CN117117370A - Recycling method of cobalt-free positive electrode material, regenerated positive electrode material and battery - Google Patents

Recycling method of cobalt-free positive electrode material, regenerated positive electrode material and battery Download PDF

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CN117117370A
CN117117370A CN202310998133.1A CN202310998133A CN117117370A CN 117117370 A CN117117370 A CN 117117370A CN 202310998133 A CN202310998133 A CN 202310998133A CN 117117370 A CN117117370 A CN 117117370A
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positive electrode
cobalt
electrode material
free
roasting
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曾天谊
曾德武
魏礼勇
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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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
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    • C—CHEMISTRY; METALLURGY
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • 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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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The application relates to the technical field of lithium ion battery anode materials, in particular to a recycling method of a cobalt-free anode material, a regenerated anode material and a battery. The recycling method of the cobalt-free positive electrode material comprises the following steps: discharging and disassembling the waste cobalt-free battery to obtain a cobalt-free positive electrode sheet, soaking the cobalt-free positive electrode sheet in a solvent, drying and first roasting to obtain a first electrode sheet; crushing the first pole piece, removing the positive pole current collector to obtain a first positive pole material, and performing ball milling to obtain a second positive pole material; and mixing the second positive electrode material with a lithium source to obtain a material A, mixing the material A with a fluxing agent, and performing second roasting to obtain the regenerated positive electrode material. The method can effectively recycle the positive electrode material, and can obtain the regenerated positive electrode material with excellent electrochemical performance through recycling.

Description

Recycling method of cobalt-free positive electrode material, regenerated positive electrode material and battery
Technical Field
The application relates to the technical field of lithium ion battery anode materials, in particular to a recycling method of a cobalt-free anode material, a regenerated anode material and a battery.
Background
With the rapid expansion of electric vehicles (ev) and Hybrid Electric Vehicles (HEVs) in the high-end automotive market, there is an increasing demand for high-performance power batteries, in which cobalt-free positive electrode materials are positive electrode materials for many batteries due to their moderate price and high capacity. Therefore, the treatment of cobalt-free power batteries is becoming an environmental challenge and a social problem, and the disposal of waste batteries, especially the effective recovery of cobalt-free cathode materials, can not only save the limited reserves of expensive metals (such as Li, ni, mn, al), but also protect the earth environment from secondary pollution by toxic chemicals. Unfortunately, the mature metallurgical-based recovery techniques are not entirely suitable for the processing of cobalt-free cathode materials, as these methods aimed at extracting specific elements from electrode materials require the use of various environmentally unfriendly reactants, such as acids, bases, organic solvents, etc., which can produce large amounts of wastewater, dust, and other pollutants, and consume large amounts of energy. Thus, global research interest has turned to direct regeneration techniques in an attempt to achieve reuse of degraded positive electrode materials after long-term cycling.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a recycling method of cobalt-free positive electrode materials, which can effectively recycle the positive electrode materials in waste batteries and obtain regenerated positive electrode materials with excellent electrochemical performance through recycling.
Another object of the present application is to provide a regenerated positive electrode material as described.
Another object of the present application is to provide a battery.
In order to achieve the above object of the present application, the following technical solutions are specifically adopted:
the method for recycling the cobalt-free positive electrode material comprises the following steps:
(a) Discharging and disassembling the waste cobalt-free battery to obtain a cobalt-free positive electrode sheet, soaking the cobalt-free positive electrode sheet in a solvent, drying and first roasting to obtain a first electrode sheet;
(b) Crushing the first pole piece in the step (a), removing the positive pole current collector to obtain a first positive pole material, and performing ball milling to obtain a second positive pole material;
(c) Mixing the second positive electrode material in the step (b) with a lithium source to obtain a material A, mixing the material A with a fluxing agent, and performing second roasting to obtain the regenerated positive electrode material.
In one embodiment, in the cobalt-free battery, the cobalt-free positive electrode material has a chemical formula of LiNi q M 1-q O 2 Wherein, q is more than or equal to 0.5 and less than or equal to 0.95, and M is at least one of Mn and Al.
In one embodiment, the solvent comprises at least one of dimethyl carbonate and diethyl carbonate.
In one embodiment, the soaking time is 20 to 30 hours.
In one embodiment, the drying temperature is 70 to 85 ℃.
In one embodiment, the temperature of the first calcination is 300 to 500 ℃ and the time of the first calcination is 4 to 6 hours.
In one embodiment, the first firing is performed under an air atmosphere.
In one embodiment, the ball milling process is performed for a period of 50 to 70 minutes.
In one embodiment, during the ball milling process, the ball milling medium has a diameter of 3 to 8mm and a linear velocity of 3 to 8m/s.
In one embodiment, the average particle size D50 of the second positive electrode material is less than or equal to 6.5 μm.
In one embodiment, the molar ratio of the lithium source to the second positive electrode material is 0.05 to 0.1.
In one embodiment, the fluxing agent comprises at least one of molybdenum oxide, ammonium molybdate, boron oxide, potassium fluoride, calcium chloride, lithium chloride, lead oxide, vanadium trioxide, vanadium pentoxide, ammonium metavanadate, and sodium chloride.
In one embodiment, the addition amount X of the fluxing agent is 1% -5%, and the addition amount X of the fluxing agent is a percentage of the mass of the fluxing agent to the mass of the material a.
In one embodiment, the addition amount X of the flux and the average particle diameter Y of the second positive electrode material satisfy the relation: y=100x+1.
In one embodiment, the average particle diameter Y of the second positive electrode material satisfies the relationship with the cycle retention rate Z: z= (- (Y-4) 2 +96)/100。
In one embodiment, the temperature of the second calcination is 700 to 900 ℃ and the time of the second calcination is 5 to 11 hours.
In one embodiment, the second firing is performed under an oxygen atmosphere.
In one embodiment, after the second firing, the material is cooled, crushed, sieved, and demagnetized.
The regenerated positive electrode material is obtained by a recycling method of the cobalt-free positive electrode material.
A battery comprises the regenerated positive electrode material obtained by the recovery and reuse method of the cobalt-free positive electrode material or the regenerated positive electrode material.
Compared with the prior art, the application has the beneficial effects that:
(1) According to the recycling method of the cobalt-free positive electrode material, the waste polycrystalline cobalt-free positive electrode material particles with cracks are subjected to ball milling and crushing to form the small particle morphology, then the crushed small particles are recrystallized for the second time to form complete particles by means of the methods of re-preparing lithium, adding a fluxing agent and high-temperature calcination, and the fluxing agent can also cooperate with lithium salt to form a coating layer of a fast ion conductor on the particle surface, so that the electrical property of the regenerated cobalt-free single-crystal positive electrode material is improved.
(2) The regenerated positive electrode material obtained by the application has excellent electrochemical performance.
(3) The battery containing the regenerated positive electrode material has excellent first coulombic efficiency and capacity retention rate.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the recovered single crystal cobalt-free positive electrode material in example 3 of the present application;
FIG. 2 is a transmission electron microscope image of the single crystal cobalt-free positive electrode material recovered in example 3 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
According to one aspect of the application, the application relates to a method for recycling cobalt-free positive electrode materials, comprising the following steps:
(a) Discharging and disassembling the waste cobalt-free battery to obtain a cobalt-free positive electrode sheet, soaking the cobalt-free positive electrode sheet in a solvent, drying and first roasting to obtain a first electrode sheet;
(b) Crushing the first pole piece in the step (a), removing the positive pole current collector to obtain a first positive pole material, and performing ball milling to obtain a second positive pole material;
(c) Mixing the second positive electrode material in the step (b) with a lithium source to obtain a material A, mixing the material A with a fluxing agent, and performing second roasting to obtain the regenerated positive electrode material.
The recovery method of the cobalt-free positive electrode material comprises the steps of separating aluminum foil from a cobalt-free positive electrode plate, crushing, re-preparing lithium, adding fluxing agent and calcining at high temperature the separated cobalt-free positive electrode material according to a recrystallization mechanism of a fluxing agent lithium salt system, constructing the electrical property relation between the addition amount of the fluxing agent and a regenerated material, repairing lithium defects and damage structures generated in the repeated deintercalation process of the cobalt-free positive electrode material, forming a layer of fast ion conductor on the surface of the material, improving the electrochemical property of the regenerated material, and finishing the reutilization of the material.
In one embodiment, the cobalt-free positive electrode material has the chemical formula LiNi q M 1-q O 2 Wherein, q is more than or equal to 0.5 and less than or equal to 0.95, and M is at least one of Mn and Al.
In one embodiment, the organic solvent comprises at least one of dimethyl carbonate and diethyl carbonate; the soaking time is 20-30 h, such as 21h, 22h, 25h, 28h and 30h, and electrolyte and additives in the cobalt-free positive plate can be removed by soaking.
After soaking, solid-liquid separation is performed, and the solid is collected and dried at a temperature of 70 to 85 ℃, for example, 70 ℃, 75 ℃,80 ℃,85 ℃, and the like.
In one embodiment, the temperature of the first firing is 300 to 500 ℃, e.g., 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, etc., and the time of the first firing is 4 to 6 hours, e.g., 4.5 hours, 5 hours, 5.5 hours, etc. The application effectively removes impurities such as conductive carbon and binder on the surface through proper first roasting temperature and time. In one embodiment, the first firing is performed under an air atmosphere.
In one embodiment, the ball milling process is performed for a period of time ranging from 50 to 70 minutes, such as 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, and the like. In the ball milling treatment process, the diameter of a ball milling medium is 3-8 mm, and the linear speed is 3-8 m/s.
In one embodiment, the average particle size D50 of the second positive electrode material is less than or equal to 6.5 μm, for example, 1 to 5 μm. In one embodiment, the particle diameter D50 of the second positive electrode material may be 1 μm, 1.5 μm, 2 μm, 3 μm, 3.5 μm, 3.8 μm, 4 μm, 4.1 μm, 4.2 μm, 4.5 μm, 5 μm, or the like.
In one embodiment, the molar ratio of the lithium source to the second positive electrode material is 0.05 to 0.1, such as 0.06, 0.07, 0.08, 0.09, or 0.1, etc. The lithium source includes one or more of lithium hydroxide, lithium carbonate, and lithium nitrate.
In one embodiment, the fluxing agent comprises boron oxide (B 2 O 3 ) Molybdenum oxide (MoO) 3 ) Ammonium molybdate ((NH) 4 ) 2 MoO 4 ) Boron oxide (B) 2 O 3 ) Potassium fluoride (KF), calcium chloride (CaCl) 2 ) Lithium chloride (LiCl), lead oxide (PbO), vanadium trioxide (V) 2 O 3 ) Vanadium pentoxide (V) 2 O 5 ) Ammonium metavanadate (NH) 4 VO 3 ) And one or at least two of sodium chloride (NaCl).
In one embodiment, the fluxing agent includes fluxing agent a, fluxing agent B, and fluxing agent C, wherein fluxing agent a is at least one of molybdenum oxide and ammonium molybdate, fluxing agent B is at least one of boron oxide, potassium fluoride, calcium chloride, lead oxide, sodium chloride, and lithium chloride, and fluxing agent C is at least one of vanadium trioxide, vanadium pentoxide, and ammonium metavanadate; the mass ratio of the fluxing agent A to the fluxing agent B to the fluxing agent C is (2-4) 1:1.
In one embodiment, the addition amount X of the fluxing agent is 1% -5%, and the addition amount X of the fluxing agent is a percentage of the mass of the fluxing agent to the mass of the material a. The addition amount X of the flux may be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 5%, etc.
In one embodiment, the addition amount X of the flux and the average particle diameter Y of the second positive electrode material satisfy the relation: y=100+1 (±0.15). The flux can influence the particle size of the material, but the single crystal particle size has close relation with the electrical performance, and when the particle size is about 4 mu m, the diffusion path is optimal, the lithium ion diffusion coefficient is maximum, so the electrical performance is better.
In one embodiment, the average particle diameter Y of the second positive electrode material satisfies the relationship with the cycle retention rate Z: z= (- (Y-4) 2 +96)/100 (+ -0.2). In one embodiment, the average particle size Y of the second positive electrode material is in the range of 2 to 6.12. The lithium ion diffusion path is closely related to the particle size, the side reaction is increased due to the fact that too small particle size can affect the diffusion coefficient, and the relationship between the average particle size Y of the second positive electrode material and the circulation retention rate Z is obtained through origin fitting according to circulation actual data. In one embodiment, the cycle retention rate Z is the test result of 200 cycles of the battery.
In one embodiment, the second firing temperature is 700 to 900 ℃, e.g., 700 ℃, 750 ℃,800 ℃,850 ℃,900 ℃, etc., and the second firing time is 5 to 11 hours, e.g., 6 hours, 8 hours, 10 hours, etc. Through the second roasting treatment, the microstructure of the material can be optimized by adopting proper temperature and time, and the electrochemical performance of the obtained regenerated positive electrode material is improved. In one embodiment, the second firing is performed under an oxygen atmosphere.
In one embodiment, after the second firing, the material is cooled, crushed, sieved, and demagnetized.
According to another aspect of the application, the application relates to a regenerated positive electrode material, which is obtained by the recovery and reuse method of the cobalt-free positive electrode material. The regenerated positive electrode material has excellent electrochemical performance.
According to another aspect of the application, the application relates to a battery comprising the regenerated positive electrode material obtained by the method for recycling cobalt-free positive electrode material or the regenerated positive electrode material.
The battery containing the regenerated positive electrode material has excellent first coulombic efficiency and capacity retention rate.
The following is a further explanation in connection with specific examples and comparative examples.
Example 1
The method for recycling the cobalt-free positive electrode material comprises the following steps:
(a) Discharging the waste cobalt-free battery (the type of the waste cobalt-free battery is 5Ah small soft package, and the positive electrode material is composed of LiNi 0.8 Mn 0.2 O 2 ) And (3) the cobalt-free positive electrode sheet is obtained by disassembly and soaked in dimethyl carbonate (DMC) for 1 day to remove electrolyte and additives, and after filtration, the positive electrode sheet is dried at 80 ℃.
(b) Roasting the cobalt-free positive plate obtained in the step (a) for 5 hours at 400 ℃ in an air atmosphere so as to remove impurities such as conductive carbon and binder on the surface.
(c) Mechanically crushing the positive plate obtained in the step (b), separating out aluminum foil, and sieving; and then crushing large particles with cracks through ball milling for 1h to obtain a first anode material with uneven particle size, wherein the diameter of the zirconium balls is 5mm, and the linear speed is 5m/s.
(d) And (3) passing the first positive electrode material through 3000 meshes to obtain a second positive electrode material with the powder particle size D50 of 2.05 mu m.
(e) Mixing the second positive electrode material with lithium hydroxide to obtain a material A, wherein the mass fraction of the lithium hydroxide is 5%; then adding a fluxing agent molybdenum oxide with the mass fraction of 1% to obtain mixed powder, placing the mixed powder into an oxygen atmosphere, roasting for 6 hours at 850 ℃, naturally cooling, crushing, sieving, and demagnetizing to obtain the regenerated monocrystal cobalt-free positive electrode powder with the surface coated with lithium molybdate.
Example 2
The method for recycling the cobalt-free positive electrode material comprises the following steps:
(a) Discharging the waste cobalt-free battery (the waste cobalt-free battery is the same as in example 1), disassembling to obtain a cobalt-free positive electrode plate, soaking the cobalt-free positive electrode plate in dimethyl carbonate for 1 day to remove electrolyte and additives, filtering, and drying the positive electrode plate at 80 ℃.
(b) Roasting the cobalt-free positive electrode sheet obtained in the step (a) for 5 hours at 400 ℃ in an air atmosphere so as to remove impurities such as conductive carbon and binder on the surface.
(c) Mechanically crushing the positive electrode piece obtained in the step (b), separating out aluminum foil, and sieving; and then crushing large particles with cracks through ball milling for 1h to obtain a first anode material with uneven particle size, wherein the diameter of the zirconium balls is 5mm, and the linear speed is 5m/s.
(d) And (3) passing the first positive electrode material through 3000 meshes to obtain a second positive electrode material with the powder particle diameter D50 of 3.01 mu m.
(e) Mixing the second positive electrode material with lithium hydroxide to obtain a material A, wherein the mass fraction of the lithium hydroxide is 5%; then adding 2% of flux molybdenum oxide by mass fraction to obtain mixed powder, placing the mixed powder into an oxygen atmosphere, roasting for 6 hours at 850 ℃, naturally cooling, crushing, sieving, and demagnetizing to obtain regenerated monocrystal cobalt-free positive electrode powder with the surface coated with lithium molybdate.
Example 3
The method for recycling the cobalt-free positive electrode material comprises the following steps:
(a) Discharging the waste cobalt-free battery (the waste cobalt-free battery is the same as in example 1), disassembling to obtain a cobalt-free positive electrode plate, soaking the cobalt-free positive electrode plate in dimethyl carbonate for 1 day to remove electrolyte and additives, filtering, and drying the positive electrode plate at 80 ℃.
(b) Roasting the cobalt-free positive electrode sheet obtained in the step (a) for 5 hours at 400 ℃ in an air atmosphere so as to remove impurities such as conductive carbon and binder on the surface.
(c) Mechanically crushing the positive electrode piece obtained in the step (b), separating out aluminum foil, and sieving; and then crushing large particles with cracks through ball milling for 1h to obtain a first anode material with uneven particle size, wherein the diameter of the zirconium balls is 5mm, and the linear speed is 5m/s.
(d) And (3) passing the first positive electrode material through 3000 meshes to obtain a second positive electrode material with the powder particle size D50 of 4.02 mu m.
(e) Mixing the second positive electrode material with lithium hydroxide to obtain a material A, wherein the mass fraction of the lithium hydroxide is 5%; then adding 3% of fluxing agent molybdenum oxide by mass fraction to obtain mixed powder, placing the mixed powder into an oxygen atmosphere, roasting for 6 hours at 850 ℃, naturally cooling, crushing, sieving, and demagnetizing to obtain regenerated monocrystal cobalt-free positive electrode powder with the surface coated with lithium molybdate.
Example 4
The method for recycling the cobalt-free positive electrode material comprises the following steps:
(a) Discharging the waste cobalt-free battery (the waste cobalt-free battery is the same as in example 1), disassembling to obtain a cobalt-free positive electrode plate, soaking the cobalt-free positive electrode plate in dimethyl carbonate for 1 day to remove electrolyte and additives, filtering, and drying the positive electrode plate at 80 ℃.
(b) Roasting the cobalt-free positive electrode sheet obtained in the step (a) for 5 hours at 400 ℃ in an air atmosphere so as to remove impurities such as conductive carbon and binder on the surface.
(c) Mechanically crushing the positive electrode piece obtained in the step (b), separating out aluminum foil, and sieving; and then crushing large particles with cracks through ball milling for 1h to obtain a first anode material with uneven particle size, wherein the diameter of the zirconium balls is 5mm, and the linear speed is 5m/s.
(d) And (3) passing the first positive electrode material through 3000 meshes to obtain a second positive electrode material with the powder particle size D50 of 5.12 mu m.
(e) Mixing the second positive electrode material with lithium hydroxide to obtain a material A, wherein the mass fraction of the lithium hydroxide is 5%; then adding 4% of flux molybdenum oxide by mass percent to obtain mixed powder, placing the mixed powder into an oxygen atmosphere, roasting for 6 hours at 850 ℃, naturally cooling, crushing, sieving, and demagnetizing to obtain the regenerated monocrystal cobalt-free positive electrode powder with the surface coated with lithium molybdate.
Example 5
The method for recycling the cobalt-free positive electrode material comprises the following steps:
(a) Discharging the waste cobalt-free battery (the waste cobalt-free battery is the same as in example 1), disassembling to obtain a cobalt-free positive electrode plate, soaking the cobalt-free positive electrode plate in dimethyl carbonate for 1 day to remove electrolyte and additives, filtering, and drying the positive electrode plate at 80 ℃.
(b) Roasting the cobalt-free positive electrode sheet obtained in the step (a) for 5 hours at 400 ℃ in an air atmosphere so as to remove impurities such as conductive carbon and binder on the surface.
(c) Mechanically crushing the positive electrode piece obtained in the step (b), separating out aluminum foil, and sieving; and then crushing large particles with cracks through ball milling for 1h to obtain a first anode material with uneven particle size, wherein the diameter of the zirconium balls is 5mm, and the linear speed is 5m/s.
(d) And (3) passing the first positive electrode material through 3000 meshes to obtain a second positive electrode material with the powder particle size D50 of 6.12 mu m.
(e) Mixing the second positive electrode material with lithium hydroxide to obtain a material A, wherein the mass fraction of the lithium hydroxide is 5%; then adding 5% of flux molybdenum oxide by mass fraction to obtain mixed powder, placing the mixed powder into an oxygen atmosphere, roasting for 6 hours at 850 ℃, naturally cooling, crushing, sieving, and demagnetizing to obtain regenerated monocrystal cobalt-free positive electrode powder with the surface coated with lithium molybdate.
Example 6
The recycling method of the cobalt-free positive electrode material comprises the steps of (a) soaking for 20 hours and drying at 70 ℃; roasting the cobalt-free positive electrode sheet in the step (b) for 6 hours at 300 ℃ in an air atmosphere; in the step (c), ball milling is carried out for 50min, wherein the diameter of the zirconium ball is 3mm, and the linear speed is 3m/s; in step (e), the mixed powder was calcined at 800℃for 10 hours under an oxygen atmosphere, and the particle diameter D50 of the second positive electrode material was 3.12. Mu.m, with the other conditions being the same as in example 3.
Example 7
The recycling method of the cobalt-free positive electrode material comprises the steps of (a) removing soaking time of 26 hours and drying temperature of 85 ℃; roasting the cobalt-free positive electrode sheet in the step (b) for 4 hours at 500 ℃ in an air atmosphere; in the step (c), ball milling is carried out for 70min, wherein the diameter of the zirconium ball is 8mm, and the linear speed is 8m/s; in step (e), the mixed powder was calcined at 900℃for 5 hours under oxygen atmosphere, the particle size D50 of the second positive electrode material being 3.21. Mu.m, and the other conditions being the same as in example 3.
Example 8
The recycling method of the cobalt-free positive electrode material comprises the steps of removing fluxing agents of molybdenum oxide, ammonium metavanadate and ammonium molybdate, wherein the mass ratio of the molybdenum oxide to the ammonium metavanadate to the ammonium molybdate is 3:1:1, the particle size D50 of the second positive electrode material is 2.71 mu m, and other conditions are the same as in example 3.
Comparative example 1
The method for recycling cobalt-free cathode material was the same as in example 3 except that the flux molybdenum oxide was not added in step (e).
Comparative example 2
The method for recycling the cobalt-free positive electrode material comprises the following steps:
(a) Discharging the waste cobalt-free battery, disassembling to obtain a cobalt-free positive electrode sheet, soaking the cobalt-free positive electrode sheet in dimethyl carbonate for 1 day to remove electrolyte and additives, filtering, and drying the positive electrode sheet at 80 ℃.
(b) Mechanically crushing the obtained positive pole piece, separating out aluminum foil, and sieving; and then crushing large particles with cracks through ball milling for 1h to obtain a first anode material with uneven particle size, wherein the diameter of the zirconium balls is 5mm, and the linear speed is 5m/s.
(c) And (3) passing the first positive electrode material through 3000 meshes to obtain a second positive electrode material with the powder particle size D50 of 2.52 mu m.
(d) Mixing the second positive electrode material with lithium hydroxide to obtain a material A, wherein the mass fraction of the lithium hydroxide is 5%; then adding 3% of flux molybdenum oxide by mass fraction to obtain mixed powder, placing the mixed powder into an oxygen atmosphere, roasting for 6 hours at 850 ℃, naturally cooling, crushing, sieving and demagnetizing.
Experimental example
1. Scanning electron microscope image and transmission electron microscope image
FIG. 1 is a Scanning Electron Microscope (SEM) image of the single crystal cobalt-free positive electrode material recovered in example 3, with a particle size of about 4 μm, and secondary recrystallization after addition of flux to achieve a complete particle morphology, as shown in the transmission electron microscope image (TEM) of FIG. 2, with a coating on the surface of the recovered single crystal particles, indicating that the recovered material was improved.
2. Battery performance test
The regenerated positive electrode material prepared in each example and comparative example is prepared into a positive electrode plate, and the specific preparation process is as follows: firstly, weighing 0.2g of positive electrode material, 0.025g of PVDF and 0.025g of graphite, and mixing the materials according to a mass ratio of 8:1:1 grinding for 40 min, adding 0.8ml of N-methyl-2-pyrrolidone (NMP) and stirring for 10 min to make the slurry have no granule, coating on aluminum foil with scraper, drying at 100deg.C for 30min in air drying oven, taking out, and cuttingCutting into round pole pieces and aluminum sheets with the diameter of 12mm, putting the round pole pieces and the aluminum sheets into a vacuum drying oven, drying at 60 ℃ for 12 hours, taking out, weighing by an electronic balance, and finally assembling the positive pole pieces, the lithium pieces, the elastic pieces, the gaskets, the positive pole shells, the negative pole shells, the diaphragms and the electrolyte into a CR2025 type button half battery in a glove box. Adopts metallic lithium as a negative plate and adopts 1.0MLiPF 6 EC: DEC: EMC (1% vc) electrolyte was assembled into 2032 type coin cells, and the 2032 type coin cells were subjected to specific capacity and cycle performance tests, and the results are shown in table 1.
Table 1 battery performance
As shown in table 1, as the flux content increases, the particle diameter D50 of the recovered material becomes larger gradually, positively correlating with the flux ratio; the 200-turn capacity retention and first coulombic efficiency of example 3 were highest. Comparative example 1 was free of fluxing agent and the electrical properties of the recycled material were inferior to example 1.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (10)

1. The method for recycling the cobalt-free positive electrode material is characterized by comprising the following steps of:
(a) Discharging and disassembling the waste cobalt-free battery to obtain a cobalt-free positive electrode sheet, soaking the cobalt-free positive electrode sheet in a solvent, drying and first roasting to obtain a first electrode sheet;
(b) Crushing the first pole piece in the step (a), removing the positive pole current collector to obtain a first positive pole material, and performing ball milling to obtain a second positive pole material;
(c) Mixing the second positive electrode material in the step (b) with a lithium source to obtain a material A, mixing the material A with a fluxing agent, and performing second roasting to obtain the regenerated positive electrode material.
2. The recycling method of cobalt-free positive electrode material according to claim 1, wherein the cobalt-free battery has a chemical formula of LiNi q M 1-q O 2 Wherein, q is more than or equal to 0.5 and less than or equal to 0.95, and M is at least one of Mn and Al.
3. The recycling method of cobalt-free positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (5):
(1) The solvent comprises at least one of dimethyl carbonate and diethyl carbonate;
(2) The soaking time is 20-30 hours;
(3) The drying temperature is 70-85 ℃;
(4) The temperature of the first roasting is 300-500 ℃, and the time of the first roasting is 4-6 h;
(5) The first firing is performed under an air atmosphere.
4. The recycling method of cobalt-free positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The ball milling treatment time is 50-70 min;
(2) In the ball milling treatment process, the diameter of a ball milling medium is 3-8 mm, and the linear speed is 3-8 m/s.
5. The recycling method of cobalt-free positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The average particle diameter D50 of the second anode material is less than or equal to 6.5 mu m;
(2) The molar ratio of the lithium source to the second positive electrode material is 0.05-0.1.
6. The recycling method of cobalt-free positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The fluxing agent comprises at least one of molybdenum oxide, ammonium molybdate, boron oxide, potassium fluoride, calcium chloride, lithium chloride, lead oxide, vanadium trioxide, vanadium pentoxide, ammonium metavanadate and sodium chloride;
(2) The addition amount X of the fluxing agent is 1-5%, and the addition amount X of the fluxing agent is the mass percentage of the fluxing agent in the material A.
7. The method for recycling cobalt-free positive electrode material according to claim 6, comprising at least one of the following features (1) to (2):
(1) The addition amount X of the fluxing agent and the average particle size Y of the second positive electrode material satisfy the relation: y=100x+1;
(2) The average particle size Y of the second positive electrode material and the circulation retention rate Z satisfy the relation: z= (- (Y-4) 2 +96)/100。
8. The recycling method of cobalt-free positive electrode material according to claim 1, comprising at least one of the following features (1) to (3):
(1) The temperature of the second roasting is 700-900 ℃, and the time of the second roasting is 5-11 h;
(2) The second roasting is carried out under an oxygen atmosphere;
(3) And after the second roasting, cooling, crushing, screening and demagnetizing the materials.
9. A regenerated positive electrode material characterized by being obtained by the recovery and reuse method of a cobalt-free positive electrode material according to any one of claims 1 to 8.
10. A battery comprising the regenerated positive electrode material obtained by the method for recycling cobalt-free positive electrode material according to any one of claims 1 to 8 or the regenerated positive electrode material according to claim 9.
CN202310998133.1A 2023-08-08 2023-08-08 Recycling method of cobalt-free positive electrode material, regenerated positive electrode material and battery Pending CN117117370A (en)

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