Method for preparing glass pumice loaded waste lithium battery material composite catalyst without calcination

Abstract

The invention discloses a method for preparing a glass pumice loaded waste lithium battery material composite catalyst without calcination, and relates to the technical field of light environment functional materials and resource recycling. The preparation method specifically comprises the following steps: discharging, disassembling, crushing and screening a retired waste lithium battery to obtain positive electrode powder, and cleaning and drying the positive electrode powder to obtain recycled positive electrode material powder; the glass pumice is soaked with acid liquor, then washed with water and dried, and the treated glass pumice is obtained; preparing the recycled positive electrode material powder into suspension liquid; and adding the treated glass pumice into the suspension to obtain a loaded suspension, drying the loaded suspension, carrying out gradient drying in an inert gas atmosphere, and cleaning to obtain the composite catalyst. According to the method, the normal-temperature in-situ fixation of the active components is realized by utilizing capillary and adsorption effects of solvent volatilization, and the process is simple, green and energy-saving. The catalyst can efficiently and stably activate PMS to degrade tetracycline, and high-valued utilization of urban mines and industrial solid waste is achieved.

Description

Technical Field

[0001] This invention relates to a method for preparing glass-light stone-supported composite catalysts from waste lithium-ion batteries without calcination, belonging to the field of environmental functional materials and resource recycling technology. Background Technology

[0002] With the widespread application of lithium-ion batteries, their decommissioning volume has increased dramatically. How to achieve high-value resource utilization of waste battery materials has become a research hotspot in the fields of environment and materials. In recent years, the recycling of cathode materials (such as LiNi) has become a focus. 0.8 Co 0.1 Mn 0.1 O2 and LiCoO2 are used to prepare persulfate (PMS) activated catalysts, realizing "waste treatment with waste" and showing great application potential.

[0003] In the prior art, the preparation of such composite catalysts generally relies on high-temperature heat treatment (such as muffle furnace calcination, usually at 400-800℃) to achieve crystallization of active components, removal of organic binders, and enhancement of the binding force with the support. For example, Chinese invention patent application 202010392514.1 discloses a method for activating persulfate to remove antibiotics from water using a catalyst prepared from waste lithium batteries. The key steps include calcining the cathode material to obtain the catalyst; the calcination temperature is 850℃. However, high-temperature treatment has many drawbacks: (1) high energy consumption, which does not conform to the concept of green and low-carbon development; (2) it leads to the dissolution or phase transformation of active metals (such as Co and Ni), reducing catalytic activity; (3) it poses a challenge to the structural stability of porous supports (such as glass pumice), causing pore collapse or a decrease in specific surface area.

[0004] Therefore, developing a composite catalyst preparation method that does not require high-temperature calcination, is simple in process, and is environmentally friendly is of great significance for promoting the application of waste battery materials in the field of environmental governance. Summary of the Invention

[0005] One objective of this invention is to provide a method for preparing glass pumice-supported composite catalysts from spent lithium-ion battery materials without calcination, specifically comprising the following steps: (1) Pretreatment of waste cathode material: After the retired waste lithium battery is discharged and disassembled, the cathode material is crushed and screened to obtain cathode powder. Then the cathode powder is cleaned and dried to obtain recycled cathode material powder.

[0006] (2) Activation of glass pumice carrier: The glass pumice is soaked in acid solution (preferably soaked in 0.5mol / L nitric acid aqueous solution for 2h), then washed with water until neutral and dried to obtain activated glass pumice.

[0007] (3) Preparation of composite suspension: Disperse the recovered positive electrode material powder in a mixture of organic solvent (preferably anhydrous ethanol) and water, then add a dispersant and ultrasonically disperse (preferably ultrasonically for 30 minutes at an ultrasonic power of 200W) to obtain a suspension.

[0008] (4) Loading and drying: The activated glass pumice is added to the suspension and ultrasonically dispersed to obtain a loaded suspension. The loaded suspension is then subjected to gradient drying in an inert gas atmosphere (preferably nitrogen or argon) to obtain a solid substance.

[0009] (5) Product collection: The solid material is washed to obtain the composite catalyst.

[0010] Preferably, the cathode material in step (1) is composed of LiNi. 0.8 Co 0.1 Mn 0.1 O2, LiCoO2 or LiFePO4 or a combination of one or more of them; the crushed positive electrode material is sieved through a 200-mesh sieve, and the positive electrode material passing through the sieve through a 200-mesh sieve is collected to obtain positive electrode powder; the conditions for cleaning the positive electrode powder are: washing with deionized water and anhydrous ethanol 2 to 3 times each.

[0011] Preferably, in step (3), the organic solvent and water mixture is prepared in a volume ratio of (3~5):1; the amount of recovered positive electrode material powder added to the suspension is 5-50 g / L.

[0012] Preferably, the dispersant in the suspension in step (3) is polyvinylpyrrolidone (PVP) with a molecular weight of 40,000 to 60,000; the amount of dispersant added in the suspension is 0.05-1.2 g / L.

[0013] Preferably, the amount of glass pumice added to the loaded suspension in step (4) is 50-200 g / L; the ultrasonic dispersion conditions are: ultrasonic dispersion for 30-90 min at an ultrasonic power of 100-300 W.

[0014] Preferably, the gradient drying conditions in step (4) are: first drying at 60~80℃ for 2~4h, drying at 80~100℃ for 4~12h, and then heating to 100~150℃ for continuous drying for 6~24h.

[0015] The second objective of this invention is to provide a glass-pumice-supported composite catalyst for waste lithium battery materials prepared by the method of this invention.

[0016] The third objective of this invention is to provide an application of a glass pumice-supported waste lithium battery material composite catalyst prepared by the method of this invention in the degradation of organic pollutants (such as tetracycline) by activating PMS / H2O2 / O3.

[0017] Mechanism of the invention: This invention uses porous glass pumice as a carrier, utilizing the capillary force generated by its abundant pore structure to drive the penetration of a suspension of spent lithium-ion battery cathode material into the carrier. Simultaneously, the cathode material particles and the glass pumice surface interact through hydrogen bonds and physical adsorption interfaces, achieving effective anchoring. During the subsequent low-temperature drying process, solvent evaporation further strengthens the bond between the particles and the carrier, thus achieving a uniform and stable loading of the active components on the carrier under mild conditions. This synergistic strategy of "capillary transport-interface anchoring-drying and curing" is key to the excellent PMS activation performance and good cycle stability of the resulting composite catalyst.

[0018] The beneficial effects of this invention are: (1) No calcination and low energy consumption: This invention eliminates the high-temperature calcination step in the traditional preparation process and completes the catalyst preparation by drying in an atmosphere below 150°C. During the drying process, the capillary pressure generated by the slow evaporation of the solvent tightly fixes the positive electrode material particles to the glass pumice pore wall. At the same time, the surface hydroxyl groups form coordination bonds with metal ions to achieve chemical anchoring, which greatly reduces energy consumption and conforms to the concept of green manufacturing.

[0019] (2) Simple process and easy to scale up: The preparation process of this invention only involves routine operations such as cleaning, soaking, ultrasonication and drying. No special high-temperature equipment is required, the operation is safe and it is easy to achieve large-scale production.

[0020] (3) Protecting active components: Low-temperature drying avoids the dissolution of active metals, crystal phase transformation or destruction of carrier structure caused by high temperature, and effectively preserves the original crystal structure and multi-metal synergistic catalytic effect of the recycled material.

[0021] (4) Strong bonding and stable performance: The preparation method uses glass pumice as a catalyst support and utilizes the synergistic effect of capillary pressure and surface chemical adsorption to achieve uniform distribution and firm fixation of active components in the pores of the support. The catalyst prepared by the synergistic effect of low temperature drying has excellent PMS activation and tetracycline degradation performance. After being recycled 5 times, the removal rate of tetracycline is still above 85%.

[0022] (5) "Waste-to-waste" and economic and environmental protection: This invention realizes the synergistic resource utilization of complex waste lithium battery materials and industrial solid waste (glass pumice). The preparation cost is reduced by more than 50% compared with commercial cobalt-based catalysts, and it has significant economic and environmental benefits. Attached Figure Description

[0023] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0024] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0025] The glass pumice used in the embodiments and comparative examples of this invention is a commercially available industrial solid waste product with a pore size of 20~100μm.

[0026] Example 1 A method for preparing glass-light stone-supported composite catalysts from spent lithium-ion battery materials without calcination is described in the process flow diagram below. Figure 1 As shown, the specific steps include: (1) Pretreatment of waste cathode materials: The retired waste lithium battery NCM811 (composed of LiNi) is pretreated. 0.8 Co 0.1 Mn 0.1 After discharge and disassembly, the positive electrode material is crushed and sieved through a 200-mesh sieve. The positive electrode material passing through the 200-mesh sieve is collected to obtain positive electrode powder. The positive electrode powder is then washed three times each with deionized water and anhydrous ethanol, and then vacuum dried at 60°C for 12 hours to obtain recovered positive electrode material powder.

[0027] (2) Activation of glass pumice carrier: The glass pumice was soaked in 0.5 mol / L nitric acid aqueous solution for 2 h to remove surface impurities and increase the surface hydroxyl content. Then it was washed with deionized water until neutral and dried at 80 °C to remove moisture, thus obtaining activated glass pumice.

[0028] (3) Preparation of composite suspension: Disperse the recovered positive electrode material powder in a mixture of anhydrous ethanol and deionized water (the mixture is prepared in a volume ratio of anhydrous ethanol to water of 3:1), then add PVP with an average molecular weight of 40,000 and ultrasonically disperse at room temperature for 30 min with an ultrasonic power of 200W to obtain a suspension. The amount of recovered positive electrode material powder added to the suspension is 10 g / L, and the amount of PVP added to the suspension is 0.1 g / L.

[0029] (4) Loading and drying: The activated glass pumice was added to the suspension and ultrasonically dispersed at room temperature for 30 minutes with an ultrasonic power of 200W to allow the suspension to fully penetrate into the pores of the glass pumice, thus obtaining a loaded suspension (the amount of glass pumice added in the loaded suspension was 100g / L). The loaded suspension was transferred to a vacuum drying oven and then dried at 60℃ for 2 hours, 80℃ for 4 hours, and then heated to 100℃ for 8 hours under a nitrogen atmosphere to obtain a solid substance.

[0030] (5) Product collection: The surface floating material of the solid material is washed with deionized water to obtain the composite catalyst.

[0031] Example 2 A method for preparing glass pumice-supported composite catalysts from spent lithium-ion battery materials without calcination specifically includes the following steps: (1) Pretreatment of waste cathode materials: retired waste lithium batteries (composed of LiNi) 0.8 Co 0.1 Mn 0.1 O2 and LiCoO2 are mixed in a mass ratio of 1:1. After discharge and disassembly, the positive electrode material is crushed and sieved through a 200-mesh sieve. The positive electrode material passing through the 200-mesh sieve is collected to obtain positive electrode powder. The positive electrode powder is then washed twice with deionized water and twice with anhydrous ethanol, and then vacuum dried at 80℃ for 12 hours to obtain recovered positive electrode material powder.

[0032] (2) Activation of glass pumice carrier: The glass pumice was soaked in 0.5 mol / L nitric acid aqueous solution for 2 h to remove surface impurities and increase the surface hydroxyl content. Then it was washed with deionized water until neutral and dried at 120℃ to remove moisture, thus obtaining activated glass pumice.

[0033] (3) Preparation of composite suspension: Disperse the recovered positive electrode material powder in a mixture of anhydrous ethanol and deionized water (the mixture is prepared in a volume ratio of anhydrous ethanol to water of 5:1), then add PVP with an average molecular weight of 60,000 and ultrasonically disperse at room temperature for 30 min with an ultrasonic power of 200W to obtain a suspension. The amount of recovered positive electrode material powder added to the suspension is 5 g / L, and the amount of PVP added to the suspension is 0.05 g / L.

[0034] (4) Loading and drying: The activated glass pumice was added to the suspension and ultrasonically dispersed at room temperature for 90 minutes with an ultrasonic power of 100W to allow the suspension to fully penetrate into the pores of the glass pumice, thus obtaining a loaded suspension (the amount of glass pumice added in the loaded suspension was 50g / L). The loaded suspension was transferred to a vacuum drying oven and then dried at 70℃ for 4 hours, 90℃ for 12 hours, and then heated to 150℃ for 6 hours under an argon atmosphere to obtain a solid substance.

[0035] (5) Product collection: The surface floating material of the solid material is washed with deionized water to obtain the composite catalyst.

[0036] Example 3 A method for preparing glass pumice-supported composite catalysts from spent lithium-ion battery materials without calcination specifically includes the following steps: (1) Pretreatment of waste cathode material: After the retired waste lithium battery (composed of LiFePO4) is discharged and disassembled, the cathode material is crushed and screened through a 200-mesh sieve. The cathode material passing through the 200-mesh sieve is collected to obtain cathode powder. Then the cathode powder is washed three times each with deionized water and anhydrous ethanol and vacuum dried at 120℃ for 12h to obtain recycled cathode material powder.

[0037] (2) Activation of glass pumice carrier: The glass pumice was soaked in 0.5 mol / L nitric acid aqueous solution for 2 h to remove surface impurities and increase the surface hydroxyl content. Then it was washed with deionized water until neutral and dried at 60 °C to remove moisture, thus obtaining activated glass pumice.

[0038] (3) Preparation of composite suspension: The recovered positive electrode material powder is dispersed in a mixture of anhydrous ethanol and deionized water (the mixture is prepared in a volume ratio of anhydrous ethanol to water of 4:1). Then, PVP with an average molecular weight of 55,000 is added and ultrasonically dispersed at room temperature for 30 minutes with an ultrasonic power of 200W to obtain a suspension. The amount of recovered positive electrode material powder added to the suspension is 50 g / L, and the amount of PVP added to the suspension is 1.2 g / L.

[0039] (4) Loading and drying: The activated glass pumice was added to the suspension and ultrasonically dispersed at room temperature for 60 minutes with an ultrasonic power of 300W to allow the suspension to fully penetrate into the pores of the glass pumice, thus obtaining a loaded suspension (the amount of glass pumice added to the loaded suspension was 200g / L). The loaded suspension was transferred to a vacuum drying oven and then dried at 80℃ for 3 hours, 100℃ for 8 hours, and then heated to 120℃ for 24 hours under a nitrogen atmosphere to obtain a solid substance.

[0040] (5) Product collection: The surface floating material of the solid material is washed with deionized water to obtain the composite catalyst.

[0041] Comparative Example 1 This comparative example uses pumice as a blank control. The specific processing steps are as follows: Activation of glass pumice carrier: The glass pumice was soaked in 0.5 mol / L nitric acid aqueous solution for 2 h to remove surface impurities and increase the surface hydroxyl content. Then it was washed with deionized water until neutral and dried at 80 °C to obtain the treated glass pumice.

[0042] Comparative Example 2 A method for preparing a glass pumice-supported composite catalyst from spent lithium-ion battery materials specifically includes the following steps: (1) Pretreatment of waste cathode materials: The retired waste lithium battery NCM811 (composed of LiNi) is pretreated. 0.8 Co 0.1 Mn0.1 After discharge and disassembly, the positive electrode material is crushed and sieved through a 200-mesh sieve. The positive electrode material passing through the 200-mesh sieve is collected to obtain positive electrode powder. The positive electrode powder is then washed three times each with deionized water and anhydrous ethanol, and then vacuum dried at 60°C for 12 hours to obtain recovered positive electrode material powder.

[0043] (2) Activation of glass pumice carrier: The glass pumice was soaked in 0.5 mol / L nitric acid aqueous solution for 2 h to remove surface impurities and increase the surface hydroxyl content. Then it was washed with deionized water until neutral and dried at 80 °C to remove moisture, thus obtaining activated glass pumice.

[0044] (3) Preparation of composite suspension: Disperse the recovered positive electrode material powder in a mixture of anhydrous ethanol and deionized water (the mixture is prepared in a volume ratio of anhydrous ethanol to water of 3:1), then add PVP with an average molecular weight of 40,000 and ultrasonically disperse at room temperature for 30 min with an ultrasonic power of 200W to obtain a suspension. The amount of recovered positive electrode material powder added to the suspension is 10 g / L, and the amount of PVP added to the suspension is 0.1 g / L.

[0045] (4) Loading and drying: The activated glass pumice was added to the suspension and ultrasonically dispersed at room temperature for 30 minutes with an ultrasonic power of 200W to allow the suspension to fully penetrate into the pores of the glass pumice, thus obtaining a loaded suspension (the amount of glass pumice added to the loaded suspension was 100g / L). The loaded suspension was transferred to a vacuum drying oven and then calcined in a muffle furnace at 500℃ for 2 hours in air atmosphere to obtain a solid substance.

[0046] (5) Product collection: The surface floating material of the solid material is washed with deionized water to obtain the composite catalyst.

[0047] The application of the glass pumice-supported waste lithium battery material composite catalyst prepared in this invention in the activation of PMS and degradation of tetracycline specifically includes the following steps: 0.2g of the catalysts prepared in Examples 1-3 and Comparative Examples 1-2 of this invention were added to 100mL of a solution containing 20mg / L tetracycline. PMS was added to the tetracycline solution to form a tetracycline solution with a PMS concentration of 0.4mmol / L. The pH of the solution was adjusted to 7. After 60min, the removal effect of different catalysts on tetracycline was evaluated. The specific test method was as follows: high performance liquid chromatography (HPLC) was used for determination. The chromatographic conditions were as follows: C18 column (250mm×4.6mm×5μm), mobile phase acetonitrile:0.01M NaH2PO4 (pH=2.5)=35:65 (v / v), flow rate 1.0mL / min, detection wavelength 270nm, column temperature 30℃. The sample was filtered through a 0.22μm filter membrane before injection analysis. The removal rate of tetracycline was calculated by formula R%=[(C0-C t Calculate using ) / C0]×100%.

[0048] Tests showed that the composite catalyst prepared in Example 1 achieved a tetracycline removal rate of 90.8% after 60 minutes. A cyclic experiment was conducted, with the catalyst washed twice each with deionized water and anhydrous ethanol after each reaction, dried at 60°C for 6 hours, and then reused. After five consecutive uses, the removal rate remained at 85.3%, indicating that the catalyst, using pumice as a catalyst support, achieves uniform distribution and firm fixation of the active component within the support pores through the synergistic effect of capillary pressure and surface chemisorption. Furthermore, the synergistic effect of low-temperature drying further facilitates the preparation of a composite catalyst with excellent catalytic activity and stability.

[0049] Tests showed that the composite catalyst prepared in Example 2 achieved a tetracycline removal rate of 94.9% after 60 minutes. A cyclic experiment was conducted, with the catalyst washed twice each with deionized water and anhydrous ethanol after each reaction, dried at 60°C for 6 hours, and then reused. After five consecutive uses, the removal rate remained at 86.5%, indicating that the catalyst, using pumice as a catalyst support, achieves uniform distribution and firm fixation of the active component within the support pores through the synergistic effect of capillary pressure and surface chemisorption. Furthermore, the synergistic effect of low-temperature drying further facilitates the preparation of a composite catalyst with excellent catalytic activity and stability.

[0050] Tests showed that the composite catalyst prepared in Example 3 achieved a tetracycline removal rate of 96.8% after 60 minutes. A cyclic experiment was conducted, with the catalyst washed twice each with deionized water and anhydrous ethanol after each reaction, dried at 60°C for 6 hours, and then reused. After five consecutive uses, the removal rate remained at 88.3%, indicating that the catalyst, using pumice as a catalyst support, achieves uniform distribution and firm fixation of the active component within the support pores through the synergistic effect of capillary pressure and surface chemisorption. Furthermore, the synergistic effect of low-temperature drying further facilitates the preparation of a composite catalyst with excellent catalytic activity and stability.

[0051] The tests showed that the glass pumice support prepared in Comparative Example 1 achieved a tetracycline removal rate of 32.1% after 60 minutes. This glass pumice support exhibited no catalytic activity in the PMS system. Since no active component was added to Comparative Example 1, the removal of tetracycline was mainly attributed to the physical adsorption of pollutants by its porous structure, resulting in poor tetracycline removal efficiency.

[0052] Tests showed that the composite catalyst prepared in Comparative Example 2 achieved a tetracycline removal rate of 78.5% after 60 minutes. A cyclic experiment was conducted, where the catalyst was washed twice each with deionized water and anhydrous ethanol after each reaction, dried at 60°C for 6 hours, and then reused. After five consecutive uses, the removal rate dropped to 65.2%, indicating that high-temperature treatment leads to sintering of the active component supported by the glass pumice or destruction of the glass pumice support structure, thus reducing catalytic performance.

[0053] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or improvement of the technology in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing a composite catalyst of glassy trachyte supported waste old lithium battery material without calcination, characterized in that, Specifically comprising the following steps: (1) waste positive material pretreatment: after the retired waste lithium battery is discharged and disassembled, the positive material is crushed and sieved to obtain positive powder, and then the positive powder is washed and dried to obtain recycled positive material powder; (2) glass lightweight carrier activation: the glass lightweight is soaked with acid solution, then washed with water to neutral, and dried to obtain activated glass lightweight; (3) preparation of composite suspension: the recycled positive material powder is dispersed in a mixed solution of organic solvent and water, then a dispersing agent is added and ultrasonic dispersion is carried out to obtain a suspension; (4) loading and drying: the activated glass lightweight is added to the suspension and ultrasonic dispersion is carried out to obtain a loaded suspension, and the loaded suspension is gradient dried under inert gas atmosphere to obtain a solid material; (5) product collection: the solid material is washed to obtain a composite catalyst.

2. The method for preparing the composite catalyst of the glassy trachyte loaded waste and old lithium battery material without calcination according to claim 1, characterized in that, The composition of the cathode material in step (1) is LiNi 0.8 Co 0.1 Mn 0.1 O2, LiCoO2 or LiFePO4 or a combination of one or more thereof; the broken cathode material is sieved through a 200-mesh screen, the cathode material passing through the screen -200 mesh is collected to obtain a cathode powder; the cathode powder is cleaned by using deionized water and anhydrous ethanol for 2-3 times.

3. The method for preparing the composite catalyst of the glassy trachyte loaded waste and old lithium battery material without calcination according to claim 1, characterized in that, In step (3), the mixed solution of organic solvent and water is prepared in a ratio of (3-5):1 by volume; the addition amount of recycled positive material powder in the suspension is 5-50g / L.

4. The method for preparing the composite catalyst of the glassy trachyte loaded waste and old lithium battery material without calcination according to claim 1, characterized in that, In step (3), the dispersing agent in the suspension is polyvinylpyrrolidone with a molecular weight of 40000-60000; the addition amount of dispersing agent in the suspension is 0.05-1.2g / L.

5. The method for preparing glass pumice-supported waste lithium battery material composite catalyst without calcination according to claim 1, characterized in that, In step (4), the addition amount of glass lightweight in the loaded suspension is 50-200g / L; the ultrasonic dispersion conditions are: ultrasonic dispersion for 30-90min under ultrasonic power of 100-300W.

6. The method for preparing the composite catalyst of the calcined glass-ceramic and the waste lithium battery material according to claim 1, wherein, In step (4), the gradient drying conditions are: first drying at 60-80℃ for 2-4h, drying at 80-100℃ for 4-12h, and then increasing the temperature to 100-150℃ for continuous drying for 6-24h.

7. The glass lightweight loaded waste lithium battery material composite catalyst prepared by the method of any one of claims 1-6.

8. The application of the glass lightweight loaded waste lithium battery material composite catalyst prepared by the method of any one of claims 1-6 in the activation of PMS / H2O2 / O3 for degrading organic pollutants.

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