Topologically doped carbon material as well as preparation method and application thereof in electrochemistry
By combining halogen polymers with small organic molecules through low-temperature hydrothermal reaction and calcination, topologically doped carbon materials with specific doping configurations were prepared, solving the problem of unstable electrochemical performance of carbon materials and achieving efficient electrocatalysis and energy storage performance.
Patent Information
- Application Number
- CN202511042972.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-28
- Publication Date
- 2025-11-04
AI Technical Summary
Existing technologies struggle to accurately synthesize carbon materials with specific doping configurations, and the doping sites are prone to change under high-temperature conditions, leading to unstable electrochemical performance that is difficult to match with noble metal catalysts.
Topologically doped carbon materials are prepared by combining halogen polymers with organic small molecule dopants through low-temperature hydrothermal reaction and calcination. The spatial positions of heteroatoms are locked by low-temperature precursor covalent bonding, avoiding random evolution at high temperatures.
The prepared topologically doped carbon materials have well-defined and controllable active sites, exhibit excellent electrochemical performance, are suitable for various electrochemical systems, and are simple, safe, efficient, and inexpensive to operate.
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Figure CN120887408A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of new material synthesis, and particularly relates to a topological doped carbon material, a preparation method thereof and application thereof in electrochemistry. BACKGROUND
[0002] In recent years, the contradiction between supply and demand of traditional fossil energy is increasingly prominent, and it is difficult to meet the continuous demand of human production and life. Developing an environmentally friendly, efficient and safe new energy system has become an inevitable choice to alleviate energy crisis and protect the environment. Clean energy storage and conversion technologies based on electrochemistry, such as fuel cells and metal-air batteries, have the advantage of using environmentally friendly substances as reactants and products, and can realize the mutual conversion of chemical energy and electrical energy through electrochemical reactions at the cathode and anode, providing an effective way to obtain green renewable energy. However, current technologies mainly rely on noble metal-based catalyst materials such as Pt, Ru and Ir to achieve efficient catalytic conversion and utilization of energy, but the high price and limited reserves of noble metals greatly limit the large-scale commercial application of clean energy storage and conversion technologies. In contrast, carbon materials have broad application prospects in the field of electrochemical energy conversion and storage due to their wide availability, low cost, good electrical conductivity and controllable structure and morphology. However, pure carbon materials have strong surface chemical inertness and need to be modified to improve their electrochemical catalytic and energy storage performance. At present, the most common method for modifying carbon materials is to dope them with heteroatoms or form carbon defect sites by high-temperature pyrolysis of carbon precursors containing heteroatoms or mixing carbon sources / doping sources.
[0003] Despite numerous studies on carbon material modification, there are still many technical problems in practical application. On the one hand, heteroatoms (mainly including B, N, O, P, etc.) are active under high-temperature conditions and are prone to gasification and loss, making it extremely difficult to precisely synthesize carbon materials with specific doping configurations. On the other hand, high-temperature environments can also cause the evolution of high-activity configurations of doping sites to low-activity or inactive configurations, resulting in unstable electrochemical performance. Due to the above problems, the type, combination and configuration of doping elements are not clear for the promotion mechanism of clean energy storage and conversion technology, making it difficult for modified carbon materials to match the electrochemical performance of noble metal catalysts in fuel cells, metal-air batteries and other energy storage devices. Therefore, how to synthesize doped carbon materials with specific configurations and improve their electrochemically active sites has become a key technical problem to be solved. SUMMARY
[0004] The present application aims to provide a topological doped carbon material, a preparation method thereof and application thereof in electrochemistry, so as to solve the problems of difficulty in precisely synthesizing carbon materials with specific doping configurations and poor electrochemical performance of topological doped carbon materials in the prior art.
[0005] To achieve the above object, the present application provides the following technical solutions: a preparation method of topological doped carbon material, specifically comprising the following steps:
[0006] S1, dissolving halogen polymer in organic solvent to obtain halogen polymer solution;
[0007] S2, adding organic small molecule doping source and dehalogenating agent to the halogen polymer solution, then performing room temperature ball milling or low temperature hydrothermal reaction, drying after the reaction, washing the dried product with deionized water, then performing secondary drying, finally obtaining co-doped carbon precursor;
[0008] S3, calcining the co-doped carbon precursor in inert gas atmosphere to obtain calcined product, then washing the calcined product with dilute hydrochloric acid and deionized water, finally vacuum drying the calcined product to obtain topological doped carbon material.
[0009] Further, the halogen polymer in S1 is at least one of polyvinyl chloride, polyvinylidene chloride and polyvinylidene fluoride; the organic solvent in S1 is at least one of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
[0010] Further, the organic small molecule doping source in S2 is at least one of cyclopentane, furan, pyrrole, 3-dihydropyrrole, pyrrolidine, 1,3-dioxolane, pyrazole, 2-pyrazoline, pyrazolidine, imidazole, thiazole, 1,2,3-oxadiazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,4-thiadiazole, 4H-pyran, pyridine, piperidine, 1,4-dioxane, aromatic amine, boron-nitrogen six-ring, 9,10-boronazophenanthrene, sodium hypophosphite and pyrrole mixture, phenyl phosphorodiamide and diphenyl-2-pyrrole phosphine.
[0011] Further, the dehalogenating agent in S2 is at least one of potassium hydroxide, sodium hydroxide, calcium hydroxide, zinc hydroxide, aluminum hydroxide, ammonia hydroxide, sodium carbonate, potassium carbonate, sodium ethoxide, potassium ethoxide and tert-butyl potassium alcohol.
[0012] Further, the rotation speed of the room temperature ball milling reaction in S2 is set to 100-200 rpm, and the reaction time is set to 1-99 h; the temperature of the low temperature hydrothermal reaction in S2 is set to 20-200℃, and the reaction time is set to 1-99 h.
[0013] Further, the mass ratio of the organic small molecule doping source to the dehalogenating agent in S2 is 0.5-3:1.
[0014] Further, the inert gas in the S3 is at least one of helium, neon, argon, krypton and xenon; the sintering temperature in the S3 is set to 500-1100 DEG C, the heating rate is set to 3-10 DEG C / min, and the reaction time is set to 1-99h.
[0015] The application further discloses a topological doped carbon material prepared by the preparation method.
[0016] The application further discloses application of the topological doped carbon material in electrocatalytic oxygen reaction, aluminum / zinc-air battery and fuel cell.
[0017] The application further discloses application of the topological doped carbon material in supercapacitor.
[0018] Compared with the prior art, the topological doped carbon material, the preparation method and the application in electrochemistry have the following beneficial effects:
[0019] 1. The topological doped carbon material prepared by the application is prepared by selecting an organic small molecule with a specific configuration as a doping source, combining low-temperature hydrothermal reaction and sintering treatment, and has a specific doping configuration.
[0020] 2. The preparation method is suitable for various organic small molecules and halogen-containing polymers, has a wide application range, can adjust the types and proportions of the doping source and the carbon source according to actual needs, and can prepare topological doped carbon materials with different electrochemical properties to meet the application needs of different electrochemical systems.
[0021] 3. The preparation method of the topological doped carbon material is simple and safe, does not need metal catalysts or acid washing post-treatment, is green and efficient, has low cost, and is suitable for industrial scale production. DETAILED DESCRIPTION
[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed in the embodiments will be briefly introduced. Obviously, the drawings in the following description are only some embodiments described in the present application, and other drawings can also be obtained by those skilled in the art according to these drawings.
[0023] Figure 1 The synthesis schematic diagrams of N / P-C, N-P-C and N-C-P provided by the first to third embodiments of the present application are shown in the following figures.
[0024] Figure 2A scanning electron microscope image of N / P-C provided for the first embodiment of the present application;
[0025] Figure 3 A scanning electron microscope image of N-P-C provided for the second embodiment of the present application;
[0026] Figure 4 A scanning electron microscope image of N-C-P provided for the third embodiment of the present application;
[0027] Figure 5 X-ray diffraction patterns of N / P-C, N-P-C and N-C-P provided for the first to third embodiments of the present application;
[0028] Figure 6 Polarization curve diagrams of N / P-C, N-P-C and N-C-P provided for the first to third embodiments of the present application;
[0029] Figure 7 A volt-ampere characteristic curve and a power density diagram of a Zn-air battery assembled by N-C-P provided by the present application. DETAILED DESCRIPTION
[0030] In order for those skilled in the art to better understand the technical solutions of the present application, the present application will be further described in detail below in conjunction with the accompanying drawings.
[0031] Embodiment one:
[0032] Please refer to Figure 1 , Figure 2 and Figure 5 , a preparation method of a topological doped carbon material, specifically comprising the following steps:
[0033] S1, dissolving a halogen polymer in an organic solvent to obtain a halogen polymer solution; the halogen polymer in S1 is at least one of polyvinyl chloride, polyvinylidene chloride and polyvinylidene fluoride; the organic solvent in S1 is at least one of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
[0034] The specific implementation is to add 2.00g of polyvinylidene chloride (PVDC) into 30mL of N,N-dimethylformamide solution to obtain a mixed solution, then heat and stir the above mixed solution until it is completely dissolved to obtain a polyvinylidene chloride solution.
[0035] S2, adding an organic small molecule doping source and a dehalogenating agent to the halogen polymer solution, then performing room temperature ball milling or low temperature hydrothermal reaction, drying after the reaction, then washing the dried product with deionized water, drying again, and finally obtaining a co-doped carbon precursor; the organic small molecule doping source is at least one of cyclopentane, furan, pyrrole, 3-dihydro-pyrrole, pyrrolidine, 1,3-dioxolane, pyrazole, 2-pyrazoline, pyrazolidine, imidazole, thiazole, 1,2,3-oxadiazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,4-thiadiazole, 4H-pyrane, pyridine, piperidine, 1,4-dioxane, aromatic amine, boron-nitrogen hexacyclic ring, 9,10-boron-azaphenanthrene, sodium hypophosphite and pyrrole mixture, phenyl phosphorodiamidate, and diphenyl-2-pyrrole phosphine; the dehalogenating agent is at least one of potassium hydroxide, sodium hydroxide, calcium hydroxide, zinc hydroxide, aluminum hydroxide, ammonia hydroxide, sodium carbonate, potassium carbonate, sodium ethoxide, potassium ethoxide, and tert-butyl potassium alcohol; the rotation speed of the room temperature ball milling reaction is set to 100-200 rpm, and the reaction time is set to 1-99 h; the temperature of the low temperature hydrothermal reaction is set to 20-200℃, and the reaction time is set to 1-99 h; and the mass ratio of the organic small molecule doping source to the dehalogenating agent is 0.5-3:1.
[0036] In a specific embodiment, the above polyvinylidene chloride solution is added to a ball milling tank, 2.03 g of sodium hypophosphite and pyrrole mixture and 3.00 g of potassium hydroxide are then added, and the mixture is ground at a rotation speed of 150 rpm for 3 h at room temperature to form a red-brown slurry, which is then dried at 60℃ to obtain a dried product, the dried product is then repeatedly washed with deionized water, dried again, and finally a N, P co-doped carbon precursor RT-N / P-C is obtained.
[0037] S3, the co-doped carbon precursor is calcined in an inert gas atmosphere to obtain a calcined product, the calcined product is then washed with dilute hydrochloric acid and deionized water, and finally the calcined product is vacuum dried to obtain a topologically doped carbon material; the inert gas is at least one of helium, neon, argon, krypton, and xenon; in S3, the calcination temperature is set to 500-1100℃, the heating rate is set to 3-10℃ / min, and the reaction time is set to 1-99 h.
[0038] In a specific embodiment, the co-doped carbon precursor RT-N / P-C is placed in a tube furnace and calcined at 900℃ under an argon atmosphere for 2 h, with a heating rate of 3℃ / min, to obtain a calcined product, which is then washed with dilute hydrochloric acid and deionized water, and finally dried in a vacuum drying oven at 60℃ to obtain a topologically doped carbon material N / P-C. The synthesis schematic of N / P-C is shown in Figure 1 , the scanning electron microscope image of N / P-C is shown in Figure 2 , and the X-ray diffraction pattern is shown in Figure 5 .
[0039] Embodiment Two
[0040] Please refer to Figure 1 , Figure 3 and Figure 5 , this embodiment provides a technical solution on the basis of Embodiment One: a preparation method of topological doped carbon material, specifically comprising the following steps:
[0041] S1, 2.00g of polyvinylidene chloride (PVDC) is added to 25mL of N,N-dimethylformamide solution to obtain a mixed solution, and then the mixed solution is heated and stirred until it is completely dissolved to obtain a polyvinylidene chloride solution.
[0042] S2, the above polyvinylidene chloride solution is added to a ball mill tank, then 2.02g of phenyl phosphor diamide and 3.00g of potassium hydroxide are added, and then it is ground at a speed of 150rpm for 3h at room temperature to form a red-brown slurry, which is dried at low temperature to obtain a dry product, then the dry product is repeatedly washed with deionized water, and then dried again to obtain an N,P co-doped carbon precursor RT-N-P-C.
[0043] S3, the co-doped carbon precursor RT-N-P-C is placed in a tube furnace and calcined at 900℃ for 2h under an argon atmosphere, with a heating rate of 3℃ / min, to obtain a calcined product, then the calcined product is washed with dilute hydrochloric acid and deionized water, and finally the calcined product is dried in a vacuum drying oven at 60℃ to obtain a topological doped carbon material N-P-C. The synthesis schematic diagram of N-P-C is shown in Figure 1 , the scanning electron microscope image of N-P-C is shown in Figure 3 , and the X-ray diffraction pattern is shown in Figure 5 .
[0044] Embodiment Three
[0045] Please refer to Figures 1 to 5 , this embodiment provides a technical solution on the basis of Embodiment One: a preparation method of topological doped carbon material, specifically comprising the following steps:
[0046] S1, 2.00g of polyvinylidene chloride (PVDC) is added to 25mL of N,N-dimethylformamide solution to obtain a mixed solution, and then the mixed solution is heated and stirred until it is completely dissolved to obtain a polyvinylidene chloride solution.
[0047] S2, the polyvinylidene chloride solution is added into a ball mill tank, then 2.72 g of diphenyl-2-pyrrole phosphine and 3.00 g of potassium hydroxide are added, then the mixture is ground at room temperature at a speed of 150 rpm for 3 h to form a red-brown slurry, which is dried at low temperature to obtain a dry product, then the dry product is repeatedly washed with deionized water, and dried again to obtain a precursor of N, S co-doped carbon RT-N-C-P.
[0048] S3, the co-doped carbon precursor RT-N-C-P is placed in a tube furnace and calcined at 900℃ for 2 h under an argon atmosphere, with a heating rate of 3℃ / min, to obtain a calcined product, then the calcined product is washed with dilute hydrochloric acid and deionized water, and finally dried in a vacuum drying oven at 60℃ to obtain a topologically doped carbon material N-C-P, the synthesis schematic of N-C-P is shown in Figure 1 , the scanning electron microscope image of N-C-P is shown in Figure 4 , and the X-ray diffraction pattern is shown in Figure 5 .
[0049] As shown in Figures 2 to 4 , N / P-C is an indefinite block structure with a size of about 1-2 nm; N-P-C is an irregular cylindrical shape with a diameter of 4-5 nm; and N-C-P is a flocculent structure, indicating that the type of dopant can affect the morphology of the topologically doped carbon material.
[0050] As shown in Figure 5 , the XRD patterns of the topologically doped carbon materials N / P-C, N-P-C and N-C-P all show a broad diffraction peak at 23° near 2θ, corresponding to the standard graphite (002) lattice diffraction peak. In addition, N-C-P has a graphite (001) lattice diffraction peak near 43°.
[0051] Example Four
[0052] Please refer to Figure 6 , the present embodiment provides applications of the topologically doped carbon material in electrocatalytic oxygen reaction and fuel cell, and evaluates the electrocatalytic oxygen reduction catalytic performance of the topologically doped carbon material fuel cell, which specifically includes:
[0053] 5 mg of topologically doped carbon materials N / PC, NPC, and NCP, and 20 μL of perfluorosulfonic acid polymer solution (Nafion) were placed in different containers, and 980 μL of anhydrous ethanol was added to each. The mixtures were then sonicated to form homogeneous suspensions for 10–60 min. 20 μL of each suspension was dropped onto a glassy carbon electrode, and after the ethanol evaporated, a dense electrode film was formed. The three-electrode system assembled from the electrode films formed by the topologically doped carbon materials N / PC, NPC, and NCP was tested using an oxygen-saturated 0.1 mol·L⁻¹ electrolyte. -1 KOH or 0.1 mol·L -1 The test used an HClO4 solution, with a platinum electrode as the counter electrode and a saturated calomel electrode or a silver / silver chloride electrode as the reference electrode. Oxygen was continuously introduced at a rate of 0.1 mol·L⁻¹ throughout the test. -1 In KOH solution. Polarization curves of topologically doped carbon materials N / PC, NPC, and NCP are attached. Figure 6 .
[0054] As shown in the figure, the initial potential of the NCP sample is 0.965V (vs RHE), the half-wave potential is 0.842V (vs RHE), and the limiting current is 4.80mA cm⁻¹. -2 It outperforms N / PC and NPC samples.
[0055] Example 5:
[0056] Please see Figure 7 This embodiment provides the application of topologically doped carbon material NCP in aluminum-air batteries, and its performance testing and evaluation specifically includes:
[0057] A zinc-air battery mainly consists of an anode, a cathode, and an electrolyte. The anode of a zinc-air battery is zinc; the electrolyte consists of 6 mol / L... -1 It is prepared from KOH solution; the cathode is a catalyst layer.
[0058] Method for fabricating the cathode catalyst layer: First, align the hydrophobic carbon paper with the vent hole on the air electrode side of the mold, and mark it 1cm apart. 2 The reaction area serves as the catalyst; then 100 μL of the NCP suspension prepared in Example 4 is uniformly drop-coated onto the reaction area of the air electrode; finally, the cut waterproof and breathable layer is attached to the other side of the hydrophobic carbon paper to obtain the catalyst layer / diffusion layer.
[0059] Battery Assembly: The assembly mold for the zinc-air battery is made of acrylic material. The steps are as follows: First, insert air electrodes and zinc plates on both sides of the mold. Then, drip electrolyte into the mold through the central vent. Finally, assemble the zinc-air battery in the order of zinc plate, electrolyte, and catalyst / diffusion layer.
[0060] The performance of the zinc-air battery was tested at room temperature. The current-voltage characteristics and power density performance of the zinc-air battery using the topologically doped carbon material NCP synthesized in Example 3 are as follows: Figure 7 As shown, its power density is 139.9 mW / cm². -2 Superior to 115.3 mW cm⁻¹ of commercial platinum Pt / C -2 .
[0061] Example 6:
[0062] Please see Figure 7 This embodiment provides the application of topologically doped carbon materials in supercapacitors. In supercapacitors, the current-voltage characteristic curve can reflect the voltage change during the charging and discharging process. Ideally, the voltage of a supercapacitor should have a linear relationship with the change of charge (similar to the characteristics of a capacitor), but in practice, it may deviate from linearity due to factors such as internal resistance and polarization. Figure 7 The red curve (NCP material) in the diagram can be compared to the charge-discharge curve of a supercapacitor under specific conditions, showing how the voltage changes with the current density.
[0063] Power density is an important performance indicator of supercapacitors, representing the power output capacity per unit area or unit volume. Figure 7 The power density curve (right vertical axis) in the figure shows the trend of power density as current density increases. For supercapacitors, high power density means that they can quickly release or absorb a large amount of energy, making them suitable for applications that require instantaneous high power output.
[0064] The application of current-voltage characteristic curves and power density diagrams in air batteries provides strong evidence for a deeper understanding of the charge-discharge behavior, energy conversion efficiency, and applicability of supercapacitors.
[0065] The foregoing has only described certain exemplary embodiments of the present invention by way of illustration. Undoubtedly, those skilled in the art can modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the foregoing drawings and descriptions are illustrative in nature and should not be construed as limiting the scope of protection of the claims of the present invention.
Claims
1. A method for producing a topologically doped carbon material, characterized by, Specifically comprising the following steps: S1, dissolving halogen polymer in organic solvent to obtain halogen polymer solution; S2, adding organic small molecule doping source and dehalogenating agent to the halogen polymer solution, then carrying out room temperature ball milling or low temperature hydrothermal reaction, drying after the reaction, obtaining dry product, then washing the dry product with deionized water, carrying out secondary drying, finally obtaining co-doped carbon precursor; S3, calcining the co-doped carbon precursor in inert gas atmosphere to obtain calcined product, then washing the calcined product with dilute hydrochloric acid and deionized water, finally vacuum drying the calcined product to obtain topological doped carbon material.
2. The method for preparing a topologically doped carbon material according to claim 1, characterized in that, The halogen polymer in S1 is at least one of polyvinyl chloride, polyvinylidene chloride and polyvinylidene fluoride; the organic solvent in S1 is at least one of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
3. The method for preparing a topologically doped carbon material according to claim 1, characterized in that, The organic small molecule doping source in S2 is at least one of cyclopentane, furan, pyrrole, 3-dihydropyrrole, pyrrolidine, 1,3-dioxolane, pyrazole, 2-pyrazoline, pyrazolidine, imidazole, thiazole, 1,2,3-oxadiazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,4-thiadiazole, 4H-pyran, pyridine, piperidine, 1,4-dioxane, aromatic amine, borazine, 9,10-benzophenazine, sodium hypophosphite and pyrrole mixture, phenyl phosphorodiamidate and diphenyl-2-pyrrolophosphine.
4. The method for preparing a topologically doped carbon material according to claim 1, characterized in that, The dehalogenating agent in S2 is at least one of potassium hydroxide, sodium hydroxide, calcium hydroxide, zinc hydroxide, aluminum hydroxide, ammonia hydroxide, sodium carbonate, potassium carbonate, sodium ethoxide, potassium ethoxide and tert-butyl potassium alcohol.
5. The method for preparing a topologically doped carbon material according to claim 1, characterized in that, The rotation speed of the room temperature ball milling reaction in S2 is set to 100-200 rpm, and the reaction time is set to 1-99 h; the temperature of the low temperature hydrothermal reaction in S2 is set to 20-200℃, and the reaction time is set to 1-99 h.
6. The method for preparing a topologically doped carbon material according to claim 1, characterized in that, The mass ratio of the organic small molecule doping source to the dehalogenating agent in S2 is 0.5-3:
1.
7. The method for preparing a topologically doped carbon material according to claim 1, characterized in that, The inert gas in S3 is at least one of helium, neon, argon, krypton and xenon; the calcination temperature in S3 is set to 500-1100℃, the heating rate is set to 3-10℃ / min, and the reaction time is set to 1-99 h.
8. A topologically doped carbon material, characterized in that, It is suitable for the preparation method of the topological doped carbon material in any one of claims 1-7.
9. The application of the topological doped carbon material in claim 8 in electrocatalytic oxygen reaction, aluminum / zinc-air battery and fuel cell.
10. The application of the topological doped carbon material in claim 8 in supercapacitor.