CN117361649B - Method for preparing positive electrode material by using scrapped battery - Google Patents
Method for preparing positive electrode material by using scrapped battery Download PDFInfo
- Publication number
- CN117361649B CN117361649B CN202311411090.9A CN202311411090A CN117361649B CN 117361649 B CN117361649 B CN 117361649B CN 202311411090 A CN202311411090 A CN 202311411090A CN 117361649 B CN117361649 B CN 117361649B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- preparing
- scrapped
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 49
- 238000005245 sintering Methods 0.000 claims abstract description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- -1 grinding aid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 provides a method for preparing a positive electrode material by utilizing a scrapped battery, which relates to the technical field of scrapped battery recycling and comprises the following steps: s1, separating active components of the scrapped battery; s2, preparing a precursor; and S3, sintering and molding. The method for preparing the anode material by using the scrapped battery has the advantages of simple process, convenient operation control, safety, rapidness and high efficiency, and is environment-friendly and high in recovery rate.
Description
Technical Field
The invention relates to the technical field of recycling of scrapped batteries, in particular to a method for preparing an anode material by utilizing scrapped batteries.
Background
The scrapped battery contains a large amount of valuable metal resources, and whether the recovery technology is excellent directly influences the sustainable development of the lithium ion battery industry. It is seen that it is imperative to find a more suitable method for preparing the positive electrode material using the discarded battery.
The recyclable scrapped lithium battery mainly comprises a battery pole piece, a diaphragm, a shell and the like, wherein the battery pole piece is a key point and a difficult point in the recycling process due to the fact that the battery pole piece has a large number of high-value components and is relatively complex in structure. At present, the mode of recycling the scrapped lithium battery pole piece mainly comprises the steps of roasting the battery pole piece to crack the binder, and then leaching and recycling raw materials such as lithium. However, the method in the prior art has a plurality of problems such as long roasting time and high energy consumption, the generated gas can cause atmospheric pollution, the subsequent treatment of the gas is complex, high-salt wastewater needs to be treated, the recovery cost is high, the waste residues (iron slag, magnesium phosphorus slag, iron phosphorus slag and the like) generated after lithium extraction are generally used as raw materials of building materials, and the iron phosphorus component is not utilized in a high value.
In order to solve the problems, the Chinese patent publication CN116154348B discloses a method for preparing a lithium iron phosphate anode material by scrapping a lithium battery pole piece, which comprises the steps of pole piece stripping, mechanical priority lithium extraction, lithium precipitation, acid leaching, crystallization control and sintering, and the scrapped lithium battery pole piece is recycled to prepare the lithium iron phosphate anode material, so that the recycling of resources is realized. The adhesive force of the pole piece coating to the aluminum foil and the copper foil is reduced by soaking the pole piece in the organic solvent, so that the aluminum foil, the copper foil and the pole piece coating on the aluminum foil and the copper foil are peeled off nondestructively, copper-aluminum impurities are not required to be treated subsequently, the impurity removal cost is greatly reduced, the generation of high-salt wastewater is greatly reduced, the production cost is effectively reduced, and the environmental protection disposal pressure is greatly reduced; the grinding aid ball milling lithium extraction mode is adopted, so that the consumption of a leaching agent is greatly reduced, the generation of high-salt wastewater is further reduced, and the wastewater disposal cost is reduced; and then adding an oxidant in the acid leaching process to oxidize ferrous iron into ferric iron, thereby obtaining the battery grade ferric phosphate. Wherein, the adoption of the organic solvent can cause environmental pollution and waste; and more auxiliary materials such as grinding aid, sodium hypochlorite, sulfuric acid, sodium hydroxide and the like are required to be consumed, so that the recovery cost of the scrapped battery is high, and waste and pollution are easy to cause.
Therefore, the method for preparing the anode material by using the scrapped battery has the advantages of simple process, convenient operation control, safety, rapidness and high efficiency, and good environmental protection and high recovery rate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the method for preparing the anode material by using the scrapped battery, which has the advantages of simple process, convenient operation control, safety, rapidness and high efficiency, and is environment-friendly and high in recovery rate.
The invention can be realized by the following technical scheme:
The method for preparing the positive electrode material by utilizing the scrapped battery comprises the following steps of:
Step S1, separating active components of the scrapped battery: adding the scrapped lithium battery positive plate into an organic solvent, respectively adopting ultrasonic auxiliary treatment and microwave auxiliary treatment, and separating and removing aluminum foil, copper foil and a plate coating of a current collector; centrifugally separating and drying to obtain the active components of the scrapped battery; the organic solvent is recovered by distillation;
Step S2, preparing a precursor: dissolving the active components of the scrapped battery obtained in the step S1 by using a citric acid solution, separating and removing insoluble matters, detecting and supplementing corresponding elements in the solution to prepare a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, performing hydrothermal reaction for 8-16 hours at 190-210 ℃, cooling to room temperature, washing for 3-6 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 95-105 ℃ to constant weight to obtain a precursor;
Step S3, sintering and forming: and (3) sintering the precursor prepared in the step (S2) to prepare the positive electrode material.
Preferably, the organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Preferably, the ultrasonic power of the ultrasonic auxiliary treatment is 400-600W, and the treatment time is 15-25min.
Preferably, the microwave power of the microwave auxiliary treatment is 100-350W, and the treatment time is 20-30min.
Preferably, in step S1, the positive electrode material in the positive electrode sheet of the discarded lithium battery is a lithium nickel manganese oxide positive electrode material.
Preferably, the concentration of the citric acid solution in the step S2 is 5-8mol/L.
Preferably, in step S2, the precursor is lithium nickel manganese oxide LiNi 0.5Mn1.5O4.
Preferably, the precursor in step S2 is prepared from the following components in molar ratio: li: ni: M: mn=1:0.4:0.1:1.5; wherein M is any one of rare earth element, ti and Nb.
Preferably, the rare earth element is any one of Ce, pr and La.
Preferably, the sintering temperature in the step S3 is 550-750 ℃, the sintering time is 4-6 h, and the heating rate is 4-12 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for preparing the anode material by utilizing the scrapped battery realizes the recycling of heavy metals in the scrapped battery, changes waste into valuable, improves the resource utilization rate and avoids environmental pollution caused by the heavy metals; meanwhile, the added value of the product is improved, and the production cost of the anode material is reduced.
(2) The method for preparing the anode material by utilizing the scrapped battery has the advantages of simple process, convenient operation control, safety, rapidness and high efficiency, and is good in environmental protection and high in recovery rate by reasonably selecting the process steps and the process parameters. The scrapped battery positive plate adopts an ultrasonic wave and microwave auxiliary organic solvent dissolution method to extract active ingredients in the scrapped battery positive plate, so that the recovery rate is high, the recovery efficiency is good, and the obtained active ingredients have few impurities; the organic solvent is recycled, so that the waste is reduced.
(3) According to the method for preparing the positive electrode material by utilizing the scrapped battery, disclosed by the invention, the precursor of the positive electrode material is prepared by dissolution of the citric acid solution and hydrothermal reaction, and the step of separating insoluble matters is performed in the dissolution process, so that the purity of active ingredients is further improved; the use of hydrothermal reaction can obviously reduce the reaction temperature; the obtained precursor has complete crystal form, uniform particle size distribution and good dispersibility. By supplementing corresponding elements, a precursor with a fixed composition is formed, so that the activity of the positive electrode material can be effectively improved, and the cycle service life and specific capacity are further improved.
(4) The method for preparing the positive electrode material by using the scrapped battery has the advantages of simple process, convenient operation control, safety, rapidness, high efficiency, good environmental protection and high recovery rate by reasonably selecting the sintering, the preparation of the precursor and the separation process parameters of the active components of the scrapped battery. The lithium battery of the positive electrode material prepared by the method has long cycle service life and good electrochemical performance.
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
Example 1
A method for preparing a positive electrode material by using a scrapped battery, comprising the following steps:
Step S1, separating active components of the scrapped battery: adding the scrapped lithium battery positive plate into an organic solvent, respectively adopting ultrasonic auxiliary treatment and microwave auxiliary treatment, and separating and removing aluminum foil, copper foil and a plate coating of a current collector; centrifugally separating and drying to obtain the active components of the scrapped battery; the organic solvent is recovered by distillation;
Step S2, preparing a precursor: dissolving the active components of the scrapped battery obtained in the step S1 by using a citric acid solution, separating and removing insoluble matters, detecting and supplementing corresponding elements in the solution to prepare a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, performing hydrothermal reaction for 8 hours at 190 ℃, cooling to room temperature, washing for 3-6 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 95 ℃ to constant weight to obtain a precursor;
Step S3, sintering and forming: and (3) sintering the precursor prepared in the step (S2) to prepare the positive electrode material.
The organic solvent is dimethyl sulfoxide; the ultrasonic power of the ultrasonic auxiliary treatment is 400W, and the treatment time is 15min; the microwave power of the microwave auxiliary treatment is 100W, and the treatment time is 20min.
The positive electrode material in the positive electrode plate of the scrapped lithium battery in the step S1 is a lithium nickel manganese oxide positive electrode material; the concentration of the citric acid solution in the step S2 is 5mol/L; in the step S2, the precursor is lithium nickel manganese oxide LiNi 0.5Mn1.5O4.
The sintering temperature in the step S3 is 550 ℃, the sintering time is 4 hours, and the heating rate is 4 ℃/min.
Example 2
A method for preparing a positive electrode material by using a scrapped battery, comprising the following steps:
Step S1, separating active components of the scrapped battery: adding the scrapped lithium battery positive plate into an organic solvent, respectively adopting ultrasonic auxiliary treatment and microwave auxiliary treatment, and separating and removing aluminum foil, copper foil and a plate coating of a current collector; centrifugally separating and drying to obtain the active components of the scrapped battery; the organic solvent is recovered by distillation;
Step S2, preparing a precursor: dissolving the active components of the scrapped battery obtained in the step S1 by using a citric acid solution, separating and removing insoluble matters, detecting and supplementing corresponding elements in the solution to prepare a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, performing hydrothermal reaction for 10 hours at 195 ℃, cooling to room temperature, washing for 4 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 98 ℃ to constant weight to obtain a precursor;
Step S3, sintering and forming: and (3) sintering the precursor prepared in the step (S2) to prepare the positive electrode material.
The organic solvent is N, N-dimethylformamide; the ultrasonic power of the ultrasonic auxiliary treatment is 450W, and the treatment time is 18min; the microwave power of the microwave auxiliary treatment is 200W, and the treatment time is 23min.
The positive electrode material in the positive electrode plate of the scrapped lithium battery in the step S1 is a lithium nickel manganese oxide positive electrode material; the concentration of the citric acid solution in the step S2 is 6mol/L.
The precursor in the step S2 is prepared from the following components in mole ratio: li: ni: M: mn=1:0.4:0.1:1.5; wherein M is a rare earth element; the rare earth element is Ce.
The sintering temperature in the step S3 is 600 ℃, the sintering time is 4.5h, and the heating rate is 6 ℃/min.
Example 3
A method for preparing a positive electrode material by using a scrapped battery, comprising the following steps:
Step S1, separating active components of the scrapped battery: adding the scrapped lithium battery positive plate into an organic solvent, respectively adopting ultrasonic auxiliary treatment and microwave auxiliary treatment, and separating and removing aluminum foil, copper foil and a plate coating of a current collector; centrifugally separating and drying to obtain the active components of the scrapped battery; the organic solvent is recovered by distillation;
Step S2, preparing a precursor: dissolving the active components of the scrapped battery obtained in the step S1 by using a citric acid solution, separating and removing insoluble matters, detecting and supplementing corresponding elements in the solution to prepare a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, performing hydrothermal reaction for 12 hours at 200 ℃, cooling to room temperature, washing for 5 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 100 ℃ to constant weight to obtain a precursor;
Step S3, sintering and forming: and (3) sintering the precursor prepared in the step (S2) to prepare the positive electrode material.
The organic solvent is N-methyl pyrrolidone; the ultrasonic power of the ultrasonic auxiliary treatment is 500W, and the treatment time is 20min; the microwave power of the microwave auxiliary treatment is 250W, and the treatment time is 25min.
The positive electrode material in the positive electrode plate of the scrapped lithium battery in the step S1 is a lithium nickel manganese oxide positive electrode material; the concentration of the citric acid solution in the step S2 is 6.5mol/L.
The precursor in the step S2 is prepared from the following components in mole ratio: li: ni: M: mn=1:0.4:0.1:1.5; wherein M is Ti.
The sintering temperature in the step S3 is 650 ℃, the sintering time is 5 hours, and the heating rate is 8 ℃/min.
Example 4
A method for preparing a positive electrode material by using a scrapped battery, comprising the following steps:
Step S1, separating active components of the scrapped battery: adding the scrapped lithium battery positive plate into an organic solvent, respectively adopting ultrasonic auxiliary treatment and microwave auxiliary treatment, and separating and removing aluminum foil, copper foil and a plate coating of a current collector; centrifugally separating and drying to obtain the active components of the scrapped battery; the organic solvent is recovered by distillation;
Step S2, preparing a precursor: dissolving the active components of the scrapped battery obtained in the step S1 by using a citric acid solution, separating and removing insoluble matters, detecting and supplementing corresponding elements in the solution to prepare a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, performing hydrothermal reaction for 14 hours at 205 ℃, cooling to room temperature, washing for 5 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 103 ℃ to constant weight to obtain a precursor;
Step S3, sintering and forming: and (3) sintering the precursor prepared in the step (S2) to prepare the positive electrode material.
The organic solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to a mass ratio of 1:3:5; the ultrasonic power of the ultrasonic auxiliary treatment is 550W, and the treatment time is 23min; the microwave power of the microwave auxiliary treatment is 320W, and the treatment time is 28min.
The positive electrode material in the positive electrode plate of the scrapped lithium battery in the step S1 is a lithium nickel manganese oxide positive electrode material; the concentration of the citric acid solution in the step S2 is 7mol/L; the precursor in the step S2 is prepared from the following components in mole ratio: li: ni: M: mn=1:0.4:0.1:1.5; wherein M is Nb.
The sintering temperature in the step S3 is 700 ℃, the sintering time is 5.5h, and the heating rate is 10 ℃/min.
Example 5
A method for preparing a positive electrode material by using a scrapped battery, comprising the following steps:
Step S1, separating active components of the scrapped battery: adding the scrapped lithium battery positive plate into an organic solvent, respectively adopting ultrasonic auxiliary treatment and microwave auxiliary treatment, and separating and removing aluminum foil, copper foil and a plate coating of a current collector; centrifugally separating and drying to obtain the active components of the scrapped battery; the organic solvent is recovered by distillation;
Step S2, preparing a precursor: dissolving the active components of the scrapped battery obtained in the step S1 by using a citric acid solution, separating and removing insoluble matters, detecting and supplementing corresponding elements in the solution to prepare a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, performing hydrothermal reaction for 16 hours at 210 ℃, cooling to room temperature, washing for 6 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 105 ℃ to constant weight to obtain a precursor;
Step S3, sintering and forming: and (3) sintering the precursor prepared in the step (S2) to prepare the positive electrode material.
The organic solvent is N, N-dimethylformamide; the ultrasonic power of the ultrasonic auxiliary treatment is 600W, and the treatment time is 25min; the microwave power of the microwave auxiliary treatment is 350W, and the treatment time is 30min.
The positive electrode material in the positive electrode plate of the scrapped lithium battery in the step S1 is a lithium nickel manganese oxide positive electrode material; the concentration of the citric acid solution in the step S2 is 8mol/L; the precursor in the step S2 is prepared from the following components in mole ratio: li: ni: M: mn=1:0.4:0.1:1.5; wherein M is a rare earth element; the rare earth element is Pr.
The sintering temperature in the step S3 is 750 ℃, the sintering time is 6 hours, and the heating rate is 12 ℃/min.
In order to further illustrate the unexpected positive technical effects obtained by the products of the embodiments of the present invention, the positive electrode materials prepared by the embodiments are subjected to the relevant performance test, and the test method is as follows: the positive electrode materials prepared in each example, superP (high conductivity carbon black SUPERPLi lithium battery conductive agent in switzerland) and PVDF (PVDF 5130 in the United states of America, suwei) were mixed in a mass ratio of 8:1:1, uniformly dispersed with an appropriate amount of NMP, and then uniformly coated on an aluminum foil. Drying for 12 hours in a vacuum drying oven at 120 ℃, and cutting the aluminum foil into wafers with the diameter of 14mm to obtain a battery pole piece; then, the electrode sheet was punched into a round shape, and the battery was assembled in an argon glove box, using a Celgard2400 separator, an electrolyte of 1MLiPF6/ec+dec (volume ratio 1:1), and a metallic lithium sheet negative electrode, to assemble a CR2032 coin-type battery. The prepared button cell was respectively subjected to charge-discharge cycle performance test by using LANDCT-2001 type cell test system, the test temperature was 25 ℃, the voltage window was 3.0-4.3V, the charge-discharge multiplying power was 1C, and the test results are shown in table 1.
TABLE 1
| Project | First charge and discharge efficiency | Cycle life 1C@2000 turns |
| Unit (B) | ％ | ％ |
| Example 1 | 98.7 | 94.2 |
| Example 2 | 99.2 | 95.5 |
| Example 3 | 99.5 | 96.0 |
| Example 4 | 99.6 | 96.7 |
| Example 5 | 99.8 | 97.1 |
As can be seen from table 1, the positive electrode material prepared by the method for preparing the positive electrode material by using the scrapped battery disclosed by the embodiment of the invention is applied to a lithium battery, and has better first charge and discharge efficiency and longer cycle life compared with the comparative example.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those of ordinary skill in the art will readily implement the invention as described above; however, those skilled in the art should not depart from the scope of the invention, and make various changes, modifications and adaptations of the invention using the principles disclosed above; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (10)
1. A method for preparing a positive electrode material by using a scrapped battery, which is characterized by comprising the following steps:
Step S1, separating active components of the scrapped battery: adding the scrapped lithium battery positive plate into an organic solvent, respectively adopting ultrasonic auxiliary treatment and microwave auxiliary treatment, and separating and removing aluminum foil, copper foil and a plate coating of a current collector; centrifugally separating and drying to obtain the active components of the scrapped battery; the organic solvent is recovered by distillation;
Step S2, preparing a precursor: dissolving the active components of the scrapped battery obtained in the step S1 by using a citric acid solution, separating and removing insoluble matters, detecting and supplementing corresponding elements in the solution to prepare a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, performing hydrothermal reaction for 8-16 hours at 190-210 ℃, cooling to room temperature, washing for 3-6 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 95-105 ℃ to constant weight to obtain a precursor;
Step S3, sintering and forming: and (3) sintering the precursor prepared in the step (S2) to prepare the positive electrode material.
2. The method for preparing a positive electrode material using a scrapped battery according to claim 1, wherein the organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, and N-methylpyrrolidone.
3. The method for preparing the positive electrode material by using the scrapped battery according to claim 1, wherein the ultrasonic power of the ultrasonic auxiliary treatment is 400-600W, and the treatment time is 15-25min.
4. The method for preparing the positive electrode material by using the scrapped battery according to claim 1, wherein the microwave power of the microwave auxiliary treatment is 100-350W, and the treatment time is 20-30min.
5. The method for preparing a positive electrode material by using a scrapped battery according to claim 1, wherein the positive electrode material in the scrapped lithium battery positive electrode sheet in the step S1 is a lithium nickel manganese oxide positive electrode material.
6. The method for preparing a positive electrode material using a scrapped battery according to claim 1, wherein the concentration of the citric acid solution in the step S2 is 5-8mol/L.
7. The method for preparing a positive electrode material by using a scrapped battery according to claim 1, wherein the precursor in the step S2 is lithium nickel manganese oxide LiNi 0.5Mn1.5O4.
8. The method for preparing a positive electrode material using a scrapped battery according to claim 1, wherein the precursor in the step S2 comprises the following components in terms of mole ratio: li: ni: M: mn=1:0.4:0.1:1.5; wherein M is any one of rare earth element, ti and Nb.
9. The method for preparing a positive electrode material using a scrapped battery according to claim 8, wherein the rare earth element is any one of Ce, pr, la.
10. The method for preparing a positive electrode material using a scrapped battery according to any one of claims 1 to 9, wherein the sintering temperature in step S3 is 550 ℃ to 750 ℃, the sintering time is 4h to 6h, and the temperature rising rate is 4 ℃ to 12 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311411090.9A CN117361649B (en) | 2023-10-28 | 2023-10-28 | Method for preparing positive electrode material by using scrapped battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311411090.9A CN117361649B (en) | 2023-10-28 | 2023-10-28 | Method for preparing positive electrode material by using scrapped battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117361649A CN117361649A (en) | 2024-01-09 |
| CN117361649B true CN117361649B (en) | 2024-04-16 |
Family
ID=89396266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311411090.9A Active CN117361649B (en) | 2023-10-28 | 2023-10-28 | Method for preparing positive electrode material by using scrapped battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117361649B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108565419A (en) * | 2018-03-30 | 2018-09-21 | 华南师范大学 | A kind of regenerative lithium ion anode material and preparation method thereof |
| CN111129487A (en) * | 2020-01-03 | 2020-05-08 | 昆明理工大学 | Hydrothermal lithium supplement-spray remodeling regeneration method for waste ternary cathode material |
| CN111961860A (en) * | 2020-08-21 | 2020-11-20 | 昆明理工大学 | Method for recovering lithium ion battery by ultrasonic-microwave assistance |
| CN114540640A (en) * | 2022-03-03 | 2022-05-27 | 合肥国轩高科动力能源有限公司 | Lithium battery recycling method |
| CN115513547A (en) * | 2022-08-23 | 2022-12-23 | 北京三才绿碳新能源科技有限公司 | Method for separating anode powder and aluminum foil of waste lithium battery |
| CN115652095A (en) * | 2022-10-27 | 2023-01-31 | 内蒙古蒙能环保科技有限公司 | Extraction process of degraded ternary lithium battery positive electrode material |
-
2023
- 2023-10-28 CN CN202311411090.9A patent/CN117361649B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108565419A (en) * | 2018-03-30 | 2018-09-21 | 华南师范大学 | A kind of regenerative lithium ion anode material and preparation method thereof |
| CN111129487A (en) * | 2020-01-03 | 2020-05-08 | 昆明理工大学 | Hydrothermal lithium supplement-spray remodeling regeneration method for waste ternary cathode material |
| CN111961860A (en) * | 2020-08-21 | 2020-11-20 | 昆明理工大学 | Method for recovering lithium ion battery by ultrasonic-microwave assistance |
| CN114540640A (en) * | 2022-03-03 | 2022-05-27 | 合肥国轩高科动力能源有限公司 | Lithium battery recycling method |
| CN115513547A (en) * | 2022-08-23 | 2022-12-23 | 北京三才绿碳新能源科技有限公司 | Method for separating anode powder and aluminum foil of waste lithium battery |
| CN115652095A (en) * | 2022-10-27 | 2023-01-31 | 内蒙古蒙能环保科技有限公司 | Extraction process of degraded ternary lithium battery positive electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117361649A (en) | 2024-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102751548B (en) | Method for recovering and preparing lithium iron phosphate from waste lithium iron phosphate battery | |
| CN106848469A (en) | A kind of method that valuable metal is reclaimed in the material from waste lithium ion cell anode | |
| CN104953200A (en) | Method for recycling battery-grade iron phosphate in lithium iron phosphate battery and preparing lithium iron phosphate positive material by utilizing waste lithium ion phosphate battery | |
| CN112490527B (en) | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery | |
| CN110526301A (en) | The method that recasting is mended in a kind of pair of lithium battery anode failure cobalt acid lithium structure feedback | |
| CN112038722A (en) | Method for efficiently treating waste lithium iron phosphate positive plate | |
| CN111994891A (en) | Recycling method of lithium iron phosphate cathode material | |
| CN111321297A (en) | Method for recovering valuable metals from waste lithium ion batteries | |
| WO2022142582A1 (en) | Silicon-doped graphene composite material, preparation method for same, and applications thereof | |
| CN113584589A (en) | Method for preparing single crystal ternary positive electrode material from scrapped lithium battery pole piece | |
| CN111326814A (en) | Method for repairing anode material of waste ternary battery by ultrasonic hydrothermal method | |
| CN117361649B (en) | Method for preparing positive electrode material by using scrapped battery | |
| CN115360452A (en) | Method for preparing lithium battery negative electrode material by using waste power battery | |
| CN116315214A (en) | Pyrolysis and reduction cooperative treatment method for waste lithium battery pole pieces | |
| CN103094579B (en) | Method for preparing cathode material-lithium iron phosphate of lithium ion battery by utilizing steel slag | |
| CN112093787B (en) | Method for recycling and preparing olivine type five-element high-entropy lithium battery precursor | |
| CN111392706B (en) | Method for recycling waste lithium iron phosphate anode material | |
| CN108963223A (en) | A kind of graphene power battery material and preparation method thereof | |
| CN113193255B (en) | New energy battery material recycling and regenerating treatment method | |
| CN110304666B (en) | Method for recovering valuable elements from waste lithium ion battery anode material | |
| CN110323509B (en) | Process for recovering valuable elements from lithium ion battery anode material | |
| CN116553582A (en) | Method for extracting lithium carbonate from scrapped lithium battery | |
| CN113860351A (en) | Preparation method and application of CuO-graphite composite material prepared from waste graphite | |
| CN117430109A (en) | Preparation method of lithium iron manganese phosphate material, lithium iron manganese phosphate material and lithium ion battery | |
| CN117583600A (en) | Preparation method of sodium ion battery sodium-modified positive electrode material and sodium-modified positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |