfonic acid lithium prepared with above-described embodiment 1, is added to conventional electrolysis liquid than 5% by electrolyte quality
In, Soft Roll ternary lithium ion battery is made and conventional electrolysis liquid compares test.Test data such as table 2, and battery room temperature follows
Ring curve comparison such as Fig. 1, high temperature circulation curve comparison such as Fig. 2.
The test of 2 electrolyte property of table
By above-mentioned table 2 it is found that the trifluoromethyl sulfonic acid lithium that the present invention designs, which is conducive to, improves the high-temperature storage of battery
Performance.
In conjunction with Fig. 1 and Fig. 2 it is found that the trifluoromethyl sulfonic acid lithium that designs of the present invention is in different temperatures, repeatedly circulation makes
With rear, capacity retention ratio is good, and as cycle-index increases, capacity attenuation is slower, therefore adds the lithium electricity of trifluoromethyl sulfonic acid lithium
Pond cyclical stability is preferable.
Above embodiments are only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment
Outside, there are also other embodiments by the present invention.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention
It is required that protection scope.
Claims (6)
1. a kind of preparation method of the trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte, it includes taking sulfan
Reacted under atmosphere of inert gases with fluoroform gas be made include trifluoromethane sulfonic acid reaction solution, wherein at tail gas
Reason device is sequentially connected sodium hydroxide solution, the first organic solvent；By it is described include trifluoromethane sulfonic acid reaction solution be added
Fully reacting in the aqueous suspension of lithium carbonate filters, is evaporated mother liquor, obtains trifluoromethyl sulfonic acid lithium crude product, continues using the
Two organic solvents dissolve the trifluoromethyl sulfonic acid lithium crude product, filter, recrystallize and are dried, and obtain purity and are greater than
99.9% trifluoromethyl sulfonic acid lithium.
2. the preparation method of the trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte according to claim 1, feature
Be: second organic solvent is at least one of dimethyl carbonate or methyl ethyl carbonate.
3. the preparation method of the trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte according to claim 1, feature
Be: the molar ratio between the sulfan and fluoroform gas is (1.5~2.0): 1.
4. the preparation method of the trifluoromethyl sulfonic acid lithium as lithium ion battery electrolyte according to claim 1, feature
Be: the reaction temperature of the sulfan and fluoroform gas is 20 DEG C~35 DEG C.
5. the system of the trifluoromethyl sulfonic acid lithium described according to claim 1~any one of 4 as lithium ion battery electrolyte
Preparation Method, it is characterised in that: first organic solvent is one or more of acetone, methanol or n-butanol.
6. the system of the trifluoromethyl sulfonic acid lithium described according to claim 1~any one of 4 as lithium ion battery electrolyte
Preparation Method, it is characterised in that: in the aqueous suspension of the lithium carbonate lithium carbonate and the mass ratio of deionized water be 1:(10~
14)。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778170A (en) * | 2020-12-30 | 2021-05-11 | 中船重工（邯郸）派瑞特种气体有限公司 | Method and device for preparing lithium trifluoromethanesulfonate |
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| CN109659608A (en) * | 2018-11-16 | 2019-04-19 | 湖北锂诺新能源科技有限公司 | A kind of preparation method and application of tetrafluoro lithium aluminate |
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2019
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| JP2005232040A (en) * | 2004-02-18 | 2005-09-02 | Mitsubishi Materials Corp | Method for producing lithium trifluoromethanesulfonate |
| CN102272096A (en) * | 2009-01-05 | 2011-12-07 | 三菱综合材料株式会社 | Process for producing perfluoroalkylsulfonic acid salt |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112778170A (en) * | 2020-12-30 | 2021-05-11 | 中船重工（邯郸）派瑞特种气体有限公司 | Method and device for preparing lithium trifluoromethanesulfonate |
| CN112778170B (en) * | 2020-12-30 | 2022-12-27 | 中船(邯郸)派瑞特种气体股份有限公司 | Method and device for preparing lithium trifluoromethanesulfonate |
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