CN115621598A - Method for recycling and regenerating waste NCM523 type ternary lithium battery positive electrode material - Google Patents
Method for recycling and regenerating waste NCM523 type ternary lithium battery positive electrode material Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000002386 leaching Methods 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 239000011975 tartaric acid Substances 0.000 claims abstract description 8
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940071257 lithium acetate Drugs 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 lithium metals Chemical class 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003723 Smelting Methods 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
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal 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
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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 discloses a method for recycling a waste NCM523 type ternary lithium battery positive electrode material, which comprises the following steps: pre-treating; roasting and reducing: performing high-temperature reduction treatment on LiNi0.5Co0.2Mn0.3O2 cathode powder in a hydrogen-nitrogen mixed gas with a reducing gas molar ratio of 3:1, and almost completely converting lithium, nickel, cobalt and manganese in a cathode material into Li2OH, ni, co and MnO after roasting; acid leaching treatment: leaching the reduced anode powder with citric acid and tartaric acid, filtering the filtrate with a filter membrane after leaching is finished, and measuring the content of metal ions in the filtrate; and (3) regenerating a LiNi0.5Co0.2Mn0.3O2 positive electrode material. The invention can realize harmless treatment and resource utilization of waste lithium batteries, is convenient for regeneration of LiNi0.5Co0.2Mn0.3O2 cathode materials, and solves the problems of high recovery cost and high energy consumption.
Description
Technical Field
The invention relates to the technical field of lithium battery treatment, in particular to a method for recycling a waste NCM523 type ternary lithium battery positive electrode material.
Background
In recent years, with the rapid development of society, the consumption of fossil energy is becoming more and more severe, which promotes a new change in energy supply manner, i.e., a change from conventional energy to new energy. Among them, lithium Ion Batteries (LIBs) are one of typical representatives of new energy sources, and compared with conventional nickel-cadmium batteries, lead-acid batteries and nickel-copper batteries, lithium ion batteries have the advantages of being recyclable, high in capacity, long in service life, high in safety performance, free of memory effect and the like, so that Lithium ion batteries are developed rapidly since the advent, and are widely applied to various fields as a good energy storage device, such as national power grids, electronic devices, power vehicles and the like.
The lithium ion battery comprises a positive electrode material, a negative electrode material, a diaphragm, a binder, a conductive agent and the like, wherein the positive electrode material mainly comprises lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, a ternary material (nickel cobalt lithium manganate) and the like, and the positive electrode material accounts for about 40% in content and plays a decisive role in the performance of the battery. Lithium cobaltate has been commercialized due to its excellent electrochemical properties, but cobalt metal is expensive, so lithium ion batteries have begun to develop from lithium cobaltate, lithium manganate, lithium nickelate, and lithium nickel cobaltate batteries to ternary lithium batteries. The lithium ion battery generally becomes a waste battery after being used for 3-5 years, and finally becomes a retired battery after being subjected to cascade utilization. With the heavy use of lithium ion batteries, the number of retired batteries has increased in a blowout manner in recent years. According to the prediction of relevant scholars, the global lithium ion battery recycling market is predicted to reach more than 64 ten thousand tons in 2025, wherein the Chinese market occupies about 2/3 of the global market, and therefore, the treatment of the retired lithium ion battery is not slow.
Typical lithium ion battery (ternary lithium battery) anode materials contain Li, co, ni, mn and other key components, wherein the cobalt, the nickel and the manganese as heavy metal elements have serious pollution, so that the pH value of the environment is increased, and huge environmental hidden dangers and even harm to the life and health of human beings are caused by random stacking without effective treatment. Li, co and Ni in the decommissioned ternary cathode material have high recovery value, the average price of metal Li is 54 ten thousand per ton, the average price of metal Co is 60 ten thousand per ton, the average price of metal Ni is 11 ten thousand per ton, and the average price of metal Mn is 2 ten thousand per ton, so that the lithium, cobalt, nickel and manganese recovered from the decommissioned lithium ion battery have obvious economic benefit. In addition, the storage capacity of the cobalt and lithium resources in China is small, the occurrence degree of the cobalt and lithium resources in ores is low, and cobalt and lithium metals occupy a higher proportion in the cathode materials of the retired batteries, so that the cobalt and lithium metals recovered from the raw materials can shorten the smelting process and relieve the resource pressure. Therefore, the harmless treatment and resource utilization of the retired lithium ion battery are a great challenge for the new energy enterprises at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for recycling and regenerating a waste NCM523 type ternary lithium battery positive electrode material.
The invention provides a method for recycling a waste NCM523 type ternary lithium battery positive electrode material, which comprises the following steps:
s1, preprocessing;
placing the waste lithium battery in 50g/l sodium chloride aqueous solution for discharging treatment, and manually disassembling to obtain a positive active material coated by a battery aluminum foil;
cutting an aluminum foil-coated LiNi0.5Co0.2Mn0.3O2 positive electrode active material into sheets of about 1 multiplied by 1cm, and placing the sheets in an NMP solution to remove the aluminum foil in an ultrasonic-assisted manner to obtain the positive electrode active material;
pyrolyzing the obtained positive active material at low temperature to remove a binder PVDF in the positive active material to obtain relatively pure positive powder, drying at 75 ℃, and uniformly grinding;
s2, roasting and reducing:
performing high-temperature reduction treatment on LiNi0.5Co0.2Mn0.3O2 cathode powder in a hydrogen-nitrogen mixed gas with a reducing gas molar ratio of 3:1, and almost completely converting lithium, nickel, cobalt and manganese in a cathode material into Li2OH, ni, co and MnO after roasting;
s3, acid leaching treatment:
leaching the reduced anode powder with citric acid and tartaric acid, filtering the filtrate with a filter membrane after leaching is finished, and measuring the content of metal ions in the filtrate;
s4 LiNi0.5Co0.2Mn0.3O2 cathode material regeneration:
the mol ratio of the elements of replenishing nickel, cobalt, manganese and lithium is 0.5:0.2: 1, adding ammonia water to adjust the pH =8 of the solution, heating the solution in a water bath at 80 ℃ and rapidly stirring the solution until gel is formed, drying the gel sample in vacuum at 120 ℃ for 48h to obtain dry gel, calcining the dry gel in a muffle furnace at 450 ℃ for 6h to remove redundant organic matters, grinding the calcined material for 30min, sieving the ground material, and calcining the calcined material in the muffle furnace at 900 ℃ for 12h to obtain the cathode material.
Preferably, in the step S1, the waste lithium battery is a waste NCM523 type ternary lithium battery, and the waste NCM523 type ternary lithium battery is manually disassembled to obtain the shell, the diaphragm and the positive active material.
Preferably, the roasting reduction reaction furnace of the step S2 is heated to 450 ℃ within 2 hours, and the reduction reaction is kept at 450 ℃ for 3.5 hours.
Preferably, the molar ratio of citric acid to tartaric acid is 1:1.
preferably, the leaching conditions in step S3 are: the solid-liquid ratio of the citric acid to the roasted anode powder is 20g/l, the concentration of the citric acid is 1mol/l, the leaching temperature is 70 ℃, the leaching time is 1.5h, and the rotor rotating speed in the leaching process is 400r/min.
Preferably, the metal salts used in step S4 are nickel acetate, cobalt acetate, manganese acetate, and lithium acetate, respectively.
According to the method for recycling and regenerating the anode material of the waste NCM523 type ternary lithium battery, lithium, nickel, cobalt and manganese in the anode material are almost completely converted into Li2OH, ni, co and MnO by adopting a roasting reduction method of high-temperature hydrogen reduction; then obtaining metal pickle liquor through acid leaching treatment; mixing organic acid to obtain gel, and calcining to obtain a positive electrode material;
the method can realize harmless treatment and resource utilization of the waste lithium battery, is convenient for regeneration of LiNi0.5Co0.2Mn0.3O2 cathode materials, and solves the problems of high recovery cost and high energy consumption.
Drawings
FIG. 1 is a battery recycling process flow chart of a method for recycling and regenerating a waste NCM523 type ternary lithium battery positive electrode material provided by the invention;
fig. 2 is a schematic diagram of the positive electrode material regeneration of the method for recovering and regenerating the positive electrode material of the waste NCM523 type ternary lithium battery provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1-2, a method for recycling a positive electrode material of a waste NCM523 type ternary lithium battery includes the following steps:
s1, preprocessing;
placing the waste lithium battery in 50g/l sodium chloride aqueous solution for discharging treatment, and manually disassembling to obtain a positive active material coated by a battery aluminum foil;
cutting an aluminum foil coated LiNi0.5Co0.2Mn0.3O2 positive electrode active material into sheets of about 1 multiplied by 1cm, and placing the sheets in an NMP solution to be separated from the aluminum foil in an ultrasonic-assisted manner to obtain the positive electrode active material;
pyrolyzing the obtained positive active material at low temperature to remove a binder PVDF in the positive active material to obtain relatively pure positive powder, drying at 75 ℃, and uniformly grinding;
s2, roasting and reducing:
performing high-temperature reduction treatment on LiNi0.5Co0.2Mn0.3O2 cathode powder in a mixed gas of hydrogen and nitrogen with a reduction gas molar ratio of 3:1, and almost completely converting lithium, nickel, cobalt and manganese in a cathode material after roasting into Li2OH, ni, co and MnO to exist;
s3, acid leaching treatment:
leaching the reduced anode powder with citric acid and tartaric acid, filtering the filtrate with a filter membrane after leaching is finished, and measuring the content of metal ions in the filtrate;
s4 LiNi0.5Co0.2Mn0.3O2 positive electrode material regeneration:
the mol ratio of the elements of replenishing nickel, cobalt, manganese and lithium is 0.5:0.2: 1, adding ammonia water to adjust the pH =8 of the solution, heating the solution in a water bath at 80 ℃ and rapidly stirring the solution until gel is formed, drying the gel sample in vacuum at 120 ℃ for 48h to obtain dry gel, calcining the dry gel in a muffle furnace at 450 ℃ for 6h to remove redundant organic matters, grinding the calcined material for 30min, sieving the ground material, and calcining the calcined material in the muffle furnace at 900 ℃ for 12h to obtain the cathode material.
In the invention, the waste lithium battery in the step S1 is a waste NCM523 type ternary lithium battery, and the waste NCM523 type ternary lithium battery is manually disassembled to obtain a shell, a diaphragm and a positive active material.
In the invention, the temperature of the roasting reduction reaction furnace in the step S2 is raised to 450 ℃ within 2 hours, and the reduction reaction is kept at 450 ℃ for 3.5 hours.
In the invention, the molar ratio of the citric acid to the tartaric acid is 1:1.
in the invention, the leaching conditions in the step S3 are as follows: the solid-liquid ratio of the citric acid to the roasted anode powder is 20g/l, the concentration of the citric acid is 1mol/l, the leaching temperature is 70 ℃, the leaching time is 1.5h, and the rotor rotating speed in the leaching process is 400r/min.
In the present invention, the metal salts adopted in step S4 are respectively nickel acetate, cobalt acetate, manganese acetate, and lithium acetate.
The invention comprises the following steps: placing the waste NCM523 type ternary lithium battery in a 50g/l sodium chloride aqueous solution for discharging treatment, manually disassembling to obtain a battery aluminum foil coated positive active material, cutting the aluminum foil coated LiNi0.5Co0.2Mn0.3O2 positive active material into sheets of about 1 multiplied by 1cm, placing the sheets in an NMP solution for ultrasonic auxiliary separation to obtain the positive active material, performing low-temperature pyrolysis on the obtained positive active material to remove a binder PVDF in the positive active material to obtain relatively pure positive powder, drying at 75 ℃, and uniformly grinding; carrying out high-temperature reduction treatment on LiNi0.5Co0.2Mn0.3O2 cathode powder in a hydrogen-nitrogen mixed gas with a reducing gas molar ratio of 3:1, heating a reaction furnace to 450 ℃ within 2 hours, keeping the reduction reaction at 450 ℃ for 3.5 hours, and almost completely converting lithium, nickel, cobalt and manganese in the cathode material into Li2OH, ni, co and MnO after roasting; leaching the reduced anode powder by citric acid and tartaric acid (the molar ratio is 1:1), wherein the leaching conditions are as follows: the solid-liquid ratio of citric acid to the roasted anode powder is 20g/l, the concentration of citric acid is 1mol/l, the leaching temperature is 70 ℃, the leaching time is 1.5h, the rotor rotating speed is 400r/min in the leaching process, and after the leaching is finished, the filtrate is filtered by a filter membrane, and the content of metal ions in the filtrate is measured; the mol ratio of the elements of replenishing nickel, cobalt, manganese and lithium is 0.5:0.2: 1, adding ammonia water to adjust the pH =8 of the solution, heating the solution in a water bath at 80 ℃ and rapidly stirring the solution until gel is formed, drying the gel sample in vacuum at 120 ℃ for 48h to obtain dry gel, calcining the dry gel in a muffle furnace at 450 ℃ for 6h to remove redundant organic matters, grinding the calcined material for 30min, sieving the ground material, and calcining the calcined material in the muffle furnace at 900 ℃ for 12h to obtain the cathode material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A method for recycling a waste NCM523 type ternary lithium battery positive electrode material is characterized by comprising the following steps:
s1, preprocessing;
placing the waste lithium battery in 50g/l sodium chloride aqueous solution for discharging treatment, and manually disassembling to obtain a positive active material coated by a battery aluminum foil;
cutting an aluminum foil-coated LiNi0.5Co0.2Mn0.3O2 positive electrode active material into sheets of about 1 multiplied by 1cm, and placing the sheets in an NMP solution to remove the aluminum foil in an ultrasonic-assisted manner to obtain the positive electrode active material;
pyrolyzing the obtained positive active material at low temperature to remove a binder PVDF in the positive active material to obtain relatively pure positive powder, drying at 75 ℃, and uniformly grinding;
s2, roasting and reducing:
performing high-temperature reduction treatment on LiNi0.5Co0.2Mn0.3O2 cathode powder in a hydrogen-nitrogen mixed gas with a reducing gas molar ratio of 3:1, and almost completely converting lithium, nickel, cobalt and manganese in a cathode material into Li2OH, ni, co and MnO after roasting;
s3, acid leaching treatment:
leaching the reduced anode powder with citric acid and tartaric acid, filtering the filtrate with a filter membrane after leaching is finished, and measuring the content of metal ions in the filtrate;
s4 LiNi0.5Co0.2Mn0.3O2 positive electrode material regeneration:
the mol ratio of the elements of replenishing nickel, cobalt, manganese and lithium is 0.5:0.2: 1, adding ammonia water to adjust the pH =8 of the solution, heating the solution in a water bath at 80 ℃ and rapidly stirring the solution until gel is formed, drying the gel sample in vacuum at 120 ℃ for 48h to obtain dry gel, calcining the dry gel in a muffle furnace at 450 ℃ for 6h to remove redundant organic matters, grinding the calcined material for 30min, sieving the ground material, and calcining the calcined material in the muffle furnace at 900 ℃ for 12h to obtain the cathode material.
2. The method for recycling and regenerating the anode material of the waste NCM523 type ternary lithium battery as claimed in claim 1, wherein the waste lithium battery in the step S1 is the waste NCM523 type ternary lithium battery, and the waste NCM523 type ternary lithium battery is manually disassembled to obtain a shell, a diaphragm and the anode active material.
3. The method for recycling and regenerating the anode material of the waste NCM523 type ternary lithium battery as claimed in claim 1, wherein the temperature of the roasting reduction reaction furnace of the step S2 is raised to 450 ℃ within 2 hours, and the reduction reaction is maintained at 450 ℃ for 3.5 hours.
4. The method for recycling and regenerating the anode material of the waste NCM 523-type ternary lithium battery as claimed in claim 1, wherein the molar ratio of the citric acid to the tartaric acid is 1:1.
5. the method for recycling and regenerating the anode material of the waste NCM523 type ternary lithium battery as claimed in claim 1, wherein the leaching conditions in the step S3 are as follows: the solid-liquid ratio of the citric acid to the roasted anode powder is 20g/l, the concentration of the citric acid is 1mol/l, the leaching temperature is 70 ℃, the leaching time is 1.5h, and the rotor rotating speed in the leaching process is 400r/min.
6. The method for recycling and regenerating the anode material of the waste NCM523 type ternary lithium battery as claimed in claim 1, wherein the metal salts adopted in the step S4 are nickel acetate, cobalt acetate, manganese acetate and lithium acetate, respectively.
Priority Applications (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116722253A (en) * | 2023-08-09 | 2023-09-08 | 深圳市杰成镍钴新能源科技有限公司 | Polar material leaching method and device for retired ternary lithium battery |
| CN116864850A (en) * | 2023-08-21 | 2023-10-10 | 中国矿业大学 | Method for regenerating ternary positive electrode material from waste ternary lithium ion battery leaching liquid |
| CN117619859A (en) * | 2023-11-28 | 2024-03-01 | 吉奥环朋科技(扬州)有限公司 | Recycling recovery method of waste lithium ion power battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116722253A (en) * | 2023-08-09 | 2023-09-08 | 深圳市杰成镍钴新能源科技有限公司 | Polar material leaching method and device for retired ternary lithium battery |
| CN116722253B (en) * | 2023-08-09 | 2023-12-01 | 深圳市杰成镍钴新能源科技有限公司 | Polar material leaching method and device for retired ternary lithium battery |
| CN116864850A (en) * | 2023-08-21 | 2023-10-10 | 中国矿业大学 | Method for regenerating ternary positive electrode material from waste ternary lithium ion battery leaching liquid |
| CN117619859A (en) * | 2023-11-28 | 2024-03-01 | 吉奥环朋科技(扬州)有限公司 | Recycling recovery method of waste lithium ion power battery |
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