CN113948788B - Lithium cobalt oxide positive electrode material and regeneration and repair method and application thereof - Google Patents
Lithium cobalt oxide positive electrode material and regeneration and repair method and application thereof Download PDFInfo
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title claims abstract description 91
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000011069 regeneration method Methods 0.000 title claims abstract description 30
- 230000008929 regeneration Effects 0.000 title claims abstract description 27
- 230000008439 repair process Effects 0.000 title claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 117
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 117
- 239000000463 material Substances 0.000 claims abstract description 61
- 238000001354 calcination Methods 0.000 claims abstract description 51
- 239000002699 waste material Substances 0.000 claims abstract description 44
- 239000002912 waste gas Substances 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims description 42
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 230000001172 regenerating effect Effects 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 229910013553 LiNO Inorganic materials 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 11
- 208000028659 discharge Diseases 0.000 description 20
- 239000010406 cathode material Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 238000009841 combustion method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000036541 health Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000009766 low-temperature sintering Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004880 explosion Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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 application discloses a lithium cobalt oxide positive electrode material, a regeneration repair method and application thereof, wherein the regeneration repair method of the lithium cobalt oxide positive electrode material comprises the following steps: A. disassembling the waste lithium battery to obtain a positive plate; B. calcining the positive plate in a vacuum environment, and extracting waste gas generated in the vacuum environment in the calcining process and absorbing the waste gas by alkali liquor; C. crushing and three-stage screening are carried out on the calcined positive plate to obtain a third material with more than 300 meshes; D. adding a lithium source into the third material for mixing to obtain a mixture; E. and (3) carrying out secondary calcination on the mixture to obtain the lithium cobaltate anode material. According to the lithium cobalt oxide positive electrode material, the regeneration and repair method and the application thereof, which are provided by the technical scheme, the discharge of waste water and waste gas in the regeneration and repair process of the lithium cobalt oxide positive electrode material can be effectively reduced, and the technical problem of overhigh cost caused in the recovery process of the conventional waste lithium battery positive electrode material is solved.
Description
Technical Field
The application relates to the technical field of lithium battery recovery, in particular to a lithium cobalt oxide positive electrode material, a regeneration and repair method and application thereof.
Background
Lithium and lithium compounds are important energy materials and are widely applied to energy storage power supplies and national defense construction. Although the scrapped lithium ion battery does not contain heavy metals such as lead, cadmium, mercury and the like and has relatively small environmental pollution, the scrapped lithium ion battery contains valuable metals such as cobalt, nickel, manganese, lithium and the like and toxic and harmful substances such as lithium hexafluorophosphate and the like, and serious pollution and resource waste are caused by improper disposal. Cobalt, lithium, copper, a metal shell, a nickel sheet and the like in the waste lithium battery are precious resources, and the lithium-containing compound, the plastic diaphragm and the like have extremely high recovery value. Therefore, the method for treating the waste lithium batteries scientifically and effectively has remarkable environmental benefit and good economic benefit.
Common methods for recycling the positive electrode material of waste lithium batteries generally include dry calcination and hydrometallurgy. Wherein, dry calcination refers to recovery of electrode materials by means of high-temperature calcination treatment; hydrometallurgy refers to extracting heavy metal substances in the anode and the cathode by an extracting agent, enriching the heavy metal substances into salts, and finally obtaining a precursor by a coprecipitation technology.
When the existing dry-process calcination is used for recycling the waste lithium battery anode material, as lithium hexafluorophosphate and moisture in the air are subjected to decomposition reaction in the processes of shredding, crushing and separating the lithium battery, harmful gas is generated to harm the environment and human health, an air compressor is needed to provide dry and dehumidified air for calcination in the process of recycling the waste lithium battery anode material by dry-process calcination, and the recycling cost is high easily. In addition, in the lithium battery recovery process, the binder in the lithium battery is generally removed by using a solvent, and the impurity removal method can lead to the generation of waste water and waste gas in the lithium battery recovery process, such as leakage of the waste water and the waste gas, and the pollution to soil, underground water and the like, so that an external waste discharge treatment system is required to be added in the existing recovery process to treat the waste water and the waste gas, and the recovery cost of the waste lithium battery anode material is further improved; furthermore, there is also a method for removing impurities by removing the binder in the lithium battery by air combustion, and similarly, in order to avoid the decomposition reaction of lithium hexafluorophosphate and water in the air, harmful gas is generated to harm the environment and the health of human body, the air in the impurity removal treatment by the air combustion method is also required to be dried and dehumidified, and the ideal impurity removal effect can be achieved by high-temperature combustion.
Disclosure of Invention
The first object of the present application is to provide a method for regenerating and repairing a lithium cobalt oxide positive electrode material, which can effectively reduce the discharge of waste water and waste gas in the regeneration and repair process of the lithium cobalt oxide positive electrode material, solve the technical problem of too high cost in the recovery process of the existing waste lithium battery positive electrode material, and facilitate the simplification of the regeneration and repair process of the lithium cobalt oxide positive electrode material and the improvement of the purity of the lithium cobalt oxide positive electrode material, so as to overcome the defects in the prior art.
The second object of the present application is to provide a lithium cobalt oxide positive electrode material prepared by the regeneration and repair method of the lithium cobalt oxide positive electrode material, which has higher purity.
The third object of the present application is to provide an application of the above lithium cobaltate positive electrode material in preparing a low impurity lithium battery, which is beneficial to preparing a lithium battery with low impurity content.
To achieve the purpose, the application adopts the following technical scheme:
the regeneration and repair method of the lithium cobalt oxide positive electrode material comprises the following steps:
A. discharging the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
B. calcining the positive plate at 400-550 ℃ in a vacuum environment with the vacuum degree of-0.1 to-1 Mpa, and extracting waste gas generated in the vacuum environment in the calcining process and absorbing with alkali liquor;
C. crushing and three-stage screening are carried out on the calcined positive plate to obtain a first material below 50 meshes, a second material between 50 and 300 meshes and a third material above 300 meshes;
D. adding a lithium source into the third material for mixing to obtain a mixture;
E. and (3) carrying out secondary calcination on the mixture to obtain the lithium cobaltate anode material.
Preferably, in the step B, the calcination time of the primary calcination is 0.5 to 3 hours.
Preferably, in the step D, the molar ratio of the third material to the lithium source is (1 to 1.2): 1.
preferably, in the step D, the lithium source is any one or a combination of more than one of LiOH, li2CO3, liNO3 and LiCOOCH 3.
Preferably, in the step E, the calcination temperature of the secondary calcination is 700-900 ℃ and the calcination time is 4-12 h.
Preferably, in the step A, the voltage of the discharged waste lithium battery is less than or equal to 2.8V.
The lithium cobalt oxide positive electrode material is prepared by the regeneration and repair method of the lithium cobalt oxide positive electrode material.
The application of the lithium cobalt oxide positive electrode material in preparing the low-impurity lithium battery uses the lithium cobalt oxide positive electrode material.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
1. the waste lithium battery is discharged, so that explosion combustion of the waste lithium battery during disassembly can be avoided; the method is simple and convenient to operate, and can prevent lithium hexafluorophosphate in the battery from decomposing with water in the air, and harmful gas can be generated to harm the environment and human health.
2. Impurities such as polyvinylidene fluoride, acetylene black and the like in the positive plate are removed in a vacuum low-temperature sintering mode, so that the high-purity ineffective lithium cobalt oxide positive electrode material is obtained. Specifically, the mode of removing impurities through the vacuum low-temperature sintering mode has the following advantages: (1) Compared with the existing impurity removal mode of removing impurities by adding relevant solvents, the method can effectively reduce the discharge of waste water and waste gas in the regeneration and repair process of the lithium cobalt oxide positive electrode material, and is environment-friendly; (2) Compared with the existing impurity removal mode of removing impurities by an air combustion method, the method does not need an air compressor to provide dry and dehumidified air, achieves the energy-saving effect, is beneficial to simplifying the regeneration process, has better regeneration effect and higher purity of regenerated products, and has very high social and economic values; (3) Compared with the existing impurity removing mode of removing impurities by an air combustion method, the vacuum sintering method has the advantages that the temperature used by vacuum sintering is lower, active substances of the lithium cobaltate anode material are easier to separate from the impurities, impurities such as polyvinylidene fluoride, acetylene black and the like can be disabled only when the calcining temperature reaches 400-550 ℃, the energy consumption can be effectively reduced, and the follow-up process is convenient to carry out.
3. The calcined positive plate is crushed and screened in three stages, so that the aluminum current collector in the waste lithium battery is prevented from being introduced into the lithium cobalt oxide positive material in the form of aluminum impurities after being crushed, and the purity of a regenerated product is improved.
4. The lithium source is added to perform high-temperature calcination lithium supplementation on the spent lithium cobaltate, so that the lithium content, the crystal structure of the bulk phase/surface and the electrochemical performance of the spent lithium cobaltate can be effectively restored to the original state.
Drawings
Fig. 1 is an SEM photograph of a third material and a lithium cobalt oxide cathode material in example 1 of a method for regenerating and repairing a lithium cobalt oxide cathode material according to the present application.
Fig. 2 is an X-ray diffraction pattern of a lithium cobalt oxide cathode material in example 1 of a method for regenerating and repairing a lithium cobalt oxide cathode material according to the present application.
Fig. 3 is a comparison of 0.1C charge-discharge test of the third material and the lithium cobalt oxide cathode material in example 1 of a method for regenerating and repairing a lithium cobalt oxide cathode material according to the present application.
Fig. 4 is a comparative discharge rate performance test result of the third material and the lithium cobalt oxide cathode material in example 1 of a method for regenerating and repairing a lithium cobalt oxide cathode material according to the present application.
Fig. 5 is a comparison of the charge and discharge cycle number test of the third material and the lithium cobalt oxide cathode material in example 1 of a method for regenerating and repairing a lithium cobalt oxide cathode material according to the present application.
Detailed Description
The regeneration and repair method of the lithium cobalt oxide positive electrode material comprises the following steps:
A. discharging the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
B. calcining the positive plate at 400-550 ℃ in a vacuum environment with the vacuum degree of-0.1 to-1 Mpa, and extracting waste gas generated in the vacuum environment in the calcining process and absorbing with alkali liquor;
C. crushing and three-stage screening are carried out on the calcined positive plate to obtain a first material below 50 meshes, a second material between 50 and 300 meshes and a third material above 300 meshes;
D. adding a lithium source into the third material for mixing to obtain a mixture;
E. and (3) carrying out secondary calcination on the mixture to obtain the lithium cobaltate anode material.
When the existing dry-process calcination is used for recycling the waste lithium battery anode material, as lithium hexafluorophosphate and moisture in the air are subjected to decomposition reaction in the processes of shredding, crushing and separating the lithium battery, harmful gas is generated to harm the environment and human health, an air compressor is needed to provide dry and dehumidified air for calcination in the process of recycling the waste lithium battery anode material by dry-process calcination, and the recycling cost is high easily. In addition, in the lithium battery recovery process, the binder in the lithium battery is generally removed by using a solvent, and the impurity removal method can lead to the generation of waste water and waste gas in the lithium battery recovery process, such as leakage of the waste water and the waste gas, and the pollution to soil, underground water and the like, so that an external waste discharge treatment system is required to be added in the existing recovery process to treat the waste water and the waste gas, and the recovery cost of the waste lithium battery anode material is further improved; furthermore, there is also a method for removing impurities by removing the binder in the lithium battery by air combustion, and similarly, in order to avoid the decomposition reaction of lithium hexafluorophosphate and water in the air, harmful gas is generated to harm the environment and the health of human body, the air in the impurity removal treatment by the air combustion method is also required to be dried and dehumidified, and the ideal impurity removal effect can be achieved by high-temperature combustion.
In order to reduce the discharge of waste water and waste gas in the regeneration and repair process of the lithium cobalt oxide positive electrode material and solve the technical problem of overhigh cost caused in the recovery process of the existing waste lithium battery positive electrode material, the technical scheme provides a regeneration and repair method of the lithium cobalt oxide positive electrode material, which comprises the following steps:
A. discharging the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate; specifically, the waste lithium battery is subjected to discharge treatment, so that explosion combustion of the waste lithium battery during disassembly can be avoided; the method has the advantages that the waste lithium batteries are disassembled in an inert gas environment, so that decomposition reaction of lithium hexafluorophosphate in the batteries and moisture in the air is prevented, harmful gas can be generated to harm the environment and human health, and the method is simple and convenient to operate; in the present technical solution, the discarded lithium battery refers to a lithium battery whose appearance, electrical performance, safety, etc. are reduced to the initial minimum standard, for example, when the specific capacity of the lithium battery is less than 80%, the lithium battery is determined to be unacceptable, and a decommissioning process is required.
B. Calcining the positive plate at 400-550 ℃ in a vacuum environment with the vacuum degree of-0.1 to-1 Mpa, and extracting waste gas generated in the vacuum environment in the calcining process and absorbing with alkali liquor; according to the technical scheme, impurities such as polyvinylidene fluoride (PVDF) and acetylene black in the positive plate are removed in a vacuum low-temperature sintering mode, so that the high-purity ineffective lithium cobalt oxide positive electrode material is obtained. Specifically, the mode of removing impurities through the vacuum low-temperature sintering mode has the following advantages: (1) Compared with the existing impurity removal mode of removing impurities by adding relevant solvents, the method can effectively reduce the discharge of waste water and waste gas in the regeneration and repair process of the lithium cobalt oxide positive electrode material, and is environment-friendly; (2) Compared with the existing impurity removal mode of removing impurities by an air combustion method, the method does not need an air compressor to provide dry and dehumidified air, achieves the energy-saving effect, is beneficial to simplifying the regeneration process, has better regeneration effect and higher purity of regenerated products, and has very high social and economic values; (3) Compared with the existing impurity removing mode of removing impurities by an air combustion method, the vacuum sintering method has the advantages that the temperature used by vacuum sintering is lower, active substances of the lithium cobaltate anode material are easier to separate from the impurities, impurities such as polyvinylidene fluoride, acetylene black and the like can be disabled only when the calcining temperature reaches 400-550 ℃, the energy consumption can be effectively reduced, and the follow-up process is convenient to carry out.
C. Crushing and three-stage screening are carried out on the calcined positive plate to obtain a first material below 50 meshes, a second material between 50 and 300 meshes and a third material above 300 meshes; according to the technical scheme, the calcined positive plate is crushed and subjected to three-stage screening, and the obtained first material is mainly metal particles such as aluminum; the second material is mainly aluminum foil and the like; the third material is spent lithium cobalt oxide in the spent lithium battery. According to the technical scheme, the calcined positive plate is crushed and screened in three stages, so that the phenomenon that the aluminum current collector in the waste lithium battery is introduced into the lithium cobalt oxide positive plate material in the form of aluminum impurities after being crushed is avoided, and the purity of a regenerated product is improved.
D. Adding a lithium source into the third material for mixing to obtain a mixture;
E. and (3) carrying out secondary calcination on the mixture to obtain the lithium cobalt oxide positive electrode material (namely the regenerated lithium cobalt oxide). Lithium depletion and a change in crystal phase structure are main causes of a decrease in specific capacity of the positive electrode material. As lithium ions are lost, transition metal cations begin to migrate between layers, changing during repeated charge and discharge, slowly causing irreversible phase structure changes. The crystal structure of the lithium cobaltate is changed from the original layered structure into a mixed structure of spinel and rock salt phase. These crystal structure changes may cause a portion of lithium ions not to freely intercalate and deintercalate within the crystal structure, resulting in serious to no specific capacity fade. According to the technical scheme, the lithium source is added to perform high-temperature calcination lithium supplement on the ineffective lithium cobaltate, so that the lithium content, the crystal structure of the bulk phase/surface and the electrochemical performance of the ineffective lithium cobaltate can be effectively restored to the original state.
It should be noted that, the waste lithium battery used in the present technical solution may include a soft-pack, cylindrical or hard-shell lithium battery, which is not limited herein.
Further, in the step B, the calcination time for the primary calcination is 0.5 to 3 hours.
In a preferred embodiment of the technical scheme, the vacuum low-temperature sintering time is 0.5-3 h, which is favorable for sufficiently removing impurities such as polyvinylidene fluoride (PVDF) and acetylene black in the positive plate, thereby obtaining the high-purity ineffective lithium cobaltate positive electrode material.
Further, in the step D, the molar ratio of the third material to the lithium source is (1 to 1.2): 1.
in the technical scheme, the molar ratio of the third material (namely the ineffective lithium cobalt oxide) to the lithium source is defined as (1-1.2): 1, the lithium content, the crystal structure of the bulk phase/surface and the electrochemical performance of the ineffective lithium cobaltate are recovered to the original state, and the performance index of a regenerated product is ensured to reach the qualified standard, so that the regeneration and repair effects of the lithium cobaltate are ensured.
Further described, in step D, the lithium source is LiOH, li 2 CO 3 、LiNO 3 And LiCoOOCH 3 Any one or a combination of a plurality of the above.
Further, in the step E, the calcination temperature of the secondary calcination is 700-900 ℃ and the calcination time is 4-12 h.
In a preferred embodiment of the technical scheme, the calcination temperature of the high-temperature combustion lithium supplement is limited to 700-900 ℃, which is favorable for avoiding volatilization of a lithium source and reducing the lithium supplement effect; the calcination time is limited to 4-12 h, so that the full reaction between the third material and the lithium source is facilitated, and the regenerated and repaired lithium cobalt oxide positive electrode material is ensured to form a complete layered structure.
Further, in the step A, the voltage of the discharged waste lithium battery is less than or equal to 2.8V.
In a preferred embodiment of the technical scheme, the voltage of the discharged waste lithium battery is less than or equal to 2.8V, so that the explosion combustion of the waste lithium battery during disassembly is avoided, and the normal operation of a regeneration repair process is ensured.
The lithium cobalt oxide positive electrode material is prepared by the regeneration and repair method of the lithium cobalt oxide positive electrode material.
The technical scheme also provides the lithium cobalt oxide positive electrode material prepared by the regeneration and repair method of the lithium cobalt oxide positive electrode material, and the lithium cobalt oxide positive electrode material has higher purity.
The application of the lithium cobalt oxide positive electrode material in preparing the low-impurity lithium battery uses the lithium cobalt oxide positive electrode material.
The technical scheme also provides the application of the lithium cobaltate anode material in preparing the low-impurity lithium battery, and the lithium cobaltate anode material is favorable for preparing the lithium battery with low impurity content.
The technical scheme of the application is further described by the following specific embodiments.
Example 1-regeneration repair method of lithium cobalt oxide cathode Material
A. Discharging the waste lithium battery to 2V, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
B. calcining the positive plate at 430 ℃ for 1h in a vacuum environment with the vacuum degree of-0.7 Mpa, and extracting waste gas generated in the vacuum environment and absorbing the waste gas by alkali liquor in the calcining process;
C. crushing and three-stage screening are carried out on the calcined positive plate to obtain a first material below 50 meshes, a second material between 50 and 300 meshes and a third material above 300 meshes;
D. adding Li to the third material 2 CO 3 Mixing to obtain a mixture, and mixing the third material with Li 2 CO 3 The molar ratio of (2) is 1.05:1, a step of;
E. and (3) carrying out secondary calcination at 850 ℃ on the mixture for 8 hours to obtain the lithium cobalt oxide anode material.
The third material obtained in step C of example 1 (i.e. spent lithium cobalt oxide) and the lithium cobalt oxide positive electrode material obtained in step E (i.e. regenerated lithium cobalt oxide) were observed by a scanning electron microscope, wherein the SEM photograph of the third material obtained in step C is shown in fig. 1 a, and the SEM photograph of the lithium cobalt oxide positive electrode material obtained in step E is shown in fig. 1 b, and it can be seen that the regenerated and repaired lithium cobalt oxide positive electrode material has intact particles, and has clean surfaces without impurities and cracks.
And E, observing an X-ray diffraction pattern of the lithium cobalt oxide positive electrode material obtained in the step, wherein as shown in figure 2, no impurity phase is generated from the XRD pattern, the diffraction peak is strong and sharp, the half-peak width is narrow, and the crystal crystallinity of the regenerated and repaired lithium cobalt oxide positive electrode material is good.
Performing a 0.1C charge-discharge test on the third material obtained in the step C and the lithium cobalt oxide positive electrode material obtained in the step E, wherein the test comparison result is shown in figure 3; performing discharge rate performance test on the third material obtained in the step C and the lithium cobalt oxide positive electrode material obtained in the step E, wherein the test comparison result is shown in fig. 4; and C, carrying out charge and discharge cycle times test on the third material obtained in the step C and the lithium cobalt oxide positive electrode material obtained in the step E, wherein the test comparison result is shown in figure 5. The third material in this example is a spent lithium cobalt oxide icon in fig. 3 to 5, and the regenerated lithium cobalt oxide icon is a lithium cobalt oxide cathode material in this example.
Comparing the test result of the regenerated and repaired lithium cobalt oxide positive electrode material with the standard performance test result of the commercial lithium cobalt oxide positive electrode material, the lithium content, crystal structure and electrochemical performance of the lithium cobalt oxide positive electrode material prepared by the regenerated and repaired method of the embodiment 1 can be obtained to be restored to the original state, and the commercial standard is reached.
Example 2-regeneration repair method of lithium cobalt oxide cathode Material
A. Discharging the waste lithium battery to 2V, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
B. calcining the positive plate at 400 ℃ for 3 hours in a vacuum environment with the vacuum degree of-0.1 Mpa, and extracting waste gas generated in the vacuum environment and absorbing the waste gas by alkali liquor in the calcining process;
C. crushing and three-stage screening are carried out on the calcined positive plate to obtain a first material below 50 meshes, a second material between 50 and 300 meshes and a third material above 300 meshes;
D. addition of LiNO in the third Material 3 Mixing to obtain a mixture, and mixing the third material with LiNO 3 The molar ratio of (2) is 1.2:1, a step of;
E. and (3) carrying out secondary calcination at 700 ℃ on the mixture for 12 hours to obtain the lithium cobalt oxide anode material.
And C, placing the third material obtained in the step C in the example 2 and the lithium cobalt oxide positive electrode material obtained in the step E into a scanning electron microscope for observation, and observing to see that the regenerated and repaired lithium cobalt oxide positive electrode material has good particles, clean surfaces, no impurities and no cracks.
And E, observing an X-ray diffraction pattern of the lithium cobalt oxide positive electrode material obtained in the step E, wherein no hetero-phase is generated from the XRD pattern, and the diffraction peak is strong and sharp, and the half-peak width is narrow, so that the regenerated and repaired lithium cobalt oxide positive electrode material crystal has good crystallinity.
And C, performing a 0.1C charge-discharge test, a discharge rate performance test and a charge-discharge cycle number test on the third material obtained in the step C and the lithium cobalt oxide positive electrode material obtained in the step E, and comparing the test result of the regenerated and repaired lithium cobalt oxide positive electrode material with the standard performance test result of the commercial lithium cobalt oxide positive electrode material to obtain that the lithium content, the crystal structure and the electrochemical performance of the lithium cobalt oxide positive electrode material prepared by the regeneration and repair method of the embodiment 2 are restored to the original state and reach the commercial standard.
Example 3-regeneration repair method of lithium cobalt oxide cathode Material
A. Discharging the waste lithium battery to 2V, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
B. calcining the positive plate at 550 ℃ for 0.5h in a vacuum environment with the vacuum degree of-1 Mpa, and extracting waste gas generated in the vacuum environment and absorbing the waste gas by alkali liquor in the calcining process;
C. crushing and three-stage screening are carried out on the calcined positive plate to obtain a first material below 50 meshes, a second material between 50 and 300 meshes and a third material above 300 meshes;
D. adding LiOH into the third material for mixing to obtain a mixture, wherein the molar ratio of the third material to the LiOH is 1:1, a step of;
E. and (3) carrying out secondary calcination at 900 ℃ on the mixture for 4 hours to obtain the lithium cobalt oxide anode material.
And C, placing the third material obtained in the step C in the example 3 and the lithium cobalt oxide positive electrode material obtained in the step E into a scanning electron microscope for observation, and observing to see that the regenerated and repaired lithium cobalt oxide positive electrode material has good particles, clean surfaces, no impurities and no cracks.
And E, observing an X-ray diffraction pattern of the lithium cobalt oxide positive electrode material obtained in the step E, wherein no hetero-phase is generated from the XRD pattern, and the diffraction peak is strong and sharp, and the half-peak width is narrow, so that the regenerated and repaired lithium cobalt oxide positive electrode material crystal has good crystallinity.
And C, performing a 0.1C charge-discharge test, a discharge rate performance test and a charge-discharge cycle number test on the third material obtained in the step C and the lithium cobalt oxide positive electrode material obtained in the step E, and comparing the test result of the regenerated and repaired lithium cobalt oxide positive electrode material with the standard performance test result of the commercial lithium cobalt oxide positive electrode material to obtain that the lithium content, the crystal structure and the electrochemical performance of the lithium cobalt oxide positive electrode material prepared by the regenerated and repaired method of the embodiment 3 are restored to the original state and reach the commercial standard.
The technical principle of the present application is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the application and should not be taken in any way as limiting the scope of the application. Other embodiments of the application will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (6)
1. The regeneration and repair method of the lithium cobalt oxide anode material is characterized by comprising the following steps of:
A. discharging the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
B. calcining the positive plate at 400-550 ℃ in a vacuum environment with the vacuum degree of-0.1 to-1 MPa, and extracting waste gas generated in the vacuum environment in the calcining process and absorbing with alkali liquor;
C. crushing and three-stage screening are carried out on the calcined positive plate to obtain a first material below 50 meshes, a second material between 50 and 300 meshes and a third material above 300 meshes; the first material is mainly metal particles, the second material is mainly aluminum foil, and the third material is spent lithium cobalt oxide in the waste lithium battery;
D. adding a lithium source into the third material for mixing to obtain a mixture;
E. secondary calcination is carried out on the mixture to obtain a lithium cobaltate anode material;
in the step B, the calcination time of primary calcination is 0.5-3 h;
in the step E, the calcining temperature of the secondary calcining is 700-900 ℃ and the calcining time is 4-12 h.
2. The method for regenerating and repairing a lithium cobaltate positive electrode material according to claim 1, wherein the method comprises the following steps: in step D, the molar ratio of the third material to the lithium source is (1 to 1.2): 1.
3. the method for regenerating and repairing a lithium cobaltate positive electrode material according to claim 1, wherein the method comprises the following steps: in the step D, the lithium source is LiOH or Li 2 CO 3 、LiNO 3 And LiCoOOCH 3 Any one or a combination of a plurality of the above.
4. The method for regenerating and repairing a lithium cobaltate positive electrode material according to claim 1, wherein the method comprises the following steps: in the step A, the voltage of the discharged waste lithium battery is less than or equal to 2.8V.
5. A lithium cobaltate positive electrode material characterized in that: a method for regenerating and repairing a lithium cobalt oxide positive electrode material according to any one of claims 1 to 4.
6. Use of a lithium cobalt oxide positive electrode material according to claim 5 for the preparation of a low-impurity lithium battery.
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| CN104485493A (en) * | 2014-12-30 | 2015-04-01 | 兰州理工大学 | Repair and regeneration method for lithium cobaltate positive active material in waste lithium ion battery |
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| CN112707447A (en) * | 2020-12-25 | 2021-04-27 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for recycling and regenerating anode material from waste lithium cobalt oxide battery |
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| CN104485493A (en) * | 2014-12-30 | 2015-04-01 | 兰州理工大学 | Repair and regeneration method for lithium cobaltate positive active material in waste lithium ion battery |
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