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KR-20260066973-A - CARBON COMPOSITE DOPED WITH SINGLE-ATOM-SIZED TRANSITION METALS AND NITROGEN, AND METHOD FOR PREPARING THE SAME

KR20260066973AKR 20260066973 AKR20260066973 AKR 20260066973AKR-20260066973-A

Abstract

One embodiment of the present invention provides a method for manufacturing a carbon composite doped with a single atomic-sized transition metal and nitrogen, comprising: (S10) mixing and drying a zinc (Zn) precursor, a transition metal precursor, a nitrogen precursor, a polymer precursor, and a solvent to produce an organic composite containing a zeolitic imidazolate framework (ZIF); (S20) performing a first heat treatment on the organic composite; (S30) performing an acid treatment after the first heat treatment; and (S40) performing a second heat treatment after the acid treatment to produce a carbon composite, wherein the transition metal is not zinc. The present invention provides a carbon composite doped with a single atomic-sized transition metal and nitrogen that can improve the performance of the oxygen reduction reaction at the anode.

Inventors

  • 김진수
  • 응우엔 쿠옥 하오
  • 임경민

Assignees

  • 경희대학교 산학협력단

Dates

Publication Date
20260512
Application Date
20241105

Claims (13)

  1. A method for manufacturing a single-atom-sized transition metal and nitrogen-doped carbon composite, (S10) A step of mixing and drying a zinc (Zn) precursor, a transition metal precursor, a nitrogen precursor, a polymer precursor, and a solvent to produce an organic composite containing ZIF; (S20) A step of performing a first heat treatment on the above organic composite; (S30) A step of acid treatment after the above first heat treatment; (S40) A step of manufacturing a carbon composite by performing a secondary heat treatment after the above acid treatment, and The above transition metal is not zinc, manufacturing method.
  2. In paragraph 1, A method for manufacturing a carbon composite, wherein the above transition metal is one or more selected from Ti, V, Cr, Fe, Co, Ni, Cu, Mn, Zr, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, and Hs.
  3. In paragraph 1, A method for manufacturing a carbon composite, wherein the above polymer is one or more selected from polyaniline, polypyrrole, polythiophene, PEDOT, polyacetylene, polyphenylenevinylene, polyfluorene, polysulfide, etc.
  4. In paragraph 1, The above nitrogen precursor is melamine, glucosamine, urea, thiourea, dicyandiamide, 2-cyanoguanidine, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEOA), diisopropanolamine, tetraethylenepentaamine (TEPA), triethylenetetraamine (TEA), pentaethylenehexaamine, ethylenediamine (ED), diethylenetriamine (DETA), piperazine (PZ), polyethyleneimine, A method for preparing a carbon complex comprising one or more selected from 3,5-diamino-1,2,4-triazol, adenine, 2-amino-1,4-benzenedicarboxylic acid, diisopropylamine, 3-amino-tetrazol, and dodecylamine.
  5. In paragraph 1, A method for manufacturing a carbon composite, wherein the solvent is one or more selected from deionized water, C1 to C6 lower alcohol-based solvents, C1 to C10 saturated aliphatic hydrocarbon-based solvents, and C6 to C20 aromatic hydrocarbon-based solvents.
  6. In paragraph 1, A method for manufacturing a carbon composite in which the above ZIF precursor is a combination of cobalt (Co), zinc (Zn), and an imidazole-based organic compound.
  7. In paragraph 1, A method for manufacturing a carbon composite, wherein steps (S20) and (S40) are performed at a temperature of 800 ℃ or higher and 1000 ℃ or lower.
  8. In paragraph 1, A method for manufacturing a carbon composite, wherein the steps (S20) and (S40) are performed for 1.5 hours or more and 2.5 hours or less.
  9. In paragraph 1, The above step (S30) is a method for manufacturing a carbon composite, wherein an acidic solution is further added to the organic composite to maintain the pH at 1 or higher and 3 or lower.
  10. In paragraph 1, A method for manufacturing a carbon composite, wherein the mixing weight ratio of the zinc precursor and the transition metal precursor is 1:3 to 1:4.
  11. In paragraph 1, A method for manufacturing a carbon composite, wherein the carbon composite is one selected from a catalyst for an oxygen reduction reaction, a catalyst for a hydrogen generation reaction, a catalyst for carbon dioxide reduction, and a catalyst for a fuel cell electrode.
  12. A carbon composite manufactured according to any one of claims 1 to 11.
  13. A catalyst for a fuel cell comprising a carbon composite according to paragraph 12.

Description

Carbon composite doped with single-atom-sized transition metals and nitrogen and method for preparing the same The present invention relates to a method for manufacturing a carbon composite doped with a single-atom-sized transition metal and nitrogen, and to a carbon composite manufactured thereby. To solve energy and environmental problems, it is necessary to develop efficient and durable energy systems. Fuel cells are emerging as the most promising next-generation energy systems due to their high power conversion efficiency, durability, eco-friendliness, and rapid recharging capabilities. Among fuel cells, proton exchange membrane fuel cells (PEMFCs) have the advantages of excellent power density and fast reaction rates, but their high manufacturing costs and low durability have acted as limitations to commercialization. Anion exchange membrane fuel cells (AEMFCs) have the advantage of enabling the use of inexpensive catalysts and various materials because they operate in an alkaline environment. Therefore, AEMFCs have been evaluated as superior to PEMFCs in terms of cost and efficiency. However, AEMFCs are characterized by being significantly affected by the Hydrogen Oxidation Reaction (HOR) at the cathode and the Oxygen Reduction Reaction (ORR) at the anode. While AEMFCs primarily utilize platinum group metals in their electrodes, they face limitations in terms of cost-effectiveness. Consequently, there is a growing need to develop more efficient and stable ORR catalysts by eliminating the use of platinum group metals or reducing their usage to improve both cost efficiency and performance. FIG. 1 is a schematic diagram showing a method for manufacturing a carbon composite (CoFe-NC-PPy) of the present invention. Figure 2 shows the XRD and Raman spectrum measurement results of ZnCoBZIF, Fe-ZnCoBZIF, and ZnCoBZIF-PPy-Fe. Figure 3 shows FE-SEM images of ZnCoBZIF, Fe-ZnCoBZIF, and ZnCoBZIF-PPy-Fe. Figure 4 shows the XRD, Raman spectra, nitrogen isotherm plot, XPS spectra, high-resolution N1s spectra, and nitrogen content ratio measurement results of CoFe-NC-PPy, CoFe-NC, and Co-NC. Figure 5 shows the FE-SEM, HR-TEM, HADDF-STEM, EDX mapping, and STEM measurement results of CoFe-NC-PPy. Figure 6 shows the XAS spectrum of CoFe-NC-PPy. Figure 7 shows the ORR activity of CoFe-NC-PPy. Figure 8 shows the AEMFC performance evaluation of CoFe-NC-PPy. Figure 9 shows the LSV curve of CoFe-NC-PPy according to heat treatment temperature. Hereinafter, each component of the present invention is described in more detail so that a person skilled in the art to which the present invention pertains can easily implement it; however, this is merely an example, and the scope of the rights of the present invention is not limited by the following. In this specification, the term "comprising" is used when listing materials, compositions, devices, and methods useful for the present invention, and is not limited to the examples listed. FIG. 1 is a schematic diagram illustrating a method for manufacturing a carbon composite of the present invention. Hereinafter, a method for manufacturing a carbon composite of the present invention will be described with reference to FIG. 1. One embodiment of the present invention provides a method for manufacturing a carbon composite doped with a single atomic-sized transition metal and nitrogen, comprising: (S10) mixing and drying a zinc (Zn) precursor, a transition metal precursor, a nitrogen precursor, a polymer precursor, and a solvent to produce an organic composite containing a zeolitic imidazolate framework (ZIF); (S20) performing a first heat treatment on the organic composite; (S30) performing an acid treatment after the first heat treatment; and (S40) performing a second heat treatment after the acid treatment to produce a carbon composite, wherein the transition metal is not zinc. According to one embodiment of the present invention, a method for preparing a single-atom-sized carbon composite doped with a transition metal and nitrogen comprises (S10) a step of mixing and drying a zinc precursor, a transition metal precursor, a nitrogen precursor, a polymer precursor, and a solvent to prepare an organic composite containing ZIF. The carbon composite according to this embodiment can be used as an M-N-C catalyst, and the M-N-C catalyst (metal-nitrogen-carbon, carbon doped with a transition metal and nitrogen) can replace a platinum-based catalyst. However, the high-temperature pyrolysis process for synthesizing the M-N-C catalyst is characterized by causing metal aggregation and significant loss of nitrogen, which causes a problem of reducing the density of active sites of the catalyst. Step (S10) above involves mixing and drying a zinc precursor, a transition metal precursor, a nitrogen precursor, a polymer precursor, and the solvent in the solvent to synthesize an organic composite containing ZIF. Specifically, Step (S10) can form an organic composite through the synthesis of a metal-organic