A nitrogen- and sulfur-codoped carbon material, preparation method thereof and application thereof in a zinc-air battery

Abstract

The present invention belongs to the preparation of electrocatalysts in the field of zinc-air batteries, and specifically relates to an N and S co-doped carbon material, a preparation method and an application in a zinc-air battery. First, a metal macrocyclic compound is uniformly dispersed and deposited on the surface of a carbon material by adjusting the pH value of a solution, and then it is modified with a ligand containing N and S. At the same time, a zinc salt is used as a microporous pore former, and a porous N and S co-doped carbon material is prepared after high-temperature pyrolysis. This method in-situ assembles the metal macrocyclic compound on the surface of the carbon material, significantly improving the dispersion of metal active sites. By utilizing the synergistic effect between the N and S co-doped carbon and multiple active metal components (such as metal oxides, metal nitrides, and metal sulfides), the activity of the catalyst, such as the power density, is improved, and it can be used in zinc-air batteries.

Description

Technical Field

[0001] The present invention belongs to the preparation of electrocatalysts in the field of zinc-air batteries, and particularly relates to an N- and S-codoped carbon material, a preparation method thereof, and an application thereof in zinc-air batteries. Background Art

[0002] In order to replace fossil fuels and achieve sustainable green development of energy, fuel cells have become the focus of research. Fuel cells can convert chemical energy and electrical energy into each other and store them. In particular, zinc-air batteries use oxygen in the air or pure oxygen as the positive electrode material, metallic zinc as the negative electrode, and an alkaline electrolyte as the electrolyte. OH - migrates between the electrodes to form a closed circuit inside the battery, completing the battery charging / discharging process, and is an extremely clean new energy storage device. Zinc-air batteries have high energy density, wide sources, good safety, and low cost, and are an important technical direction for efficient conversion and storage of electrical energy. Therefore, they are highly favored by researchers.

[0003] In the zinc-air battery system, the catalyst is one of the key components of the battery. Preparing an efficient electrocatalyst is directly related to improving the performance of zinc-air batteries. Among them, improving the performance of the positive electrode catalyst material and improving the electrode structure to enhance the mass transfer ability are the primary ways to reduce electrochemical polarization and concentration polarization.

[0004] There is still a lack of highly efficient non-precious metal electrocatalysts in the prior art. Summary of the Invention

[0005] To make up for the deficiencies of the prior art, the present invention uses a method of adjusting the pH value to reprecipitate porphyrin and in-situ assemble it on the surface of the carbon material. After assembly, the metal active species of the material can be more evenly dispersed ( bond interaction is beneficial to the dispersion of metal macrocyclic compounds on the carbon material). And the addition of N- and S-containing / N, S-ligands can further anchor Zn. For high-temperature calcination at 900 °C, zinc can be sublimated, so that a rich microporous structure can be created on the carbon material.

[0006] The above object of the present invention is achieved by the following method:

[0007] A preparation method of an N- and S-codoped carbon material, comprising the following steps:

[0008] (a) At 0 - 60 °C, dissolve the metal macrocyclic compound in an acidic aqueous solution, mix it thoroughly with commercial carbon materials, and then adjust the pH value of the solution from 1 - 5 to 8 - 13 with an alkaline aqueous solution; or dissolve the metal macrocyclic compound in an alkaline aqueous solution, mix it thoroughly with commercial carbon materials, and then adjust the pH value of the solution from 8 - 13 to 1 - 5 with an acidic aqueous solution. Using the reprecipitation method, in-situ reprecipitate the dissolved metal macrocyclic compound on the surface of the carbon material, wash it with water until neutral, and then dry it to obtain solid sample 1;

[0009] (b) Grind the N-containing complex, S-containing complex, or N-containing complex, N,S-containing complex together with solid sample 1 and zinc salt; or mix and evaporate the N-containing complex, S-containing complex, or N-containing complex, N,S-containing complex with the zinc salt solution to modify the surface of solid sample 1, and then pyrolyze it under an inert atmosphere to obtain the final catalyst.

[0010] Furthermore, the central metal of the metal macrocyclic compound is one or a mixture of two or more of iron, cobalt, nickel, copper, and manganese. Among them, the macrocyclic compounds dissolved in acidic aqueous solutions are one or a mixture of two or more of aminophenyl porphyrin, pyridyl porphyrin, aminophenyl phthalocyanine, and pyridyl phthalocyanine; among them, the macrocyclic compounds dissolved in alkaline aqueous solutions are one or a mixture of two or more of carboxyphenyl porphyrin, hydroxyporphyrin, hemin, and protoporphyrin; the loading amount of the metal macrocyclic compound on the carbon material is 5 - 80 wt%.

[0011] Furthermore, the alkaline aqueous solution is one of NaOH, KOH, NaHCO3, KHCO3, Na2CO3, or K2CO3, and its concentration is 0.1 - 1000 mmol / L; the acidic aqueous solution is one of sulfuric acid, hydrochloric acid, nitric acid, and perchloric acid, and its concentration is 0.1 - 1000 mmol / L.

[0012] Furthermore, the N-containing ligand is one or a mixture of two or more of melamine, tetraaminobenzoquinone, bis(pyridyl)benzene, bis(4-pyridyl)anthracene, bipyridine, dipyridylamine, bisimidazolylbenzene, amino acids and their derivatives, aliphatic amines, and phenanthroline and its derivatives.

[0013] Furthermore, the S-containing ligand is one or a mixture of two or more of tetramercaptobenzene, hexamercaptobenzene, and hexamercaptobenzene trimer; the mass ratio of the N-containing ligand to the S-containing ligand is 1:10 - 10:1.

[0014] Furthermore, the N,S-containing ligand is one or a mixture of two or more of tetrakis(4-pyridyl)tetrathiafulvalene, methionine, cysteine, mercaptoethylamine, ethanedithiol, mercaptoethylamine, dithiooxamide, and pyridine-2-carboxylic acid amide; the mass ratio of the N-containing ligand to the N,S-containing ligand is 1:10 - 10:1.

[0015] Further, the zinc salt is one or a mixture of two or more of zinc chloride, zinc nitrate, zinc acetate, zinc diethyldithiocarbamate, and zinc perchlorate hexahydrate; the mass ratio of the zinc salt to the mass of the N-containing ligand is 1:10 to 10:1.

[0016] Further, the treatment conditions under an inert atmosphere are one of helium, argon, and nitrogen, the holding temperature is 300 - 500 °C at low temperature, the holding time is 0.5 - 8 h, then at high temperature of 900 - 1000 °C, the holding time is 0.5 - 8 h, and the heating rate is 1 - 10 °C / min.

[0017] Further, an aqueous solution of one of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and perchloric acid is used in the pickling, and its concentration is 0.05 - 5 moL / L.

[0018] The material prepared by the method for preparing the N and S co-doped carbon material can be used for assembling a zinc-air battery, efficiently catalyzing the oxygen reduction to occur in a four-electron reaction, and obtaining a higher power density and an open-circuit voltage close to the standard electromotive force (1.65 V) during the process of reducing oxygen to water.

[0019] Principle: In the present invention, the metal macrocyclic compound is first dissolved, so that the solution can be fully mixed with the carbon material. The metal macrocyclic compound is in-situ assembled on the surface of the carbon material by the reprecipitation method. At the same time, the N-containing and N / N,S-ligands are used for modification. During this process, Zn is added as a microporous pore former, and the ligand coordinates with zinc. During the pyrolysis process, zinc sublimes, and a large number of microporous structures appear in the carbon material, which can anchor more active species such as metal-N, and at the same time, is more conducive to the diffusion of O2. The active species in the pore structure are exposed and contact with the oxygen atmosphere, and an oxidation-reduction process occurs.

[0020] Compared with the existing technology, the present invention has the following advantages:

[0021] The self-assembly reprecipitation method improves the dispersibility and uniformity of the active species; while the N,S co-doping increases the active sites, the presence of a large number of micropores can increase the content of metal N x and metal S x content, improving the diffusion of oxygen and the transport of protons; at the same time, increasing the content of N and S, improving the synergistic effect of N-C and S-C, and further improving the oxygen reduction activity. The synthesis process of this preparation method is simple, highly operable, and conducive to the large-scale production of catalysts. Description of the Drawings

[0022] Figure 1 It is a transmission electron microscope image of the catalyst 3 obtained in Example 1 at 200 nm;

[0023] Figure 2It is the transmission electron microscopy image of catalyst 3 obtained in Example 1 at 50 nm;

[0024] Figure 3 It is the comparison chart of N2 adsorption - desorption curves of the catalysts obtained in Comparative Example 1, Comparative Example 2 and Example 1;

[0025] Figure 4 It is the power density curve of the zinc - air battery of the catalysts obtained in Comparative Example 2 and Example 1;

[0026] Figure 5 It is the structural formula of hemin;

[0027] Figure 6 It is the structural formula of iron(III) 5,10,15,20 - tetrakis(4 - aminophenyl)porphyrin;

[0028] Figure 7 It is the structural formula of nickel(II) (tetraaminophthalocyanine); Detailed implementation manners

[0029] To make the above - mentioned objects, features and advantages of the present invention more obvious and understandable, the following specifically describes the specific examples of the present invention with reference to the accompanying drawings. Unless otherwise specified, the experimental methods adopted in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can all be obtained from commercial channels.

[0030] Comparative Example 1: Preparation of catalyst 1

[0031] Dissolve hemin in 50 mL of 10 mM NaOH aqueous solution, add commercial carbon spheres, and the pH at this time is 10.1. Dropwise add 3M HCl aqueous solution to the system until the pH is about 0.2. At this time, hemin is in - situ precipitated on the carbon spheres. Then add 180 mg of melamine and an aqueous solution containing 175 mg of ZnCl2, mix well and stir at 80 °C until the solution completely evaporates, and dry overnight in an oven at 70 °C. Finally, heat the solid sample at 500 °C for 2 h, and then at 950 °C for 2 h. Mark the obtained final sample as catalyst 1. The power density is 55.2 mW cm -2 , which is significantly lower than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0032] Comparative Example 2: Preparation of catalyst 2

[0033] Hemin was dissolved in 50 mL of an aqueous NaOH solution with a concentration of 10 mM. Commercial carbon spheres were added, and the pH at this time was 10.1. An aqueous 3M HCl solution was added dropwise to the system until the pH was about 0.2. At this time, hemin was in-situ precipitated on the carbon spheres. Then, 30 mg of melamine and 150 mg of cysteine were added, and the mixture was thoroughly mixed and stirred at 80 °C until the solution completely evaporated, and then dried overnight in an oven at 70 °C. Finally, the solid sample was held at 500 °C for 2 h, and then held at 950 °C for 2 h. The final sample obtained was labeled as Catalyst 2. The power density was 36.2 mW cm -2 , significantly lower than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0034] Example 1: Preparation of Catalyst 3

[0035] Hemin was dissolved in 50 mL of an aqueous NaOH solution with a concentration of 10 mM. Commercial carbon spheres were added, and the pH at this time was 10.1. An aqueous 3M HCl solution was added dropwise to the system until the pH was about 0.2. At this time, hemin was in-situ precipitated on the carbon spheres. Then, 30 mg of melamine, 150 mg of cysteine and an aqueous solution containing 175 mg of ZnCl2 were added, and the mixture was thoroughly mixed and stirred at 80 °C until the solution completely evaporated, and then dried overnight in an oven at 70 °C. Finally, the solid sample was held at 500 °C for 2 h, and then held at 950 °C for 2 h. The final sample obtained was labeled as Catalyst 3.

[0036] Figure 1 It shows that: The transmission electron microscopy of Catalyst 3 obtained in Example 1 shows that metal particles are uniformly dispersed on the carbon material. The higher dispersion of the active species is more conducive to the effective exposure of the active sites to the three-phase reaction interface, and is more easily exposed to oxygen, electrons and protons, thus improving the reaction activity.

[0037] Figure 2 It shows that: The transmission electron microscopy of Catalyst 3 obtained in Example 1 shows that the obtained material has a hierarchical pore structure.

[0038] Figure 3 It shows that: The N2 adsorption-desorption curves of the catalysts obtained in Comparative Example 1, Comparative Example 2 and Example 1 show that when Zn is used as a microporous pore former, the specific surface areas of the catalysts obtained in Comparative Example 1 and Example 1 are both larger than that of the catalyst obtained in Comparative Example 2. The specific surface area of the catalyst obtained in Comparative Example 1 is 801.2 m 2 g -1 , the specific surface area of the catalyst obtained in Comparative Example 2 is 669.0 m 2 g -1 , and the specific surface area of the catalyst obtained in Example 1 is 951.5 m2 g -1 That is, when the ligand contains both N and S co-doping, it plays an anchoring coordination role for zinc, allowing more zinc to intercalate into the carbon material. After high-temperature pyrolysis, zinc sublimes, resulting in a large number of microporous structures. During this period, due to the loss of small-molecule functional groups and the release of gases such as CO2 and SO2 during the pyrolysis process, at the same time, the collapse and decomposition of ligand structures such as metal macrocyclic compounds during the pyrolysis process will also lead to the generation of certain pore structures in the carbon material. Therefore, the obtained material has a structure of micropores, mesopores, and macropores, and this structure can be clearly observed from the electron microscope Figure 1 and 2 and is clearly observable from the electron microscope

[0039] Figure 4 shows that the power density of the catalyst using Zn salt as a microporous pore-forming agent in Example 1 is significantly higher than that of the catalyst in Comparative Example 2 without using Zn salt as a microporous pore-forming agent. The main reason is that after pore formation by zinc, the diffusion and mass transfer of oxygen will be further improved, significantly enhancing the three-phase reaction interface effect and increasing the effective exposure of active species in the catalyst, thereby improving its activity. At the same time, the power of the catalyst provided by the present invention is significantly higher than the power density of commercial Pt / C, indicating that the catalyst obtained in this patent has the potential to replace commercial catalysts. In addition, the open-circuit voltage value of the catalyst obtained in Example 1 is 1.450V, which is closer to the standard value of 1.650V. The power density of the catalyst obtained in Example 1 is 121.9mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5mW cm -2 ), and significantly higher than the power density of 36.2mW cm of catalyst 2 without zinc as a pore-forming agent -2 .

[0040] Example 2: Preparation of Catalyst 4

[0041] Hemin was dissolved in 50 mL of an aqueous NaOH solution with a concentration of 10 mM, and commercial carbon spheres were added. At this time, the pH was 10.1. An aqueous solution of 3M HCl was added dropwise to the system until the pH was about 0.2. At this time, hemin was in-situ precipitated on the carbon spheres. Then, 30 mg of o-phenanthroline, 150 mg of mercaptoethylamine, and an aqueous solution containing 175 mg of ZnCl2 were added, mixed well, and stirred at 80°C until the solution completely evaporated, and then dried overnight in an oven at 70°C. Finally, the solid sample was kept at 500°C for 2 h, and then kept at 950°C for 2 h. The final sample obtained was labeled as Catalyst 4. The power density is 115.3mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5mW cm -2 ).

[0042] Example 3: Preparation of Catalyst 5

[0043] Hemin was dissolved in 50 mL of an aqueous KOH solution with a concentration of 10 mM. Commercial carbon spheres were added, and the pH at this time was 10.1. An aqueous 3M HCl solution was added dropwise to the system until the pH was about 0.2. At this time, hemin was in-situ precipitated on the carbon spheres. Then, 100 mg of o-phenanthroline, 80 mg of mercaptoethylamine, and 1 mL of an aqueous solution containing 243.1 mg of Zn(NO3)2 were added, mixed well, and stirred at 80 °C until the solution completely evaporated. It was dried overnight in an oven at 70 °C. Finally, the solid sample was maintained at 500 °C for 2 h, and then at 950 °C for 2 h. The final sample obtained was labeled as Catalyst 5. The power density was 110.1 mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0044] Example 4: Preparation of Catalyst 6

[0045] Hemin was dissolved in 50 mL of an aqueous KOH solution with a concentration of 10 mM. Commercial carbon spheres were added, and the pH at this time was 10.1. An aqueous 3M H2SO4 solution was added dropwise to the system until the pH was about 0.2. At this time, hemin was in-situ precipitated on the carbon spheres. Then, 100 mg of o-phenanthroline, 80 mg of dithiooxamide, and 1 mL of an aqueous solution containing 243.1 mg of Zn(NO3)2 were added, mixed well, and stirred at 80 °C until the solution completely evaporated. It was dried overnight in an oven at 70 °C. Finally, the solid sample was maintained at 500 °C for 2 h, and then at 950 °C for 2 h. The final sample obtained was labeled as Catalyst 6. The power density was 120.1 mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0046] Example 5: Preparation of Catalyst 7

[0047] Hemin was dissolved in 50 mL of an aqueous KOH solution with a concentration of 10 mM. Commercial carbon spheres were added, and the pH at this time was 10.1. An aqueous 3M H2SO4 solution was added dropwise to the system until the pH was about 0.2. At this time, hemin was in-situ precipitated on the carbon spheres. Then, 150 mg of o-phenanthroline, 30 mg of tetramercaptobenzene, and 1 mL of an aqueous solution containing 243.1 mg of Zn(NO3)2 were added, mixed well, and stirred at 80 °C until the solution completely evaporated. It was dried overnight in an oven at 70 °C. Finally, the solid sample was maintained at 500 °C for 2 h, and then at 950 °C for 2 h. The final sample obtained was labeled as Catalyst 7. The power density was 108.1 mWcm -2, significantly higher than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0048] Example 6: Preparation of Catalyst 8

[0049] Dissolve iron 5,10,15,20 - tetra(4 - aminophenyl)porphyrin in 50 mL of an aqueous HCl solution with a concentration of 10 mM. Add commercial carbon spheres, and the pH at this time is 1. Dropwise add 1 M aqueous NaOH solution to the system until the pH is around 10. At this time, iron 5,10,15,20 - tetra(4 - aminophenyl)porphyrin precipitates in situ on the carbon spheres. Then add 30 mg of melamine, 150 mg of cysteine, and 1 mL of an aqueous solution containing 243.1 mg of Zn(NO3)2. Mix well and stir at 80 °C until the solution completely evaporates. Dry overnight in an oven at 70 °C. Finally, heat the solid sample at 500 °C for 2 h, and then at 950 °C for 2 h. Label the obtained final sample as Catalyst 8.

[0050] The power density of Catalyst 8 obtained in Example 6 is 105.4 mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0051] Example 7: Preparation of Catalyst 9

[0052] Dissolve iron 5,10,15,20 - tetra(4 - aminophenyl)porphyrin in 50 mL of an aqueous HCl solution with a concentration of 10 mM. Add commercial carbon spheres, and the pH at this time is 1. Dropwise add 1 M aqueous NaOH solution to the system until the pH is around 10. At this time, iron 5,10,15,20 - tetra(4 - aminophenyl)porphyrin precipitates in situ on the carbon spheres. Then add 30 mg of ethylenediamine, 150 mg of cysteine, and 1 mL of an aqueous solution containing 243.1 mg of Zn(NO3)2. Mix well and stir at 80 °C until the solution completely evaporates. Dry overnight in an oven at 70 °C. Finally, heat the solid sample at 500 °C for 2 h, and then at 950 °C for 2 h. Label the obtained final sample as Catalyst 9.

[0053] Figure 6 is the structural formula of iron 5,10,15,20 - tetra(4 - aminophenyl)porphyrin.

[0054] The power density of Catalyst 9 obtained in Example 7 is 115.4 mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0055] Example 8: Preparation of Catalyst 10

[0056] Dissolve nickel(II) (tetraaminophthalocyanine) in 50 mL of an aqueous HCl solution with a concentration of 10 mM. Add commercial carbon spheres. At this time, the pH is 1. Dropwise add 1 M aqueous NaOH solution to the system until the pH is about 10. At this time, nickel(II) (tetraaminophthalocyanine) precipitates in situ on the carbon spheres. Then add 30 mg of triethylamine, 150 mg of cysteine, and an aqueous solution containing 175 mg of ZnCl2. Mix well and stir at 80 °C until the solution completely evaporates. Dry overnight in an oven at 70 °C. Finally, keep the solid sample at 500 °C for 2 h, and then keep it at 950 °C for 2 h. Mark the obtained final sample as Catalyst 10.

[0057] Figure 7 is the structural formula of nickel(II) (tetraaminophthalocyanine).

[0058] The power density of Catalyst 10 obtained in Example 8 is 100.4 mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0059] Example 9: Preparation of Catalyst 11

[0060] Dissolve cobalt (tetraaminophthalocyanine) in 50 mL of an aqueous HCl solution with a concentration of 10 mM. Add commercial carbon spheres. At this time, the pH is 1. Dropwise add 1 M aqueous NaOH solution to the system until the pH is about 10. At this time, nickel(II) (tetraaminophthalocyanine) precipitates in situ on the carbon spheres. Then add 30 mg of dipyridylamine, 150 mg of pyridine-2-carboxylic acid amide, and an aqueous solution containing 175 mg of ZnCl2. Mix well and stir at 80 °C until the solution completely evaporates. Dry overnight in an oven at 70 °C. Finally, keep the solid sample at 500 °C for 2 h, and then keep it at 950 °C for 2 h. Mark the obtained final sample as Catalyst 11.

[0061] The power density of Catalyst 11 obtained in Example 9 is 112.4 mW cm -2 . Significantly higher than the power density of commercial Pt / C (73.5 mW cm -2 ).

[0062] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A preparation method of N and S co-doped carbon materials, characterized in that: The following steps are involved: (a) dissolving a metal macrocyclic compound in an acidic aqueous solution at 0-60° C., thoroughly mixing the metal macrocyclic compound with a commercial carbon material, and then adjusting the pH of the solution from 1-5 to 8-13 with an alkaline aqueous solution; or dissolving the metal macrocyclic compound in an alkaline aqueous solution, thoroughly mixing the metal macrocyclic compound with a commercial carbon material, and then adjusting the pH of the solution from 8-13 to 1-5 with an acidic aqueous solution, reprecipitating the dissolved metal macrocyclic compound in situ on the surface of the carbon material, washing with water until the carbon material is neutral, and drying to obtain a solid sample 1; (b) grinding a N-containing complex, a S-containing complex, or a N-containing complex, a N,S-containing complex, a solid sample 1, and a zinc salt; or mixing a N-containing complex, a S-containing complex, or a N-containing complex, a N,S-containing complex, and a zinc salt solution, evaporating and modifying the surface of the solid sample 1, and then pyrolyzing the mixture under an inert atmosphere to obtain a final catalyst; The N-containing ligand is one or a mixture of two or more of melamine, tetraaminobenzoquinone, di(p-pyridyl)benzene, di(4-pyridyl)anthracene, bipyridine, dipyridylamine, diimidazolylbenzene, amino acids and their derivatives, fatty amines, o-phenanthroline and its derivatives; The N,S-containing ligand is one or a mixture of two or more of tetrakis(4-pyridyl)tetrathiafulvalene, methionine, cysteine, mercaptoethylamine, ethanedithiol, mercaptoethylamine, dithiooxalylamine, and pyridine-2-carboxysulfate; the mass ratio of the N-containing ligand to the N,S-containing ligand is 1:10 to 10:1; The treatment condition under inert atmosphere is one of helium, argon and nitrogen, the holding temperature is 300-500°C at low temperature, the holding time is 0.5-8h, and then pyrolysis is carried out at high temperature of 900-1000°C, the holding time is 0.5-8h, and the heating rate is 1-10°C / min.

2. The preparation method of the N and S co-doped carbon material according to claim 1, wherein: The central metal of the metal macrocyclic compound is one or a mixture of two or more of iron, cobalt, nickel, copper, and manganese; the macrocyclic compound soluble in acidic aqueous solution is one or a mixture of two or more of aminophenylporphyrin, pyridylporphyrin, aminophenylphthalocyanine, and pyridylphthalocyanine; the macrocyclic compound soluble in alkaline aqueous solution is one or a mixture of two or more of carboxyphenylporphyrin, hydroxyporphyrin, hemin, and protoporphyrin; and the loading amount of the metal macrocyclic compound on the carbon material is 5-80wt%.

3. The preparation method of the N and S co-doped carbon material according to claim 1, characterized in that: The alkaline aqueous solution is one of NaOH, KOH, NaHCO3, KHCO3, Na2CO3 or K2CO3, and its concentration is 0.1-1000mmol / L; the acidic aqueous solution is one of sulfuric acid, hydrochloric acid, nitric acid and perchloric acid, and its concentration is 0.1-1000mmol / L.

4. The preparation method of the N and S co-doped carbon material according to claim 1, characterized in that: The S-containing ligand is one or a mixture of two or more of tetramercaptobenzene, hexamercaptobenzene and hexamercaptotriphenylene; the mass ratio of the N-containing ligand to the S-containing ligand is 1:10 to 10:

1.

5. The preparation method of the N and S co-doped carbon material according to claim 1, wherein: The zinc salt is one or a mixture of two or more of zinc chloride, zinc nitrate, zinc acetate, zinc diethyldithiocarbamate, and zinc perchlorate hexahydrate; and the mass ratio of the zinc salt to the N-containing ligand is 1:10 to 10:

1.

6. The material prepared by the method for preparing the N and S co-doped carbon material according to claim 1, characterized in that: Used in the assembly of zinc-air batteries.

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