CN117374446A - Recycling method of graphite anode material of waste lithium ion battery - Google Patents
Recycling method of graphite anode material of waste lithium ion battery Download PDFInfo
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- CN117374446A CN117374446A CN202311642013.4A CN202311642013A CN117374446A CN 117374446 A CN117374446 A CN 117374446A CN 202311642013 A CN202311642013 A CN 202311642013A CN 117374446 A CN117374446 A CN 117374446A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000010439 graphite Substances 0.000 title claims abstract description 98
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 98
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 239000010405 anode material Substances 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 26
- 239000010426 asphalt Substances 0.000 claims abstract description 21
- 239000003208 petroleum Substances 0.000 claims abstract description 20
- 239000010406 cathode material Substances 0.000 claims abstract description 18
- 239000002893 slag Substances 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 230000004927 fusion Effects 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- 238000005087 graphitization Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 238000002386 leaching Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000007499 fusion processing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 238000010309 melting process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention belongs to the technical field of lithium ion battery material recovery, and discloses a recovery and regeneration method of a graphite anode material of a waste lithium ion battery. The recovery and regeneration method comprises the following steps: uniformly mixing a graphite cathode material of a waste lithium ion battery with an alkaline solution, drying, and then carrying out alkali fusion calcination treatment in an inert atmosphere at 500-900 ℃; washing the calcined alkali fusion slag by deionized water, then adding the alkali fusion slag into an acid solution, and carrying out acid dissolution reaction at 25-100 ℃, and washing the reaction material to be neutral to obtain impurity-removed graphite; mixing the impurity-removed graphite with petroleum asphalt, and coating and granulating under an inert atmosphere at 300-800 ℃ to obtain the recovered graphite. The recycling method disclosed by the invention is simple in process flow, and the recycled graphite anode material is good in performance, so that industrialization and value can be realized.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery material recovery, and particularly relates to a recovery and regeneration method of a graphite anode material of a waste lithium ion battery.
Background
With the rapid development of new energy industries, lithium ion batteries have been widely used in various fields. Meanwhile, the scrappage of the batteries is increased year by year, and the waste batteries are recycled from the aspects of resource circulation and environmental protection. However, at present, hot spots and emphasis of lithium battery recovery are focused on positive electrode materials with higher recovery values, and the technology is still immature for the recovery of negative electrode materials. The components of the cathode waste residue after the cathode material is recovered and extracted by the battery are complex, the main component is graphite, the output is large, and the regeneration and recovery of the cathode waste residue are expected to generate more values.
In the prior art, for example, CN116435635a, graphite negative electrode waste is subjected to heat treatment, two-step acid dissolution treatment and electrochemical treatment in sequence to adsorb residual metal ions. However, the operation of adsorbing metal ions from dispersed graphite is difficult, the feasibility is poor, the electrochemical method is difficult to use on a large scale in industrial production, and the practicability is not high. CN116282000a sequentially adopts water-soluble carbonate solution to carry out microwave transformation treatment on graphite carbon slag separated from waste batteries, acid leaching separation is carried out, and finally heat treatment is carried out in an oxygen-containing atmosphere, so that the regenerated graphite is prepared. But this solution requires a heat treatment with an oxygen-containing atmosphere comprising nitric acid, hydrofluoric acid vapour. The treatment scheme is complex, the types of acid are more, the harm of nitric acid and hydrofluoric acid is larger, and the economic value is lower. CN115954572a sequentially performs oxidative roasting, inorganic acid leaching, organic liquid phase coating and graphitization on the waste graphite negative electrode powder to obtain a regenerated negative electrode. However, the impurity removal in the scheme is only carried out by oxidizing roasting and acid leaching, and the impurity removal effect is general. And the industrialization of the organic solvent treatment and the high energy consumption of the graphitization process in the liquid phase coating are also limited.
In summary, the above scheme generally has the problems that the impurity removal effect is general and the industrialization is difficult to realize.
The method for treating the graphite by alkali fusion is a method which is simple in industrialization realization and good in impurity removal effect, and as disclosed in patent CN112320794A, the graphite after pretreatment impurity removal and the composite alkali are subjected to fusion deep impurity removal treatment at low temperature, and then acid leaching is carried out to obtain the deep impurity removal recovered graphite. However, in the patent, the composite alkali is melted at a lower temperature (180-300 ℃) to form a eutectic compound for deep impurity removal, so that solvent leaching and screening grading pretreatment are needed before alkali melting to improve the alkali melting effect, the treatment process is complex, and the structure of the recovered graphite is not repaired. Patent CN116040626a discloses a method for purifying reduced pressure alkali-melted graphite, which comprises the steps of sequentially carrying out reduced pressure alkali leaching and heating on graphite powder in sodium hydroxide solution, and carrying out reduced pressure alkali-melted roasting and acid leaching treatment to obtain purified graphite. However, in the method, acid leaching adopts one or more of hydrochloric acid, nitric acid and sulfuric acid, the difference between different acid leaching treatments is not disclosed, and meanwhile, the treatment object is raw graphite powder, and the repairing treatment is not carried out on the structure of the recovered graphite from the waste lithium ion battery.
The graphite cathode material of the lithium ion battery is subjected to repeated charge and discharge, the graphite surface is exposed, the graphite structure is irregular, the fragmentation is serious, and the electrochemical influence is large. The graphite whose structure is destroyed can be repaired by performing the carbon coating treatment. However, the prior art generally has the problems that the carbonization temperature is higher (more than 900 ℃) and the shape of graphite after carbonization treatment cannot be controlled, so that the corresponding performance cannot meet the use requirement.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a recycling method of graphite cathode materials of waste lithium ion batteries. The recycling method disclosed by the invention is simple in process flow, and the recycled graphite anode material is good in performance, so that industrialization and value can be realized.
The invention aims at realizing the following technical scheme:
a method for recycling graphite cathode materials of waste lithium ion batteries comprises the following steps:
(1) Uniformly mixing a graphite cathode material of a waste lithium ion battery with an alkaline solution, drying, and then carrying out alkali fusion calcination treatment in an inert atmosphere at 500-900 ℃;
(2) Washing the alkali molten slag after the calcination treatment in the step (1) by deionized water, adding the washed material into an acid solution, and carrying out acid dissolution reaction at 25-100 ℃, and washing the reaction material to be neutral to obtain impurity-removed graphite;
(3) Mixing the impurity-removed graphite with petroleum asphalt, and coating and granulating under an inert atmosphere at 300-800 ℃ to obtain the recovered graphite.
Further, the graphite anode material of the waste lithium ion battery in the step (1) is derived from waste graphite slag or waste anode powder and anode sheets obtained by disassembling and crushing waste lithium ion batteries (such as lithium iron phosphate batteries, ternary lithium ion batteries and the like with graphite as an anode) and extracting anode materials (by a fire method, a wet method and the like).
Further, in the step (1), the alkaline solution is one or a combination of more than one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and a potassium carbonate solution with the mass fraction of 10% -32%; more preferably, the mass fraction is 18% -25%.
Further, in the step (1), the solid-liquid mass ratio (w/w) of the graphite anode material of the waste lithium ion battery and the alkaline solution is 1:0.5-1:4.
Further, the inert atmosphere in the step (1) and the step (3) refers to a nitrogen atmosphere.
Further, in the step (1), the time of the alkali fusion calcination treatment is 1-5 hours.
Further, in the step (2), the solid-liquid mass ratio of the alkali molten slag washed by deionized water is 1:4-1:8.
Further, the acid solution in the step (2) is hydrochloric acid solution, sulfuric acid solution or nitric acid solution; the solid-liquid mass ratio of the washed material to the acid solution is 1:3-1:8, and the acid dissolution reaction time is 1-24 h.
Further preferably, the acid solution is hydrochloric acid solution with a mass concentration of 5% -37%. More preferably, the concentration of hydrochloric acid solution is 10% -30% by mass.
Further, the petroleum asphalt in the step (3) is preferably petroleum asphalt with a softening point of 180-300 ℃. More preferably, the petroleum asphalt has a softening point of 250 to 280 ℃.
Further, in the step (3), the mass ratio of the petroleum asphalt to the impurity-removed graphite is 1:2-1:30. More preferably, the mass ratio is 1:5-1:20.
Further, the time of coating granulation in the step (3) is 1-4 hours.
Further, the coated graphite obtained after the coating granulation treatment in the step (3) is subjected to spheroidizing shaping and sieving to obtain recovered graphite; the rotational speed of the spheroidizing wheel for spheroidizing shaping is 4000-8000 r/min, the rotational speed of the grading wheel is 2500-4000 r/min, and the air quantity is 3-6 m 3 And/min, spheroidizing and shaping time is 0.5-5 h; the screening adopts a 300-mesh screen.
Further, the quality index of the recovered graphite obtained in the step (3) is as follows:D50 = (18.0±2.0) μm, the specific surface area is 4.0±0.5m 2 Per gram, tap density is not less than 1.0g/cm 3 The compaction density is 1.30-1.45 g/cm 3 The graphitization degree is more than or equal to 92 percent.
The technical principle of the invention is as follows: the waste graphite slag contains a plurality of impurities, mainly aluminum, copper, iron, phosphorus, nickel, cobalt, manganese, lithium and the like, and the existence forms of metal impurities are diversified, simple substances, oxides, sulfates and the like through the processes of crushing, pyrogenic process, wet recovery and the like. Most of the acid is treated by the wet recovery process, but the acid is still difficult to dissolve, so that the common acid is difficult to remove impurities. In particular, the aluminum oxide exists in the waste graphite slag, and even if aqua regia or hydrofluoric acid is used in the presence of a large amount of graphite, the effect is poor by using the common alkali acid method. The invention adopts an alkali fusion process, can well react alumina with alkali, and then separate aluminum ions by acid, thereby effectively removing indissolvable impurities. And other metal impurities can be changed into hydroxide under the action of alkali melting, so that the metal impurities are more easily reacted and dissolved with acid. In addition, the acid dissolution of the invention adopts specific hydrochloric acid, the chloride ions of the hydrochloric acid are more easily coordinated with metal ions, the metal chloride is more easily dissolved, the invention has better impurity removal effect compared with other acids such as sulfuric acid, nitric acid and the like, and finally the graphite recovered has better cycle performance.
Although the breaking process, the wet recycling process and the front-stage impurity removal process of the battery have small damage to the graphite structure, the graphite structure is irregular, the breaking is serious, and the electrochemical influence is large after the battery is subjected to multiple charge and discharge. Therefore, coating modification is needed, and the invention discovers that the asphalt with a proper softening point (250-280 ℃) is adopted for coating, so that a better coating effect can be obtained, and the gram capacity and the cycle performance of the recovered graphite battery are obviously improved. The graphite structure can be controlled through further spheroidization plastic, the tap density is improved, the cycle performance is improved, and finally, the product graphite is obtained through screening, and the quality index is as follows: d50 = (18.0±2.0) μm, the specific surface area is 4.0±0.5m 2 Per gram, tap density is not less than 1.0g/cm 3 The compaction density is 1.30-1.45 g/cm 3 The graphitization degree is more than or equal to 92 percent.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts an alkali fusion process to react with alumina in the waste graphite slag, which is beneficial to improving the aluminum removal effect. And further determining the concentration conditions of the alkaline solution to achieve the optimal aluminum removal effect and to significantly improve the electrochemical performance thereof.
(2) According to the invention, acid solution, especially hydrochloric acid, is used for acid dissolution of alkali fusion slag, so that metal impurities in waste graphite slag can be dissolved, and the impurity-removed graphite with qualified impurity content can be obtained. And further determining the concentration conditions of the liquid acid for achieving the optimal metal impurity removal effect and remarkably improving the electrochemical performance of the liquid acid.
(3) The invention can improve the surface and structure of graphite and the electrochemical performance by further coating granulation and spheroidizing treatment of petroleum asphalt, thereby reaching the commercial graphite standard. And further define the range of petroleum asphalt softening points that achieve optimal electrochemical performance.
(4) The treatment process disclosed by the invention can be used for treating the most complex waste graphite slag, waste negative electrode powder, negative electrode plates and the like, does not need a complex pretreatment process, and is wide in application range and low in cost.
(5) The quality index of the graphite obtained by the treatment process is as follows: d50 = (18.0±2.0) μm, the specific surface area is 4.0±0.5m 2 The tap density per gram is more than or equal to 1.0g/cm < 3 >, the compaction density is 1.30-1.45 g/cm < 3 >, the graphitization degree is more than or equal to 92%, and the standard of commercial graphite is met.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
(1) Mixing waste graphite slag with a sodium hydroxide solution with the mass fraction of 18%, wherein the solid-liquid mass ratio is 1:2, uniformly mixing, drying, and calcining at 700 ℃ for 2 hours in a nitrogen environment.
(2) And washing the alkali molten slag with deionized water, wherein the solid-liquid mass ratio is 1:6. And (3) carrying out hydrochloric acid dissolution on the washing material, wherein the mass ratio of solid to liquid is 1:4, the mass concentration of hydrochloric acid is 10%, reacting for 3 hours at 70 ℃, and carrying out stirring washing and leaching for multiple times until the washing material is neutral, thereby obtaining the impurity-removed graphite.
(3) Mixing the impurity-removed graphite with petroleum asphalt with a softening point of 280 ℃ according to a mass ratio of 10:1, and coating and granulating for 3 hours under the nitrogen condition at 700 ℃ to obtain coated graphite.
(4) Spheroidizing and shaping the coated graphite, wherein the rotation speed of a spheroidizing wheel is 6000r/min, the rotation speed of a grading wheel is 3900r/min, and the air quantity is 4.54 and 4.54 m 3 And (3) carrying out shaping for 3 hours to obtain shaped graphite. And sieving the shaped graphite through a 300-mesh screen to obtain the recovered graphite anode material.
Through detection, the aluminum content in the recovered graphite anode material is 3.12ppm, the initial gram capacity of assembled buckling is 352.71mAh/g, the initial cycle coulomb efficiency is 92.07%, and the capacity retention rate after 100 cycles of circulation under the condition of 0.1C is 99.73%.
Examples 2 to 19 and comparative examples 1 to 4
Different examples 2-19 and comparative examples 1-4 were set up according to the following table 1 conditions, with other unnoticed process conditions and parameters being the same as example 1:
TABLE 1
| Sequence number | Alkaline solution and concentration | Acid and concentration | Softening point of petroleum asphalt | Aluminum content (ppm) | Gram capacity (mAh/g) | Coulombic efficiency (%) | Capacity retention (%) |
| Example 1 | 18% sodium hydroxide | 10% hydrochloric acid | 280℃ | 3.12 | 352.71 | 92.07 | 99.73 |
| Example 2 | 10% sodium hydroxide | 10% hydrochloric acid | 280℃ | 253.71 | 344.19 | 91.25 | 96.52 |
| Example 3 | 15% sodium hydroxide | 10% hydrochloric acid | 280℃ | 37.41 | 348.37 | 92.03 | 99.63 |
| Example 4 | 25% sodium hydroxide | 10% hydrochloric acid | 280℃ | 4.17 | 348.82 | 92.01 | 98.74 |
| Example 5 | 30% sodium hydroxide | 10% hydrochloric acid | 280℃ | 3.82 | 347.71 | 91.38 | 97.92 |
| Example 6 | 32% sodium hydroxide | 10% hydrochloric acid | 280℃ | 3.26 | 346.59 | 90.81 | 96.76 |
| Example 7 | 18% sodium hydroxide | 5% hydrochloric acid | 280℃ | 74.28 | 348.92 | 91.43 | 97.04 |
| Example 8 | 18% sodium hydroxide | 15% hydrochloric acid | 280℃ | 3.63 | 348.94 | 92.02 | 98.68 |
| Example 9 | 18% sodium hydroxide | 30% hydrochloric acid | 280℃ | 3.52 | 347.57 | 91.36 | 97.59 |
| Example 10 | 18% sodium hydroxide | 37% hydrochloric acid | 280℃ | 3.49 | 346.81 | 90.69 | 96.48 |
| Example 11 | 18% sodium hydroxide | 10% hydrochloric acid | 180℃ | 3.12 | 341.36 | 87.95 | 93.76 |
| Example 12 | 18% sodium hydroxide | 10% hydrochloric acid | 250℃ | 3.12 | 343.84 | 89.63 | 94.28 |
| Example 13 | 18% sodium hydroxide | 10% hydrochloric acid | 300℃ | 3.12 | 346.28 | 88.50 | 93.76 |
| Example 14 | 18% potassium hydroxide | 10% hydrochloric acid | 280℃ | 3.16 | 352.69 | 92.06 | 99.72 |
| Example 15 | 18% sodium carbonate | 10% hydrochloric acid | 280℃ | 3.20 | 352.68 | 92.05 | 99.70 |
| Example 16 | 18% potassium carbonate | 10% hydrochloric acid | 280℃ | 3.19 | 352.67 | 92.06 | 99.71 |
| Example 17 | 9% sodium hydroxide+9% potassium hydroxide | 10% hydrochloric acid | 280℃ | 3.13 | 352.70 | 92.06 | 99.73 |
| Example 18 | 9% sodium hydroxide+9% sodium carbonate | 10% hydrochloric acid | 280℃ | 3.14 | 352.69 | 92.07 | 99.71 |
| Example 19 | 9% sodium carbonate+9% Potassium carbonate | 10% hydrochloric acid | 280℃ | 3.21 | 352.66 | 92.05 | 99.69 |
| Comparative example 1 | / | 10% hydrochloric acid | 280℃ | 5385.37 | 312.79 | 85.39 | 85.47 |
| Comparative example 2 | 18% sodium hydroxide | 10% hydrochloric acid | / | 3.12 | 338.52 | 86.16 | 83.41 |
| Comparative example 3 | 18% sodium hydroxide | 10% sulfuric acid | 280℃ | 2471.34 | 334.27 | 87.13 | 86.48 |
| Comparative example 4 | 18% sodium hydroxide | 10% nitric acid | 280℃ | 582.94 | 342.83 | 87.94 | 88.45 |
As is clear from the results of examples 1 to 10 in Table 1, when the acid or alkali concentration is too low, the impurity removal effect is not complete, and aluminum remains much. When the concentration of the acid or the alkali is too high, the graphite structure is damaged to a certain extent, which is unfavorable for the subsequent repair process, and the circulation performance is reduced. The high-concentration alkali has high viscosity, increases the risk of impurity separation, has a certain corrosion risk on equipment due to high-concentration hydrochloric acid, has high water consumption, and is not beneficial to industrialized implementation. As can be seen from the comparison between examples 11-13 and example 1, the softening point of the petroleum asphalt has a significant effect on the cycle performance of the obtained recycled graphite negative electrode, and too high or too low softening point can cause the cycle performance to be reduced, so that the petroleum asphalt can achieve better cycle performance when the softening point of the petroleum asphalt is in the range of 250-280 ℃. As can be seen from the comparison between examples 14 to 19 and example 1, the effects of potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydroxide and combinations thereof are similar, and the alkaline solution has more optional species.
As can be seen from the comparison of comparative example 1 with example 1, a good aluminum removal effect cannot be achieved without an alkali melting process, and the recovered graphite has an excessively high aluminum content and causes a significant decrease in electrochemical properties. As can be seen from the comparison of comparative example 2 with example 1, the absence of the coating treatment with petroleum pitch resulted in a significant decrease in the electrochemical performance of the recycled graphite negative electrode. Meanwhile, the comparison of the comparative examples 3-4 and the example 1 shows that the aluminum removal effect of hydrochloric acid is better than that of sulfuric acid and nitric acid under the condition of alkali melting, and the reason is that chloride ions in the hydrochloric acid are more easily coordinated with metal ions, the metal chloride is more easily dissolved, the impurity removal effect is better than that of other acids such as sulfuric acid and nitric acid, and the electrochemical performance of the finally recovered graphite anode material is better.
Comparative example 5
In this comparative example, the calcination temperature was 300℃under nitrogen in the alkali fusion process of step (1) in comparison with example 1, and the other conditions were identical.
According to detection, the aluminum content in the recovered graphite material of the comparative example is 5174.27ppm, the initial gram capacity of the assembled buckling is 317.53mAh/g, the initial cycle coulomb efficiency is 85.64%, and the capacity retention rate after 100 cycles of 0.1C is 85.61%.
From the above results, it can be seen that when the alkali fusion calcination temperature is low, the alkali and alumina do not start to react, and only part of the elemental aluminum can be removed. And the electrochemical performance of the obtained recycled graphite anode material is obviously reduced.
Comparative example 6
In this comparative example, the calcination atmosphere in the alkali fusion process in the step (1) was air, and the other conditions were the same.
According to detection, the aluminum content in the recovered graphite material of the comparative example is 6837.42ppm, the initial gram capacity of the assembled and buckled battery is 310.38mAh/g, the initial cycle coulomb efficiency is 83.37%, and the capacity retention rate after 100 cycles of 0.1C is 84.89%.
From the above results, it is clear that the simple substance of impurities is easily converted into oxides, especially aluminum, without alkali fusion calcination under inert conditions, and the difficulty of impurity removal is increased.
Comparative example 7
Compared with the comparative example 1, the spheroidizing and shaping process of the step (4) is omitted, and the coated graphite of the step (3) is directly ground and crushed and screened by a 300-mesh screen to obtain the recycled graphite anode material.
Through detection, the initial gram capacity of the assembled and buckled graphite cathode material of the comparative example is 351.85mAh/g, the initial cycle coulomb efficiency is 92.04%, and the capacity retention rate after 100 cycles is 92.15%.
From the above results, it was found that the graphite material was not spheroidized and had a morphology that was not uniform and a tap density of 1.12g/cm 3 Lower than commercial graphite standard, and has poor cycle performance.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (12)
1. The method for recycling the graphite cathode material of the waste lithium ion battery is characterized by comprising the following steps of:
(1) Uniformly mixing a graphite cathode material of a waste lithium ion battery with an alkaline solution, drying, and then carrying out alkali fusion calcination treatment in an inert atmosphere at 500-900 ℃;
(2) Washing the alkali molten slag after the calcination treatment in the step (1) by deionized water, adding the washed material into an acid solution, and carrying out acid dissolution reaction at 25-100 ℃, and washing the reaction material to be neutral to obtain impurity-removed graphite;
(3) Mixing the impurity-removed graphite with petroleum asphalt, and coating and granulating under an inert atmosphere at 300-800 ℃ to obtain the recovered graphite.
2. The method for recycling the graphite cathode material of the waste lithium ion battery according to claim 1, wherein the graphite cathode material of the waste lithium ion battery in the step (1) is derived from waste graphite slag obtained by disassembling, crushing and extracting the cathode material of the waste lithium ion battery, or waste cathode powder and cathode sheets.
3. The method for recycling the graphite cathode material of the waste lithium ion battery according to claim 1, wherein the alkaline solution in the step (1) is one or a combination of more than one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and a potassium carbonate solution with the mass fraction of 10% -32%; the solid-liquid mass ratio of the graphite anode material of the waste lithium ion battery to the alkaline solution is 1:0.5-1:4.
4. The recycling method for the graphite anode material of the waste lithium ion battery according to claim 3, wherein the mass fraction of the alkaline solution is 18% -25%.
5. The method for recycling graphite cathode materials of waste lithium ion batteries according to claim 1, wherein the inert atmosphere in the step (1) and the step (3) is nitrogen atmosphere; the alkali fusion calcination treatment time in the step (1) is 1-5 h; in the step (2), the solid-liquid mass ratio of the alkali molten slag washed by deionized water is 1:4-1:8.
6. The method for recycling graphite cathode materials of waste lithium ion batteries according to claim 1, wherein the acid solution in the step (2) is hydrochloric acid solution, sulfuric acid solution or nitric acid solution; the solid-liquid mass ratio of the washed material to the acid solution is 1:3-1:8, and the acid dissolution reaction time is 1-24 h.
7. The recycling method for graphite cathode materials of waste lithium ion batteries according to claim 6, wherein the acid solution is hydrochloric acid solution with mass concentration of 5% -37%.
8. The recycling method for graphite cathode materials of waste lithium ion batteries according to claim 7, wherein the mass concentration of the hydrochloric acid solution is 10% -30%.
9. The recycling method of the graphite anode material of the waste lithium ion battery, according to claim 1, is characterized in that in the step (3), the petroleum asphalt is petroleum asphalt with a softening point of 180-300 ℃, and the mass ratio of the petroleum asphalt to the impurity-removed graphite is 1:2-1:30; and the time for coating and granulating is 1-4 hours.
10. The recycling method of the graphite anode material of the waste lithium ion battery, according to claim 9, is characterized in that the petroleum asphalt is petroleum asphalt with a softening point of 250-280 ℃, and the mass ratio of the petroleum asphalt to the impurity-removed graphite is 1:5-1:20.
11. The method for recycling the graphite cathode material of the waste lithium ion battery according to claim 1, wherein the step (3) further comprises spheroidizing and shaping the coated graphite obtained after the coating and granulating treatment, and sieving to obtain recycled graphite; the rotational speed of the spheroidizing wheel for spheroidizing shaping is 4000-8000 r/min, the rotational speed of the grading wheel is 2500-4000 r/min, and the air quantity is 3-6 m 3 And/min, spheroidizing and shaping time is 0.5-5 h; the screening adopts a 300-mesh screen.
12. A graphite obtained by a method for recycling a graphite anode material of a waste lithium ion battery according to any one of claims 1 to 11, wherein the graphite has the following quality indexes:D50 = (18.0±2.0) μm, the specific surface area is 4.0±0.5m 2 Per gram, tap density is not less than 1.0g/cm 3 The compaction density is 1.30-1.45 g/cm 3 The graphitization degree is more than or equal to 92 percent.
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