CN112054262A - Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent - Google Patents
Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent Download PDFInfo
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- CN112054262A CN112054262A CN202010888128.1A CN202010888128A CN112054262A CN 112054262 A CN112054262 A CN 112054262A CN 202010888128 A CN202010888128 A CN 202010888128A CN 112054262 A CN112054262 A CN 112054262A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 94
- 239000002904 solvent Substances 0.000 title claims abstract description 86
- 238000002386 leaching Methods 0.000 title claims abstract description 78
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004064 recycling Methods 0.000 title description 7
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005194 fractionation Methods 0.000 claims abstract description 9
- 239000013557 residual solvent Substances 0.000 claims description 28
- 238000011084 recovery Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical group F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 8
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 22
- -1 lithium hexafluorophosphate Chemical compound 0.000 abstract description 16
- 238000009835 boiling Methods 0.000 abstract description 12
- 231100000053 low toxicity Toxicity 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011978 dissolution method Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
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Classifications
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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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a leaching solvent suitable for electrolyte in a retired lithium battery and a method for separating and recovering the electrolyte from the retired lithium battery by using the leaching solvent, which comprises the following steps: and (3) tetrafluoropropene. The electrolyte leaching solvent for the decommissioned lithium battery is made of tetrafluoropropene, has the characteristics of low toxicity and non-flammability, can dissolve electrolytes such as lithium hexafluorophosphate, has a boiling point lower than the pyrolysis temperature of the lithium hexafluorophosphate, and can not release harmful substances in the leaching fractionation process, so that the electrolytes such as the lithium hexafluorophosphate can be fully recovered, and the environment cannot be polluted.
Description
Technical Field
The invention belongs to the field of lithium battery material recovery, and particularly relates to a leaching solvent suitable for an electrolyte in a retired lithium battery and a method for separating and recovering the electrolyte from the retired lithium battery by using the leaching solvent.
Background
In recent years, with the rapid development of electric automobiles and large-scale energy storage markets, the yield of lithium ion power batteries is rapidly increased, and the number of waste lithium ion batteries generated along with the rapid increase is shown. The waste lithium ion power battery contains a large amount of non-ferrous metal elements such as cobalt, lithium, nickel, manganese, copper, aluminum and the like which are in short supply, and also contains toxic and harmful substances such as electrolyte, electrolyte lithium hexafluorophosphate, binder and the like, particularly the electrolyte lithium hexafluorophosphate in the electrolyte has poor thermal stability, and can be decomposed at 60 ℃ to generate PF5With accompanying HF gas and further generation of highly hazardous hydrofluoric acid.
PF is easily generated in the traditional treatment process of the retired lithium battery5HF or other fluorides pollute the atmosphere, water and soil, causing serious environmental pollution. In addition, heavy metal compounds in the anode material can also cause water and soil pollution; the negative electrode material can cause dust pollution; the separator material causes white contamination. Meanwhile, the loss of high-value metals such as copper, nickel, cobalt, manganese, lithium and the like causes resource waste, so that the resource recovery and harmless treatment of the retired lithium battery have great economic and social values.
Currently, the problem of recycling and reusing lithium ion power batteries has become a focus of great social attention. The safe disposal and recycling of the waste lithium ion battery materials are ensured, and the method has profound significance for realizing circular economy and sustainable development.
The existing lithium ion power battery recovery process route is complicated, and in the existing theoretical research and industrial application case, the recovery process mainly comprises the following three steps: pretreatment, secondary treatment and advanced treatment. The specific method is summarized as follows:
a pretreatment step: waste lithium batteries generally have residual electricity, so that the batteries need to be discharged before being recycled. In addition, an electrolyte (electrolyte) contained in a lithium battery generates toxic HF when it comes into contact with water. In view of this, the recycled lithium battery should first be subjected to appropriate pre-treatment to eliminate potential hazards. The pretreatment step mainly comprises a deep discharge process and an inert gas protection process in a crushing link, and the method is known in the industry and adopted by the mainstream process.
A secondary treatment step: the secondary treatment step aims at realizing the complete separation of the positive and negative electrode active materials of the lithium battery and the copper-aluminum pole piece, and the current common methods comprise a pyrogenic process thermal decomposition method, an organic solvent dissolution method, an acid-alkali solution dissolution method and an electrolysis method.
The pyro-thermolysis is to put the battery at 380-500 ℃ to promote the decomposition and volatilization of the electrolyte (electrolyte) and the binding agent, thereby realizing the separation of the anode and cathode materials and the copper-aluminum foil pole piece. The pyrogenic process thermal decomposition process is simple, the operation is convenient, and the electrolyte (electrolyte) and the binder can be effectively removed. However, the thermal decomposition process necessarily generates a large amount of toxic and harmful gases, and if the gases are improperly absorbed and purified, serious secondary pollution is easily caused.
The organic solvent dissolution method is a method for separating a positive electrode material and a negative electrode material from a copper aluminum foil, and comprises the steps of dissolving out an electrolyte by using organic solvents such as dichloromethane, chloroform, acetone, ethanol and the like, and separating the electrolyte from the solvent by distillation. However, the solvents are all flammable and explosive substances and have high dangerousness, and more importantly, in the process of separating the electrolyte (electrolyte) and the solvents by distillation, the electrolyte lithium hexafluorophosphate in the electrolyte can be decomposed to generate toxic and harmful fluorides due to high working temperature, so that the production and environmental safety are endangered. Under the common conditions, residual solvents attached to the anode and cathode materials, copper and aluminum foils and the plastic surfaces of the lithium batteries cannot be recycled, so that fire-fighting hidden dangers and secondary pollution are inevitably formed.
The acid-alkali solution dissolving method is that firstly, the broken battery is placed in an alkaline solution, wherein the aluminum foil can be dissolved in the alkaline solution, and the copper foil does not react with the alkali; calcining the copper foil and the carbon powder material after alkaline leaching at high temperature or dissolving the copper foil and the carbon powder material in an organic matter to decompose or dissolve the binder, and then performing acid leaching on the remainder to realize the separation of the active material. The method can not completely remove fluoride, and the intervention of acid-base solution inevitably causes pollution to production environment, water body environment,The air environment causes pollution; in addition, the method needs to consume a large amount of acid and alkali solution, and generates a large amount of AlO after dissolution2 -1And the subsequent separation and purification of the active material are not facilitated.
The electrolytic method is characterized in that a lead plate is used as an anode, a battery anode is used as a cathode, an electrolyte is a sulfuric acid solution, the falling of an anode material is realized under the action of an external electric field, and an aluminum foil is recovered. The method can realize the separation of the anode material and the aluminum foil to obtain pure aluminum foil, and can promote part of the anode material to be electrolyzed and converted into an ion form to be present in the electrolyte, thereby facilitating the subsequent treatment. But has the disadvantages of large electric energy consumption and low electrolysis efficiency; the retired sulfuric acid needs to be subjected to harmless treatment; hydrogen generated in the electrolysis process causes fire-fighting hidden danger in the production environment.
Deep treatment: the traditional wet smelting process is adopted to recover and regenerate the heavy metals such as nickel, cobalt, manganese, lithium and the like contained in the lithium battery anode material, and the method is known in the industry and adopted by the mainstream process.
In conclusion, the existing method in the industry can achieve the purpose of partially separating and recycling the lithium battery materials, but common problems of high energy consumption, large acid and alkali loss, serious environmental pollution and large burning explosion risk exist in different degrees, particularly electrolyte (electrolyte) cannot be recycled, and the industrial application process of recycling the retired lithium battery is restricted. The above problems are technical problems to be solved in the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a leaching solvent suitable for an electrolyte in a retired lithium battery and a method for separating and recovering the electrolyte from the retired lithium battery by using the leaching solvent.
The technical scheme for solving the technical problems is as follows: a solvent suitable for electrolyte leaching in a decommissioned lithium battery, comprising: and (3) tetrafluoropropene.
The invention has the beneficial effects that: the electrolyte leaching solvent for the decommissioned lithium battery is made of tetrafluoropropene, has the characteristics of low toxicity and non-flammability, can dissolve electrolytes such as lithium hexafluorophosphate, has a boiling point lower than the pyrolysis temperature of the lithium hexafluorophosphate, and can not release harmful substances in the leaching fractionation process, so that the electrolytes such as the lithium hexafluorophosphate can be fully recovered, and the environment cannot be polluted.
Further, the tetrafluoropropene is 1,3,3, 3-tetrafluoropropene and/or 2,3,3, 3-tetrafluoropropene.
Further, the solvent also comprises tetrafluoroethane, and the volume percentage of the tetrafluoroethane in the solvent is 10% -90%.
The tetrafluoroethane is used as an electrolyte leaching solvent of an retired lithium battery, has the characteristics of low toxicity and nonflammability, can dissolve electrolytes such as lithium hexafluorophosphate and the like, has a boiling point lower than the pyrolysis temperature of the lithium hexafluorophosphate, and does not release harmful substances in the leaching fractionation process, so that the tetrafluoroethane can be mixed with tetrafluoropropene to fully recover the electrolytes such as the lithium hexafluorophosphate and the like, and does not cause pollution to the environment.
The application also discloses a separation and recovery method for leaching the electrolyte in the retired lithium battery, which comprises the following steps of:
s100: mixing the discharged and crushed retired lithium battery with the solvent in a vacuum environment, and then leaching at 20-50 ℃ and under the condition of 0.6-1.6MPa to respectively obtain leaching mixed liquor and insoluble solids;
s200: heating the leaching mixed solution to 20-50 ℃ and fractionating under the condition of-0.08 MPa-1.6MPa to obtain a first recovery solvent and an electrolyte.
The electrolyte/electrolyte in the retired electromagnetism can be leached and separated through two steps, the method is simple and efficient, the recovery rate of the electrolyte can reach more than 97%, the recovered solvent can be reused, the leaching solution and the retired lithium battery are mixed under the vacuum condition, the probability and time of hazardous substances generated by contact of the electrolyte or the electrolyte and air are reduced, and therefore the whole leaching process is more environment-friendly.
Further, in the step S200, the fractionating step includes:
s201: heating the leaching mixed solution to 20-50 ℃ under the condition of 0.6-1.6Mpa until the working pressure is reduced to below 0.6Mpa, collecting steam and condensing to obtain a first distillate;
s202: heating the leaching mixed solution at 20-50 ℃ until the working pressure is reduced to below 0.2Mpa, pressurizing the steam to 0.6Mpa-1.6Mpa, and condensing to obtain a second distillate;
s203: heating the leaching mixed solution at 20-50 ℃, sucking steam in vacuum until the working pressure is reduced to be below-0.08 MPa, pressurizing the steam to be 0.6-1.6MPa, and condensing to obtain a third distillate;
s204: and mixing the first distillate, the second distillate and the third distillate to obtain the first recovered solvent, and collecting the residual unevaporated liquid to obtain the electrolyte.
The solvent is fractionated in three stages, and the solvent can be sufficiently fractionated from the electrolyte.
Further, the step S100 is followed by a step S300: and heating the insoluble solid to 20-50 ℃ under the condition of-0.08 MPa-1.6MPa, removing residual solvent on the surface of the insoluble solid and recovering to obtain a second recovered solvent and a lithium battery solid material.
Further, in the step S300, the step of recovering the residual solvent includes:
s301: heating the insoluble solid to 20-50 ℃ under the condition of 0.6-1.6Mpa until the working pressure is reduced to below 0.6Mpa, collecting steam and condensing to obtain a first residual solvent;
s302: heating the insoluble solid at 20-50 deg.C until the working pressure is reduced to below 0.2Mpa, and condensing the steam under 0.6-1.6Mpa to obtain a second residual solvent;
s303: heating the insoluble solid at 20-50 deg.C, vacuum-pumping steam until the working pressure is reduced to below-0.08 MPa, pressurizing the steam to 0.6-1.6MPa, and condensing to obtain a third residual solvent;
s304: mixing the first residual solvent, the second residual solvent and the third residual solvent to obtain the second recovered solvent.
The residual solvent on the surface of the insoluble solid can be effectively removed and collected by distilling the residual solvent on the surface of the insoluble solid in three stages.
Further, the steps S200 and S300 are followed by a step S400: and collecting and mixing the first recovered solvent and the second recovered solvent to obtain a recovered solvent, and using the recovered solvent for leaching the electrolyte in the retired lithium battery.
This application is collected and is mixed first recovered solvent and second recovered solvent, can recycle, reduce cost.
Further, in the step S100, the solid-to-liquid volume ratio of the retired lithium battery to the solvent is 1:1 to 1: 4.
Further, in step S100, the leaching step includes: leaching at stirring speed of 3-5r/Min for 20-40Min, and repeating for 1-4 times.
The electrolyte can be fully dissolved by leaching for multiple times under the stirring condition.
Drawings
FIG. 1 is a general flow chart of the present application;
FIG. 2 is a schematic flow chart of the fractionation step in step S100;
FIG. 3 is a schematic flow chart of the step of recovering the residual solvent on the surface of the insoluble solid in step S300;
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
The following discloses many different embodiments or examples for implementing the subject technology described. While specific examples of one or more arrangements of features are described below to simplify the disclosure, the examples should not be construed as limiting the invention, and the first feature described later in the specification in conjunction with the second feature may include embodiments that are directly related, may also include embodiments that form additional features, and further may include embodiments in which one or more additional intervening features are used to indirectly connect or combine the first and second features to each other, so that the first and second features may not be directly related.
It should be understood that, in the following embodiments provided in the present application, the steps are not invariable, and some steps may be performed in a different order or synchronously without affecting the experimental results of the present application.
It should be understood that the present disclosure is based on experiments conducted on industrial production equipment where temperature and pressure are difficult to maintain at a precise specific value and pressure generally varies with temperature, and therefore in the examples disclosed below, both operating pressure and temperature are adjusted within a range of values.
Example 1
The solvent is selected from a single component 1,3,3, 3-tetrafluoropropene (HFO-1234ze (type E)), and is marked as solvent I. The main parameters are as follows:
| boiling point | ODP | GWP | Level of security | Toxicity | Pressure at 20 deg.C | Pressure at 50 deg.C |
| -19℃ | 0 | 6 | A1 | Is non-toxic | 0.6MPa | 1.3MPa |
S101: filling the crushed lithium battery into a proper closed container, vacuumizing at normal temperature, wherein the working gauge pressure is between-0.06 MPa and-0.08 MPa, and removing residual gas in the container;
s102: adding a solvent I into the closed container, wherein the adding volume of the solvent I is 1-2 times of the volume of the lithium battery material, heating to 20-50 ℃, boosting the pressure to 0.6-1.3Mpa, and stirring and leaching for 20-40 minutes to fully dissolve the electrolyte and the electrolyte in the solvent I;
s103: starting a filtering system in the container to enable the liquid to penetrate through a filter screen so as to be separated from the solid, respectively obtaining leaching mixed liquor and insoluble solid in which electrolyte and electrolyte are dissolved, and repeatedly leaching and filtering for 1-2 times to enable the electrolyte and the electrolyte in the battery to be completely leached;
s200: in a closed container, the leaching mixed solution of the electrolyte is continuously heated to 20-50 ℃, and the solvent is fractionated.
In this example, the fractionation may be carried out by the following specific steps:
s201: heating the leaching mixed solution to 20-50 ℃ under the condition of 1.3Mpa until the working pressure is reduced to 0.6Mpa, collecting steam and condensing to obtain a first distillate;
s202: heating at 20-50 deg.C to evaporate and leach the mixed solution, pumping steam through compressor, pressurizing to 0.6-1.3Mpa, and condensing to obtain second distillate until the working pressure is reduced to 0.2 Mpa;
s203: heating the leaching mixed solution at the temperature of 20-50 ℃, sucking steam by a vacuum pump until the interior of the container is changed from positive pressure to vacuum and stably reaches the working gauge pressure ranging from-0.08 MPa to-0.09 MPa, keeping the temperature at 20-50 ℃, continuing for more than 5 minutes to indicate that the leaching solvent is completely evaporated, pressurizing the steam to 0.6-1.3MPa and condensing to obtain a third distillate;
s204, mixing the first distillate, the second distillate and the third distillate to obtain the first recovered solvent, and collecting the residual liquid to obtain the electrolyte.
S300: in a closed container, the insoluble solid material is continuously heated to 20-50 ℃ until the residual solvent on the surface of the insoluble solid is desorbed and evaporated.
In the examples of the present application, the evaporated residual solvent can be recovered, specifically, the following steps can be performed:
s301: heating the insoluble solid to 20-50 ℃ under the condition of 1.3Mpa until the working pressure is reduced to 0.6Mpa, collecting steam and condensing to obtain a first residual solvent;
s302: heating and evaporating the insoluble solid at the temperature of 20-50 ℃, pumping by a compressor until the working pressure in the container is reduced to 0.2Mpa, pressurizing the steam to 0.6-1.3Mpa by the compressor, and condensing to obtain a second residual solvent;
s303: heating the insoluble solid at the temperature of 20-50 ℃, starting a vacuum pump to extract steam in vacuum until the working pressure is reduced to-0.08 MPa, then pressurizing the steam to 0.6-1.3MPa by a compressor and condensing to obtain a third residual solvent until the interior of the container is changed from positive pressure to vacuum and is stabilized to the working gauge pressure of-0.08-0.09 MPa for more than 5 minutes, which indicates that the leaching solvent is completely evaporated;
s304: mixing the first residual solvent, the second residual solvent and the third residual solvent to obtain the second recovered solvent.
The principle of the application is that the boiling point of the electrolyte is more than 90 ℃, and the electrolyte cannot be evaporated in the range of 20-50 ℃, so that the leaching mixed solution can be fractionated into the electrolyte and the solvent in the temperature range; the thermal decomposition temperature of the electrolyte lithium hexafluorophosphate in the electrolyte is 60 ℃, and the electrolyte lithium hexafluorophosphate is not decomposed when the working temperature is not more than 50 ℃, so that the environmental hazard is avoided.
In the embodiment, on the basis of effectively separating the retired lithium battery material, the leaching solvent can be effectively recovered at the same time, so that the environmental pollution and the material waste are avoided, the energy is effectively saved, and the cost is reduced.
Example 2
The solvent is 2,3,3, 3-tetrafluoropropene (HFO-1234yf) which is a single component and is marked as a solvent II. The main parameters are as follows:
| boiling point | ODP | GWP | Level of security | Toxicity | Pressure at 25 deg.C | Pressure of 40 deg.C |
| -29℃ | 0 | 4 | A2 | Low toxicity | 0.67MPa | <1.6MPa |
The volume of the solvent II is 1 to 3 times of the volume of the lithium battery material, wherein the leaching temperature is 25 to 40 ℃, the pressure is 0.6 to 1.6Mpa, and the stirring leaching is carried out for 25 to 40 minutes.
The electrolyte was fractionated and recovered by referring to the procedure in example 1.
Example 3
The solvent was selected from 90% by volume of 1,3,3, 3-tetrafluoropropene (HFO-1234ze (type E)), to which 10% by volume of tetrafluoroethane (R134a) was added to formulate the leaching solvent iii. The main parameters are as follows:
| boiling point | ODP | Level of security | Toxicity | Pressure of 30 DEG C | Pressure at 50 deg.C |
| About-20 deg.C | 0 | A2 | Low toxicity | 0.7MPa | 1.4MPa |
And (3) putting the crushed lithium battery into a proper closed container, vacuumizing, and discharging gas in the container under the working gauge pressure of-0.06 to-0.08 MPa.
Wherein the volume of the solvent III is 1 to 4 times of the volume of the lithium battery material, the leaching temperature is 30 to 50 ℃, the pressure is 0.7 to 1.4Mpa, and the stirring leaching is carried out for 30 to 35 minutes.
Reference example 1 procedure for electrolyte leaching, fractionation and recovery.
Example 4
The solvent is selected from 10 percent by volume of 2,3,3, 3-tetrafluoropropene (HFO-1234yf), and 90 percent by volume of tetrafluoroethane (R134a) is added to the solvent to prepare a leaching solvent IV. The main parameters are as follows:
| boiling point | ODP | Level of security | Toxicity | Pressure of 30 DEG C | Pressure of 45 DEG C |
| About-29 deg.C | 0 | A2 | Low toxicity | 0.75MPa | 1.2MPa |
And (3) putting the crushed lithium battery into a proper closed container, vacuumizing, and discharging gas in the container under the working gauge pressure of-0.06 to-0.08 MPa.
The adding volume of the solvent IV is 1 to 2.5 times of the volume of the lithium battery material, the leaching temperature is 30 to 45 ℃, the pressure is 0.6 to 1.2Mpa, and the stirring leaching is carried out for 20 to 40 minutes.
Reference example 1 procedure for electrolyte leaching, fractionation and recovery.
Example 5
The leaching solvent was 1/3 of 1,3,3, 3-tetrafluoropropene (HFO-1234ze (type E)), 1/3 of 2,3,3, 3-tetrafluoropropene (HFO-1234yf), to which 1/3 of tetrafluoroethane (R134a) was added to formulate leaching solvent V. The main parameters are as follows:
| boiling point | ODP | Level of security | Toxicity | Pressure of 30 DEG C | Pressure at 50 deg.C |
| About-29 deg.C | 0 | A2 | Low toxicity | 0.75MPa | 1.5MPa |
And (3) putting the crushed lithium battery into a proper closed container, vacuumizing, and discharging gas in the container under the working gauge pressure of-0.06 to-0.08 MPa.
The addition volume of the solvent V is 2 to 3 times of the volume of the lithium battery material, the leaching temperature is 30 to 50 ℃, the pressure is 0.75 to 1.5Mpa, and the stirring leaching is carried out for 30 minutes.
Reference example 1 procedure for electrolyte leaching, fractionation and recovery.
The recovery rates of the electrolyte and solvent were tested in the various examples disclosed in this application and the results are shown in the following table:
as can be seen from the above table, the embodiments disclosed in the present application can effectively recover the electrolyte in the retired lithium battery, the recovery rate of the electrolyte reaches more than 97%, the solvent can be fully recovered after leaching, and the recovery rate reaches more than 95%, so that the solvent can be recycled, subsequent retired lithium batteries can be leached, and the waste is less. The electrolyte and the electrolyte of the lithium battery are recovered by adopting the prior industry technology, the recovery rate cannot reach the level, and a large amount of pollution can be caused.
The application aims at the retired lithium battery losing the use value, the appropriate solvent is adopted, the potential safety hazard and the environmental hazard of the retired lithium battery are eliminated after the electrolyte in the lithium battery is leached and recovered and the electrolyte in the lithium battery is dissolved under the condition of low energy consumption, then the separation of a positive electrode material, a negative electrode material, a copper foil, an aluminum foil, plastic and an iron shell can be realized under the open condition of normal temperature and normal pressure, and meanwhile, the solvent adopted in the embodiment can be efficiently recovered and recycled.
The application has the following advantages:
the contact between electrolyte or electrolyte and air is reduced, so that the probability and time for generating hazardous substances are reduced, and the possible environmental pollution and fire-fighting hidden danger caused by the fact that the electrolyte of the lithium battery is gathered into the surrounding environment can be effectively relieved. Meanwhile, the leaching and separating processes are carried out in a fully-closed container, and no polluting gas or liquid is discharged in the whole process.
The low-toxicity and non-flammable tetrafluoropropene and tetrafluoroethane are used as solvents for leaching electrolyte and electrolyte in a lithium battery, firstly, the viscosity of mixed liquor in the leaching process is reduced, the fluidity is improved, and the smooth performance of the leaching process is facilitated; secondly, the boiling points of the tetrafluoropropene and the tetrafluoroethane with low boiling points are far lower than the pyrolysis temperature (60 ℃) of the electrolyte lithium hexafluorophosphate in the electrolyte, so that the electrolyte lithium hexafluorophosphate in the electrolyte is fully recovered on the premise of not decomposing, meanwhile, the solvent can be fully recovered for recycling, and the process is green and environment-friendly; thirdly, the non-toxic and non-inflammable tetrafluoropropene and tetrafluoroethane are used as leaching solvents, so that the flammability of the lithium battery electrolyte can be greatly reduced, and the production process can be carried out in a safe environment.
The leaching solvent disclosed by the application has the boiling point of less than 0 ℃, can realize solvent evaporation and condensation recovery under mild conditions, and avoids energy waste in the traditional solvent recovery method.
After the electrolyte in the retired lithium battery is leached and removed, the solid battery material is in a completely loose mixed state, and therefore a foundation is laid for further separating materials such as nickel, cobalt, lithium, manganese, copper, aluminum, iron and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A solvent suitable for electrolyte leaching in a decommissioned lithium battery, the solvent comprising: and (3) tetrafluoropropene.
2. The solvent suitable for electrolyte leaching in decommissioned lithium batteries according to claim 1, wherein the tetrafluoropropene is 1,3,3, 3-tetrafluoropropene and/or 2,3,3, 3-tetrafluoropropene.
3. The solvent suitable for electrolyte leaching in lithium ex-service batteries according to claim 1 or 2, wherein said solvent further comprises tetrafluoroethane, the volume percentage of said tetrafluoroethane in said solvent being between 10% and 90%.
4. A method for separate recovery of electrolyte leaching in ex-service lithium batteries, comprising the solvent according to any one of claims 1 to 3, characterized in that it comprises the following steps:
s100: mixing the discharged and crushed retired lithium battery with the solvent in a vacuum environment, and then leaching at 20-50 ℃ and under the condition of 0.6-1.6MPa to respectively obtain leaching mixed liquor and insoluble solids;
s200: heating the leaching mixed solution to 20-50 ℃ and fractionating under the condition of-0.08 MPa-1.6MPa to obtain a first recovery solvent and an electrolyte.
5. The separation and recovery method according to claim 4, wherein the fractionation step in the step S200 includes:
s201: heating the leaching mixed solution to 20-50 ℃ under the condition of 0.6-1.6Mpa, evaporating the leaching mixed solution until the working pressure is reduced to below 0.6Mpa, collecting steam and condensing to obtain a first distillate;
s202: heating and evaporating the leaching mixed solution at 20-50 ℃ until the working pressure is reduced to below 0.2Mpa, pressurizing the steam to 0.6Mpa-1.6Mpa, and condensing to obtain a second distillate;
s203: heating the leaching mixed solution at 20-50 ℃, sucking steam in vacuum until the working pressure is reduced to be below-0.08 MPa, pressurizing the steam to be 0.6-1.6MPa, and condensing to obtain a third distillate;
s204: and mixing the first distillate, the second distillate and the third distillate to obtain the first recovered solvent, and collecting the residual unevaporated liquid to obtain the electrolyte.
6. The separation and recovery method according to claim 4, further comprising a step S300 after the step S100: and heating the insoluble solid to 20-50 ℃ under the condition of-0.08 MPa-1.6MPa, evaporating to remove residual solvent on the surface of the insoluble solid, and recovering to obtain a second recovered solvent and a lithium battery solid material.
7. The separation and recovery method according to claim 6, wherein the recovering of the residual solvent in the step S300 comprises:
s301: heating the insoluble solid to 20-50 ℃ under the condition of 0.6-1.6Mpa until the working pressure is reduced to below 0.6Mpa, collecting steam and condensing to obtain a first residual solvent;
s302: heating the insoluble solid at 20-50 deg.C until the working pressure is reduced to below 0.2Mpa, and condensing the steam under 0.6-1.6Mpa to obtain a second residual solvent;
s303: heating the insoluble solid at 20-50 deg.C, vacuum-pumping steam until the working pressure is reduced to below-0.08 MPa, pressurizing the steam to 0.6-1.6MPa, and condensing to obtain a third residual solvent;
s304: mixing the first residual solvent, the second residual solvent and the third residual solvent to obtain the second recovered solvent.
8. The separation and recovery method according to claim 6 or 7, further comprising a step S400 after the steps S200 and S300: and collecting and mixing the first recovered solvent and the second recovered solvent to obtain a recovered solvent, and using the recovered solvent for circularly leaching the electrolyte in the retired lithium battery.
9. The separation and recovery method according to claim 4, wherein in the step S100, the solid-liquid volume ratio of the retired lithium battery to the solvent is 1:1 to 1:4 v/v.
10. The separation and recovery method according to claim 4 or 9, wherein in step S100, the leaching step comprises: leaching at stirring speed of 3-5r/Min for 20-40Min, and repeating for 1-4 times.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010888128.1A CN112054262A (en) | 2020-08-28 | 2020-08-28 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
| PCT/CN2020/114735 WO2022041327A1 (en) | 2020-08-28 | 2020-09-11 | Extraction solvent applied to electrolyte in decommissioned lithium battery and method for separating and recovering electrolyte from decommissioned lithium battery by using same |
| DE102020129186.8A DE102020129186A1 (en) | 2020-08-28 | 2020-11-05 | SOLVENT FOR LEAKING AN ELECTROLYTE SOLUTION IN A DEPLETED LITHIUM BATTERY AND METHOD FOR SEPARATE AND RECOVERING AN ELECTROLYTE SOLUTION FROM A DEPLETED LITHIUM BATTERY |
| FR2011508A FR3113682B1 (en) | 2020-08-28 | 2020-11-10 | leaching solvent suitable for an electrolyte solution in a decommissioned lithium battery, use of the solvent and method for separating and recycling an electrolyte solution from a decommissioned lithium battery using a leaching solvent |
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| CN202010888128.1A CN112054262A (en) | 2020-08-28 | 2020-08-28 | Leaching solvent suitable for electrolyte in retired lithium battery and method for separating and recycling electrolyte from retired lithium battery by using leaching solvent |
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| CN (1) | CN112054262A (en) |
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| 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 |
| CN116525989B (en) * | 2023-02-03 | 2024-01-19 | 广东杰成新能源材料科技有限公司 | Harmless treatment method and device for retired lithium battery electrolyte |
| CN116231137A (en) * | 2023-02-16 | 2023-06-06 | 广东邦普循环科技有限公司 | Method for recycling waste lithium battery electrolyte |
| CN116646633B (en) * | 2023-05-31 | 2023-12-12 | 科立鑫(珠海)新能源有限公司 | Method for recycling active substances in lithium ion positive electrode material |
| CN116531851B (en) * | 2023-07-06 | 2023-09-26 | 东莞市鹏锦机械科技有限公司 | A waste lithium battery electrolyte recycling system and process |
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| FR3113682B1 (en) | 2023-12-08 |
| WO2022041327A1 (en) | 2022-03-03 |
| FR3113682A1 (en) | 2022-03-04 |
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