CN114122552A - LiAlO prepared by recycling retired lithium ion battery2Method for coating single crystal anode material - Google Patents
LiAlO prepared by recycling retired lithium ion battery2Method for coating single crystal anode material Download PDFInfo
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Abstract
The invention discloses a method for preparing LiAlO by recycling retired lithium ion batteries2A method for coating a single crystal positive electrode material. Firstly, disassembling a retired lithium ion battery, pretreating a positive plate, and separating an aluminum foil and a waste positive material; then, taking the waste anode material containing residual aluminum foil as a raw material, removing the residual aluminum foil by using a NaOH alkaline leaching method, and obtaining an aluminum-containing alkaline leaching solution; crushing, mixing lithium and roasting the waste anode material particles at high temperature to obtain a single crystal anode material; finally, the prepared single crystal anode material is added into the aluminum-containing alkali immersion liquid for Al (OH)3Coating, mixing lithium and roasting after the reaction is finished to obtain LiAlO2A coated single crystal positive electrode material. The method of the invention not only can regenerate the recycled waste anode material into the single crystal anode material, but also can effectively solve the problem of treatment of the aluminum-containing alkali leaching solution, thereby realizing the recycling of nickel, cobalt, manganese and aluminum elements in the retired lithium ion battery.
Description
Technical Field
The invention relates toLiAlO prepared by recycling retired lithium ion battery2A method for coating a single crystal anode material belongs to the field of lithium ion battery recovery and anode material preparation.
Background
Lithium ion battery positive electrode materials are widely used in new energy automobile power storage batteries due to their advantages of high energy density and low cost. Due to capacity fade, the power storage battery will reach its service life after 3-5 years of use. The ex-service power lithium battery in 2025 is expected to reach 134.49GWh, and the ex-service amount reaches 80.36 ten thousand tons. In order to standardize and urge the development of a power battery recycling system, automobile standardization technical committees in China issue requirements for recycling materials of power batteries for vehicles, and seven ministries such as Ministry of industry and credibility issue notices about the completion of new energy automobile power battery recycling pilot works. Therefore, recycling and remanufacturing lithium ion batteries to achieve sustainable energy storage is imminent.
Currently, the mainstream methods for recycling lithium ion batteries include pyrometallurgy and hydrometallurgy. However, these two methods are energy-consuming, complicated in steps, and cause a large amount of environmental pollution, and the particle structure of the positive electrode material is completely destroyed in the recovery process. Although the direct regeneration method abandons the method of completely destroying particles in pyrometallurgy and hydrometallurgy, the capacity, rate capability and cycle performance of the cathode material after lithium supplement recovery regeneration are different from those of a fresh material, the particle morphology is still secondary particles (possibly containing a large amount of broken particles) consisting of primary particles, and the structural characteristics cause the cathode material to be easily broken in the charging and discharging processes and shorten the cycle service life. The single crystal anode material prepared by the molten salt method has the following advantages: (1) the single crystal material has stronger cycle performance, particularly has the advantages in high-temperature cycle, has better thermal stability and can be used as a high-voltage material; (2) the single crystal anode material has better mechanical strength, can better inhibit the particle from being broken, and reduces the side reaction and phase change in contact with the electrolyte.
In addition, most of the existing technologies for recycling and preparing the cathode material adopt a NaOH alkaline leaching method to remove aluminum foil, but the problems of treatment of aluminum-containing alkaline leaching solution are not involved. In the actual process, if the alkaline leaching solution containing aluminum is directly discharged, serious secondary pollution and aluminum resource waste are caused. In addition, as the regenerated cathode material has more defects, the electrochemical performance of the currently recycled and regenerated cathode material cannot meet the requirement of commercial application.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing LiAlO by recycling retired lithium ion batteries2The method for coating the single crystal cathode material aims at solving the following two problems: (1) the recycled and re-prepared anode material particles are easy to break, and are easy to contact with electrolyte to generate side reaction and phase change, so that the problems of short cycle life, poor rate capability and weak thermal stability of the material are caused; (2) the problem of treating the aluminum-containing alkali leaching solution.
In order to realize the purpose of the invention, the following technical scheme is adopted:
LiAlO prepared by recycling retired lithium ion battery2The method for coating the single crystal cathode material comprises the following steps:
step 1: discharging and disassembling a retired lithium ion battery to obtain a positive plate, then using a polar aprotic solvent, pretreating the positive plate by ultrasonic cleaning, separating an aluminum foil and a waste positive material, and filtering, washing and drying to obtain the waste positive material containing residual aluminum foil;
step 2: taking a waste anode material containing residual aluminum foil as a raw material, removing the residual aluminum foil by using a NaOH alkaline leaching method, filtering, washing and drying to obtain waste anode material particles, and obtaining an aluminum-containing alkaline leaching solution;
and step 3: crushing the waste anode material particles by adopting a solid-phase ball milling method, grinding and mixing the crushed particles and lithium-based salt according to a stoichiometric ratio, roasting the crushed particles in air or oxygen atmosphere to obtain a regenerated single-crystal anode material and lithium salt mixture, and washing the regenerated single-crystal anode material and lithium salt mixture by using deionized water to remove excessive lithium salt;
and 4, step 4: using inductively coupled plasma spectroscopyMeasuring the aluminum ion concentration in the aluminum-containing alkaline leaching solution obtained in the step 2 by an instrument, controlling the aluminum ion concentration in the alkaline leaching solution by adding deionized water or an aluminum source, adding the regenerated single crystal positive electrode material after water washing into the aluminum-containing alkaline leaching solution, and adjusting the pH value of the alkaline leaching solution by dripping HCl solution to generate Al (OH)3Uniformly depositing the mixture on the surface of a single crystal anode material prepared by regeneration, and obtaining LiAlO through the steps of filtering, washing, drying, mixing lithium and roasting after the reaction is finished2A single crystal anode material coated by a fast ion conductor.
Further, the polar aprotic solvent is N-methylpyrrolidone.
Further, step 1: discharging and disassembling a retired lithium ion battery to obtain a positive plate, then pretreating and separating an aluminum foil and a waste positive material by using N-methyl pyrrolidone as a solvent through ultrasonic cleaning of the positive plate, wherein the ultrasonic power of the ultrasonic cleaning is 50-720W, the ultrasonic time is 10-240 min, after the ultrasonic cleaning is finished, filtering, washing with deionized water for 2-5 times, and drying at 40-120 ℃ for 6-48 h to obtain the waste positive material containing residual aluminum foil, wherein the concentration of the aluminum foil is 0.5-30 g/Kg;
the ex-service lithium ion battery is one of a lithium cobalt oxide battery, a lithium nickel cobalt manganese oxide battery and a lithium nickel cobalt aluminate battery.
Further, step 2: taking a waste anode material containing residual aluminum foil as a raw material, removing the residual metal aluminum foil in a 0.1-2 mol/LNaOH solution under the conditions of a reaction temperature of room temperature to 80 ℃, a reaction stirring speed of 50-600 rpm, a reaction time of 20-200 min and a solid-to-liquid ratio of 10-300 g/L, filtering, washing for 2-5 times by deionized water and drying at 40-120 ℃ for 6-48 h to obtain the waste anode material, and obtaining an aluminum-containing alkali immersion liquid (NaAlO)2A solution).
Further, step 3: crushing the waste anode material particles by adopting a solid-phase ball milling method under the conditions that the rotating speed is 150-1500 rpm and the ball milling time is 0.5-6 h, and then, mixing the crushed particles according to a stoichiometric ratio of 1: 2-1: grinding and mixing the lithium-based lithium salt and the ground lithium salt, roasting in air or oxygen atmosphere in two steps, firstly heating to 350-550 ℃ at a heating rate of 2-6 ℃/min, carrying out heat preservation treatment for 2-8 h, then heating to 700-1100 ℃ at a heating rate of 2-6 ℃/min, carrying out heat preservation treatment for 12-24 h, and finally naturally cooling to room temperature to obtain a mixture of a regenerated single crystal positive electrode material and a lithium salt, and then washing the mixture of the regenerated single crystal positive electrode material and the lithium salt with deionized water for 2-5 times to remove excessive lithium salt;
the lithium-based salt is one or more of lithium oxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate and lithium hydroxide.
Further, step 4: measuring the aluminum ion concentration in the aluminum-containing alkaline leaching solution obtained in the step 2 by using an inductively coupled plasma spectrometer, controlling the aluminum ion concentration in the alkaline leaching solution to be within the range of 0.2-4 g/L by adding deionized water or an aluminum source, then adding the regenerated single crystal positive electrode material prepared by water washing into the aluminum-containing alkaline leaching solution under the condition that the solid-to-liquid ratio is 20-200 g/L, adjusting the pH value of the alkaline leaching solution to be 5.5-11.5 by dropwise adding an HCl solution, reacting at the stirring speed of 200-600 rpm for 0.5-4 h, and enabling the generated Al (OH)3Uniformly depositing the mixture on the surface of a single crystal anode material prepared by regeneration, after the reaction is finished, filtering, washing with deionized water for 2-5 times, drying at 40-120 ℃ for 6-48 h, mixing lithium, heating to 500-1000 ℃ at a heating rate of 2-6 ℃/min in an air atmosphere, roasting for 2-12 h and the like to obtain LiAlO2And coating the fast ion conductor to prepare the monocrystal cathode material.
The aluminum source is one or more of aluminum chloride, aluminum sulfate, alum, aluminum sulfate, aluminum nitrate, aluminum isopropoxide or aluminum acetylacetonate.
And in the lithium mixing step, the lithium salt is one or more of lithium oxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate and lithium hydroxide.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a method for preparing LiAlO by recycling retired lithium ion batteries2A method for coating a single crystal anode material comprises the steps of preparing the single crystal anode material by carrying out a molten salt method on the recovered waste anode material, and then carrying out LiAlO (lithium aluminum oxide) on the regenerated single crystal anode material by using an aluminum-containing alkaline leaching solution as a raw material2The fast ion conductor is coated and modified to reduce the occurrence of surface side reaction and improve the diffusion rate, electrochemical performance and thermal stability of lithium ions in the material. The method can effectively solve the problem of treatment of the aluminum-containing alkaline leaching solution while improving the electrochemical performance of the regenerated single crystal anode material, and realizes the recycling of nickel, cobalt, manganese and aluminum elements in the retired lithium ion battery.
Drawings
FIG. 1 is a view showing waste LiNi recovered in example 1 of the present invention0.5Co0.2Mn0.3O2An XRD pattern of the anode material;
FIG. 2 is a view showing LiNi, a single crystal produced by the molten salt method of example 1 of the present invention0.5Co0.2Mn0.3O2An XRD pattern of the anode material;
FIG. 3 shows LiAlO prepared after treatment of an alkaline leaching solution containing aluminum in example 1 of the present invention2Coated single crystal LiNi0.5Co0.2Mn0.3O2An XRD pattern of the anode material;
FIG. 4 is a view showing waste LiNi recovered in example 1 of the present invention0.5Co0.2Mn0.3O2FESEM image of positive electrode material;
FIG. 5 is a view showing LiNi, a single crystal produced by the molten salt method of example 1 of the present invention0.5Co0.2Mn0.3O2FESEM image of positive electrode material;
FIG. 6 shows LiAlO prepared after the treatment of the alkaline leaching solution containing aluminum in example 1 of the present invention2Coated single crystal LiNi0.5Co0.2Mn0.3O2FESEM image of positive electrode material;
FIG. 7 is a view showing a single-crystal LiNi which was regeneratively produced in example 1 of the present invention0.5Co0.2Mn0.3O2Sample and LiAlO2Coated reconstituted single crystal LiNi0.5Co0.2Mn0.3O2A graph of rate performance of the sample;
FIG. 8 is a view showing a single-crystal LiNi which was regeneratively produced in example 1 of the present invention0.5Co0.2Mn0.3O2Sample and LiAlO2Coated reconstituted single crystal LiNi0.5Co0.2Mn0.3O2Cycle performance plot of the samples。
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1: recovery of LiNi0.5Co0.2Mn0.3O2LiAlO prepared by using retired lithium ion battery2Fast ion conductor coated single crystal LiNi0.5Co0.2Mn0.3O2Positive electrode material
Reacting LiNi0.5Co0.2Mn0.3O2Discharging and disassembling a retired lithium ion battery to obtain a positive plate, then pretreating the positive plate by using N-methylpyrrolidone as a solvent through ultrasonic cleaning to separate aluminum foil and waste LiNi0.5Co0.2Mn0.3O2And (3) preparing the anode material, wherein the ultrasonic power of ultrasonic cleaning is 240W, and the ultrasonic time is 60 min. Filtering, washing for 3 times by deionized water and drying for 20 hours at 80 ℃ after ultrasonic cleaning is finished to obtain waste LiNi containing residual aluminum foil0.5Co0.2Mn0.3O2The concentration range of the aluminum foil is 0.5-30 g/Kg.
Waste LiNi containing residual aluminum foil0.5Co0.2Mn0.3O2The anode material is used as a raw material, and is prepared by reacting 1mol/LNaOH solution at the reaction temperature of 60 ℃, the reaction stirring speed of 350rpm, the reaction time of 80min and the solid-to-liquid ratio of 200g/L (wherein the solid-to-liquid ratio refers to waste LiNi containing residual aluminum foil)0.5Co0.2Mn0.3O2The mass ratio of the anode material to the volume of the NaOH solution), removing residual metal aluminum foil, filtering, washing with deionized water for 3 times, and drying at 80 ℃ for 20 hours to obtain the waste LiNi0.5Co0.2Mn0.3O2Positive electrode material, and obtaining an aluminum-containing alkaline leaching solution (NaAlO)2Solution);
adopting a solid phase ball milling method to carry out ball milling on the waste anode material under the conditions that the rotating speed is 1350rpm and the ball milling time is 2 hoursCrushing the particles, and then mixing the crushed particles according to a stoichiometric ratio of 1: 3 grinding and mixing the lithium carbonate and lithium hydroxide (the stoichiometric ratio is 1: 4), roasting in air atmosphere in two steps, firstly heating to 500 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 6h, then heating to 950 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 15h, and finally naturally cooling to room temperature to obtain the regenerated and prepared single crystal LiNi0.5Co0.2Mn0.3O2The method comprises the following steps of (1) washing a mixture of a positive electrode material and a lithium salt for 3 times by using deionized water to remove excessive lithium salt;
measuring the concentration of aluminum ions in the obtained aluminum-containing alkaline leaching solution by using an inductively coupled plasma spectrometer, controlling the concentration of the aluminum ions in the alkaline leaching solution to be 1.5g/L by adding deionized water or aluminum nitrate, and then carrying out solid-to-liquid ratio (the solid-to-liquid ratio refers to the LiNi of the single crystal prepared by regeneration after water washing)0.5Co0.2Mn0.3O2The ratio of the mass of the positive electrode material to the volume of the aluminum-containing alkali immersion liquid) was 150g/L, and the single crystal LiNi prepared by regeneration after washing with water was used0.5Co0.2Mn0.3O2Adding the positive electrode material into the aluminum-containing alkaline leaching solution, adjusting pH value of the alkaline leaching solution to 6 by dripping HCl solution, reacting at stirring speed of 350rpm for 2h to generate Al (OH)3Uniformly depositing on the surface of the regenerated single crystal anode material, after the reaction is finished, filtering, washing 3 times with deionized water, drying at 80 ℃ for 20h, and mixing with lithium carbonate according to a stoichiometric ratio of 1: 1.05 are mixed evenly and are roasted for 6h at the temperature rising rate of 2 ℃/min to 850 ℃ in the air atmosphere to obtain LiAlO2Fast ion conductor coated remanufactured single crystal LiNi0.5Co0.2Mn0.3O2And (3) a positive electrode material.
FIGS. 1 and 2 are views showing the waste LiNi recovered in this example0.5Co0.2Mn0.3O2Positive electrode material and single crystal LiNi prepared by molten salt method0.5Co0.2Mn0.3O2The XRD pattern of the anode material can show that both materials can be indexed as typical layered alpha-NaFeO2The structure is that the space group is R-3 m. Both materials have a chemical bond with LiCoO2Like a layered structure ofThe Li and O ions occupy the 3a and 6c sites of the crystal structure respectively; the transition metal ions of Ni, Mn and Co occupy 3b sites.
FIG. 3 shows LiAlO prepared after treatment of an aluminum-containing alkaline leaching solution2Coated single crystal LiNi0.5Co0.2Mn0.3O2XRD pattern of positive electrode material, it can be seen that after coating, the material exhibits LiNi0.5Co0.2Mn0.3O2Similar structure of the material, indicating LiNi during the coating process0.5Co0.2Mn0.3O2The structure of (2) is not destroyed. In addition, LiAlO is used as2The amount of coating is low, so that no corresponding characteristic peak appears on the XRD pattern.
FIG. 4 shows waste LiNi obtained by recovery in this embodiment0.5Co0.2Mn0.3O2The FESEM image of the cathode material shows that the material is spherical particles with the size of about 8 μm, and the particles of the material are seriously damaged after being recycled.
FIGS. 5 and 6 are respectively views of a single crystal LiNi prepared by a molten salt method0.5Co0.2Mn0.3O2LiAlO prepared by treating anode material and aluminum-containing alkaline leaching solution2Coated single crystal LiNi0.5Co0.2Mn0.3O2FESEM image of positive electrode material. As shown in FIG. 5, single-crystal LiNi prepared by the molten salt method0.5Co0.2Mn0.3O2The positive electrode material exhibits a particle shape and a size of 0.5 to 2 μm. LiAlO2Thereafter, single-crystal LiNi0.5Co0.2Mn0.3O2There were no significant differences in the morphology and size of the samples (fig. 6). But in contrast to single crystal LiNi0.5Co0.2Mn0.3O2The surface of the sample, which became slightly blurred after coating, was probably due to the single-crystal LiNi0.5Co0.2Mn0.3O2The surface of the sample is coated with a layer of LiAlO2And the result is that.
LiAlO obtained in the example2Single crystal LiNi before and after coating0.5Co0.2Mn0.3O2Sample and acetylene black, polyvinylidene fluoride(PVDF) is fully mixed according to the mass ratio of 8:1:1, is mixed into paste, is uniformly coated on an aluminum foil, is coated with the thickness of 100 mu m, is dried at 80 ℃, is rolled and is sheared into a positive plate with the diameter of 12mm, and is dried in vacuum for standby. A metal lithium sheet is used as a cathode, a Cellgard2400 type polypropylene membrane is used as a diaphragm, an experimental battery is assembled in an argon glove box, and then the battery is subjected to constant voltage and constant current charge and discharge test at 25 ℃.
FIG. 7 is a single crystal LiNi0.5Co0.2Mn0.3O2Positive electrode material and LiAlO2Coated single crystal LiNi0.5Co0.2Mn0.3O2And the rate performance graph of the cathode material under different current densities. From the figure, it can be seen that LiAlO increases with current density from 0.1C to 2C2Coated single crystal LiNi0.5Co0.2Mn0.3O2The positive electrode materials all exhibited LiNi which is more single crystalline than LiNi0.5Co0.2Mn0.3O2The cathode material has more excellent rate performance. For example, LiAlO at 0.1C, 0.5C and 2C current densities2Coated single crystal LiNi0.5Co0.2Mn0.3O2The average specific discharge capacity of the cathode material is 170.5, 155.9 and 140.7mAhg-1Are all higher than single crystal LiNi0.5Co0.2Mn0.3O2Average specific discharge capacities of 169.2, 154.4 and 135.0mAhg of the positive electrode material-1。
FIG. 8 is a single crystal LiNi0.5Co0.2Mn0.3O2Positive electrode material and LiAlO2Coated single crystal LiNi0.5Co0.2Mn0.3O2Cycle performance of the positive electrode material at 1C current density. As can be seen from the figure, LiAlO2Coated single crystal LiNi0.5Co0.2Mn0.3O2The initial discharge capacity of the positive electrode material was 148.6mAhg-1Higher than single crystal LiNi0.5Co0.2Mn0.3O2143.3mAhg of positive electrode material-1. In addition, LiAlO increases the number of cycles2Coated single crystal LiNi0.5Co0.2Mn0.3O2Discharge of positive electrode materialThe capacity attenuation is also slow, and after 100 cycles of charge and discharge test, the discharge capacity still has 126.1mAhg-1The attenuation rate of the capacity per circle is only 0.151%; in contrast, single crystal LiNi0.5Co0.2Mn0.3O2The positive electrode material has a capacity attenuation rate per circle as high as 0.259% (106.2 mAhg)-1). The electrochemical test result shows that the proper amount of LiAlO2The coating contributes to improvement of single crystal LiNi0.5Co0.2Mn0.3O2Rate capability and cycle performance of the cathode material.
Example 2: recovery of LiNi0.6Co0.2Mn0.2O2LiAlO prepared by regeneration of retired lithium ion battery2Fast ion conductor coated single crystal LiCoO2Positive electrode material
Reacting LiNi0.6Co0.2Mn0.2O2Discharging and disassembling a retired lithium ion battery to obtain a positive plate, then pretreating the positive plate by using N-methylpyrrolidone as a solvent through ultrasonic cleaning to separate aluminum foil and waste LiNi0.6Co0.2Mn0.2O2And the ultrasonic power of the ultrasonic cleaning of the anode material is 200W, and the ultrasonic time is 90 min. Filtering, washing for 3 times by deionized water and drying for 10 hours at 110 ℃ after ultrasonic cleaning is finished to obtain waste LiNi containing residual aluminum foil0.6Co0.2Mn0.2O2The concentration range of the aluminum foil is 0.5-30 g/Kg.
Waste LiNi containing residual aluminum foil0.6Co0.2Mn0.2O2The anode material is used as a raw material, and is prepared by reacting 2mol/LNaOH solution at 55 ℃, the reaction stirring speed of 300rpm, the reaction time of 50min and the solid-to-liquid ratio of 150g/L (wherein the solid-to-liquid ratio refers to waste LiNi containing residual aluminum foil)0.6Co0.2Mn0.2O2The mass ratio of the anode material to the volume of the NaOH solution), removing residual metal aluminum foil, filtering, washing with deionized water for 3 times, and drying at 110 ℃ for 10h to obtain the waste LiNi0.6Co0.2Mn0.2O2Positive electrode material, and obtaining an aluminum-containing alkaline leaching solution (NaAlO)2Solutions of)；
Crushing the waste anode material particles by adopting a solid-phase ball milling method under the conditions that the rotating speed is 1100rpm and the ball milling time is 2 hours, and then, mixing the crushed particles according to the stoichiometric ratio of 1: 2 grinding and mixing the lithium carbonate and lithium nitrate (the stoichiometric ratio is 2: 3), roasting in air atmosphere in two steps, firstly heating to 450 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation treatment for 8h, then heating to 900 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation treatment for 16h, and finally naturally cooling to room temperature to obtain the regenerated monocrystal LiNi0.6Co0.2Mn0.2O2The method comprises the following steps of (1) washing a mixture of a positive electrode material and a lithium salt for 3 times by using deionized water to remove excessive lithium salt;
measuring the concentration of aluminum ions in the obtained aluminum-containing alkaline leaching solution by using an inductively coupled plasma spectrometer, controlling the concentration of the aluminum ions in the alkaline leaching solution to be 2g/L by adding deionized water or aluminum chloride, and then carrying out regeneration preparation on the obtained aluminum-containing alkaline leaching solution according to a solid-to-liquid ratio (the solid-to-liquid ratio refers to the ratio of the aluminum ions in the single crystal LiNi prepared by regeneration after washing with water)0.6Co0.2Mn0.2O2The ratio of the mass of the positive electrode material to the volume of the aluminum-containing alkali immersion liquid) is 100g/L, and the single crystal LiNi prepared by regeneration after washing with water is used0.6Co0.2Mn0.2O2Adding the positive electrode material into the aluminum-containing alkaline leaching solution, adjusting pH of the alkaline leaching solution to 7.5 by dropwise adding HCl solution, and reacting at stirring speed of 450rpm for 1.5h to obtain Al (OH)3Uniformly depositing on the surface of the regenerated and prepared single crystal anode material, after the reaction is finished, filtering, washing 3 times with deionized water, drying for 10h at 110 ℃, and mixing with lithium hydroxide according to a stoichiometric ratio of 1: 1.05 are mixed evenly and are roasted for 8 hours at the temperature rising rate of 3 ℃/min to 800 ℃ in the air atmosphere to obtain LiAlO2Fast ion conductor coated remanufactured single crystal LiNi0.6Co0.2Mn0.2O2And (3) a positive electrode material.
Example 3: recovery of LiCoO2LiAlO prepared by using retired lithium ion battery2Single crystal anode material coated by fast ion conductor
Subjecting LiCoO to condensation2Discharging and disassembling the retired lithium ion battery to obtain a positive plate, and then taking N-methyl pyrrolidone as a solventAn agent for pretreating and separating the positive plate by ultrasonic cleaning to obtain aluminum foil and waste LiCoO2And the ultrasonic power of the ultrasonic cleaning of the anode material is 150W, and the ultrasonic time is 120 min. Filtering, washing for 3 times by deionized water and drying for 20 hours at 80 ℃ after ultrasonic cleaning is finished to obtain waste LiCoO containing residual aluminum foil2The concentration range of the aluminum foil is 0.5-30 g/Kg.
Waste LiCoO containing residual aluminum foil2The anode material is used as a raw material, and is subjected to reaction by using 1.5mol/LNaOH solution under the conditions of reaction temperature of 60 ℃, reaction stirring speed of 400rpm, reaction time of 70min and solid-liquid ratio of 250g/L (wherein the solid-liquid ratio refers to waste LiCoO containing residual aluminum foil2The ratio of the mass of the anode material to the volume of the NaOH solution), removing residual metal aluminum foil, filtering, washing with deionized water for 3 times, and drying at 80 ℃ for 20 hours to obtain waste LiCoO2Positive electrode material, and obtaining an aluminum-containing alkaline leaching solution (NaAlO)2Solution);
crushing the waste anode material particles by adopting a solid-phase ball milling method under the conditions that the rotating speed is 800rpm and the ball milling time is 3 hours, and then, mixing the crushed particles according to the stoichiometric ratio of 1: 2.5 grinding and mixing the lithium carbonate and the mixture, roasting the mixture in two steps under the air atmosphere, firstly heating the mixture to 500 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 8 hours, then heating the mixture to 1000 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 18 hours, and finally naturally cooling the mixture to room temperature to obtain the regenerated and prepared single crystal LiCoO2The method comprises the following steps of (1) washing a mixture of a positive electrode material and a lithium salt for 3 times by using deionized water to remove excessive lithium salt;
measuring the aluminum ion concentration in the aluminum-containing alkaline leaching solution by using an inductively coupled plasma spectrometer, controlling the aluminum ion concentration in the alkaline leaching solution to be 1g/L by adding deionized water or aluminum sulfate, and then performing regeneration preparation on the obtained single crystal LiCoO at a solid-to-liquid ratio (the solid-to-liquid ratio refers to the regenerated single crystal LiCoO after washing)2The ratio of the mass of the positive electrode material to the volume of the aluminum-containing alkaline leaching solution) was 200g/L, and the single crystal LiCoO was prepared by regeneration after washing with water2Adding the positive electrode material into the aluminum-containing alkaline leaching solution, adjusting pH of the alkaline leaching solution to 8 by dropwise adding HCl solution, and reacting at stirring speed of 400rpm for 1h to obtain Al (OH)3UniformityDepositing on the surface of the regenerated single crystal anode material, after the reaction is finished, filtering, washing 3 times by deionized water, drying for 20h at 80 ℃, and mixing with lithium carbonate according to a stoichiometric ratio of 1: 1.1, heating to 900 ℃ at the heating rate of 2 ℃/min in the air atmosphere, roasting for 7h and the like to obtain LiAlO2Fast ion conductor coated remanufactured single crystal LiCoO2And (3) a positive electrode material.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (16)
1. LiAlO prepared by recycling retired lithium ion battery2The method for coating the single crystal cathode material is characterized by comprising the following steps of:
step 1: discharging and disassembling a retired lithium ion battery to obtain a positive plate, then using a polar aprotic solvent, pretreating the positive plate by ultrasonic cleaning, separating an aluminum foil and a waste positive material, and filtering, washing and drying to obtain the waste positive material containing residual aluminum foil;
step 2: taking a waste anode material containing residual aluminum foil as a raw material, removing the residual aluminum foil by using a NaOH alkaline leaching method, filtering, washing and drying to obtain waste anode material particles, and obtaining an aluminum-containing alkaline leaching solution;
and step 3: crushing the waste anode material particles by adopting a solid-phase ball milling method, grinding and mixing the crushed particles and lithium-based salt according to a stoichiometric ratio, roasting the crushed particles in air or oxygen atmosphere to obtain a regenerated single-crystal anode material and lithium salt mixture, and washing the regenerated single-crystal anode material and lithium salt mixture by using deionized water to remove excessive lithium salt;
and 4, step 4: measuring the aluminum ion concentration in the aluminum-containing alkaline leaching solution obtained in the step 2 by using an inductively coupled plasma spectrometer, controlling the aluminum ion concentration in the alkaline leaching solution by adding deionized water or an aluminum source, and adding the single crystal anode material prepared by regeneration after washing into the solution containing aluminumAdding HCl solution dropwise into the aluminum alkali immersion liquid to adjust pH value of the alkali immersion liquid to generate Al (OH)3Uniformly depositing the mixture on the surface of a single crystal anode material prepared by regeneration, and obtaining LiAlO through the steps of filtering, washing, drying, mixing lithium and roasting after the reaction is finished2A single crystal anode material coated by a fast ion conductor.
2. The method of claim 1, wherein:
in the step 1, the retired lithium ion battery is one of a lithium cobalt oxide battery, a lithium nickel cobalt manganese oxide battery and a lithium nickel cobalt aluminate battery; preferably, the polar aprotic solvent is N-methylpyrrolidone.
3. The method of claim 1, wherein:
in the step 1, the ultrasonic power range of ultrasonic cleaning is 50-720W, and the ultrasonic time range is 10-240 min.
4. The method of claim 1, wherein:
in the step 2, the concentration range of NaOH in the NaOH alkaline leaching method is 0.1-2 mol/L, the reaction temperature range is room temperature-80 ℃, the reaction stirring speed range is 50-600 rpm, the reaction time range is 20-200 min, and the solid-to-liquid ratio range is 10-300 g/L.
5. The method of claim 1, wherein:
in the step 3, the rotating speed range of the solid phase ball milling is 150-1500 rpm, and the ball milling time range is 0.5-6 h.
6. The method of claim 1, wherein:
in the step 3, the stoichiometric ratio range of the mixture of the waste positive electrode material and the lithium-based salt is 1: 2-1: 5.
7. the method of claim 1, wherein:
in step 3, the lithium-based salt is one or more of lithium oxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate and lithium hydroxide.
8. The method of claim 1, wherein:
in the step 3, the roasting mode is two-step roasting, the roasting temperature range of the first step is 350-550 ℃, the roasting time range is 2-8 h, the roasting temperature range of the second step is 700-1100 ℃, the roasting time range is 12-24 h, and the temperature rise rate range of the two-step roasting is 2-6 ℃/min.
9. The method of claim 1, wherein:
in the step 4, the concentration range of aluminum ions in the aluminum-containing alkaline leaching solution is 0.2-4 g/L.
10. The method of claim 1, wherein:
in the step 4, the aluminum source is one or more of aluminum chloride, aluminum sulfate, alum, aluminum sulfate, aluminum nitrate, aluminum isopropoxide or aluminum acetylacetonate.
11. The method of claim 1, wherein:
in the step 4, the regenerated single crystal anode material is added into an aluminum-containing alkaline leaching solution, and the solid-to-liquid ratio is controlled to be 20-200 g/L.
12. The method of claim 1, wherein:
in the step 4, the regenerated single crystal anode material is added into the aluminum-containing alkali immersion liquid for reaction for 0.5-4 h, the stirring speed ranges from 200 rpm to 600rpm, and the pH value of the solution ranges from 5.5 to 11.5.
13. The method of claim 1, wherein:
in the step 4, the lithium salt in the lithium mixing step is one or more of lithium oxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate and lithium hydroxide.
14. The method of claim 1, wherein:
in the step 4, the roasting temperature in the roasting step is 500-1000 ℃, the roasting time is 2-12 h, and the temperature rise rate is 2-6 ℃/min.
15. The method of claim 1, wherein:
in the steps 1 and 2, the concentration range of the aluminum foil in the waste anode material containing the residual aluminum foil is 0.5-30 g/Kg.
16. The method of claim 1, wherein:
in the steps 1, 2 and 4, solutions used for washing in the washing step and the drying step independently are deionized water, the washing times are 2-5 times, the drying temperature range is 40-120 ℃, and the drying time range is 6-48 hours.
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