CN115353088B - Method for recycling lithium ion battery electrolyte - Google Patents
Method for recycling lithium ion battery electrolyte Download PDFInfo
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- CN115353088B CN115353088B CN202211018230.1A CN202211018230A CN115353088B CN 115353088 B CN115353088 B CN 115353088B CN 202211018230 A CN202211018230 A CN 202211018230A CN 115353088 B CN115353088 B CN 115353088B
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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
- C01D15/005—Lithium hexafluorophosphate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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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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- 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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- 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
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Abstract
The invention discloses a method for recycling lithium ion battery electrolyte, which comprises the steps of freezing waste lithium ion batteries, then disassembling, avoiding volatilization and decomposition of the electrolyte to pollute the environment, placing disassembled battery cells in carbon tetrachloride, enabling the electrolyte to be completely dissolved in the carbon tetrachloride, adding acetonitrile, complexing electrolyte solute lithium hexafluorophosphate with the acetonitrile, and forming stable Li (CH) 3 CN) 4 PF 6 And protecting lithium hexafluorophosphate from decomposition during negative pressure evaporation and concentration, cooling and crystallizing the concentrated solution, and understanding and complexing precipitated solid at a drying position to obtain lithium hexafluorophosphate.
Description
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a method for recovering lithium ion battery electrolyte.
Background
At present, the recovery research of the waste lithium ion battery is mainly focused on the recovery of anode and cathode materials and current collectors, and the recovery of electrolyte is less concerned. Currently, organic liquid electrolytes remain the main electrolyte materials in the market in various commercial lithium ion battery systems. The organic liquid electrolyte generally consists of three parts: electrolyte lithium salt and organic solventAgents and additives. The electrolyte salt in the electrolyte solutions currently in commercial use is typically LiPF 6 、LiCF 3 SO 3 And LiBF 4 Examples of the common solvents include Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), and methyl ethyl carbonate (EMC). The additive is used as an unnecessary component in the electrolyte, and the addition amount is small. The electrolyte composition is complex, in particular LiPF 6 The electrolyte is easy to decompose when contacting with the external environment, and toxic and harmful substances are generated.
Because electrolyte is volatile, the recovery difficulty is high, and researches and treatments are seldom conducted on electrolyte recovery. The volatilization of the electrolyte can generate unpleasant and pungent smell, and lithium salt in the electrolyte can generate toxic arsenides, phosphides and fluorides, which are serious harm to human bodies and the environment and become a problem which is difficult to avoid.
Patent CN108666644A discloses a method for recovering fluorine and lithium from lithium battery waste electrolyte, which adopts CaO or Ca (OH) 2 Reacts with lithium battery waste electrolyte, ca 2+ Reacts with fluoride ions in the electrolyte to generate CaF 2 And then adopting a multistage manganese fiber adsorption column and a titanium fiber adsorption column to perform physical directional adsorption of lithium ions, thereby recovering fluorine and lithium in the electrolyte. Patent CN108155434A discloses a method for recovering lithium from lithium ion battery waste electrolyte, which comprises mixing the waste electrolyte with a halide solution containing large cation radius for reaction, and PF in the electrolyte 6 -1 And (3) integrally separating, and carrying out deep purification and lithium precipitation treatment on the separated lithium-containing solution to obtain lithium carbonate. Both of the above methods cannot completely recover the expensive lithium hexafluorophosphate electrolyte salt.
Patent CN110203949a discloses a method for recovering electrolyte by performing reduced pressure distillation on waste electrolyte to separate each component one by one. However, the distillation process is complicated, the electrolyte composition is complicated, and the electrolyte is decomposed into small molecular substances through long-term circulation, so that the electrolyte is difficult to recycle.
Mishandling of the electrolyte can present serious safety and environmental concerns. Meanwhile, the added value of the electrolyte is high, and particularly lithium hexafluorophosphate is the most important component of the cost of the electrolyte, and accounts for about 43% of the total cost of the electrolyte. Therefore, how to reasonably recover the electrolyte salt and the solvent in the electrolyte is a problem worthy of intensive research.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a method for recycling lithium ion battery electrolyte, which can completely recycle high-purity lithium hexafluorophosphate and has lower impurities in the recycled organic solvent.
According to one aspect of the present invention, there is provided a method of recovering lithium ion battery electrolyte, comprising the steps of:
s1: after the waste lithium ion battery is discharged, freezing by adopting liquid nitrogen, and disassembling the frozen waste lithium ion battery to obtain an electric core containing electrolyte;
s2: soaking the battery cell in carbon tetrachloride, and carrying out solid-liquid separation to obtain a first liquid phase;
s3: mixing the first liquid phase with acetonitrile, and evaporating and concentrating under negative pressure to obtain an evaporation liquid and a concentrated solution, wherein the main component of the evaporation liquid is carbon tetrachloride;
s4: cooling and crystallizing the concentrated solution, and carrying out solid-liquid separation to obtain a second liquid phase and a solid; washing the solid by anhydrous hydrogen fluoride, and drying the solid in an inert atmosphere to obtain lithium hexafluorophosphate; rectifying the second liquid phase to obtain low-boiling-point substances and high-boiling-point substances;
s5: and mixing the low-boiling-point substances with the potassium permanganate aqueous solution, standing, removing the aqueous phase, adding quicklime, and carrying out solid-liquid separation to obtain the anhydrous carbon tetrachloride.
In some embodiments of the invention, in step S1, the temperature of the freezing is-60 ℃ or lower.
In some embodiments of the invention, in step S2, the solid-to-liquid ratio of the cell and carbon tetrachloride is 100-200g/L.
In some embodiments of the invention, in step S2, the soaking time is 10-30min.
In some embodiments of the present invention, in step S2, after the soaking is finished, the method further includes a washing process: taking out the soaked battery cell to obtain a soaked liquid, flushing the battery cell with carbon tetrachloride, mixing the flushed liquid with the soaked liquid, and filtering to obtain the first liquid phase.
In some embodiments of the invention, in step S3, the volume ratio of acetonitrile to the first liquid phase is 20-60mL/L.
In some embodiments of the present invention, in step S3, the pressure of the evaporation concentration is-0.1 to-0.08 MPa, the temperature is 65-70 ℃, and the evaporation concentration is performed until the volume of the first liquid phase is reduced to 1/4-1/5 of the original volume.
In some embodiments of the present invention, in step S4, the cooling crystallization temperature is-15 to-10 ℃.
In some embodiments of the invention, in step S4, the temperature of the anhydrous hydrogen fluoride wash is from 0 to 5 ℃. The subsequent drying is carried out at low temperature, so that residues (such as high-boiling-point organic matters) on the solid surface are not easy to remove, the purity is influenced, surface impurities are required to be removed through washing, and the anhydrous hydrogen fluoride has a good washing effect when used as a detergent.
In some embodiments of the invention, in step S4, the drying is performed under negative pressure, the pressure is-0.1 to-0.08 MPa, the drying temperature is 0-5 ℃, and the time is 12-24 hours.
In some embodiments of the invention, in step S4, the rectification is atmospheric rectification at a temperature of 120-140 ℃. The rectification temperature can ensure that small molecular impurities are almost completely distilled out.
In some embodiments of the present invention, in step S4, when the low boiling point organic solvent to be recovered is contained in the low boiling point substance, the low boiling point substance may be selectively condensed and separated during the rectification process to recover the desired organic solvent.
In some embodiments of the present invention, in step S5, the volume ratio of the low boiling substance to the potassium permanganate aqueous solution is 1: (0.5-2.0), wherein the concentration of the potassium permanganate aqueous solution is 1-2mol/L.
In some embodiments of the present invention, in step S5, after the aqueous phase is removed, a crude carbon tetrachloride product is obtained, and a solid-to-liquid ratio of quicklime to the crude carbon tetrachloride product is 20-50g/L.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
1. according to the invention, firstly, the waste lithium ion batteries are frozen and then disassembled, so that the volatilization and decomposition of the electrolyte are avoided, and the environment is polluted. The disassembled battery cell is placed in carbon tetrachloride, so that the electrolyte is completely dissolved in the carbon tetrachloride, acetonitrile is further added, and the electrolyte solute lithium hexafluorophosphate is complexed with the acetonitrile to form stable Li (CH) 3 CN) 4 PF 6 And during subsequent negative pressure evaporation concentration, lithium hexafluorophosphate is protected from decomposition. Reuse of Li (CH) 3 CN) 4 PF 6 The phenomenon of low solubility in carbon tetrachloride, cooling crystallization, and further drying treatment to precipitate Li (CH) 3 CN) 4 PF 6 Decomplexing to obtain high-purity lithium hexafluorophosphate.
2. Because the electrolyte is recycled for a long time to generate a plurality of small molecular substances which are difficult to recycle, the invention uses the characteristics of low boiling point and high stability of carbon tetrachloride, and retains high boiling point substances such as ethylene carbonate and the like when the subsequent normal pressure rectification is carried out, the high boiling point substances can be directly used as the solvent of the electrolyte, the small molecular substances with low boiling point and the carbon tetrachloride are collected and then removed by potassium permanganate, and the anhydrous carbon tetrachloride is obtained by dehydration treatment of quicklime, so that the anhydrous carbon tetrachloride can be reused.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
fig. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
Referring to fig. 1, a method for recovering lithium ion battery electrolyte comprises the following specific processes:
step 1, after the waste lithium ion battery is discharged, freezing the waste lithium ion battery to below-60 ℃ by adopting liquid nitrogen;
step 2, disassembling the frozen waste lithium ion battery, and taking out the battery core containing the electrolyte;
step 3, placing the battery cell into anhydrous carbon tetrachloride according to a solid-to-liquid ratio of 100g/L, and soaking for 10min;
step 4, taking out the battery core, flushing with anhydrous carbon tetrachloride, and mixing the washing liquid with the carbon tetrachloride in the step 3 to obtain a mixed liquid;
step 5, filtering the mixed solution, and removing filter residues to obtain filtrate;
step 6, adding anhydrous acetonitrile into the filtrate according to the volume ratio acetonitrile/filtrate=20 mL/L, uniformly mixing, and evaporating and concentrating at the pressure of-0.08 MPa and the temperature of 70 ℃ until the volume of the filtrate is reduced to 1/5 of the original volume, thereby obtaining an evaporation liquid and a concentrated solution, wherein the main component of the evaporation liquid is carbon tetrachloride, and the carbon tetrachloride can be recycled;
step 7, cooling the concentrated solution to-15 ℃, and carrying out suction filtration to obtain solid and filtrate;
step 8, washing the solid with anhydrous hydrogen fluoride at 0 ℃, drying under nitrogen atmosphere, controlling the pressure to be-0.1 to-0.08 MPa and the temperature to be 0 ℃ for 24 hours, and obtaining a lithium hexafluorophosphate product;
step 9, rectifying the filtrate obtained in the step 8 at normal pressure, wherein the rectifying temperature is 120 ℃, so as to obtain low-boiling-point substances and high-boiling-point substances, wherein the high-boiling-point substances can be directly used as solvents of the electrolyte;
and step 10, collecting low-boiling-point substances, adding 1mol/L potassium permanganate aqueous solution according to a volume ratio of 1:1, mixing, standing, removing the aqueous phase, adding quicklime according to a solid-liquid ratio of 20g/L, performing solid-liquid separation to obtain anhydrous carbon tetrachloride, mixing with the evaporation liquid obtained in the step 6, and then reusing the mixture for soaking and flushing the battery cells.
Example 2
The method for recycling the lithium ion battery electrolyte comprises the following specific processes:
step 1, after the waste lithium ion battery is discharged, freezing the waste lithium ion battery to below-60 ℃ by adopting liquid nitrogen;
step 2, disassembling the frozen waste lithium ion battery, and taking out the battery core containing the electrolyte;
step 3, placing the battery cell into anhydrous carbon tetrachloride according to a solid-to-liquid ratio of 150g/L, and soaking for 20min;
step 4, taking out the battery core, flushing with anhydrous carbon tetrachloride, and mixing the washing liquid with the carbon tetrachloride in the step 3 to obtain a mixed liquid;
step 5, filtering the mixed solution, and removing filter residues to obtain filtrate;
step 6, adding anhydrous acetonitrile into the filtrate according to the volume ratio acetonitrile/filtrate=30 mL/L, uniformly mixing, and evaporating and concentrating at the pressure of-0.09 MPa and the temperature of 68 ℃ until the volume of the filtrate is reduced to 1/4 of the original volume, thereby obtaining an evaporation liquid and a concentrated solution, wherein the main component of the evaporation liquid is carbon tetrachloride, and the carbon tetrachloride can be recycled;
step 7, cooling the concentrated solution to-12 ℃, and carrying out suction filtration to obtain solid and filtrate;
step 8, washing the solid with anhydrous hydrogen fluoride at 3 ℃, drying under nitrogen atmosphere, controlling the pressure to be-0.1 to-0.08 MPa and the temperature to be 3 ℃ for 18 hours, and obtaining a lithium hexafluorophosphate product;
step 9, rectifying the filtrate obtained in the step 8 at normal pressure, wherein the rectifying temperature is 130 ℃, so as to obtain low-boiling-point substances and high-boiling-point substances, wherein the high-boiling-point substances can be directly used as solvents of the electrolyte;
and 10, collecting low-boiling-point substances, adding 1.5mol/L potassium permanganate aqueous solution according to a volume ratio of 1:1, mixing, standing, removing the aqueous phase, adding quicklime according to a solid-liquid ratio of 30g/L, performing solid-liquid separation to obtain anhydrous carbon tetrachloride, mixing with the evaporation liquid obtained in the step 6, and reusing the mixture for soaking and flushing the battery cells.
Example 3
The method for recycling the lithium ion battery electrolyte comprises the following specific processes:
step 1, after the waste lithium ion battery is discharged, freezing the waste lithium ion battery to below-60 ℃ by adopting liquid nitrogen;
step 2, disassembling the frozen waste lithium ion battery, and taking out the battery core containing the electrolyte;
step 3, placing the battery cell into anhydrous carbon tetrachloride according to a solid-to-liquid ratio of 200g/L, and soaking for 30min;
step 4, taking out the battery core, flushing with anhydrous carbon tetrachloride, and mixing the washing liquid with the carbon tetrachloride in the step 3 to obtain a mixed liquid;
step 5, filtering the mixed solution, and removing filter residues to obtain filtrate;
step 6, adding anhydrous acetonitrile into the filtrate according to the volume ratio acetonitrile/filtrate=60 mL/L, uniformly mixing, and evaporating and concentrating at the pressure of-0.1 MPa and the temperature of 65 ℃ until the volume of the filtrate is reduced to 1/5 of the original volume, thereby obtaining an evaporation liquid and a concentrated solution, wherein the main component of the evaporation liquid is carbon tetrachloride, and the carbon tetrachloride can be recycled;
step 7, cooling the concentrated solution to-10 ℃, and carrying out suction filtration to obtain solid and filtrate;
step 8, washing the solid with anhydrous hydrogen fluoride at 5 ℃, drying under nitrogen atmosphere, controlling the pressure to be-0.1 to-0.08 MPa and the temperature to be 5 ℃ for 12 hours, and obtaining a lithium hexafluorophosphate product;
step 9, rectifying the filtrate obtained in the step 8 at normal pressure, wherein the rectifying temperature is 140 ℃, so as to obtain low-boiling-point substances and high-boiling-point substances, wherein the high-boiling-point substances can be directly used as solvents of the electrolyte;
and step 10, collecting low-boiling-point substances, adding 2mol/L potassium permanganate aqueous solution according to a volume ratio of 1:1, mixing, standing, removing the aqueous phase, adding quicklime according to a solid-liquid ratio of 50g/L, performing solid-liquid separation to obtain anhydrous carbon tetrachloride, mixing with the evaporation liquid obtained in the step 6, and then reusing the mixture for soaking and flushing the battery cells.
Comparative example
The main difference between the method for recovering lithium ion battery electrolyte and the embodiment 3 is that the step 3 is soaked with acetonitrile, and the specific process is as follows:
step 1, after the waste lithium ion battery is discharged, freezing the waste lithium ion battery to below-60 ℃ by adopting liquid nitrogen;
step 2, disassembling the frozen waste lithium ion battery, and taking out the battery core containing the electrolyte;
step 3, placing the battery cell into anhydrous acetonitrile according to a solid-to-liquid ratio of 200g/L, and soaking for 30min;
step 4, taking out the battery cell, flushing with anhydrous acetonitrile, and mixing the washing solution with the acetonitrile solution in the step 3 to obtain a mixed solution;
step 5, filtering the mixed solution, and removing filter residues to obtain filtrate;
step 6, evaporating and concentrating the filtrate at the pressure of-0.1 MPa and the temperature of 70 ℃ until the volume of the filtrate is reduced to 1/5 of the original volume, so as to obtain an evaporating solution and a concentrated solution, wherein the main component of the evaporating solution is acetonitrile, and the evaporating solution can be recycled;
step 7, cooling the concentrated solution to-10 ℃, and carrying out suction filtration to obtain solid and filtrate;
step 8, washing the solid with anhydrous hydrogen fluoride at 5 ℃, drying under nitrogen atmosphere, controlling the pressure to be-0.1 to-0.08 MPa and the temperature to be 5 ℃ for 12 hours, and obtaining a lithium hexafluorophosphate product;
step 9, rectifying the filtrate obtained in the step 8 at normal pressure, wherein the rectifying temperature is 140 ℃, so as to obtain low-boiling-point substances and high-boiling-point substances, wherein the high-boiling-point substances can be directly used as solvents of the electrolyte;
and step 10, collecting low-boiling-point substances, adding 2mol/L potassium permanganate aqueous solution according to the volume ratio of 1:1, mixing, and standing to prevent the solution from layering.
The purity of the lithium hexafluorophosphate products obtained in examples 1 to 3 and comparative example and the yield of the organic solvent were examined, and the results are shown in Table 1.
TABLE 1
As can be seen from table 1, the yields of lithium hexafluorophosphate and the organic solvent used in the comparative example are significantly lower than those in the examples, since acetonitrile is used for the comparative example step 3, acetonitrile may be directly crystallized from lithium hexafluorophosphate, subsequent solid-liquid separation, and the crystals remain in the solid phase and cannot be recovered, resulting in loss of lithium hexafluorophosphate and acetonitrile.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (9)
1. A method for recovering lithium ion battery electrolyte, comprising the steps of:
s1: after the waste lithium ion battery is discharged, freezing by adopting liquid nitrogen, and disassembling the frozen waste lithium ion battery to obtain an electric core containing electrolyte;
s2: soaking the battery cell in carbon tetrachloride, and carrying out solid-liquid separation to obtain a first liquid phase;
s3: mixing the first liquid phase with acetonitrile, and evaporating and concentrating under negative pressure to obtain an evaporation liquid and a concentrated solution, wherein the main component of the evaporation liquid is carbon tetrachloride; the volume ratio of the acetonitrile to the first liquid phase is 20-60mL/L;
s4: cooling and crystallizing the concentrated solution, and carrying out solid-liquid separation to obtain a second liquid phase and a solid; washing the solid by anhydrous hydrogen fluoride, and drying the solid in an inert atmosphere to obtain lithium hexafluorophosphate; rectifying the second liquid phase to obtain low-boiling-point substances and high-boiling-point substances;
s5: and mixing the low-boiling-point substances with the potassium permanganate aqueous solution, standing, removing the aqueous phase, adding quicklime, and carrying out solid-liquid separation to obtain the anhydrous carbon tetrachloride.
2. The method of claim 1, wherein in step S2, the solid to liquid ratio of the cell to carbon tetrachloride is 100-200g/L.
3. The method according to claim 1, further comprising a washing step after the soaking step S2: taking out the soaked battery cell to obtain a soaked liquid, flushing the battery cell with carbon tetrachloride, mixing the flushed liquid with the soaked liquid, and filtering to obtain the first liquid phase.
4. The method according to claim 1, wherein in step S3, the pressure of the evaporation concentration is-0.1 to-0.08 MPa, the temperature is 65-70 ℃, and the evaporation concentration is performed until the volume of the first liquid phase is reduced to 1/4-1/5 of the original volume.
5. The method according to claim 1, wherein in step S4, the cooling crystallization temperature is-15 to-10 ℃.
6. The method according to claim 1, wherein in step S4, the drying is performed under negative pressure of-0.1 to-0.08 MPa, at a temperature of 0-5 ℃ for 12-24 hours.
7. The method according to claim 1, wherein in step S4, the rectification is atmospheric rectification at a temperature of 120-140 ℃.
8. The method according to claim 1, wherein in step S5, the volume ratio of the low boiling substance to the potassium permanganate aqueous solution is 1: (0.5-2.0), wherein the concentration of the potassium permanganate aqueous solution is 1-2mol/L.
9. The method according to claim 1, wherein in step S5, after the aqueous phase is removed, a crude carbon tetrachloride product is obtained, and a solid-to-liquid ratio of quicklime to the crude carbon tetrachloride product is 20-50g/L.
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| CN202211018230.1A CN115353088B (en) | 2022-08-24 | 2022-08-24 | Method for recycling lithium ion battery electrolyte |
| PCT/CN2023/079084 WO2024040906A1 (en) | 2022-08-24 | 2023-03-01 | Method for recycling lithium-ion battery electrolyte |
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| CN105355999A (en) * | 2015-11-30 | 2016-02-24 | 马鞍山泓宇材料科技有限公司 | Novel waste lithium battery recycling method |
| CN110289457A (en) * | 2019-06-24 | 2019-09-27 | 中国科学院过程工程研究所 | A kind of green waste and old lithium ionic cell electrolyte recovery system and method |
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| CN109292746A (en) * | 2018-09-17 | 2019-02-01 | 南昌航空大学 | The method of lithium hexafluoro phosphate is recycled in a kind of waste lithium cell |
| CN112054262A (en) * | 2020-08-28 | 2020-12-08 | 甘肃电气装备集团生物科技工程有限公司 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
| CN115353088B (en) * | 2022-08-24 | 2023-09-12 | 广东邦普循环科技有限公司 | Method for recycling lithium ion battery electrolyte |
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| CN105355999A (en) * | 2015-11-30 | 2016-02-24 | 马鞍山泓宇材料科技有限公司 | Novel waste lithium battery recycling method |
| CN110289457A (en) * | 2019-06-24 | 2019-09-27 | 中国科学院过程工程研究所 | A kind of green waste and old lithium ionic cell electrolyte recovery system and method |
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