CN114426312A - Method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate - Google Patents
Method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate Download PDFInfo
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- CN114426312A CN114426312A CN202210037714.4A CN202210037714A CN114426312A CN 114426312 A CN114426312 A CN 114426312A CN 202210037714 A CN202210037714 A CN 202210037714A CN 114426312 A CN114426312 A CN 114426312A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 103
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- 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
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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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- 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
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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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate, which comprises the steps of obtaining a positive plate by disassembling the waste lithium cobaltate, stripping the waste lithium cobaltate from a current collector, performing secondary calcination after targeted lithium supplement and the like, so that the direct regeneration of the lithium cobaltate and the remarkable improvement of high-pressure performance are realized, the recovery technology and process are simple, efficient and low in pollution, and the circular economy is realized while the closed-loop recovery of lithium ion battery resources is realized.
Description
Technical Field
The invention relates to a preparation method for directly regenerating lithium cobaltate, in particular to a method for preparing high-pressure lithium cobaltate by utilizing waste lithium cobaltate, belonging to the field of recycling of waste lithium ion batteries.
Background
As an energy storage device, a lithium ion battery is ubiquitous in daily life of people, for example, in daily life of people, the lithium ion battery is a common 3C product: computers (computers), communications (communications), and Consumer Electronics (Consumer Electronics), the existence of which makes our lives more convenient and colorful. During the past decade, the demand for lithium ion batteries has grown enormously under the stimulus of consumer electronics. At present, 71.9 million mobile phones are owned globally, which is close to 10 million notebook computers and 10 million tablet computers, and the update cycle of consumer electronics is 12-18 months, which results in the demand of the consumer electronics field for lithium ion batteries will continue to increase. The energy supply of the portable electronic device is not disconnected from the lithium ion battery. Lithium cobaltate is mainly used as a positive electrode material in lithium ion batteries for 3C electronics because lithium cobaltate batteries have high energy density and operating voltage. The globally-proven cobalt deposit in 2019 is about 700 million tons, but the distribution of the cobalt resource in the world is unbalanced, the sum of the reserves of Congo (gold), Australia and Cuba accounts for 68% of the total global reserve, and the Congo accounts for up to 48.6% of the reserve of 340 million tons, which is the country with the highest global cobalt deposit. The proven cobalt reserves in China are only 8 million tons, which only account for 1.14 percent of the total reserves in the world, and China needs a large amount of cobalt resources imported from Congo (gold) every year. Lithium cobalt oxide as the anode material of lithium ion battery along with the electronic product update gradually retires, only less than 5% of mobile phone battery recovery, the other most is abandoned at will, this has caused the environmental pollution and also caused the waste of cobalt resource.
In order to better meet the demand of market sustainable development, lithium ion battery producers and consumers at home and abroad begin to research the full life cycle of lithium ion batteries. At present, lithium cobaltate is recycled mainly aiming at valuable metals in waste batteries, a mainstream recycling method comprises dry recycling and wet recycling, but the two methods bring environmental problems including generation of toxic gases, discharge of waste water, low recycling efficiency and the like, and the problems urgently need a simple, efficient and low-pollution recycling technology and process, so that the recycling of lithium ion battery resources in a closed loop is realized, and meanwhile, the recycling economy is realized.
Disclosure of Invention
Aiming at the existing complicated technical route and lower recovery efficiency of waste lithium cobaltate recovery, the invention provides a method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate, which realizes direct regeneration of lithium cobaltate and remarkable improvement of high-pressure performance through simple defect exposure and targeted lithium supplement.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing high-pressure lithium cobaltate by utilizing waste lithium cobaltate comprises the following steps:
1) fully charging the waste lithium cobaltate, disassembling the waste lithium cobaltate in an inert gas environment to obtain a positive plate, washing the obtained positive plate to remove electrolyte remained on the surface, and naturally airing the positive plate;
2) calcining the positive plate obtained in the step 1) at the temperature of 200-;
3) and carrying out ICP detection on the obtained waste lithium cobaltate powder, testing the proportion of Li to Co, and carrying out the following steps of: adding a certain amount of lithium source into Co which is 1.00-1.05 (namely Li represents the sum of Li in the waste lithium cobaltate powder and Li needing to be added), and performing ball milling on the lithium source and the lithium cobaltate precursor to obtain mixed powder;
4) calcining the mixed powder obtained in the step 3) at the temperature of 800-;
5) adding 2000-20000ppm cobaltosic oxide particles and the powder collected in the step 4), uniformly mixing, and then carrying out ball milling to obtain mixed powder;
6) treating the mixed powder obtained in the step 5) at the temperature of 300-500 ℃ for 3-12h for secondary calcination, cooling to room temperature, taking out a sample, grinding and sieving the obtained solid to obtain the regenerated high-pressure lithium cobaltate.
Preferably, in the step 1), the charge cut-off voltage is 4.3-4.7V; the inert gas is one of argon or nitrogen.
Preferably, in step 1), the obtained positive electrode sheet is washed three times with dimethyl carbonate (DMC) to remove the electrolyte remaining on the surface.
More preferably, in the step 1), the natural airing time is 2-12 h.
Preferably, in the step 2), deionized water bath ultrasound is added according to the proportion of 40g/L for 10-60 s.
Preferably, in the step 2), the ethanol and deionized water mixed solution is prepared by mixing ethanol and deionized water according to a volume ratio of 1: 1.
Preferably, in the step 2), the rotation speed of the centrifugation is 2000-; drying at 80 deg.C for 5-48 h; the mesh number of the screen used for sieving is 200 meshes and 400 meshes.
Preferably, in step 3), the lithium source is lithium carbonate or lithium hydroxide.
Preferably, in steps 3) and 5), zirconium beads are used for ball milling, the mass ratio of the zirconium beads is 3:1-10:1, the ball milling speed is 200-.
Preferably, in steps 4) and 6), grinding is carried out by using an agate mortar; the screens used for sieving are all 300-350 meshes.
Preferably, in step 5), the diameter of the cobaltosic oxide particles is in the range of 30-300 nm.
The invention has the beneficial effects that:
the invention provides a method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate, which realizes direct regeneration of the lithium cobaltate and remarkable improvement of high-pressure performance through simple defect exposure and targeted lithium supplement, has simple recovery technology and process, is efficient and low in pollution, and realizes recycling economy while realizing closed-loop recovery of lithium ion battery resources.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an XRD pattern of spent lithium cobaltate and prepared regenerated high pressure lithium cobaltate according to example 1 of the present invention;
FIG. 3 shows a 2025 button cell assembled from commercial lithium cobaltate and recycled high pressure lithium cobaltate prepared in example 2 of the present invention at 3-4.6V at 0.5C (1C 150mAh g)-1) Cycling performance curve at current density.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be described in further detail below with reference to examples and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate, as shown in fig. 1, comprises the following steps:
(1) charging waste lithium cobaltate to 4.3V, disassembling in a glove box filled with argon, washing the obtained positive plate for 3 times by using dimethyl carbonate (DMC) to remove residual electrolyte on the surface, and naturally drying the positive plate in the glove box in the shade;
(2) transferring the positive plate to a muffle furnace, calcining for 5h at 200 ℃ to remove the binder, putting the calcined positive plate into a beaker, adding a proper amount of deionized water according to the proportion of 40g/L, carrying out water bath ultrasonic treatment for 10s to realize the stripping of lithium cobaltate and a current collector, and mixing the stripped lithium cobaltate with ethanol and deionized water (V) mixed solutionEthanol：VDeionized water1:1), centrifuging at 6000r/min for 8min, centrifuging three times, drying at 80 ℃ for 36h, and sieving by a 400-mesh sieve to obtain waste lithium cobaltate powder;
(3) and carrying out ICP detection on the obtained waste lithium cobaltate, testing the proportion of Li to Co, and carrying out the following steps of: supplementing a certain amount of lithium carbonate according to the total proportion of 1.00 Co, and carrying out ball milling on lithium carbonate and waste lithium cobaltate for 1h by using zirconium beads, wherein the mass ratio of ball materials is 3:1, so as to obtain mixed powder;
(4) transferring the mixed powder into a corundum crucible, calcining the mixed powder in a muffle furnace for 24 hours at 800 ℃, cooling the mixed powder to room temperature, taking out a sample, grinding the obtained solid for 20min by using an agate mortar, sieving the ground solid by using a 200-mesh screen, and collecting the powder;
(5) uniformly mixing the powder with 2000ppm cobaltosic oxide particles (the diameter is 30nm), and carrying out ball milling for 1h by using zirconium beads, wherein the mass ratio of balls to materials is 3:1, so as to obtain mixed powder;
(6) and transferring the mixed powder into a corundum crucible, treating the mixed powder in a muffle furnace at 300 ℃ for 12 hours for secondary calcination, cooling to room temperature, taking out a sample, grinding the obtained solid by using an agate mortar for 10min, and sieving by using a 300-mesh sieve to obtain the regenerated high-pressure lithium cobalt oxide.
FIG. 2 is an XRD (X-ray diffraction) chart of the waste lithium cobaltate and the regenerated high-pressure lithium cobaltate prepared in the embodiment, and it can be seen from FIG. 2 that the waste lithium cobaltate mainly contains spinel type cobaltosic oxide, and is mainly layered lithium cobaltate and free of Co after regeneration3O4The hetero-phase shows good crystallinity, and the crystal structure is effectively repaired.
Example 2
A method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate, as shown in fig. 1, comprises the following steps:
(1) charging waste lithium cobaltate to 4.7V, disassembling in a glove box filled with nitrogen, washing the obtained positive plate for 3 times by using dimethyl carbonate (DMC) to remove residual electrolyte on the surface, and naturally drying the positive plate in the glove box in the shade;
(2) transferring the positive plate into a muffle furnace, calcining for 1h at 500 ℃ to remove the binder, putting the calcined positive plate into a beaker, adding a proper amount of deionized water according to the proportion of 40g/L, carrying out water bath ultrasound for 1min to realize the stripping of lithium cobaltate and a current collector, and mixing the stripped lithium cobaltate with a mixed solution (V) of ethanol and deionized waterEthanol：VDeionized water1:1), centrifuging at 8000r/min for 2min, centrifuging three times, drying at 80 ℃ for 48h, and sieving by a 300-mesh sieve to obtain waste lithium cobaltate powder;
(3) and carrying out ICP detection on the obtained waste lithium cobaltate, testing the proportion of Li to Co, and carrying out the following steps of: supplementing a certain amount of lithium carbonate according to the total proportion of Co being 1.05, and carrying out ball milling on the lithium carbonate and the waste lithium cobaltate for 6 hours by using zirconium beads, wherein the mass ratio of ball materials is 7:1, so as to obtain mixed powder;
(4) transferring the mixed powder into a corundum crucible, calcining for 8 hours at 1000 ℃ in a muffle furnace, cooling to room temperature, taking out a sample, grinding the obtained solid for 30min by using an agate mortar, sieving by using a 300-mesh screen, and collecting the powder;
(5) uniformly mixing the powder with 20000ppm cobaltosic oxide particles (the diameter is 40nm), and then performing ball milling for 6 hours by using zirconium beads according to the ball-to-material mass ratio of 7:1 to obtain mixed powder;
(6) and transferring the mixed powder into a corundum crucible, treating the mixed powder in a muffle furnace at 500 ℃ for 3 hours for secondary calcination, cooling to room temperature, taking out a sample, grinding the obtained solid by using an agate mortar for 20min, and sieving by using a 350-mesh sieve to obtain the regenerated high-pressure lithium cobaltate.
Fig. 3 is a graph of cycling performance at 3-4.5V, 0.5C for a coin cell assembled with commercial lithium cobaltate and recycled high pressure lithium cobaltate prepared in this example. It can be seen that the regenerated high-pressure lithium cobaltate has better high-pressure cycle stability, and is significantly better than the common commercial lithium cobaltate.
Example 3
A method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate, as shown in fig. 1, comprises the following steps:
(1) charging waste lithium cobaltate to 4.5V, disassembling in a glove box filled with argon, washing the obtained positive plate for 3 times by using dimethyl carbonate (DMC) to remove residual electrolyte on the surface, and naturally drying the positive plate in the glove box in the shade;
(2) transferring the positive plate to a muffle furnace, calcining for 3.5h at 300 ℃ to remove the binder, putting the calcined positive plate into a beaker, adding a proper amount of deionized water according to the proportion of 40g/L, carrying out water bath ultrasonic treatment for 45s to realize the stripping of lithium cobaltate and a current collector, and mixing the stripped lithium cobaltate with a mixed solution (V) of ethanol and deionized waterEthanol：VDeionized water1:1), centrifuging at 2000r/min for 10min, centrifuging for three times, drying at 80 ℃ for 5h, and sieving by a 200-mesh sieve to obtain waste lithium cobaltate powder;
(3) and carrying out ICP detection on the obtained waste lithium cobaltate, testing the proportion of Li to Co, and carrying out the following steps of: supplementing a certain amount of lithium hydroxide according to the total proportion of Co being 1.02, and carrying out ball milling on the lithium hydroxide and the waste lithium cobaltate for 12 hours by using zirconium beads, wherein the mass ratio of ball materials is 10:1, so as to obtain mixed powder;
(4) transferring the mixed powder into a corundum crucible, calcining the mixed powder in a muffle furnace at 900 ℃ for 12 hours, cooling the mixed powder to room temperature, taking out a sample, grinding the obtained solid by using an agate mortar for 40min, sieving the ground solid by using a 400-mesh screen, and collecting the powder;
(5) uniformly mixing the powder with 6000ppm cobaltosic oxide particles (the diameter is 300nm), and then carrying out ball milling for 12 hours by using zirconium beads according to the ball material mass ratio of 10:1 to obtain mixed powder;
(6) and transferring the mixed powder into a corundum crucible, treating the mixed powder in a muffle furnace at 450 ℃ for 8 hours for secondary calcination, cooling to room temperature, taking out a sample, grinding the obtained solid by using an agate mortar for 30min, and sieving by using a 350-mesh sieve to obtain the regenerated high-pressure lithium cobaltate.
The performance of the regenerated high-pressure lithium cobaltate obtained in the example is tested to be basically consistent with the performance of the products in the examples 1 and 2.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all the embodiments of the present invention are not exhaustive, and all the obvious variations or modifications which are introduced in the technical scheme of the present invention are within the scope of the present invention.
Claims (10)
1. A method for preparing high-pressure lithium cobaltate by utilizing waste lithium cobaltate comprises the following steps:
1) fully charging the waste lithium cobaltate, disassembling the waste lithium cobaltate in an inert gas environment to obtain a positive plate, washing the obtained positive plate to remove electrolyte remained on the surface, and naturally airing the positive plate;
2) calcining the positive plate obtained in the step 1) at the temperature of 200-;
3) and carrying out ICP detection on the obtained waste lithium cobaltate powder, testing the proportion of Li to Co, and carrying out the following steps of: supplementing a certain amount of lithium source according to the total proportion of 1.00-1.05, and performing ball milling on the lithium source and a lithium cobaltate precursor to obtain mixed powder;
4) calcining the mixed powder obtained in the step 3) at the temperature of 800-;
5) 2000-20000ppm cobaltosic oxide particles are added to be uniformly mixed with the powder collected in the step 4), and then ball milling is carried out to obtain mixed powder;
6) treating the mixed powder obtained in the step 5) at the temperature of 300-500 ℃ for 3-12h for secondary calcination, cooling to room temperature, taking out a sample, grinding and sieving the obtained solid to obtain the regenerated high-pressure lithium cobaltate.
2. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate according to claim 1, wherein in the step 1), the charge cut-off voltage is 4.3-4.7V; the inert gas is one of argon or nitrogen.
3. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate according to claim 1 or 2, wherein in the step 1), the obtained positive plate is washed with dimethyl carbonate for three times to remove the electrolyte remained on the surface.
4. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate according to claim 1, wherein deionized water bath ultrasound is added according to the proportion of 40g/L in the step 2) for 10-60 s.
5. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate according to claim 1, wherein in the step 2), the ethanol and deionized water mixed solution is prepared by mixing ethanol and deionized water according to a volume ratio of 1: 1.
6. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate as claimed in claim 1, 4 or 5, wherein in the step 2), the rotation speed of the centrifugation is 2000-8000r/min, and the time is 2-10 min; drying at 80 deg.C for 5-48 h; the screen mesh used for sieving is 200 meshes and 400 meshes.
7. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate as claimed in claim 1, wherein in the step 3), the lithium source is lithium carbonate or lithium hydroxide.
8. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate as claimed in claim 1, wherein in the steps 3) and 5), zirconium beads are used for ball milling, the mass ratio of the zirconium beads to the ball materials is 3:1-10:1, the ball milling speed is 200-.
9. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate according to claim 1, wherein in the steps 4) and 6), an agate mortar is adopted for grinding; the screens used for sieving are all 300-350 meshes.
10. The method for preparing high-pressure lithium cobaltate by using waste lithium cobaltate as claimed in claim 1, wherein in the step 5), the diameter of the cobaltosic oxide particles is in the range of 30-300 nm.
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