CN117623301A - Method for recycling graphite negative electrode of waste lithium ion battery - Google Patents
Method for recycling graphite negative electrode of waste lithium ion battery Download PDFInfo
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- CN117623301A CN117623301A CN202311750567.6A CN202311750567A CN117623301A CN 117623301 A CN117623301 A CN 117623301A CN 202311750567 A CN202311750567 A CN 202311750567A CN 117623301 A CN117623301 A CN 117623301A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 64
- 239000010439 graphite Substances 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004064 recycling Methods 0.000 title claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 239000010405 anode material Substances 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 18
- 230000005496 eutectics Effects 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 10
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 10
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229960003178 choline chloride Drugs 0.000 claims abstract description 10
- 239000008103 glucose Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 6
- 230000001172 regenerating effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000011343 solid material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 238000002791 soaking Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for recycling and regenerating a graphite cathode of a waste lithium ion battery, which comprises the steps of preprocessing the waste lithium ion battery to obtain cathode material powder, carrying out heat treatment on the cathode material powder to oxidize metal impurities in the cathode material powder, leaching the heat-treated graphite cathode material by adopting a deep eutectic solvent formed by mixing choline chloride and glucose, washing solid obtained by solid-liquid separation by using the deep eutectic solvent after leaching reaction, and then directly placing the solid material obtained by washing in inert atmosphere for heat treatment and carbonization to obtain the regenerated graphite cathode material. The recycling method has good economic and environmental benefits, and the obtained regenerated graphite anode material has excellent first coulombic efficiency and long cycle performance.
Description
Technical Field
The invention belongs to the field of recovery and regeneration of waste lithium ion batteries, and particularly relates to a recovery and regeneration method of a graphite negative electrode of a waste lithium ion battery.
Background
The lithium ion battery is widely applied to electronic products such as portable equipment, electric automobiles and the like because of high working voltage, light weight, no memory effect and long cycle service life. Meanwhile, the quantity of the retired waste lithium ion batteries is also increased faster, and the waste lithium ion batteries contain various resources including lithium, cobalt, nickel, graphite and the like, so that the method has high recycling value, and the recovery of key materials (such as graphite, valuable metals and the like) in the retired batteries has great significance for sustainable development such as economic growth, environmental protection and the like.
The main component of the waste lithium ion battery cathode material is graphite, and graphite particles can generate a large amount of structural defects and bulk impurities after undergoing long-term charge and discharge cycles, so that the service life of the battery and other electrochemical performances are greatly influenced. Therefore, how to improve the electrochemical performance of the negative electrode material regenerated from the graphite material in the waste battery is a major problem at present.
In addition, the waste graphite cathode has a high content of metal element impurities, and the conventional impurity treatment mode is mainly acid leaching treatment, but a large amount of acid reagent is easy to cause great pollution to the environment, and the subsequent sewage treatment cost is high, so that the defects of the prior art are needed to be overcome.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, and therefore, the invention provides a method for recycling and regenerating a graphite negative electrode of a waste lithium ion battery, which comprises the following steps:
(1) Pretreating a waste lithium ion battery to obtain negative electrode material powder;
(2) Carrying out heat treatment on the negative electrode material powder in air or oxygen atmosphere, oxidizing metal impurities in the negative electrode material powder, cooling to room temperature, and screening to obtain graphite negative electrode material powder;
(3) Under the water bath condition, mixing and stirring choline chloride and glucose at a molar ratio of 1:1-1:2.5 to obtain a clear and transparent deep eutectic solvent, and dividing the deep eutectic solvent into two parts of a solvent A and a solvent B;
(4) Adding the graphite anode material powder obtained by screening in the step (2) into the solvent A in the step (3), heating, stirring and mixing, leaching out metal oxides in the graphite anode material powder, then carrying out solid-liquid separation, and collecting solids;
(5) And (3) washing the solid in the step (4) by using the solvent B, directly transferring the washed solid into sintering equipment without drying, and performing heat treatment carbonization under inert atmosphere to obtain the regenerated graphite anode material.
Further, the step (1) of pretreating the waste lithium ion battery comprises the steps of disassembling the waste lithium ion battery in an argon atmosphere to obtain a negative electrode plate, soaking the negative electrode plate in deionized water for ultrasonic treatment to separate a copper foil current collector from a negative electrode material, and filtering, washing and drying the negative electrode material to obtain negative electrode material powder.
Further, the temperature of the heat treatment in the step (2) is 300-500 ℃, and the time of the heat treatment is 3-12h.
Further, the particle size of the graphite anode material powder obtained by screening in the step (2) is below 25-70 mu m.
Further, the water bath temperature in the step (3) is 40-60 ℃;
further, the stirring time in the step (3) is 30-60min.
Further, in the step (4), the graphite anode material powder and the solvent A are mixed according to a solid-to-liquid ratio of 10-30 g/L.
Further, in the step (4), the temperature of heating and stirring is 60-250 ℃, and the stirring time is 3-24 hours.
Further, in the step (5), the inert atmosphere is any one or more of helium, argon and nitrogen.
Further, the carbonization temperature of the heat treatment in the step (5) is 2500-3000 ℃, and the heat treatment time is 2-6h.
Compared with the prior art, the invention has the following beneficial effects:
(1) When the regenerated graphite anode material is recovered, the deep eutectic solvent prepared by mixing choline chloride and glucose is used as a leaching reagent of metal element impurities, the glucose is used as a hydrogen bond donor, the choline chloride is used as a hydrogen bond acceptor, the metal oxide is well solvated within a certain temperature range, the metal element impurities in the graphite anode material powder can be effectively leached, the purity of the recovered graphite is improved, the impurity removal effect is ensured, meanwhile, acid liquor is avoided, and the sewage treatment burden is reduced.
(2) The invention divides the deep eutectic solvent into two parts, one part is used for removing impurities of metal elements in graphite anode material powder, the other part is used for washing the solid obtained after leaching reaction and solid-liquid separation, and the washing reagent and the leaching reagent are the same deep eutectic solvent, thereby being beneficial to improving the washing effect on the solid.
(3) The method uses the deep eutectic solvent B (i.e. the washing reagent) to wash the leached solid, the choline chloride and the glucose in the deep eutectic solvent are adsorbed on the surface of the solid, the washed solid is directly transferred into sintering equipment without drying, the choline chloride and the glucose adsorbed on the surface of the solid can be used as carbon sources to graphitize at high temperature, and structural defects in a graphite negative electrode can be repaired, so that the electrochemical performance of the recycled graphite negative electrode material is improved.
(4) The graphite anode material obtained by recycling and regenerating has excellent electrochemical performance, good first coulomb efficiency and long-cycle stability.
Drawings
Fig. 1 is an SEM image of the regenerated graphite anode material obtained in example 1.
Detailed Description
The present invention is further illustrated by the following examples and comparative examples.
Example 1
And disassembling the waste lithium cobalt oxide battery in an argon atmosphere to obtain a negative plate, soaking the negative plate in deionized water for ultrasonic treatment to separate the copper foil current collector from the negative material, and filtering, washing and drying the negative material to obtain negative material powder. And (3) carrying out heat treatment on the negative electrode material powder for 3 hours at 500 ℃ in an air atmosphere, oxidizing metal impurities in the negative electrode material powder, cooling to room temperature, and screening by a screen to obtain graphite negative electrode material powder with the granularity of less than 25 mu m.
Under the water bath condition of 60 ℃, mixing choline chloride and glucose according to the molar ratio of 1:1, and stirring for 30min to obtain a clear and transparent deep eutectic solvent, wherein the deep eutectic solvent is divided into two parts of solvent A and solvent B. Adding the graphite anode material powder obtained by screening into the solvent A, mixing the graphite anode material powder and the solvent A according to a solid-to-liquid ratio of 10g/L, heating to 250 ℃, stirring and mixing for 3 hours, leaching metal oxides in the graphite anode material powder, filtering, and collecting solids; and (3) washing the solid obtained by filtering by using the solvent B, directly transferring the washed solid into a muffle furnace without drying, carrying out heat treatment graphitization at 2500 ℃ in nitrogen atmosphere, and carrying out heat preservation for 6 hours to obtain the regenerated graphite anode material.
The resultant regenerated graphite negative electrode material was analyzed by ICP, and the results are shown in table 1 below.
Table 1 results of ICP analysis of graphite anode material powders
| Element(s) | Co | Cu | Li |
| Impurity content (wt.%) | 0.0004 | 0.0008 | 0.0013 |
And the carbon content in the regenerated graphite anode material was 99.7wt.% as detected by a carbon-sulfur analysis apparatus.
Example 2
And disassembling the waste nickel cobalt lithium manganate ternary lithium battery in an argon atmosphere to obtain a negative plate, soaking the negative plate in deionized water for ultrasonic treatment to separate the copper foil current collector from the negative material, and filtering, washing and drying the negative material to obtain negative material powder. And (3) carrying out heat treatment on the negative electrode material powder for 12 hours at 300 ℃ in an air atmosphere, oxidizing metal impurities in the negative electrode material powder, cooling to room temperature, and screening by a screen to obtain graphite negative electrode material powder with the granularity of less than 45 mu m.
Under the water bath condition of 50 ℃, mixing choline chloride and glucose according to the molar ratio of 1:2, stirring for 45min to obtain a clear and transparent deep eutectic solvent, and dividing the deep eutectic solvent into two parts of solvent A and solvent B. Adding the graphite anode material powder obtained by screening into the solvent A, mixing the graphite anode material powder and the solvent A according to a solid-to-liquid ratio of 20g/L, heating to 160 ℃, stirring and mixing for 12 hours, leaching metal oxides in the graphite anode material powder, centrifuging and separating, and collecting solids; and (3) washing the solid obtained by centrifugal separation by using a solvent B, directly transferring the washed solid into a muffle furnace without drying, carrying out heat treatment graphitization at 3000 ℃ in nitrogen atmosphere, and carrying out heat preservation for 3 hours to obtain the regenerated graphite anode material.
The resultant regenerated graphite negative electrode material was analyzed by ICP, and the results are shown in table 2 below.
Table 2 results of ICP analysis of graphite anode material powders
| Element(s) | Co | Ni | Mn | Cu | Li |
| Impurity content (wt.%) | 0.0005 | 0.0004 | 0.0005 | 0.0007 | 0.0016 |
And the carbon content in the regenerated graphite anode material is 99.5 wt percent by detection of carbon-sulfur analysis equipment.
Example 3
And disassembling the waste lithium manganate battery in an argon atmosphere to obtain a negative plate, soaking the negative plate in deionized water for ultrasonic treatment to separate the copper foil current collector from the negative material, and filtering, washing and drying the negative material to obtain negative material powder. And (3) carrying out heat treatment on the negative electrode material powder at 400 ℃ for 6 hours in an air atmosphere, oxidizing metal impurities in the negative electrode material powder, cooling to room temperature, and screening by a screen to obtain graphite negative electrode material powder with the granularity of less than 70 mu m.
Under the water bath condition of 40 ℃, mixing choline chloride and glucose according to the molar ratio of 1:2.5, stirring for 60min to obtain a clear and transparent deep eutectic solvent, and dividing the deep eutectic solvent into two parts of solvent A and solvent B. Adding the graphite anode material powder obtained by screening into the solvent A, mixing the graphite anode material powder and the solvent A according to a solid-to-liquid ratio of 30g/L, heating to 60 ℃, stirring and mixing for 24 hours, leaching metal oxides in the graphite anode material powder, filtering, and collecting solids; and (3) washing the solid obtained by filtering by using the solvent B, directly transferring the washed solid into a muffle furnace without drying, carrying out heat treatment graphitization at 3000 ℃ under the argon atmosphere, and carrying out heat preservation for 4 hours to obtain the regenerated graphite anode material.
The resultant regenerated graphite negative electrode material was analyzed by ICP, and the results are shown in table 3 below.
TABLE 3 ICP analysis results of graphite negative electrode material powder
| Element(s) | Mn | Cu | Li |
| Impurity content (wt.%) | 0.0009 | 0.0006 | 0.0018 |
And the carbon content in the regenerated graphite anode material was 99.6wt.% as detected by a carbon-sulfur analysis apparatus.
Comparative example
And disassembling the waste lithium cobalt oxide battery in an argon atmosphere to obtain a negative plate, soaking the negative plate in deionized water for ultrasonic treatment to separate the copper foil current collector from the negative material, and filtering, washing and drying the negative material to obtain negative material powder. And (3) carrying out heat treatment on the negative electrode material powder for 3 hours at 500 ℃ in an air atmosphere, oxidizing metal impurities in the negative electrode material powder, cooling to room temperature, and screening by a screen to obtain graphite negative electrode material powder with the granularity of less than 25 mu m.
Adding the graphite anode material powder obtained by screening into 1mol/L hydrochloric acid solution, mixing the graphite anode material powder and the hydrochloric acid solution according to a solid-to-liquid ratio of 10g/L, stirring and mixing for 3h, filtering, and collecting solids; and washing the solid obtained by filtering by using deionized water, directly transferring the washed solid into a muffle furnace without drying, carrying out heat treatment graphitization at 2500 ℃ in nitrogen atmosphere, and carrying out heat preservation for 6 hours to obtain the graphite anode material.
Battery performance test
The graphite anode materials obtained in the above examples 1-3 and comparative example were prepared into electrode slurry, and the slurry ratio was graphite anode materials: binder (PAA): conductive agent (SP) =75: 15:10. the slurry is uniformly stirred and then coated on a copper foil, and then dried in vacuum. Punching the dried electrode slice to obtain a working electrode of the button cell, wherein the lithium slice is used as a counter electrode, and the electrolyte is 1mol/L lithium hexafluorophosphate (LiPF) 6 ) The volume ratio of the electrolyte to the electrolyte is 1: 1) and diethyl carbonate (DEC) in a solvent. The constant current charge-discharge voltage interval is 0.01-1.5V. The current density used in the first charge-discharge cycle experiment is 0.1C, and the first charge-discharge coulomb efficiency of the battery is tested under the current density; the current density used for the long cycle test was 1C.
The test results are shown in table 4 below.
TABLE 4 Table 4
| Specific capacity of initial discharge (mAh.g) -1 ） | First coulombic efficiency | Capacity retention after 500 cycles of 1C down cycle | |
| Example 1 | 356.8 | 91.3% | 95.2% |
| Example 2 | 354.3 | 90.1% | 96.4% |
| Example 3 | 353.9 | 92.3% | 96.1% |
| Comparative example | 298.6 | 83.6% | 82.5% |
Claims (10)
1. The method for recycling the graphite cathode of the waste lithium ion battery is characterized by comprising the following steps of:
(1) Pretreating a waste lithium ion battery to obtain negative electrode material powder;
(2) Carrying out heat treatment on the negative electrode material powder in air or oxygen atmosphere, oxidizing metal impurities in the negative electrode material powder, cooling to room temperature, and screening to obtain graphite negative electrode material powder;
(3) Under the water bath condition, mixing and stirring choline chloride and glucose at a molar ratio of 1:1-1:2.5 to obtain a clear and transparent deep eutectic solvent, and dividing the deep eutectic solvent into two parts of a solvent A and a solvent B;
(4) Adding the graphite anode material powder obtained by screening in the step (2) into the solvent A in the step (3), heating, stirring and mixing, leaching out metal oxides in the graphite anode material powder, then carrying out solid-liquid separation, and collecting solids;
(5) And (3) washing the solid in the step (4) by using the solvent B, directly transferring the washed solid into sintering equipment without drying, and performing heat treatment carbonization under inert atmosphere to obtain the regenerated graphite anode material.
2. The method of claim 1, wherein the pretreating the waste lithium ion battery in step (1) comprises disassembling the waste lithium ion battery in an argon atmosphere to obtain a negative electrode sheet, immersing the negative electrode sheet in deionized water for ultrasonic treatment to separate a copper foil current collector from a negative electrode material, and filtering, washing and drying the negative electrode material to obtain negative electrode material powder.
3. The method according to claim 1, wherein the heat treatment in step (2) is performed at a temperature of 300 to 500 ℃ for a time of 3 to 12 hours.
4. The method of claim 1, wherein the particle size of the graphite negative electrode material powder obtained by the sieving in step (2) is 25 to 70 μm or less.
5. The method of claim 1, wherein the water bath temperature in step (3) is 40-60 ℃.
6. The method of claim 1, wherein the stirring in step (3) is for a period of 30 to 60 minutes.
7. The method according to claim 1, wherein the graphite anode material powder and the solvent a in step (4) are mixed at a solid-to-liquid ratio of 10 to 30 g/L.
8. The method of claim 1, wherein the temperature of the heating and stirring in step (4) is 60-250 ℃ and the stirring time is 3-24 hours.
9. The method of claim 1, wherein the inert atmosphere in step (5) is any one or more of helium, argon, and nitrogen.
10. The method according to claim 1, wherein the carbonization temperature of the heat treatment in step (5) is 2500 to 3000 ℃ and the heat treatment time is 2 to 6 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311750567.6A CN117623301A (en) | 2023-12-19 | 2023-12-19 | Method for recycling graphite negative electrode of waste lithium ion battery |
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|---|---|---|---|
| CN202311750567.6A CN117623301A (en) | 2023-12-19 | 2023-12-19 | Method for recycling graphite negative electrode of waste lithium ion battery |
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| CN117623301A true CN117623301A (en) | 2024-03-01 |
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| CN202311750567.6A Pending CN117623301A (en) | 2023-12-19 | 2023-12-19 | Method for recycling graphite negative electrode of waste lithium ion battery |
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