Catalyst preparation method and catalyst recycling method for lithium battery recycling

Abstract

The application discloses a catalyst preparation method and a catalyst recycling method for lithium battery recycling, and relates to the technical field of lithium battery recycling. In the preparation aspect, MoS2 nano microspheres with high specific surface area and 1T / 2H phase interface are synthesized through a hydrothermal reaction of a sulfur source and a molybdenum source precursor, and the sulfur vacancies and interlayer defects of the MoS2 nano microspheres enhance metal ion adsorption and catalytic activity. In the use aspect, the catalyst in-situ loads cobalt oxide nanoparticles on the surface in the recycling process, forms a MoS2@CoxOᵧ composite structure, and the heterojunction interface electron transfer effect improves the conductivity and catalytic efficiency; after 20 cycles, the cobalt leaching rate is inversely increased by 15%, and the application realizes the effect of "the more you use, the stronger you become". Economic and environmental properties: the cycle life is more than 20 times, the single cost is reduced by 80%, the energy consumption is reduced by 35%-40%, organic acid leaching agent is combined with ultrasonic auxiliary technology, and strong acid pollution is avoided. The application solves the technical problems of the existing catalysts that cannot be repeatedly used and have poor cycle stability in lithium battery recycling.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lithium battery recycling, and particularly relates to a catalyst preparation method for lithium battery recycling and a catalyst recycling method for lithium battery recycling. BACKGROUND

[0002] Lithium batteries, as the core components of new energy vehicles, have seen a surge in market demand. However, the accumulation of a large number of waste lithium ion batteries not only occupies strategic resources such as cobalt and nickel, but also exacerbates environmental pollution. Existing lithium battery recycling technologies generally have problems such as high energy consumption, low recovery rate, and secondary pollution. In comparison, catalytic recycling technology has gradually become a research hotspot due to its efficiency and environmental protection. However, the existing catalytic system still faces two major bottlenecks: first, non-recyclability. Most catalysts are used only once and cannot be reused, resulting in a significant increase in processing costs. Second, insufficient stability. During the recycling process, the active sites of the catalysts are easily deactivated due to metal ion poisoning, structural collapse, or side reactions (such as hydrogen competitive adsorption).

[0003] Li et al. (Nature Energy, 2023, 8(10): 1137-1144) used SiO2 to contact electrocatalytic materials to treat LiCoO2 cathodes. The cobalt leaching rate decreased from 82% to 80% after five cycles, and decreased by nearly 20% in the fourth cycle compared to the first cycle. Huo et al. (Chemical Engineering Journal, 2022, 436) developed a graphene-doped molybdenum disulfide catalyst, which achieved a first degradation rate of 92.15% for tetracycline, but decreased to 87.15% after 5 cycles. Chinese invention patent CN117299172B discloses a carbon nitride / molybdenum disulfide heterojunction piezophotocatalyst, which achieved a first degradation rate of 99.8% for hexavalent chromium, but decreased to 94.9% after 6 cycles.

[0004] In summary, the existing catalyst system still has great room for improvement in terms of cycle stability and performance retention rate. How to develop a catalyst that can be used multiple times and has stable cycle catalytic performance has become a core research direction in lithium battery recycling technology. SUMMARY

[0005] The first purpose of the present application is to provide a catalyst preparation method for lithium battery recycling.

[0006] The second purpose of the present application is to provide a catalyst recycling method for lithium battery recycling, which solves the technical problems of non-reusable and poor cycle stability of existing catalysts in lithium battery recycling.

[0007] The first technical solution adopted by the present application is a catalyst preparation method for lithium battery recycling, which is implemented according to the following steps:

[0008] S1, mix the sulfur source precursor with the molybdenum source precursor, add a quantitative solvent, and stir to obtain a precursor solution;

[0009] S2, transfer the precursor solution obtained in S1 into the inner liner of a reaction kettle, and perform a hydrothermal reaction under specific conditions to obtain a synthesis product;

[0010] S3, sequentially perform centrifugation, cleaning, and drying on the synthesis product obtained in S2 to obtain a flower-shaped MoS2 nanomicrosphere catalyst.

[0011] The first technical solution of the application also has the following characteristics:

[0012] In S1, the mixing ratio of the sulfur source precursor to the molybdenum source precursor is 5-70:1; the solvent is deionized water, and the mass ratio is 4wt%-10wt%; the sulfur source precursor is thiourea, and the molybdenum source precursor is ammonium molybdate tetrahydrate; the stirring is performed by magnetic stirring, the stirring rate is 600r / min-1000r / min, and the stirring time is 30min-60min.

[0013] In S2, the specific conditions are as follows: the material of the inner liner of the reaction kettle is polytetrafluoroethylene, the hydrothermal reaction temperature is 180-240℃, and the hydrothermal reaction time is 18-24h.

[0014] In S3, the centrifugation rate is 6000r / min-8000r / min, and the centrifugation time is 5min-10min; the cleaning method is alternating cleaning with anhydrous ethanol and deionized water, and the cleaning times are 8-10 times; the drying temperature is 60℃-80℃, and the drying time is 12h-24h.

[0015] The second technical solution adopted by the application is a catalyst recycling method for lithium battery recycling, which uses the catalyst obtained by the above preparation method, and is implemented according to the following steps:

[0016] S1: weigh a quantitative amount of waste lithium battery material, sequentially add a quantitative amount of leaching agent and solvent, and stir to obtain a catalytic system solution;

[0017] S2: weigh a quantitative amount of catalyst, slowly add the catalytic system solution, and perform a catalytic leaching reaction under water bath ultrasonic conditions; periodically extract the catalytic system solvent, and measure the real-time leaching rate of Co 2+ ;

[0018] S3: perform centrifugation and drying on the reaction product obtained in S2 to obtain a flower-shaped MoS2 nanomicrosphere catalyst with cobalt oxide nanoparticles bound to the surface, i.e., a MoS2@Co x O y recycling catalyst.

[0019] S4: Re-dispensing the prepared catalyst system solution according to the formula of S1, slowly adding the MoS2@Co obtained in S3 in the re-dispensed catalyst system solution according to the formula of S2 x O y Circulating the catalyst, ending after 20 cycles, detecting the Co concentration in the catalyst system after each cycle 2+ Concentration, according to the concentration change, calculating the cycle recovery rate of the obtained catalyst.

[0020] The second technical solution of the present application is also characterized in that:

[0021] In S1, the waste lithium battery material is lithium cobaltate with a concentration of 0.03mol / L~0.07mol / L; the leaching agent is an organic acid with a concentration of 0.1mol / L~0.3mol / L; the solvent is deionized water; the stirring rate is 600r / min~1000r / min, and the stirring time is 30min~60min.

[0022] The organic acid is any one of citric acid, succinic acid and malic acid.

[0023] In S2, the catalyst is flower-shaped MoS2 nanospheres catalyst, the addition amount is 10mg~100mg; the ultrasonic frequency is 30KHz~120KHz; the water bath temperature is 60℃~90℃; the catalytic reaction time is 4h; the liquid chromatography method is used to detect the Co concentration change in the catalyst system solution, 6mL~8mL of the solution is extracted each time, the interval time is 1h, and the Co recovery rate is calculated according to the concentration change. 2+ 2+

[0024] In S3, the centrifugal rate is 6000r / min~8000r / min, the centrifugal time is 5min~10min; the drying temperature is 60℃~80℃, and the drying time is 12h~24h.

[0025] In S4, the cycle recovery rate calculation method is specifically: detecting the Co concentration in the catalyst system after each cycle, and calculating the cycle recovery rate of the obtained catalyst according to the concentration change. 2+

[0026] The beneficial effects of the present application are:

[0027] Firstly, the prepared flower-shaped MoS2 nanospheres catalyst has high specific surface area and rich active sites, not only enhances the contact efficiency of the catalyst and the reactants, but also provides stable active sites for the adsorption and catalytic conversion of metal ions through the interlayer defects and edge sulfur vacancies, and there is also a 1T / 2H phase interface, which can effectively hinder the recombination efficiency of electron-hole pairs, and compared with traditional MoS2 catalyst, it exhibits higher initial catalytic activity.

[0028] ​​​Secondly, the unique recycling mechanism makes the catalyst gradually load cobalt oxide nanoparticles (Co x O y ) on the surface during each recovery process, forming a MoS2@Co x O y composite structure. This in-situ generated heterojunction significantly improves the conductivity and redox ability of the catalyst through electron transfer effect. After 20 cycles, the leaching rate of cobalt ions is increased by about 15% compared with the first use, breaking through the bottleneck of the cycle performance degradation of traditional catalysts, and realizing the feature of "the more you use, the stronger you are".

[0029] From the economic point of view, the cycle life of the catalyst is extended to more than 20 times, the single use cost is reduced by 80% compared with the traditional disposable catalyst, and the overall energy consumption can be reduced by 35%~40% under mild reaction conditions. In addition, using organic acid as leaching agent combined with ultrasonic assisted catalysis technology, the problems of equipment corrosion and secondary pollution caused by traditional strong acid system are avoided, providing an innovative solution for efficient recovery of lithium battery metal resources. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a scanning image of the flower-shaped nanometer microsphere catalyst prepared in embodiment 2 of the present application;

[0031] Figure 2 is an EDS diagram of the flower-shaped nanometer microsphere prepared in embodiment 2 of the present application;

[0032] Figure 3 is an XRD image of embodiments 2~4 of the present application;

[0033] Figure 4 is a catalytic performance diagram of the catalyst cycle acid immersion impregnation of the present application. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0035] Embodiment 1

[0036] The catalyst preparation method for lithium battery recycling disclosed in the present application is implemented according to the following steps:

[0037] S1, thiourea and ammonium molybdate tetrahydrate are added into a beaker in a molar ratio of 5-70:1, 4wt%-10wt% of deionized water is added, then magnetic stirring is carried out at a rotating speed of 600r / min-1000r / min for 30min-60min, and a precursor solution is obtained;

[0038] S2, the precursor solution obtained in S1 is transferred into a reaction kettle liner, the material of the reaction kettle liner is polytetrafluoroethylene, hydrothermal reaction is carried out at a temperature of 180 DEG C-240 DEG C for 18h-24h, and a synthesis product is obtained;

[0039] S3, the synthesis product obtained in S2 is centrifuged at a rotating speed of 6000r / min-8000r / min, then washed with anhydrous ethanol and deionized water alternately for 8-10 times, and dried at a temperature of 60-80 DEG C for 12h-24h, and a flower-shaped MoS2 nanometer microsphere catalyst is obtained.

[0040] The application further discloses a catalyst recycling method for lithium battery recycling, and the catalyst is obtained by the preparation method.

[0041] S1: 0.03mol / L-0.07mol / L of lithium cobaltate is weighed, organic acid and deionized water are sequentially added, the organic acid is 0.1mol / L-0.3mol / L, stirring is carried out at a rotating speed of 600r / min-1000r / min for 30min-60min, and a catalyst system solution is obtained; wherein the organic acid is any one of citric acid, succinic acid and malic acid.

[0042] S2: 10mg-100mg of the flower-shaped MoS2 nanometer microsphere catalyst is slowly added into the catalyst system solution, a catalytic leaching reaction is carried out under water bath ultrasonic conditions for 4h; liquid chromatography is used to detect the Co 2+ concentration change in the catalyst system solution, the real-time leaching rate of Co 2+ is measured, 6mL-8mL of the detection solution is extracted each time, the interval time between extractions is 1h, and the Co 2+ recovery rate is calculated according to the concentration change.

[0043] S3: the reaction product obtained in S2 is centrifuged and dried, and a flower-shaped MoS2 nanometer microsphere catalyst combined with cobalt oxide nanoparticles on the surface, namely MoS2@Co x O yThe circulating catalyst is centrifuged at a rate of 6000 r / min to 8000 r / min for 5 min to 10 min, and dried at a temperature of 60℃ to 80℃ for 12 h to 24 h.

[0044] S4: Prepare the catalytic system solution by readjusting the formula in S1, and slowly add the MoS2@Co obtained in S3 to the newly prepared catalytic system solution according to the formula in S2. x O y The catalyst was recycled, and the cycle was completed after 20 cycles. The Co content in the catalytic system was measured after each cycle. 2+ The concentration is used to calculate the catalyst's recycling rate based on concentration changes. Specifically, the recycling rate is calculated by detecting the Co concentration in the catalytic system after each cycle. 2+ Concentration; based on the concentration change, the catalyst recycling rate is calculated.

[0045] Example 2

[0046] The method for preparing catalysts for lithium battery recycling is carried out according to the following steps:

[0047] 49 mmol of thiourea and 1 mmol of ammonium molybdate tetrahydrate were added to 45 mL of deionized water and magnetically stirred at 600 rpm for 30 min. After homogeneous dissolution, the mixture was transferred to a 100 mL polytetrafluoroethylene (PTFE) reactor liner and hydrothermally reacted at 200 °C for 24 h. After the reaction, the product was centrifuged at 8000 rpm for 5 min. The collected precipitate was washed 8 times alternately with anhydrous ethanol and deionized water, and dried at 60 °C for 24 h to obtain the product shown below. Figure 1 The flower-shaped MoS2 nanosphere catalyst shown is from Figure 1 As can be seen, the catalyst is composed of flower-like nanospheres assembled from nanosheets, possessing a high specific surface area. This allows for the exposure of more edge active reaction sites during the catalytic process, resulting in better catalytic performance. A schematic diagram of the flower-like nanosphere EDS is shown below. Figure 2 As shown, the molybdenum-sulfur atom ratio in the catalyst is close to 1:2, which is the conventional ratio of MoS2 atoms and represents a stable coordination structure.

[0048] A catalyst recycling method for lithium battery recycling is implemented according to the following steps: 0.2 g of lithium cobaltate and 1.5 g of citric acid are sequentially added to a 40 ml deionized water solution, and magnetic stirring is performed at a speed of 1000 / min for 30 min to obtain a catalytic system solution. 100 mg of flower-shaped MoS2 nanometer microsphere catalyst is added to the solution, and water bath ultrasonic treatment is performed at 70 DEG C and a frequency of 90 KHz for 4 h. Every 1 h, 7 ml of the solution is taken, and a liquid chromatograph is used to determine the Co2+ leaching rate. After the catalytic reaction is completed, the reaction product is centrifuged at a speed of 8000 r / min for 5 min, and the precipitate is dried at 60 DEG C for 24 h to obtain MoS2@Co x O y The recycled catalyst is used for the next cycle of catalytic reaction. After 20 cycles, the catalytic reaction is completed, and the Co 2+ concentration in the catalytic system after each cycle is detected. According to the concentration change, the recycling recovery rate of the catalyst is calculated, and the results are shown in Table 1 and Table 2. Figure 4

[0049] Example 3

[0050] A catalyst preparation method for lithium battery recycling is implemented according to the following steps: 70 mmol of thiourea and 1 mmol of ammonium molybdate tetrahydrate are added to 45 ml of deionized water, and magnetic stirring is performed at a speed of 1000 r / min for 60 min. After uniform dissolution, the solution is transferred to a polytetrafluoroethylene reaction kettle inner liner, and hydrothermal reaction is performed at 240 DEG C for 18 h. After the reaction is completed, the product is centrifuged at a speed of 7000 r / min for 8 min, and the collected precipitate is washed with anhydrous ethanol and deionized water alternately for 9 times, and dried at 80 DEG C for 12 h to obtain a flower-shaped MoS2 nanometer microsphere catalyst.

[0051] A catalyst recycling method for lithium battery recycling is implemented according to the following steps: 0.2 g of lithium cobaltate and 1.5 g of citric acid are sequentially added to a 40 ml deionized water solution, and magnetic stirring is performed at a speed of 1000 / min for 30 min to obtain a catalytic system solution. 100 mg of flower-shaped MoS2 nanometer microsphere catalyst is added to the solution, and water bath ultrasonic treatment is performed at 70 DEG C and a frequency of 90 KHz for 4 h. Every 1 h, 7 ml of the solution is taken, and a liquid chromatograph is used to determine the Co2+ leaching rate. After the catalytic reaction is completed, the reaction product is centrifuged at a speed of 8000 r / min for 5 min, and the precipitate is dried at 60 DEG C for 24 h to obtain MoS2@Co 2+ The recycled catalyst is used for the next cycle of catalytic reaction. After 20 cycles, the catalytic reaction is completed, and the Co x O y The recycled catalyst is used for the next cycle of catalytic reaction. After 20 cycles, the catalytic reaction is completed, and the Co 2+ concentration in the catalytic system after each cycle is detected. According to the concentration change, the recycling recovery rate of the catalyst is calculated, and the results are shown in Table 1 and Table 2.​

[0052] Example 4

[0053] The catalyst preparation method for lithium battery recycling is implemented according to the following steps: 35 mmol of thiourea and 1 mmol of ammonium molybdate tetrahydrate are added to 45 ml of deionized water, and magnetic stirring is performed at a speed of 1000 r / min for 60 min. After uniform dissolution, it is transferred to a polytetrafluoroethylene reaction kettle liner, and hydrothermal reaction is performed at 240°C for 18 h. After the reaction is completed, the product is centrifuged at a speed of 6000 r / min for 10 min, the collected precipitate is washed with anhydrous ethanol and deionized water alternately for 10 times, and dried at 70°C for 18 h to obtain a flower-shaped MoS2 nanomicrosphere catalyst.

[0054] The catalyst recycling method for lithium battery recycling is implemented according to the following steps: 0.25 g of lithium cobaltate and 2.5 g of citric acid are sequentially added to 50 ml of deionized water solution, and magnetic stirring is performed at a speed of 600 r / min for 60 min to obtain a catalyst system solution. 10 mg of flower-shaped MoS2 nanomicrosphere catalyst is added to the solution, and water bath ultrasonic is performed at 90°C and a frequency of 50 KHz for 4 h, 8 ml of solution is taken every 1 h, and Co 2+ leaching rate is determined by using a liquid chromatograph. After the catalytic reaction is completed, the reaction product is centrifuged at a speed of 6000 r / min for 10 min, and the precipitate is dried at 70°C for 18 h to obtain MoS2@Co x O y catalyst. Subsequently, a cycle catalytic reaction is performed, and after 20 cycles, the detection of Co 2+ concentration in the catalytic system after each cycle is performed, according to the concentration change, the cycle recovery rate of the catalyst is calculated, and the results are shown in Table 2.

[0055] As Figure 3 shown in the XRD image of the catalyst prepared in Examples 2-3, it can be seen that with the increase of thiourea content, the 1T phase peak intensity appears a trend of first increasing and then decreasing, which is due to the addition of excessive thiourea which accelerates the hydrolysis of amino group, thereby promoting the insertion of ammonium ion into the MoS2 interlayer to form a 1T / 2H coexisting mixed phase.

[0056] Example 5

[0057] A catalyst preparation method for lithium battery recycling is implemented according to the following steps: 21 mmol of thiourea and 1 mmol of ammonium molybdate tetrahydrate are added to 45 ml of deionized water, and magnetic stirring is performed at a speed of 900 r / min for 60 min. After uniform dissolution, the product is transferred to a 100 ml polytetrafluoroethylene reactor liner, and hydrothermal reaction is performed at 200°C for 24 h. After the reaction is completed, the product is centrifuged at a speed of 6500 r / min for 9 min, the collected precipitate is washed with anhydrous ethanol and deionized water alternately for 8 times, and drying is performed at 60°C for 24 h to obtain flower-shaped MoS2 nanomicrosphere catalyst.

[0058] A catalyst recycling method for lithium battery recycling is implemented according to the following steps: 0.2 g of lithium cobaltate and 1.5 g of succinic acid are sequentially added to 40 ml of deionized water solution, and magnetic stirring is performed at a speed of 700 / min for 50 min to obtain a catalytic system solution. 30 mg of flower-shaped MoS2 nanomicrosphere catalyst is added to the solution, and water bath ultrasonic treatment is performed at 60°C and a frequency of 70 KHz for 4 h. 7 ml of solution is taken at intervals of 1 h, and Co 2+ leaching rate is determined by using a liquid chromatograph. x O y recycling catalyst. Subsequently, a recycling catalytic reaction is performed, and the reaction is ended after 20 cycles. The Co 2+ concentration in the catalytic system after each cycle is detected, and the recycling recovery rate of the catalyst is calculated according to the concentration change. The results are shown in Table 2.

[0059] Example 6

[0060] A catalyst preparation method for lithium battery recycling is implemented according to the following steps: 21 mmol of thiourea and 1 mmol of ammonium molybdate tetrahydrate are added to 45 ml of deionized water, and magnetic stirring is performed at a speed of 900 r / min for 60 min. After uniform dissolution, the product is transferred to a 100 ml polytetrafluoroethylene reactor liner, and hydrothermal reaction is performed at 200°C for 24 h. After the reaction is completed, the product is centrifuged at a speed of 6500 r / min for 9 min, the collected precipitate is washed with anhydrous ethanol and deionized water alternately for 8 times, and drying is performed at 60°C for 24 h to obtain flower-shaped MoS2 nanomicrosphere catalyst.

[0061] A catalyst recycling method for lithium battery recycling is implemented according to the following steps: 0.2 g of lithium cobaltate and 1.5 g of malic acid are sequentially added to a 40 ml deionized water solution, and magnetic stirring is performed at a speed of 900 / min for 35 min to obtain a catalytic system solution. 70 mg of flower-shaped MoS2 nanosphere catalyst is added to the solution, and water bath ultrasonic treatment is performed at 90°C and a frequency of 120 KHz for 4 h. Every 1 h, 8 ml of the solution is taken and used to determine the Co 2+ leaching rate by using a liquid chromatograph. After the catalytic reaction is completed, the reaction product is centrifuged at a speed of 6500 r / min for 7 min, and the precipitate is dried at 60°C for 24 h to obtain MoS2@Co x O y catalyst. Subsequently, a cycle catalytic reaction is performed, and the cycle is ended after 20 times. The Co 2+ concentration in the catalytic system after each cycle is detected, and the recycling rate of the catalyst is calculated according to the concentration change. The results are shown in Table 2.

[0062] Table 1

[0063]

[0064] Table 1 reflects the Co 2+ leaching rate of the cycle acid leaching impregnation in Example 2.

[0065] Table 2

[0066]

[0067] Table 2 reflects the Co 2+ leaching rate of the cycle acid leaching impregnation in Examples 3-6.

[0068] Table 3

[0069]

[0070] Table 3 reflects the cycle performance comparison of the catalyst prepared in Example 2 and other catalysts.

[0071] Figure 4 is a catalytic performance diagram of the catalyst cycle acid leaching impregnation, from Figure 4 it can be seen that with the increase of the number of cycle impregnation, the catalytic efficiency is continuously increased until it shows a saturation trend, and the catalytic efficiency of the impregnated catalyst is increased by more than 10% compared with the first time. This is because in the catalytic process, metal ions are continuously impregnated on the surface of the catalyst, and MoS2@Co x O y composite structure is formed after drying. The in-situ generated heterojunction interface significantly improves the conductivity and redox ability of the catalyst through electron transfer effect. The control group is Co 2+The leaching rate of Co from the organic acid leaching of the catalyst can be seen to be significantly improved by the introduction of the catalyst. 2+ The efficiency of the organic acid leaching of Co

[0072] Finally, it should be noted that the terminology used herein, such as the relationship terms "first" and "second", are merely used to differentiate one entity or action from another entity or action, and do not necessarily require or imply any such actual relationship or order between the entities or actions. Also, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can also include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by an indefinite article "a" does not exclude the existence, of additional identical elements in the process, method, article, or apparatus comprising the element.

[0073] The various embodiments in the specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be mutually referred to.

[0074] The above description of the disclosed embodiments enables a person skilled in the art to implement or use the present application. Various modifications to the embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for catalyst recycling for lithium battery recycling, characterized in that, The following steps are implemented: S1: a quantitative amount of waste lithium battery material is weighed, a quantitative amount of leaching agent and solvent are sequentially added, and stirring is performed to obtain a catalyst system solution; wherein the waste lithium battery material is lithium cobaltate with a concentration of 0.03 mol / L to 0.07 mol / L; S2: weigh the quantitative catalyst, slowly add the catalyst system solution, and carry out the catalytic leaching reaction under the condition of water bath ultrasonic; periodically extract the catalyst system solvent, and measure the real-time leaching rate of Co 2+ The flower-shaped MoS2 nanomicrosphere catalyst is prepared by the following steps: S2.1: the sulfur source precursor is mixed with the molybdenum source precursor, a quantitative amount of solvent is added, and stirring is performed to obtain a precursor solution; S2.2: the precursor solution obtained in S2.1 is transferred to the inner liner of the reaction kettle, and hydrothermal reaction is performed under specific conditions to obtain a synthesis product; S2.3: the obtained synthesis product is sequentially subjected to centrifugation, washing, and drying to obtain flower-shaped MoS2 nanomicrosphere catalyst; S3: centrifuging and drying the reaction product obtained in S2 to obtain the flower-like MoS2 nanomicrosphere circulation catalyst with cobalt oxide nanoparticles bound on the surface, i.e. MoS2@Co x O y circulation catalyst; S4: Re-dispense the prepared catalyst system solution according to the formulation of S1, slowly add MoS2@Co obtained from S3 in the re-dispensed catalyst system solution according to the formulation of S2 x O y Circulating catalyst, end after 20 cycles, detect Co in the catalyst system after each cycle 2+ Concentration, according to the change of concentration, calculate the recycling rate of the obtained catalyst.

2. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, In S1, the leaching agent is an organic acid with a concentration of 0.1 mol / L to 0.3 mol / L; the solvent is deionized water; the stirring rate is 600 r / min to 1000 r / min, and the stirring time is 30 min to 60 min.

3. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, The organic acid is any one of citric acid, succinic acid, and malic acid.

4. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, In S2, the catalyst is flower-like MoS2 nanospheres catalyst, the addition amount is 10 mg-100 mg; the ultrasonic frequency is 30 KHz-120 KHz; the water bath temperature is 60 DEG C-90 DEG C; the catalytic reaction time is 4 h; the Co 2+ concentration change is detected every time, 6 mL-8 mL of the solution is extracted each time, the interval time is 1 h, the Co 2+ recovery rate is calculated according to the concentration change.

5. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, In S2.1, the molar ratio of the sulfur source precursor to the molybdenum source precursor is 5 to 70:1; the solvent is deionized water with a mass ratio of 4wt% to 10wt%; the sulfur source precursor is thiourea, and the molybdenum source precursor is ammonium molybdate tetrahydrate; magnetic stirring is used, the stirring rate is 600 r / min to 1000 r / min, and the stirring time is 30 min to 60 min.

6. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, In S2.2, the specific conditions are: the material of the inner liner of the reaction kettle is polytetrafluoroethylene, the hydrothermal reaction temperature is 180 to 240℃, and the hydrothermal reaction time is 18 to 24h.

7. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, In S2.3, the centrifugation rate is 6000 r / min to 8000 r / min, the centrifugation time is 5 min to 10 min; the washing method is alternating washing with anhydrous ethanol and deionized water, the washing frequency is 8 to 10 times; the drying temperature is 60℃ to 80℃, and the drying time is 12h to 24h.

8. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, In S3, the centrifugation rate is 6000 r / min to 8000 r / min, the centrifugation time is 5 min to 10 min; the drying temperature is 60℃ to 80℃, and the drying time is 12h to 24h.

9. The catalyst recycling method for lithium battery recycling according to claim 1, characterized in that, In S4, the cycle recovery rate calculation method is specifically: detecting the Co in the catalytic system after each cycle 2+ concentration, according to the concentration change, the cycle recovery rate of the catalyst is calculated.

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