CN110203949A - A kind of full recovery method of waste and old lithium ionic cell electrolyte - Google Patents
A kind of full recovery method of waste and old lithium ionic cell electrolyte Download PDFInfo
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- CN110203949A CN110203949A CN201910656138.XA CN201910656138A CN110203949A CN 110203949 A CN110203949 A CN 110203949A CN 201910656138 A CN201910656138 A CN 201910656138A CN 110203949 A CN110203949 A CN 110203949A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
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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
- C01D15/08—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The present invention provides a kind of full recovery methods of waste and old lithium ionic cell electrolyte, it is therefore an objective to recycle valuable lithium salts, organic solvent and additive in waste and old electrolyte, and recycle after carrying out harmless treatment to objectionable impurities such as fluorine, phosphorus.The present invention is through over cleaning, cleaning solvent recycling, organic solvent and additive recycling, fluorine and phosphorus recycling, lithium salts recovery process, lithium salts is finally recycled in the form of lithium carbonate, organic solvent, additive separating-purifying recycle, and fluorine, phosphorus are recycled in the form precipitated.This simple process, method is feasible, is adequately recycled to waste and old electrolyte and there are no pollution to the environment, recycles waste and old electrolyte each component using this technique, the rate of recovery is suitble to heavy industrialization application up to 95% or more.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of full recovery method of waste and old lithium ionic cell electrolyte.
Background technique
With the aggravation of global energy crisis and environmental pollution, the development and application of new energy are imperative.Lithium-ion electric
Pond has just been rapidly progressed since the 1990s realizes commercialization.Compared with traditional chemical cell, there is quality
Gently, small in size, voltage is high, specific energy is high, operating temperature range is wide, specific power is big, electric discharge is steady, storage time is long, memoryless
Effect, it is pollution-free the advantages that.Currently, lithium ion battery has been widely applied to mobile phone, digital camera, laptop etc. just
It takes in formula electronic product, before showing to be widely applied on electric car (EV), hybrid vehicle (HEV) and energy-storage system
Scape is known as " the green secondary cell of 21 century ".It is predicted according to China Automotive Technology & Research Center, arrives the year two thousand twenty, China's electricity
Electrical automobile power battery adds up learies for up to 120,000~170,000 tons of scale, if dealt with improperly, will to generate serious environment dirty
Dye.The recycling of waste and old lithium ion battery is concentrated mainly on positive and negative pole material and collector at present, is studied the recycling of electrolyte
Seldom.Electrolyte is generally made of lithium salts, organic solvent and additive, and lithium salts is mainly lithium hexafluoro phosphate, and organic solvent is with carbon
Based on esters of gallic acid solvent, additive level is less.The presence of lithium hexafluoro phosphate makes electrolyte contacts external environment react, and produces
Raw a large amount of pollutants, safety and environmental problem to people bring important influence.Meanwhile electrolyte has high added value, such as
Rationally recycling electrolyte is the problem of being worth further investigation for what.
The recovery method of lithium-ion battery electrolytes has alkali absorption method, rectification under vacuum method and extraction at present.Patent CN
108666644A uses Ca (OH)2It is reacted with lithium ion battery waste electrolyte, Ca2+Generation is reacted with the fluorine ion in electrolyte
CaF2, physical orientation is carried out using multistage manganese fibers adsorption column and titanium fibers adsorption column later and adsorbs lithium ion, to recycle electricity
The fluorine and lithium in liquid are solved, can not only recycle fluorine and lithium, but also can be reduced the pollution of environment.Although the method can reduce fluorine to ring
The pollution in border, recycle lithium resource, but this patent not to carbonate organic solvent in electrolyte and additive carry out recycling and
Ca (OH) is added directly in waste and old electrolyte2Solution can destroy organic solvent and additive, result in waste of resources.Patent CN
109292746 A mix waste lithium cell core with organic solvent, can make battery positive and negative pole material and diaphragm with it is organic molten
Agent comes into full contact with, and then under ultrasonication, the lithium hexafluoro phosphate being adhered in positive and negative pole material, diaphragm and electrolyte is shifted
To in the mixed organic solvents of acetonitrile and carbonic ester, and then realize the high efficiente callback of lithium hexafluoro phosphate.Although the method can be effective
Recycling lithium hexafluoro phosphate, but lithium hexafluoro phosphate is unstable, easily decomposes, forcible entry, process of enriching are required it is high, increase technique at
This.
It is industrially at present calcining cracking processing, You Jirong after heating evaporation to the processing of waste and old lithium ionic cell electrolyte
The cracking of agent needs high-temperature calcination to handle, energy consumption, and ethylene carbonate, propene carbonate, the additive contained in electrolyte
Etc. value with higher, the strategy of sustainable development that dinectly bruning is advocated with country is disagreed.Therefore, how efficiently, it is feasible
The waste and old electrolyte of recycling in lithium salts, fluorine and phosphorus recycle after carrying out harmless treatment, and will not destroy organic solvent
Structure with additive is the problem that lithium ion battery industry faces.
Summary of the invention
The invention proposes a kind of full recovery methods of waste and old lithium ionic cell electrolyte, and lithium salts is finally in the form of lithium carbonate
Recycling, organic solvent and additive carry out separating-purifying recycling, and fluorine, phosphorus are recycled in the form precipitated, the letter of this technique
Single, method is feasible, is adequately recycled to waste and old electrolyte and there are no pollution to the environment, is recycled using this technique waste and old
Electrolyte each component, the rate of recovery are suitble to industrial large-scale application up to 95% or more.
Realize the technical scheme is that
A kind of full recovery method of waste and old lithium ionic cell electrolyte, comprises the following steps:
(1) cleaning process: with cleaning solvent impregnate contain waste and old electrolyte waste and old lithium ion battery, and it is carried out ultrasound,
Stirring, filtering；
(2) cleaning solvent recovery process: filtrate after step (1) filtering is evaporated under reduced pressure, and collects electrolyte；
(3) organic solvent and additive recovery process: add water into the electrolyte collected in step (2) and heat, filter to obtain lithium
Filtrate is passed through extraction tower by salt precipitating and filtrate, and organic phase passes through separator purification & isolation one by one, recycles organic solvent and adds
Add agent；
(4) lithium salts recovery process: lithium salts precipitating in step (3) is added in calcium hydroxide solution, filters to get filtrate I.
Cleaning solvent is dimethyl carbonate, in methyl ethyl carbonate, diethyl carbonate, propene carbonate in the step (1)
One or more.
The vacuum degree being evaporated under reduced pressure in the step (2) is 100 ~ 500mbar, and temperature is 30 ~ 100 DEG C.
Heating temperature is 30 ~ 100 DEG C in the step (3).
Separator is rectifying column in the step (3), and rectifying tower plates number is 5 ~ 80 pieces, and reflux ratio is 2 ~ 60, reaction
Temperature is 50 ~ 250 DEG C, and operating pressure is 10 ~ 80KPa.
In the step (3) plus thermogenetic escaping gas is absorbed with calcium hydroxide solution, and water phase passes through calcium hydroxide
Solution absorbs, and recycles fluorine, phosphorus, filters to get filtrate II.
It is passed through water soluble carbonate or carbon dioxide into filtrate I and filtrate II, generates lithium carbonate and is precipitated, carbonate is carbon
One or more of sour sodium, potassium carbonate, ammonium carbonate.
The beneficial effects of the present invention are: the present invention recycles waste and old lithium ionic cell electrolyte entirely, with the prior art
It compares, simple process, feasibility is high, will not generate pollution while recycling to lithium salts, organic solvent, additive, fluorine, phosphorus.This
Invention is for economizing on resources, protecting environment, sustainable development to play positive effect.
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
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is waste and old lithium ionic cell electrolyte complete recovering technique flow chart.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
The waste and old lithium ion battery for containing waste and old electrolyte is impregnated with dimethyl carbonate solvent, and ultrasound, stirring, mistake are carried out to it
Electrolyte is extracted after filter；
(2) cleaning solvent recovery process
Control vacuum degree is 100mbar, and temperature is 30 DEG C and is evaporated under reduced pressure, dimethyl carbonate used in recovery process (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
It is collected to process (2) and adds water, 30 DEG C of heating in electrolyte, filtered to obtain lithium salts precipitating and filtrate, filtrate is passed into extraction
In tower, by rectifying column, purification & isolation, the number of plates of rectifying column are 40 pieces to organic phase one by one, and reaction temperature is 150 DEG C, operation pressure
Power 20KPa, reflux ratio 5 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
It lithium salts precipitating will be added in calcium hydroxide solution in process (3), and filter to get filtrate I, water phase and calcium hydroxide in process (4)
Solution reaction, filters to get filtrate II, will obtain filtrate I, II and is put into crystallization kettle and is added sodium carbonate liquor to the inside, heating, dense
Sheepshank crystalline substance generates lithium carbonate.
Embodiment 2
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
Contain the waste and old lithium ion battery of waste and old electrolyte with methyl ethyl carbonate solvent soaking, and carries out ultrasound, stirring, mistake to it
Electrolyte is extracted after filter；
(2) cleaning solvent recovery process
Control vacuum degree is 500mbar, and temperature is 100 DEG C and is evaporated under reduced pressure, methyl ethyl carbonate used in recovery process (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
To process (2) collect electrolyte in plus water, 100 DEG C heating, filter lithium salts precipitating and filtrate, filtrate be passed into extraction tower
In, by rectifying column, purification & isolation, the number of plates of rectifying column are 80 pieces to organic phase one by one, and reaction temperature is 250 DEG C, operating pressure
80KPa, reflux ratio 60 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
It lithium salts precipitating will be added in calcium hydroxide solution in process (3), and filter to get filtrate I, water phase and calcium hydroxide in process (4)
Solution reaction, filters to get filtrate II, will obtain filtrate I, II and is put into crystallization kettle and is added solution of potassium carbonate to the inside, heating, dense
Sheepshank crystalline substance generates lithium carbonate.
Embodiment 3
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
Contain the waste and old lithium ion battery of waste and old electrolyte with diethyl carbonate solvent soaking, and carries out ultrasound, stirring, mistake to it
Electrolyte is extracted after filter；
(2) cleaning solvent recovery process
Control vacuum degree is 200mbar, and temperature is 50 DEG C and is evaporated under reduced pressure, diethyl carbonate used in recovery process (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
To process (2) collect electrolyte in plus water, 50 DEG C heating, filter lithium salts precipitating and filtrate, filtrate be passed into extraction tower
In, by rectifying column, purification & isolation, the number of plates of rectifying column are 5 pieces to organic phase one by one, and reaction temperature is 50 DEG C, operating pressure
10KPa, reflux ratio 2 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
It lithium salts precipitating will be added in calcium hydroxide solution in process (3), and filter to get filtrate I, water phase and calcium hydroxide in process (4)
Solution reaction, filters to get filtrate II, will obtain filtrate I, II and is put into crystallization kettle and is added sal volatile to the inside, heating, dense
Sheepshank crystalline substance generates lithium carbonate.
Embodiment 4
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
The waste and old lithium ion battery for containing waste and old electrolyte is impregnated with propylene carbonate solvent, and ultrasound, stirring, mistake are carried out to it
Electrolyte is extracted after filter.
(2) cleaning solvent recovery process
Control vacuum degree is 400mbar, and temperature is 80 DEG C and is evaporated under reduced pressure, propene carbonate used in recovery process (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
To process (2) collect electrolyte in plus water, 60 DEG C heating, filter lithium salts precipitating and filtrate, filtrate be passed into extraction tower
In, by rectifying column, purification & isolation, the number of plates of rectifying column are 20 pieces to organic phase one by one, and reaction temperature is 100 DEG C, operating pressure
30KPa, reflux ratio 20 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
It lithium salts precipitating will be added in calcium hydroxide solution in process (3), and filter to get filtrate I, water phase and calcium hydroxide in process (4)
Solution reaction, filters to get filtrate II, will obtain filtrate I, II and is put into crystallization kettle and is passed through carbon dioxide gas to the inside, heating,
Condensing crystallizing generates lithium carbonate.
Embodiment 5
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
Contain the waste and old lithium ion battery of waste and old electrolyte with methyl ethyl carbonate solvent soaking, and carries out ultrasound, stirring, mistake to it
Electrolyte is extracted after filter；
(2) cleaning solvent recovery process
Control vacuum degree is 300mbar, and temperature is 60 DEG C and is evaporated under reduced pressure, methyl ethyl carbonate used in recovery process (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
To process (2) collect electrolyte in plus water, 50 DEG C heating, filter lithium salts precipitating and filtrate, filtrate be passed into extraction tower
In, by rectifying column, purification & isolation, the number of plates of rectifying column are 30 pieces to organic phase one by one, and reaction temperature is 150 DEG C, operating pressure
40KPa, reflux ratio 30 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
Lithium salts precipitating addition acetic acid forms filtrate in process (3), obtains filtrate after the precipitating formed in separation removing step (4),
Filtrate will be obtained to be put into crystallization kettle and be passed through carbon dioxide gas to the inside, heating, condensing crystallizing obtain lithium carbonate.
Embodiment 6
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
The waste and old lithium ion battery for containing waste and old electrolyte is impregnated with dimethyl carbonate solvent, and ultrasound, stirring, mistake are carried out to it
Electrolyte is extracted after filter；
(2) cleaning solvent recovery process
Control vacuum degree is 400mbar, and temperature is 80 DEG C and is evaporated under reduced pressure, dimethyl carbonate used in recovery process (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
To process (2) collect electrolyte in plus water, 70 DEG C heating, filter lithium salts precipitating and filtrate, filtrate be passed into extraction tower
In, by rectifying column, purification & isolation, the number of plates of rectifying column are 40 pieces to organic phase one by one, and reaction temperature is 180 DEG C, operating pressure
50KPa, reflux ratio 40 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
It lithium salts precipitating will be added in calcium hydroxide solution in process (3), and filter to get filtrate I, water phase and calcium hydroxide in process (4)
Solution reaction, filters to get filtrate II, will obtain filtrate I, II and is put into crystallization kettle and is added solution of potassium carbonate to the inside, heating, dense
Sheepshank crystalline substance generates lithium carbonate.
Embodiment 7
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
The waste and old lithium ion battery for containing waste and old electrolyte is impregnated with propylene carbonate solvent, and ultrasound, stirring, mistake are carried out to it
Electrolyte is extracted after filter；
(2) cleaning solvent recovery process
Control vacuum degree is 200mbar, and temperature is 50 DEG C and is evaporated under reduced pressure, propene carbonate used in recovery process (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
To process (2) collect electrolyte in plus excessive water, 80 DEG C heating, filter lithium salts precipitating and filtrate, filtrate be passed into extraction
It takes in tower, by rectifying column, purification & isolation, the number of plates of rectifying column are 80 pieces to organic phase one by one, and reaction temperature is 220 DEG C, operation
Pressure 60KPa, reflux ratio 50 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
It lithium salts precipitating will be added in calcium hydroxide solution in process (3), and filter to get filtrate I, water phase and calcium hydroxide in process (4)
Solution reaction, filters to get filtrate II, will obtain filtrate I, II and is put into crystallization kettle and is added sodium carbonate liquor to the inside, heating, dense
Sheepshank crystalline substance generates lithium carbonate.
Embodiment 8
A kind of full recovery method of waste and old lithium ionic cell electrolyte, steps are as follows:
(1) cleaning process
Contain the waste and old lithium ion battery of waste and old electrolyte with diethyl carbonate solvent soaking, and carries out ultrasound, stirring, mistake to it
Electrolyte is extracted after filter；
(2) cleaning solvent recovery process
Control vacuum degree is 100mbar, and temperature is 40 DEG C and is evaporated under reduced pressure, diethyl carbonate used in recycling step (1)
Solvent, and collect electrolyte；
(3) organic solvent, additive recovery process
To process (2) collect electrolyte in plus water, 40 DEG C heating, filter lithium salts precipitating and filtrate, filtrate be passed into extraction tower
In, by rectifying column, purification & isolation, the number of plates of rectifying column are 50 pieces to organic phase one by one, and reaction temperature is 240 DEG C, operating pressure
60KPa, reflux ratio 15 recycle organic solvent and additive；
(4) fluorine, phosphorus recovery process in electrolyte
Thermogenetic escaping gas will be added to be absorbed with calcium hydroxide solution in process (3), water phase passes through hydroxide in process (3)
Calcium solution absorbs, and generates calcirm-fluoride, calcium phosphate and is recycled later；
(5) lithium salts recovery process
It lithium salts precipitating will be added in calcium hydroxide solution in process (3), and filter to get filtrate I, water phase and calcium hydroxide in process (4)
Solution reaction, filters to get filtrate II, will obtain filtrate I, II and is put into crystallization kettle and is passed through carbon dioxide gas to the inside, heating,
Condensing crystallizing generates lithium carbonate.
The waste and old electrolyte each component rate of recovery of table 1
Verification the verifying results
Table 1 is the waste and old electrolyte each component rate of recovery in embodiment.
Fig. 1 is the process flow chart that waste and old lithium ionic cell electrolyte recycles entirely, and Cong Tuzhong is clear that lithium salts, has
Effective recycling of solvent, additive, fluorine, phosphorus.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of full recovery method of waste and old lithium ionic cell electrolyte, it is characterised in that comprise the following steps:
(1) cleaning process: with cleaning solvent impregnate contain waste and old electrolyte waste and old lithium ion battery, and it is carried out ultrasound,
Stirring, filtering；
(2) cleaning solvent recovery process: filtrate after step (1) filtering is evaporated under reduced pressure, and collects electrolyte；
(3) organic solvent and additive recovery process: add water into the electrolyte collected in step (2) and heat, filter to obtain lithium
Filtrate is passed through extraction tower by salt precipitating and filtrate, and organic phase passes through separator purification & isolation one by one, recycles organic solvent and adds
Add agent；
(4) lithium salts recovery process: lithium salts precipitating in step (3) is added in calcium hydroxide solution, filters to get filtrate I.
2. the full recovery method of waste and old lithium ionic cell electrolyte according to claim 1, it is characterised in that: the step
(1) cleaning solvent is one or more of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, propene carbonate in.
3. the full recovery method of waste and old lithium ionic cell electrolyte according to claim 1, it is characterised in that: the step
(2) vacuum degree being evaporated under reduced pressure in is 100 ~ 500mbar, and temperature is 30 ~ 100 DEG C.
4. the full recovery method of waste and old lithium ionic cell electrolyte according to claim 1, it is characterised in that: the step
(3) heating temperature is 30 ~ 100 DEG C in.
5. the full recovery method of waste and old lithium ionic cell electrolyte according to claim 1, it is characterised in that: the step
(3) separator is rectifying column in, and rectifying tower plates number is 5 ~ 80 pieces, and reflux ratio is 2 ~ 60, and reaction temperature is 50 ~ 250 DEG C, behaviour
Making pressure is 5 ~ 80KPa.
6. the full recovery method of waste and old lithium ionic cell electrolyte according to claim 1-5, it is characterised in that: institute
It states in step (3) plus thermogenetic escaping gas is absorbed with calcium hydroxide solution, water phase is absorbed by calcium hydroxide solution, is returned
Fluorine, phosphorus are received, filters to get filtrate II.
7. the full recovery method of waste and old lithium ionic cell electrolyte according to claim 6, it is characterised in that: to I He of filtrate
It is passed through water soluble carbonate or carbon dioxide in filtrate II, generates lithium carbonate and is precipitated, carbonate is sodium carbonate, potassium carbonate, carbonic acid
One or more of ammonium.
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| CN110635191A (en) * | 2019-09-12 | 2019-12-31 | 金川集团股份有限公司 | Method for cleanly recovering all components of waste power lithium battery |
| CN111003736A (en) * | 2019-11-08 | 2020-04-14 | 惠州亿纬锂能股份有限公司 | Comprehensive treatment method for lithium ion battery electrolyte |
| CN111678838A (en) * | 2020-05-20 | 2020-09-18 | 超威电源集团有限公司 | Device for collecting electrolyte in AGM separator and method for obtaining electrolyte density |
| CN111924816A (en) * | 2020-07-02 | 2020-11-13 | 曲靖市华祥科技有限公司 | Method for recovering electrolyte of waste lithium ion battery |
| CN112408437A (en) * | 2020-11-19 | 2021-02-26 | 江西天新药业股份有限公司 | Method for recovering lithium salt |
| CN112421143A (en) * | 2020-11-30 | 2021-02-26 | 湖南金源新材料股份有限公司 | Comprehensive recovery method of waste lithium battery electrolyte |
| CN113363610A (en) * | 2021-06-18 | 2021-09-07 | 郑州中科新兴产业技术研究院 | Harmless treatment method for retired lithium ion battery electrolyte |
| CN113471515A (en) * | 2021-06-30 | 2021-10-01 | 广州市浩立生物科技有限公司 | Method for recycling lithium battery electrolyte by combining supercritical extraction rectification and molecular distillation |
| CN114039116A (en) * | 2021-08-30 | 2022-02-11 | 雅邦绿色过程与新材料研究院南京有限公司 | Comprehensive recycling and regenerating method for waste electrolyte of lithium ion battery |
| CN114759286A (en) * | 2022-05-30 | 2022-07-15 | 清华大学深圳国际研究生院 | Method for recovering waste electrolyte of lithium ion battery |
| CN114804162A (en) * | 2022-04-14 | 2022-07-29 | 江西理工大学 | Low-temperature recovery method for lithium ion battery electrolyte |
| CN114914570A (en) * | 2022-05-20 | 2022-08-16 | 广州天赐高新材料股份有限公司 | Method and device for recycling electrolyte of waste lithium ion battery |
| CN116443843A (en) * | 2023-05-06 | 2023-07-18 | 珠海市赛纬电子材料股份有限公司 | Waste electrolyte recovery method |
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| CN113363610A (en) * | 2021-06-18 | 2021-09-07 | 郑州中科新兴产业技术研究院 | Harmless treatment method for retired lithium ion battery electrolyte |
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| CN114804162B (en) * | 2022-04-14 | 2024-01-16 | 江西理工大学 | Low-temperature recovery method for lithium ion battery electrolyte |
| CN114914570A (en) * | 2022-05-20 | 2022-08-16 | 广州天赐高新材料股份有限公司 | Method and device for recycling electrolyte of waste lithium ion battery |
| WO2023222127A1 (en) * | 2022-05-20 | 2023-11-23 | 广州天赐高新材料股份有限公司 | Waste lithium ion battery electrolyte recycling method and apparatus |
| CN114759286A (en) * | 2022-05-30 | 2022-07-15 | 清华大学深圳国际研究生院 | Method for recovering waste electrolyte of lithium ion battery |
| CN116443843A (en) * | 2023-05-06 | 2023-07-18 | 珠海市赛纬电子材料股份有限公司 | Waste electrolyte recovery method |
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