Method for preparing cross-scale lithium-air battery cathode material from waste lithium batteries

Abstract

Method for preparing cross-scale lithium-air battery cathode material from waste lithium batteries, which relates to the technical field of recycling of transition metals in lithium batteries. Step 1: Treat waste NiCoMn ternary lithium-ion batteries to obtain a impurity-removing solution rich in Ni, Co, and Mn ions. Step 2: After the impurity-removing solution, commercially available carbon materials, and Pt-group noble metal δ precursor are heated and stirred evenly, ultrafine NiCoMnδ quaternary alloy nanoparticles are formed on the surface of the carbon material matrix through Joule heating. Step 3: Calcinate the material obtained in Step 2 in argon / ammonia, and finally obtain a carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particle / NiCoMn ternary single-atom cross-scale catalyst through ammonia dealloying. The process of the present invention is simple, environmentally friendly, low-cost, has a high recycling rate of NiCoMn, and the recycled material has excellent electrochemical performance when used as the cathode material of a lithium-air battery, and is suitable for large-scale industrial amplification.

Description

Technical Field

[0001] The present invention belongs to the technical field of recycling of transition metals in lithium batteries, and particularly relates to a method for preparing a cathode material for a cross-scale lithium-air battery by using waste lithium batteries. Background Art

[0002] The development of new energy storage systems and new energy vehicles is of great significance for humans to achieve efficient utilization of green energy, alleviate the environmental pollution dilemma, and achieve the environmental goal of sustainable development. The industrialization and large-scale leapfrog development of large energy storage systems and new energy vehicles have led to a sharp increase in the demand for ternary lithium-ion batteries, which has greatly increased the consumption of valuable metals such as Ni, Co, and Mn required for preparing ternary cathode materials. However, the normal service life of ternary lithium-ion batteries is about 4 to 10 years, which will inevitably generate a large number of retired and waste lithium batteries. Retired ternary lithium batteries belong to social source solid wastes, bringing greater potential risks to environmental safety. At the same time, in ternary lithium-ion batteries, the proportion of the cathode material is relatively large, and the Ni, Co, and Mn metal resources used are relatively scarce. Therefore, efficiently recycling and reusing resources such as Ni, Co, and Mn in waste ternary cathode materials can not only better relieve the cost pressure and promote the healthy development of the ternary lithium-ion battery industry, but also avoid environmental pollution caused by waste ternary lithium batteries. Therefore, conducting research on the resource recycling technology of retired ternary lithium battery cathode materials to achieve "turning waste into treasure" is of great social significance and practical value.

[0003] As the key technologies for recycling waste ternary lithium batteries, including the leaching and impurity removal of Ni, Co, and Mn, several relatively common methods have emerged at present, such as hydrometallurgy, pyrometallurgy, direct regeneration, electrochemical recycling, etc. However, the technology of directly using the recycled valuable metals of Ni, Co, and Mn as cathode catalysts for lithium-air batteries has not been reported.

[0004] Among all secondary energy storage battery systems, lithium-air batteries stand out due to their much higher theoretical capacity than lithium-ion batteries. However, large charge-discharge polarization, low cycle life, and poor energy efficiency are the obstacles faced by the development of lithium-air batteries. Therefore, constructing an efficient catalytic cathode material to efficiently drive the redox reaction kinetics to fully reduce the charge-discharge overpotential and improve the cycle stability is an important idea to help lithium-air batteries achieve commercial applications. Therefore, it is of great practical significance to use the valuable metals of Ni, Co, and Mn recycled from waste ternary lithium batteries as precursors to prepare lithium-air battery catalysts and realize their value reconstruction in the field of lithium-air batteries. Summary of the Invention

[0005] In view of the gaps in the existing technologies, the present invention discloses a method for preparing a cathode material for a cross-scale lithium-air battery using waste lithium batteries. First, the waste batteries are disassembled to extract Ni, Co, and Mn precursors; subsequently, Pt-group noble metal δ is introduced, and NiCoMnδ ultrafine alloy particles are loaded on the surface of commercially available carbon materials through Joule heating technology. Finally, through ammonia-assisted dealloying technology, a cross-scale catalyst with defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single atoms loaded on the surface of commercially available carbon materials is prepared. This catalyst can exhibit excellent electrochemical performance when used as the cathode material for a lithium-air battery.

[0006] To achieve the above object, the technical solution of the present invention is as follows:

[0007] A method for preparing a cathode material for a cross-scale lithium-air battery using waste lithium batteries includes the following steps:

[0008] (1) Disassemble waste NiCoMn ternary lithium-ion batteries, soak them in N-N, dimethylpyrrolidone (i.e., NMP) solution and ultrasonicate for 18 - 24 h to obtain a leaching solution containing Li, Mn, Ni, and Co. After centrifuging and drying the leaching solution, use an acid solution as a leaching agent to remove Li, carbon black, and insoluble impurities in the leaching solution to obtain a purified solution rich in Ni, Co, and Mn ion precursors; + and carbon black and insoluble impurities to obtain a purified solution rich in Ni, Co, and Mn ion precursors;

[0009] (2) Uniformly disperse the purified solution in step 1, commercially available carbon materials, and Pt-group noble metal δ precursor salts in an aqueous solution, stir and evaporate to dryness under a water bath condition at 50 - 80°C, and continue to dry at 50 - 80°C for 7 - 12 h. The obtained powder is calcined at 1000°C - 2500°C using Joule heating to form a carbon matrix loaded with NiCoMnδ ultrafine quaternary alloy nanoparticle material;

[0010] (3) Calcinate the carbon matrix loaded with NiCoMnδ ultrafine quaternary alloy nanoparticle material at 700°C - 900°C in an argon-ammonia mixed atmosphere for 1 - 5 h. Use the argon-ammonia mixed gas to partially strip the NiCoMn atoms on the surface of the NiCoMnδ alloy nanoparticles, and the NiCoMnδ alloy nanoparticles present a defective state, while the stripped NiCoMn is deposited on the surrounding carbon matrix surface in the form of single atoms. Finally, a cross-scale catalyst with defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single atoms loaded on the commercially available carbon matrix is obtained.

[0011] Preferably, in step (1), the concentration of the NMP solution is 1 - 1.5 g / mL, and the concentration of the acid solution is 1 - 5 mol / mL.

[0012] Preferably, in step (1), the acid solution is oxalic acid or nitric acid solution.

[0013] Preferably, in the step (2), the carbon material is one of carbon black, carbon nanotubes, Super P, acetylene black or Ketjen black; the heating rate of Joule heating is 200 - 800 °C / s, the duration is 2 - 5 s, and the cooling rate is 200 - 800 °C / s.

[0014] Preferably, in the step (3), the ratio of argon-ammonia mixed gas is 90:10 or 85:15, and the flow rate is 5 - 15 mL / min.

[0015] Preferably, in the step (3), the heating rate of the calcination process is 2 - 10 °C / min.

[0016] Preferably, in the step (3), in the carbon matrix supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the molar ratio of Ni, Co, and Mn is 8:1:1 or 6:2:2 or 3:3:3 or 5:2:3, and the molar ratio of the sum of Ni, Co, and Mn to δ is 3:1.

[0017] Preferably, in the step (3), in the carbon matrix supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the average diameter of the NiCoMnδ ultrafine quaternary alloy nanoparticles is 3 - 20 nm, and the mass fraction of NiCoMnδ elements in the total mass is 5% - 30%.

[0018] Application of the method for preparing a cross-scale lithium-air battery cathode material using waste lithium batteries, applying the carbon matrix supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst to a lithium-air battery and using it as the cathode material of the lithium-air battery.

[0019] Preferably, the specific method of applying the carbon matrix supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst to a lithium-air battery and using it as the cathode material of the lithium-air battery is as follows:

[0020] The carbon matrix supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst powder, conductive carbon black, and polytetrafluoroethylene binder are uniformly dispersed in NMP solution according to a mass ratio of 7:2:1, and stirred evenly for 24 h to form a mixed slurry with appropriate viscosity; the slurry is uniformly coated on the surface of a stainless steel mesh current collector, and after vacuum drying at 80 °C, a positive electrode sheet loaded with the positive electrode material is obtained, and the loading amount of the active substance of each positive electrode sheet is 2.0 - 3.0 mg / cm 2; Assembling a 2032 button lithium-air battery: Using the obtained electrode sheet as the positive electrode, metallic lithium as the negative electrode, Celgard 3500 as the separator, and a solution of lithium perchlorate dissolved in tetraethylene glycol dimethyl ether as the electrolyte, with the concentration of the electrolyte being 1 - 2 mol / L.

[0021] The beneficial effects of the method for preparing a cross-scale lithium-air battery positive electrode material from waste lithium batteries in the present invention are as follows:

[0022] 1. The present invention uses Joule heating to effectively drive the disordered mixing of Pt-group noble metal atoms, Ni, Co, and Mn atoms to form a solid solution alloy. This not only avoids the agglomeration and growth of Pt-group noble metals, but also the disordered arrangement of Pt noble metal atoms with larger atomic radii and Ni, Co, and Mn atoms with smaller atomic radii causes significant lattice distortion. Moreover, the NiCoMnδ alloying effect leads to strong electron interactions, which is beneficial to optimizing the electronic structure of active metal sites. The above is beneficial to improving the catalytic kinetics of the composite material and the structural stability of the NiCoMnδ alloy.

[0023] 2. The carbon material surface-loaded NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst can achieve dual catalytic site regulation. The first active site is the defective NiCoMnδ quaternary ultrafine alloy particles. The partial peeling of NiCoMn on the surface helps to fully expose the highly catalytically active δ metal (δ is Pt or Pd or Ir or Ru or Rh) and effectively regulate the local coordination environment of the δ metal. The second active site is the NiCoMn ternary single atom. The two active sites with different scales can achieve a synergistic effect, which can fully reduce the redox reaction barrier of the lithium-air battery and improve the electrochemical performance.

[0024] 3. In the carbon material surface-loaded NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, both the NiCoMnδ quaternary ultrafine alloy particles and the NiCoMn ternary single atom are adsorbed on the surface of the carbon material, which can fully expose the active sites and is beneficial to improving the catalytic efficiency.

[0025] 4. The materials of the present invention have a wide range of sources, low cost, and simple processes, and are suitable for large-scale production.

[0026] Description of the Drawings

[0027] Figure 1 Scanning electron microscope image of the carbon nanotube-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst.

[0028] Figure 2 X-ray diffraction pattern of the carbon nanotube-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst.

[0029] Figure 3 、TEM image of carbon nanotube-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst.

[0030] Figure 4 、HAADF-STEM image of carbon nanotube-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst.

[0031] Figure 5 、First charge-discharge curve of carbon nanotube-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst. Detailed implementation manners

[0032] The following description is only for the preferred embodiments of the present invention, and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

[0033] Example 1

[0034] A method for preparing a cross-scale lithium-air battery cathode material using waste lithium batteries, as Figures 1-5 shown, includes the following steps:

[0035] (1) Disassemble the waste NiCoMn ternary lithium-ion battery, soak it in N-N, dimethylpyrrolidone (i.e., NMP solution) and ultrasonicate for 18 h to obtain a leaching solution containing Li, Mn, Ni, and Co. After centrifuging and drying the leaching solution, use an acid solution as the leaching agent to remove Li + , carbon black, and insoluble impurities from the leaching solution to obtain a purified solution rich in Ni, Co, and Mn ion precursors;

[0036] (2) Uniformly disperse the purified solution in step 1, commercially available carbon materials, and Pt group noble metal δ precursor salts in an aqueous solution, stir and evaporate to dryness under a water bath condition at 50 °C, and continue to dry at 50 °C for 7 h. The obtained powder is calcined at 1000 °C by Joule heating to form a carbon matrix-supported NiCoMnδ ultrafine quaternary alloy nanoparticle material;

[0037] (3) Calcinate the carbon matrix-supported NiCoMnδ ultrafine quaternary alloy nanoparticle material at 700 °C for 1 h in an argon-ammonia mixed atmosphere. Use the argon-ammonia mixed gas to strip the NiCoMn atoms on the surface of the NiCoMnδ alloy nanoparticles, so that the NiCoMnδ alloy nanoparticles present a defective state, and the stripped NiCoMn is deposited on the surface of the surrounding carbon matrix in the form of single atoms, finally obtaining a commercially available carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particle / NiCoMn ternary single-atom cross-scale catalyst.

[0038] Example 2

[0039] A method for preparing a cross-scale lithium-air battery cathode material using waste lithium batteries, as Figures 1-5 shown, includes the following steps:

[0040] (1) Disassemble the waste NiCoMn ternary lithium-ion battery, soak it in N-N, dimethylpyrrolidone (i.e., NMP) solution and ultrasonicate for 24 h to obtain a leaching solution containing Li, Mn, Ni, and Co. After centrifuging and drying the leaching solution, use an acid solution as the leaching agent to remove Li + , carbon black and insoluble impurities from the leaching solution to obtain a purified solution rich in Ni, Co, and Mn ion precursors;

[0041] (2) Uniformly disperse the purified solution in step 1, commercially available carbon material, and Pt-group noble metal δ precursor salt in an aqueous solution, stir and evaporate to dryness in a water bath at 80 °C, and continue to dry at 80 °C for 12 h. The obtained powder is calcined at 2500 °C by Joule heating to form a carbon matrix-supported NiCoMnδ ultrafine quaternary alloy nanoparticle material;

[0042] (3) Calcinate the carbon matrix-supported NiCoMnδ ultrafine quaternary alloy nanoparticle material at 900 °C for 5 h in an ammonia atmosphere. Use the argon-ammonia mixed gas to strip the NiCoMn atoms on the surface of the NiCoMnδ alloy nanoparticles, so that the NiCoMnδ alloy nanoparticles present a defective state, and the stripped NiCoMn is deposited on the surface of the surrounding carbon matrix in the form of single atoms, finally obtaining a commercially available carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particle / NiCoMn ternary single-atom cross-scale catalyst.

[0043] Example 3

[0044] Based on Examples 1 and 2, this example discloses:

[0045] In the step (1) described above, the concentration of the NMP solution is 1 g / mL, and the concentration of the acid solution is 1 mol / mL.

[0046] In the step (1) described above, the acid solution is oxalic acid or nitric acid solution.

[0047] Example 4

[0048] Based on Examples 1 and 2, this example discloses:

[0049] In the step (1), the concentration of the NMP solution is 1.5 g / mL, and the concentration of the acid solution is 5 mol / mL.

[0050] In the step (1), the acid solution is oxalic acid or nitric acid solution.

[0051] Example 5

[0052] Based on Examples 3 and 4, this example discloses:

[0053] In the step (2), the carbon material is one of carbon black, carbon nanotubes, Super P, acetylene black or Ketjen black; the heating rate of Joule heating is 200 °C / s, the duration is 5 s, and the cooling rate is 200 °C / s.

[0054] Example 6

[0055] Based on Example 5, this example discloses:

[0056] In the step (2), the heating rate of Joule heating is 800 °C / s, the duration is 2 s, and the cooling rate is 800 °C / s.

[0057] In the step (3), the argon / ammonia ratio is 90:10, and the flow rate is 5 mL / min.

[0058] In the step (3), the heating rate of the calcination process is 2 °C / min.

[0059] Example 7

[0060] Based on Example 5, this example discloses:

[0061] In the step (3), the argon / ammonia ratio is 85:15, and the flow rate is 15 mL / min.

[0062] In the step (3), the heating rate of the calcination process is 10 °C / min.

[0063] Example 8

[0064] Based on Examples 6 and 7, this example discloses:

[0065] In the step (3), the molar ratio of Ni, Co, and Mn in the carbon matrix supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst is 8:1:1, and the molar ratio of the sum of Ni, Co, and Mn to δ is 3:1.

[0066] Example 9

[0067] Based on Examples 6 and 7, this example discloses:

[0068] In step (3) described above, in the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the molar ratio of Ni, Co, and Mn is 6:2:2, and the molar ratio of the sum of Ni, Co, and Mn to δ is 3:1.

[0069] Example 10

[0070] Based on Examples 6 and 7, this example discloses:

[0071] In step (3) described above, in the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the molar ratio of Ni, Co, and Mn is 3:3:3, and the molar ratio of the sum of Ni, Co, and Mn to δ is 3:1.

[0072] Example 11

[0073] Based on Examples 6 and 7, this example discloses:

[0074] In step (3) described above, in the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the molar ratio of Ni, Co, and Mn is 5:2:3, and the molar ratio of the sum of Ni, Co, and Mn to δ is 3:1.

[0075] Example 12

[0076] Based on Examples 8 - 11, this example discloses:

[0077] In step (3) described above, in the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the average diameter of the NiCoMnδ ultrafine quaternary alloy nanoparticles is 3 nm, and the mass fraction of NiCoMnδ elements in the total mass is 5%.

[0078] Example 13

[0079] Based on Examples 8 - 11, this example discloses:

[0080] In step (3) described above, in the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the average diameter of the NiCoMnδ ultrafine quaternary alloy nanoparticles is 20 nm, and the mass fraction of NiCoMnδ elements in the total mass is 30%.

[0081] Example 14

[0082] Application of a method for preparing a cathode material for a cross-scale lithium-air battery using waste lithium batteries, applying a carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particle / NiCoMn ternary single-atom cross-scale catalyst to a lithium-air battery and using it as the cathode material of the lithium-air battery.

[0083] Example 15

[0084] Based on Example 14, this example discloses:

[0085] The specific method of applying the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particle / NiCoMn ternary single-atom cross-scale catalyst to a lithium-air battery and using it as the cathode material of the lithium-air battery is as follows:

[0086] Disperse the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particle / NiCoMn ternary single-atom cross-scale catalyst powder, conductive carbon black, and polytetrafluoroethylene binder in an NMP solution in a mass ratio of 7:2:1, and stir evenly for 24 h to form a mixed slurry with appropriate viscosity; evenly coat the slurry on the surface of a stainless steel mesh current collector, and obtain a cathode sheet loaded with the cathode material after vacuum drying at 80 °C. The loading amount of the active material of each cathode sheet is 2.0 mg / cm 2 ; Assemble a 2032 coin-type lithium-air battery: use the obtained cathode sheet as the cathode, use metallic lithium as the anode, Celgard 3500 as the separator, and a solution of lithium perchlorate dissolved in tetraethylene glycol dimethyl ether as the electrolyte, and the concentration of the electrolyte is 1 mol / L.

[0087] Example 16

[0088] Based on Example 14, this example discloses:

[0089] The specific method of applying the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particle / NiCoMn ternary single-atom cross-scale catalyst to a lithium-air battery and using it as the cathode material of the lithium-air battery is as follows:

[0090] Disperse the carbon matrix-supported defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst powder, conductive carbon black, and polytetrafluoroethylene binder in an NMP solution in a mass ratio of 7:2:1, and stir evenly for 24 h to form a mixed slurry with appropriate viscosity; evenly coat the slurry on the surface of a stainless steel mesh current collector, and obtain a positive electrode sheet loaded with the positive electrode material after vacuum drying at 80 °C. The loading amount of the active material on each positive electrode sheet is 3.0 mg / cm2; assemble a 2032 coin-type lithium-air battery: use the obtained electrode sheet as the positive electrode, metallic lithium as the negative electrode, Celgard 3500 as the separator, and a solution of lithium perchlorate dissolved in tetraethylene glycol dimethyl ether as the electrolyte, and the concentration of the electrolyte is 2 mol / L.

Claims

1. A method for preparing a cross-scale lithium-air battery positive electrode material using waste lithium batteries, characterized in that it comprises the following steps: (1) Dismantle the waste NiCoMn ternary lithium-ion battery, soak it in NN, dimethylpyrrolidone (NMP) solution and ultrasonically extract it for 18-24 hours to obtain a leachate containing Li, Mn, Ni and Co. After the leachate is centrifuged and dried, an acid solution is used as a leaching agent to remove Li from the leachate. + , carbon black and insoluble impurities to obtain a de-impurity solution rich in Ni, Co and Mn ion precursors; (2) The impurity removal liquid, commercially available carbon material, and Pt group noble metal δ precursor salt in step 1 are uniformly dispersed in an aqueous solution, stirred and evaporated to dryness in a water bath at 50-80°C, and then dried at 50-80°C for 7-12 hours. The obtained powder is calcined at 1000-2500°C by Joule heating to form a carbon matrix loaded NiCoMnδ ultrafine quaternary alloy nanoparticle material; wherein, δ is Ru or Rh or Pd or Ir or Pt; (3) The carbon matrix loaded NiCoMnδ ultrafine quaternary alloy nanoparticles are calcined at 700℃~900℃ for 1~5h in an argon-ammonia mixed atmosphere. The NiCoMn atoms on the surface of the NiCoMnδ alloy nanoparticles are partially stripped away by the argon-ammonia mixed gas. The NiCoMnδ alloy nanoparticles are in a defective state, and the stripped NiCoMn is deposited on the surface of the surrounding carbon matrix in the form of single atoms. Finally, a commercially available carbon matrix loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single atom cross-scale catalyst is obtained.

2. The method for preparing a cross-scale lithium-air battery positive electrode material using waste lithium batteries as claimed in claim 1, characterized in that: In the step (1), the concentration of the NMP solution is 1 to 1.5 g / mL, and the concentration of the acid solution is 1 to 5 mol / mL; the acid solution is a nitric acid solution.

3. The method for preparing a cross-scale lithium-air battery positive electrode material using waste lithium batteries as claimed in claim 2, characterized in that: In the step (2), the carbon material is one of carbon black, carbon nanotubes, Super P, acetylene black or Ketjen black; the heating rate of Joule heating is 200-800°C / s, the duration is 2-5s, and the cooling rate is 200-800°C / s.

4. The method for preparing a cross-scale lithium-air battery positive electrode material using waste lithium batteries as claimed in claim 3, characterized in that: In the step (3), the ratio of argon to ammonia is 90:10 or 85:15, and the flow rate is 5-15 mL / min.

5. The method for preparing a cross-scale lithium-air battery positive electrode material using waste lithium batteries as claimed in claim 4, characterized in that: In the step (3), the heating rate of the calcination process is 2-10°C / min.

6. The method for preparing a cross-scale lithium-air battery positive electrode material using waste lithium batteries as claimed in claim 5, characterized in that: In the step (3), the molar ratio of Ni, Co and Mn in the carbon matrix-loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst is 8:1:1 or 6:2:2 or 3:3:3 or 5:2:3, and the molar ratio of the sum of Ni, Co and Mn to δ is 3:

1.

7. The method for preparing a cross-scale lithium-air battery positive electrode material using waste lithium batteries as claimed in claim 6, characterized in that: In the step (3), in the carbon matrix-loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst, the average diameter of the NiCoMnδ ultrafine quaternary alloy nanoparticles is 3-20 nm, and the fraction of the NiCoMnδ element in the total mass is 5%-30%.

8. The use of the carbon matrix loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single atom cross-scale catalyst prepared by the method for preparing cross-scale lithium-air battery positive electrode materials using waste lithium batteries as claimed in claim 7, characterized in that: The carbon matrix loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single atom cross-scale catalyst is applied to lithium-air batteries and used as the positive electrode material of lithium-air batteries.

9. The use of the carbon matrix loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single atom cross-scale catalyst prepared by the method for preparing cross-scale lithium-air battery positive electrode materials using waste lithium batteries as claimed in claim 8, characterized in that: The specific method of applying the carbon matrix-loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single-atom cross-scale catalyst to lithium-air batteries and using it as a positive electrode material for lithium-air batteries is as follows: The carbon matrix loaded defective NiCoMnδ quaternary ultrafine alloy particles / NiCoMn ternary single atom cross-scale catalyst powder, conductive carbon black and polytetrafluoroethylene binder were uniformly dispersed in NMP solution at a mass ratio of 7:2:1, and stirred for 24 hours to form a mixed slurry with suitable viscosity; the slurry was uniformly coated on the surface of the stainless steel mesh collector, and vacuum dried at 80°C to obtain a pole piece loaded with positive electrode material, and the loading amount of active material of each positive pole piece was 2.0-3.0 mg / cm 2 ; Assemble 2032 button-type lithium-air batteries: use the obtained electrode as the positive electrode, metallic lithium as the negative electrode, Celgard 3500 as the separator, and a solution of lithium perchlorate dissolved in tetraethylene glycol dimethyl ether as the electrolyte, with the concentration of the electrolyte being 1-2 mol / L.

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