CN113943020A - Regenerated lithium cobaltate and activation method and application thereof - Google Patents
Regenerated lithium cobaltate and activation method and application thereof Download PDFInfo
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- CN113943020A CN113943020A CN202111202464.7A CN202111202464A CN113943020A CN 113943020 A CN113943020 A CN 113943020A CN 202111202464 A CN202111202464 A CN 202111202464A CN 113943020 A CN113943020 A CN 113943020A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 232
- 238000000034 method Methods 0.000 title claims abstract description 85
- 230000004913 activation Effects 0.000 title abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 63
- 239000002699 waste material Substances 0.000 claims abstract description 40
- 239000002912 waste gas Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 21
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 238000005188 flotation Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims description 42
- 208000028659 discharge Diseases 0.000 claims description 26
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001994 activation Methods 0.000 abstract description 17
- 239000010405 anode material Substances 0.000 abstract description 11
- 239000002351 wastewater Substances 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 19
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 19
- 239000013078 crystal Substances 0.000 description 18
- 238000011084 recovery Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
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- 230000000694 effects Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000036541 health Effects 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 238000009766 low-temperature sintering Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009841 combustion method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 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
- 230000002349 favourable effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 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
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 230000002238 attenuated effect Effects 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000004880 explosion Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 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
- 230000036961 partial effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 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
-
- 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
- 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
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- 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
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- 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
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- 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
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- 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
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a regenerated lithium cobaltate and an activation method and application thereof, wherein the activation method of the regenerated lithium cobaltate comprises the following steps: a. disassembling the waste lithium battery to obtain a positive plate; b. calcining the positive plate for the first time in a vacuum environment; c. crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation; d. fully mixing the invalid lithium cobaltate and the lithium salt solution, and then carrying out hydrothermal synthesis to obtain a hydrothermal product; e. filtering and drying the hydrothermal product to obtain a filter cake, and crushing the filter cake to obtain a crushed material; f. and carrying out secondary calcination on the crushed material to obtain regenerated lithium cobaltate. The method for activating the regenerated lithium cobaltate can effectively reduce the discharge of waste water and waste gas in the process of repairing the regenerated lithium cobaltate, solves the technical problem of overhigh cost caused in the process of recycling the anode material of the existing waste lithium battery, and is beneficial to simplifying the process of repairing the regenerated lithium cobaltate and improving the purity of the regenerated lithium cobaltate.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to regenerated lithium cobaltate and an activation 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 discarded lithium ion battery does not contain heavy metals such as lead, cadmium, mercury and the like and has relatively small environmental pollution, the discarded 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 easily caused due to improper disposal. Cobalt, lithium, copper, metal shells, nickel sheets, lithium-containing compounds, plastic diaphragms and the like in the waste lithium batteries are precious resources and have extremely high recovery value. Therefore, the waste lithium batteries are scientifically and effectively treated, and the method has remarkable environmental benefit and good economic benefit.
The common methods for recovering the anode materials of the waste lithium batteries generally comprise dry calcination and hydrometallurgy. Wherein, the dry calcination refers to the recovery of the electrode material by means of high-temperature calcination treatment; the hydrometallurgy is that heavy metal substances in a positive electrode and a negative electrode are extracted by an extracting agent, salts are enriched, and finally a precursor is obtained by a coprecipitation technology.
When the existing method for recovering the anode material of the waste lithium battery by using dry calcination is used, because 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 can be generated to harm the environment and the health of a human body, and therefore, in the process of recovering the anode material of the waste lithium battery by using dry calcination, the air compressor is required to provide dry and dehumidified air for calcination, so that the recovery cost is high easily. In addition, in the lithium battery recovery process, a solvent is generally used for removing the binder in the lithium battery, and the impurity removal method can cause waste water and waste gas generated in the lithium battery recovery process, and if the waste water and the waste gas leak, soil, underground water and the like can be polluted, so that an external waste discharge treatment system is required to be added in the conventional recovery process for treating the waste water and the waste gas, and the recovery cost of the anode material of the waste lithium battery is further increased; furthermore, an impurity removal mode for removing the binder in the lithium battery in an air combustion mode is adopted, similarly, in order to avoid decomposition reaction between lithium hexafluorophosphate and moisture in the air, harmful gas can be generated to harm the environment and the human health, the air in impurity removal treatment in the air combustion mode also needs to be dried and dehumidified, and high-temperature combustion is required to achieve an ideal impurity removal effect, so that the method is easy to generate large energy consumption and is not beneficial to improving the economic benefit of regeneration and repair.
Disclosure of Invention
The first purpose of the invention is to provide an activation method of regenerated lithium cobalt oxide, which can effectively reduce the discharge of waste water and waste gas in the repair process of the regenerated lithium cobalt oxide, solve the technical problem of overhigh cost caused in the recovery process of the anode material of the existing waste lithium battery, and is beneficial to simplifying the repair process of the regenerated lithium cobalt oxide and improving the purity of the regenerated lithium cobalt oxide so as to overcome the defects in the prior art.
A second object of the present invention is to provide a regenerated lithium cobaltate prepared using the above-described method for activating a regenerated lithium cobaltate, which has a higher purity.
The third purpose of the invention is to provide the application of the regenerated lithium cobaltate in the preparation of a low-impurity lithium battery, which is beneficial to the preparation of the lithium battery with low impurity content.
In order to achieve the purpose, the invention adopts the following technical scheme:
an activation method of regenerated lithium cobaltate, comprising the following steps:
a. performing discharge treatment on the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
b. carrying out primary calcination at 400-550 ℃ on the positive plate in a vacuum environment with the vacuum degree of-0.1-1 Mpa, and extracting waste gas generated in the vacuum environment in the calcination process and absorbing the waste gas by using alkali liquor;
c. crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation;
d. preparing a lithium salt solution, fully mixing the failed lithium cobaltate and the lithium salt solution, and performing hydrothermal synthesis to obtain a hydrothermal product;
e. filtering and drying the hydrothermal product to obtain a filter cake, and crushing the filter cake to obtain a crushed material;
f. and carrying out secondary calcination on the crushed material to obtain regenerated lithium cobaltate.
Preferably, in the step b, the calcination time of the primary calcination step is 0.5-4 h.
Preferably, in the step d, the concentration of the lithium salt solution is 0.5-4 mol/L.
Preferably, in step d, the molar ratio of the spent lithium cobaltate to the lithium salt solution is 1: (0.5 to 4).
Preferably, in the step d, the reaction temperature of the hydrothermal synthesis is 180-250 ℃, and the reaction time of the hydrothermal synthesis is 3-12 h.
Preferably, in the step e, the drying temperature in the drying step is less than or equal to 150 ℃, and the drying time in the drying step is 8-24 h.
Preferably, in the step e, the particle fineness of the crushed material is 8-12 μm.
Preferably, in the step f, the calcination temperature in the secondary calcination step is 750-850 ℃, and the calcination time in the secondary calcination step is 4-24 hours.
A regenerated lithium cobaltate is prepared by using the method for activating the regenerated lithium cobaltate.
The application of the regenerated lithium cobaltate in preparing a low-impurity lithium battery uses the regenerated lithium cobaltate.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
1. the waste lithium batteries are subjected to discharge treatment, so that the waste lithium batteries can be prevented from being exploded and combusted during disassembly; the decommissioned lithium battery is disassembled in an inert gas environment, so that the lithium hexafluorophosphate in the battery and moisture in the air are prevented from undergoing decomposition reaction, harmful gas can be generated to harm the environment and the human health, the method is simple, and the operation is convenient.
2. The polyvinylidene fluoride, the acetylene black and other impurities in the positive plate are removed in a vacuum low-temperature sintering mode, so that the high-purity failure lithium cobalt oxide positive electrode material is obtained. Specifically, the mode of removing impurities by vacuum low-temperature sintering in the technical scheme has the following advantages: (1) compared with the existing impurity removal mode of removing impurities by adding related solvents, the method can effectively reduce the discharge of waste water and waste gas in the process of repairing the regenerated lithium cobaltate and embody the environmental friendliness; (2) compared with the existing impurity removal mode for removing impurities by an air combustion method, the method has the advantages that an air compressor is not needed to provide dry and dehumidified air, the energy-saving effect is achieved, the regeneration process is simplified, the regeneration effect is better, the purity of the regenerated product is higher, and the method has very high social and economic values; (3) compared with the existing impurity removal mode for removing impurities through an air combustion method, the temperature used in vacuum sintering of the technical scheme is lower, active substances of lithium cobaltate are easier to separate from impurities, and impurities such as polyvinylidene fluoride and acetylene black can be invalid as long as the calcination temperature reaches 400-550 ℃, so that the energy consumption can be effectively reduced, and meanwhile, the subsequent process can be conveniently carried out.
3. The calcined positive plate is crushed, and the invalid lithium cobalt oxide is separated through airflow flotation, so that the situation that an aluminum current collector in the waste lithium battery is crushed and then is introduced into regenerated lithium cobalt oxide in an aluminum impurity mode is avoided, and the purity of a regenerated product is improved.
4. The method is characterized in that the invalid lithium cobaltate is subjected to lithium supplement treatment through a hydrothermal synthesis method, so that lithium ions are diffused from a lithium salt solution with high concentration to the invalid lithium cobaltate with low concentration, the lithium content of the invalid lithium cobaltate can be increased on the premise of ensuring that the crystal phase of the regenerated lithium cobaltate is not changed, and the electrochemical performance of the lithium cobaltate is recovered to the original state.
5. The technical scheme performs secondary combustion on the failed lithium cobaltate after lithium supplement, is favorable for further optimizing and improving the electrochemical performance of regenerated lithium cobaltate, and effectively improves the cycle number of charge and discharge of the regenerated lithium cobaltate.
Drawings
Fig. 1 is an SEM picture of regenerated lithium cobaltate in example 1 of an activation method of regenerated lithium cobaltate according to the present invention.
Fig. 2 is an X-ray diffraction pattern of the regenerated lithium cobaltate and the commercial lithium cobaltate in example 1 of the method for activating regenerated lithium cobaltate according to the present invention.
Fig. 3 is a comparison of 0.1C charge and discharge tests of spent and regenerated lithium cobaltates from example 1 of a method for activating regenerated lithium cobaltate according to the present invention.
Fig. 4 is a comparison result of discharge rate performance tests of failed lithium cobaltate and regenerated lithium cobaltate in example 1 of the method for activating regenerated lithium cobaltate according to the present invention.
Fig. 5 is a comparison result of the number of charge and discharge cycles of the spent lithium cobaltate and the regenerated lithium cobaltate in example 1 of the method for activating regenerated lithium cobaltate according to the present invention.
Detailed Description
An activation method of regenerated lithium cobaltate, comprising the following steps:
a. performing discharge treatment on the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
b. carrying out primary calcination at 400-550 ℃ on the positive plate in a vacuum environment with the vacuum degree of-0.1-1 Mpa, and extracting waste gas generated in the vacuum environment in the calcination process and absorbing the waste gas by using alkali liquor;
c. crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation;
d. preparing a lithium salt solution, fully mixing the failed lithium cobaltate and the lithium salt solution, and performing hydrothermal synthesis to obtain a hydrothermal product;
e. filtering and drying the hydrothermal product to obtain a filter cake, and crushing the filter cake to obtain a crushed material;
f. and carrying out secondary calcination on the crushed material to obtain regenerated lithium cobaltate.
When the conventional method for calcining and recycling the anode material of the waste lithium battery by using the dry method is used, because 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 can be generated to harm the environment and the health of a human body, and therefore, in the process of calcining and recycling the anode material of the waste lithium battery by using the dry method, the air compressor is required to provide dry and dehumidified air for calcining, and the recycling cost is high easily. In addition, in the lithium battery recovery process, a solvent is generally used for removing the binder in the lithium battery, and the impurity removal method can cause wastewater and waste gas generated in the lithium battery recovery process, and if the wastewater and the waste gas leak, soil, underground water and the like can be polluted, so that an external waste discharge treatment system is required to be added in the conventional recovery process for treating the wastewater and the waste gas, and the recovery cost of the anode material of the waste lithium battery is further increased; furthermore, an impurity removal mode for removing the binder in the lithium battery in an air combustion mode is adopted, similarly, in order to avoid decomposition reaction between lithium hexafluorophosphate and moisture in the air, harmful gas can be generated to harm the environment and the human health, the air in impurity removal treatment in the air combustion mode also needs to be dried and dehumidified, and high-temperature combustion is required to achieve an ideal impurity removal effect, so that the method is easy to generate large energy consumption and is not beneficial to improving the economic benefit of regeneration and repair.
In order to reduce the discharge of waste water and waste gas in the process of repairing regenerated lithium cobaltate and solve the technical problem of overhigh cost caused in the process of recovering the anode material of the existing waste lithium battery, the technical scheme provides an activation method of the regenerated lithium cobaltate, which comprises the following steps:
a. performing discharge treatment on the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate; specifically, the waste lithium batteries are subjected to discharge treatment, so that the waste lithium batteries can be prevented from being exploded and combusted during disassembly; the waste lithium batteries are disassembled in an inert gas environment, so that the decomposition reaction between lithium hexafluorophosphate in the batteries and moisture in the air is favorably prevented, harmful gas is generated to harm the environment and the human health, the method is simple, and the operation is convenient; it should be noted that, the waste lithium battery in the technical scheme refers to a lithium battery whose appearance, electrical performance, safety and other aspects are reduced to the initial lowest standard, for example, when the specific capacity of the lithium battery is less than 80%, the lithium battery is determined to be unqualified and needs to be decommissioned; or after the lithium battery is charged and discharged for a long time, the anode material belongs to a lithium-deficient state and needs to be subjected to decommissioning treatment.
b. Calcining the positive plate at 400-550 ℃ in a vacuum environment with the vacuum degree of-0.1-1 Mpa, and extracting waste gas generated in the vacuum environment in the calcining process and absorbing the waste gas by using 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, and high-purity invalid lithium cobalt oxide can be obtained. Specifically, the mode of removing impurities by vacuum low-temperature sintering in the technical scheme has the following advantages: (1) compared with the existing impurity removal mode of removing impurities by adding related solvents, the method can effectively reduce the discharge of waste water and waste gas in the process of repairing the regenerated lithium cobaltate and embody the environmental friendliness; (2) compared with the existing impurity removal mode for removing impurities by an air combustion method, the method has the advantages that an air compressor is not needed to provide dry and dehumidified air, the energy-saving effect is achieved, the regeneration process is simplified, the regeneration effect is better, the purity of the regenerated product is higher, and the method has very high social and economic values; (3) compared with the existing impurity removal mode for removing impurities through an air combustion method, the temperature used in vacuum sintering of the technical scheme is lower, active substances of lithium cobaltate are easy to fall off, impurities such as polyvinylidene fluoride and acetylene black can be disabled as long as the calcining temperature reaches 400-550 ℃, energy consumption can be effectively reduced, and meanwhile, the subsequent process is convenient to carry out.
c. Crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation; according to the technical scheme, the calcined positive plate is crushed, and the invalid lithium cobalt oxide is separated through air flow flotation, so that the situation that an aluminum current collector in a waste lithium battery is crushed and then is introduced into regenerated lithium cobalt oxide in an aluminum impurity mode is avoided, and the improvement of the purity of a regenerated product is facilitated. It should be noted that the airflow flotation method adopted in the technical scheme is a screening method commonly used in the technical field of lithium battery recovery, and is not described herein again.
d. Preparing a lithium salt solution, fully mixing the failed lithium cobaltate and the lithium salt solution, and performing hydrothermal synthesis to obtain a hydrothermal product; lithium deficiency and crystal phase structure change are main reasons for reducing the specific capacity of the lithium cobaltate positive electrode material. With the loss of lithium ions, transition metal cations begin to migrate between layers and change during repeated charging and discharging, slowly causing irreversible phase structure changes. The crystal structure of lithium cobaltate is changed from the original layered structure phase into a mixed structure of spinel and rock salt phase. The change of the crystal structure can lead partial lithium ions to be incapable of freely inserting and extracting in the crystal structure, thereby leading the specific capacity to be seriously attenuated and even to be ineffective. According to the technical scheme, the invalid lithium cobalt oxide is subjected to lithium supplement treatment through a hydrothermal synthesis method, so that lithium ions are diffused into the invalid lithium cobalt oxide with low concentration from a lithium salt solution with high concentration, the lithium content of the invalid lithium cobalt oxide can be increased on the premise of ensuring that the crystal phase of the regenerated lithium cobalt oxide is not changed, and the electrochemical performance of the lithium cobalt oxide is recovered to the original state.
e. Filtering and drying the hydrothermal product to obtain a filter cake, and crushing the filter cake to obtain a crushed material; and the failed lithium cobaltate after lithium supplement is crushed, so that the lithium cobaltate is conveniently and fully contacted with air, and secondary combustion is facilitated.
f. Carrying out secondary calcination on the crushed material to obtain regenerated lithium cobaltate; the technical scheme performs secondary combustion on the failed lithium cobaltate after lithium supplement, is favorable for further optimizing and improving the electrochemical performance of regenerated lithium cobaltate, and effectively improves the cycle number of charge and discharge of the regenerated lithium cobaltate.
Preferably, in the step a, the voltage of the discharged waste lithium battery is less than or equal to 2.8V. The explosion combustion of the waste lithium battery during disassembly is avoided, and the normal operation of the activation process is ensured.
In step b, the calcination time in the primary calcination step is 0.5 to 4 hours.
In a preferred embodiment of the technical scheme, the vacuum low-temperature sintering time is 0.5-4 h, which is beneficial to fully removing impurities such as polyvinylidene fluoride (PVDF) and acetylene black in the positive plate, so that high-purity failed lithium cobaltate is obtained.
In step d, the concentration of the lithium salt solution is 0.5-4 mol/L.
In a preferred embodiment of the technical scheme, the concentration of the lithium salt solution is limited to 0.5-4 mol/L, on one hand, more lithium ions can be provided for lithium supplement of the failed lithium cobaltate, and on the other hand, the lithium salt solution used in the scheme can dissolve soluble impurities in the failed lithium cobaltate to a certain extent, so that the content of the impurities in the failed lithium cobaltate is reduced, and the crystallinity of the regenerated lithium cobaltate is improved conveniently.
Preferably, the solute of the lithium salt solution comprises LiOH and Li2CO3、LiNO3And LiCoOOCH3Any one or a combination of more of them.
In step d, the molar ratio of the failed lithium cobaltate to the lithium salt solution is 1: (0.5 to 4).
In the technical scheme, the molar ratio of the failed lithium cobaltate to the lithium salt solution is defined as 1: (0.5-4), the lithium content, the crystal structure of the bulk phase/surface and the electrochemical performance of the failed lithium cobaltate can be recovered to the original state, and the performance index of the regenerated product can be ensured to reach the qualified standard, so that the activation effect of the regenerated lithium cobaltate can be ensured.
In step d, the reaction temperature of the hydrothermal synthesis is 180-250 ℃, and the reaction time of the hydrothermal synthesis is 3-12 hours.
In a preferred embodiment of the technical scheme, the reaction temperature of the hydrothermal synthesis is preferably 180-250 ℃, and the reaction time of the hydrothermal synthesis is preferably 3-12 h, so that lithium ions are fully diffused into failed lithium cobaltate to supplement lithium.
In step e, the drying temperature in the drying step is less than or equal to 150 ℃, and the drying time in the drying step is 8-24 hours.
In step e, the particle fineness of the crushed material is 8-12 μm.
In order to avoid the influence of the excessive crushing of the crushed material on the recovery rate of the invalid lithium cobaltate, the particle fineness of the crushed material is further optimized to be 8-12 mu m, and the electrochemical performance of the regenerated lithium cobaltate can be effectively improved on the premise that the recovery rate of the invalid lithium cobaltate is not influenced to the maximum extent.
In step f, the calcination temperature in the secondary calcination step is 750 to 850 ℃, and the calcination time in the secondary calcination step is 4 to 24 hours.
In a more preferred embodiment of the technical scheme, the calcination temperature in the secondary calcination step is preferably 750-850 ℃, and the calcination time is preferably 4-24 hours, so that volatilization of lithium elements caused by overhigh combustion temperature and overlong combustion time is avoided, and the problem that invalid lithium cobalt oxide lacks lithium again after lithium supplement is avoided.
A regenerated lithium cobaltate is prepared by using the method for activating the regenerated lithium cobaltate.
The technical scheme also provides regenerated lithium cobaltate prepared by the method for activating the regenerated lithium cobaltate, and the regenerated lithium cobaltate has higher purity.
The application of the regenerated lithium cobaltate in preparing a low-impurity lithium battery uses the regenerated lithium cobaltate.
The technical scheme also provides the application of the regenerated lithium cobaltate in the preparation of the low-impurity lithium battery, and the preparation of the lithium battery with low impurity content is facilitated.
The technical solution of the present invention is further explained by the following embodiments.
Example 1-activation method of regenerated lithium cobaltate
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-0.5 Mpa, extracting waste gas generated in the vacuum environment in the calcining process, and absorbing the waste gas by using alkali liquor;
c. crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation;
d. preparing Li with concentration of 0.5mol/L2CO3Solution of spent lithium cobaltate and Li2CO3The solution is fully mixed and then is subjected to hydrothermal synthesis, the reaction temperature of the hydrothermal synthesis is 200 ℃, the reaction time is 4 hours, and the invalid lithium cobaltate and Li2CO3The molar ratio of the solution is 1: 2, obtaining a hydrothermal product;
e. filtering the hydrothermal product, drying at 120 ℃ for 10h to obtain a filter cake, and crushing the filter cake to obtain a crushed material with the particle fineness of 10 mu m;
f. and (3) carrying out secondary calcination on the crushed material, wherein the calcination temperature in the secondary calcination step is 750 ℃, and the calcination time is 20h, so as to obtain the regenerated lithium cobalt oxide.
When the regenerated lithium cobaltate obtained in step f of example 1 is observed by a scanning electron microscope, as shown in fig. 1, it can be seen that the activated regenerated lithium cobaltate has intact particles, clean surface, no impurities and no cracks.
Observing the X-ray diffraction patterns of the regenerated lithium cobaltate and the commercial lithium cobaltate obtained in the step f, as shown in fig. 2, as seen from the XRD pattern, compared with the commercial lithium cobaltate, the regenerated lithium cobaltate has no crystal phase change after being repaired, the diffraction peak is strong and sharp, and the half peak width is narrow, which indicates that the repaired regenerated lithium cobaltate crystal has good crystallinity.
C, performing 0.1C charge-discharge test on the failed lithium cobaltate obtained in the step C and the regenerated lithium cobaltate obtained in the step f, wherein the test comparison results are shown in FIG. 3; c, performing discharge rate performance test on the failed lithium cobaltate obtained in the step c and the regenerated lithium cobaltate obtained in the step f, wherein the test comparison results are shown in fig. 4; and (e) carrying out a charge-discharge cycle number test on the failed lithium cobaltate obtained in the step (c) and the regenerated lithium cobaltate obtained in the step (f), wherein the test comparison result is shown in FIG. 5.
Comparing the test result of the repaired regenerated lithium cobaltate with the standard performance test result of commercial lithium cobaltate, it can be known that the lithium content, crystal structure and electrochemical performance of the regenerated lithium cobaltate prepared by the activation method of example 1 are restored to the original state and reach the commercial standard.
Example 2-activation method of regenerated lithium cobaltate
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 4h in a vacuum environment with the vacuum degree of-0.1 Mpa, and extracting waste gas generated in the vacuum environment in the calcining process and absorbing the waste gas by using alkali liquor;
c. crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation;
d. preparing a LiOH solution with the concentration of 2mol/L, fully mixing the failed lithium cobaltate and the LiOH solution, and then carrying out hydrothermal synthesis, wherein the reaction temperature of the hydrothermal synthesis is 250 ℃, the reaction time is 3h, and the molar ratio of the failed lithium cobaltate to the LiOH solution is 1: 0.5, obtaining a hydrothermal product;
e. filtering the hydrothermal product, drying at 100 ℃ for 14h to obtain a filter cake, and crushing the filter cake to obtain a crushed material with the particle fineness of 8 mu m;
f. and (3) carrying out secondary calcination on the crushed material, wherein the calcination temperature in the secondary calcination step is 850 ℃, and the calcination time is 4h, so as to obtain the regenerated lithium cobalt oxide.
The regenerated lithium cobaltate obtained in the step f of the embodiment 2 is placed in a scanning electron microscope for observation, and the activated regenerated lithium cobaltate can be seen to have intact particles, clean surfaces, no impurities and no cracks.
And (f) observing the X-ray diffraction pattern of the regenerated lithium cobaltate obtained in the step f, compared with commercial lithium cobaltate, the regenerated lithium cobaltate is not changed in crystal phase after being repaired, the diffraction peak is strong and sharp, and the half-peak width is narrow, so that the repaired regenerated lithium cobaltate crystal is good in crystallinity.
And (e) performing 0.1C charge-discharge test, discharge rate performance test and charge-discharge cycle number test on the failed lithium cobaltate obtained in the step (C) and the regenerated lithium cobaltate obtained in the step (f), and comparing the test result of the repaired regenerated lithium cobaltate with the standard performance test result of the commercial lithium cobaltate, so that the fact that the lithium content, the crystal structure and the electrochemical performance of the regenerated lithium cobaltate prepared by the activation method in the embodiment 2 are restored to the original state can be known, and the lithium content, the crystal structure and the electrochemical performance of the regenerated lithium cobaltate can reach the commercial standard.
Example 3-activation method of regenerated lithium cobaltate
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 in the calcining process and absorbing the waste gas by using alkali liquor;
c. crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation;
d. preparing LiCOOCH with concentration of 4mol/L3Solution, spent lithium cobaltate and LiCoOOCH3The solution is fully mixed and then is subjected to hydrothermal synthesis, the reaction temperature of the hydrothermal synthesis is 180 ℃, the reaction time is 8 hours, and the invalid lithium cobaltate and LiCOOCH3The molar ratio of the solution is 1: 4, obtaining a hydrothermal product;
e. filtering the hydrothermal product, drying at 150 ℃ for 8h to obtain a filter cake, and crushing the filter cake to obtain a crushed material with the particle fineness of 12 mu m;
f. and (3) carrying out secondary calcination on the crushed material, wherein the calcination temperature in the secondary calcination step is 800 ℃, and the calcination time is 11h, so as to obtain the regenerated lithium cobalt oxide.
The regenerated lithium cobaltate obtained in the step f of the embodiment 3 is placed in a scanning electron microscope for observation, and the activated regenerated lithium cobaltate can be seen to have intact particles, clean surfaces, no impurities and no cracks.
And (f) observing the X-ray diffraction pattern of the regenerated lithium cobaltate obtained in the step f, compared with commercial lithium cobaltate, the regenerated lithium cobaltate is not changed in crystal phase after being repaired, the diffraction peak is strong and sharp, and the half-peak width is narrow, so that the repaired regenerated lithium cobaltate crystal is good in crystallinity.
And (e) performing 0.1C charge-discharge test, discharge rate performance test and charge-discharge cycle number test on the failed lithium cobaltate obtained in the step (C) and the regenerated lithium cobaltate obtained in the step (f), and comparing the test result of the repaired regenerated lithium cobaltate with the standard performance test result of the commercial lithium cobaltate, so that the fact that the lithium content, the crystal structure and the electrochemical performance of the regenerated lithium cobaltate prepared by the activation method in the embodiment 3 are restored to the original state can be known, and the lithium content, the crystal structure and the electrochemical performance of the regenerated lithium cobaltate can reach the commercial standard.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. A method for activating regenerated lithium cobaltate is characterized by comprising the following steps:
a. performing discharge treatment on the waste lithium battery, and disassembling the waste lithium battery in an inert gas environment to obtain a positive plate;
b. carrying out primary calcination at 400-550 ℃ on the positive plate in a vacuum environment with the vacuum degree of-0.1-1 Mpa, and extracting waste gas generated in the vacuum environment in the calcination process and absorbing the waste gas by using alkali liquor;
c. crushing the calcined positive plate, and separating out ineffective lithium cobaltate through airflow flotation;
d. preparing a lithium salt solution, fully mixing the failed lithium cobaltate and the lithium salt solution, and performing hydrothermal synthesis to obtain a hydrothermal product;
e. filtering and drying the hydrothermal product to obtain a filter cake, and crushing the filter cake to obtain a crushed material;
f. and carrying out secondary calcination on the crushed material to obtain regenerated lithium cobaltate.
2. The method according to claim 1, wherein the method comprises: in the step b, the calcination time of the primary calcination step is 0.5-4 h.
3. The method according to claim 1, wherein the method comprises: in the step d, the concentration of the lithium salt solution is 0.5-4 mol/L.
4. The method according to claim 1, wherein the method comprises: in the step d, the molar ratio of the failed lithium cobaltate to the lithium salt solution is 1: (0.5 to 4).
5. The method according to claim 1, wherein the method comprises: in the step d, the reaction temperature of the hydrothermal synthesis is 180-250 ℃, and the reaction time of the hydrothermal synthesis is 3-12 h.
6. The method according to claim 1, wherein the method comprises: in the step e, the drying temperature in the drying step is less than or equal to 150 ℃, and the drying time in the drying step is 8-24 h.
7. The method according to claim 1, wherein the method comprises: in the step e, the particle fineness of the crushed material is 8-12 mu m.
8. The method according to claim 1, wherein the method comprises: in the step f, the calcination temperature in the secondary calcination step is 750-850 ℃, and the calcination time in the secondary calcination step is 4-24 h.
9. A regenerated lithium cobaltate, characterized by: the method for activating regenerated lithium cobaltate according to any one of claims 1 to 8.
10. Use of a regenerated lithium cobaltate for the preparation of low impurity lithium batteries, characterized in that a regenerated lithium cobaltate according to claim 9 is used.
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