CN115472854A - Hollow porous carbon material, preparation method thereof and battery - Google Patents

Hollow porous carbon material, preparation method thereof and battery Download PDF

Info

Publication number
CN115472854A
CN115472854A CN202211060022.8A CN202211060022A CN115472854A CN 115472854 A CN115472854 A CN 115472854A CN 202211060022 A CN202211060022 A CN 202211060022A CN 115472854 A CN115472854 A CN 115472854A
Authority
CN
China
Prior art keywords
solution
carbon material
porous carbon
hollow porous
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211060022.8A
Other languages
Chinese (zh)
Inventor
李白滔
王英华
王秀军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202211060022.8A priority Critical patent/CN115472854A/en
Publication of CN115472854A publication Critical patent/CN115472854A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Chemistry (AREA)
  • Biochemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a hollow porous carbon material, which comprises the following steps: dissolving dimethyl imidazole in water to form a solution A; dissolving zinc nitrate and dopamine hydrochloride in water, uniformly stirring to form a solution B, and then adding the solution B into the solution A to form a solution C; after the solution C is stirred for reaction, performing centrifugal separation to obtain a catalyst precursor; and drying the catalyst precursor and then calcining at high temperature. The invention also discloses the hollow porous carbon material prepared by the preparation method and a battery using the hollow porous carbon material as a cathode. The hollow porous carbon material is synthesized in a water phase, the production process is relatively simple, the pollution is small, the mass production is easy to realize, the prepared hollow porous carbon material has good electrochemical performance when being used as an oxygen reduction electrocatalyst, and a zinc air battery or a microbial fuel cell which adopts the hollow porous carbon material as a cathode has high power density and excellent stability.

Description

Hollow porous carbon material, preparation method thereof and battery
Technical Field
The invention relates to the field of battery materials, in particular to a hollow porous carbon material, a preparation method thereof and a battery.
Background
Zinc air (zn air) batteries have received much attention because of their high energy density, simple manufacturing process, low cost, safety, reliability, environmental protection, and renewable availability. The zinc-air battery is a novel chemical power supply which takes oxygen in the air as an anode active substance and metal zinc as a cathode active substance. The microbial fuel cell is a device for directly converting chemical energy in organic matters into electric energy by taking electrogenesis microbes as an anode catalyst, and has wide application prospects in the fields of wastewater treatment and new energy development. The microbial fuel cell utilizes the metabolism of microbes to oxidize and decompose organic waste and generate electric energy, and the organic matter is oxidized at the anode to generate electrons and CO 2 Electrons are transferred to the cathode through an external circuit, and finally O 2 And the final electron acceptor is combined with protons diffused from the anode to react to generate water, thereby generating electric energy. The slow reaction rate of the Oxygen Reduction Reaction (ORR) kinetics of the cathode is a major factor that hinders the performance of zinc-air cell microbial fuel cells. Therefore, the development of a cathode catalyst having excellent ORR activity is of great significance to the development of zinc-air batteries and microbial fuel cells. The currently optimal ORR catalyst is still a platinum-based catalyst, but has the disadvantages of scarcity, high price, easy poisoning, poor methanol tolerance and the like. Therefore, the key to solve the problem is to design and develop a catalyst which is green, low in cost, high in activity, good in selectivity and high in stability. The metal-doped hollow carbon material has excellent catalytic activity, good selectivity and high stability and is widely concerned. The hollow carbon framework structure can generate more active sites and increase mass transfer capacity, thereby enhancing the ORR catalytic activity. The metal organic framework ZIF-8 serving as a precursor of a typical porous carbon material has the characteristics of good chemical stability, ultrahigh specific surface area, ultrahigh pore volume and the like. However, how to simply prepare a hollow porous carbon material with excellent performance so that the hollow porous carbon material can be better used as an ORR catalyst to be applied to zinc-air batteries and microbial fuels is still a difficulty of current research.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a hollow porous carbon material, which is synthesized in a water phase, has relatively simple production process, small pollution and easy mass production, and the prepared hollow porous carbon material has good electrochemical performance when being used as an oxygen reduction electrocatalyst.
The invention also aims to provide the hollow porous carbon material prepared by the preparation method.
It is still another object of the present invention to provide a battery having high power density and excellent stability.
The purpose of the invention is realized by the following technical scheme:
a method for producing a hollow porous carbon material, comprising the steps of:
dissolving dimethyl imidazole in water to form a solution A;
dissolving zinc nitrate and dopamine hydrochloride in water, uniformly stirring to form a solution B, and then adding the solution B into the solution A to form a solution C;
after the solution C is stirred for reaction, performing centrifugal separation to obtain a catalyst precursor;
and drying the catalyst precursor and then calcining at high temperature.
Preferably, the mass ratio of the dimethyl imidazole to the zinc nitrate to the dopamine hydrochloride is as follows: (3-13): (0.3-1.5): (0.1-0.3).
Preferably, the solution C is stirred to react, specifically: and adding metal salt after the solution C is stirred to react, and continuously stirring to react.
Preferably, the dosage ratio of the metal salt to the dopamine hydrochloride is (1-8 mmol): 1g.
Preferably, the metal salt is one or two of inorganic iron salt, inorganic cobalt salt and inorganic nickel salt.
More preferably, the metal salt is anhydrous ferric chloride, nickel nitrate hexahydrate or cobalt nitrate tetrahydrate.
Preferably, the concentration of the dimethyl imidazole in the solution A is (8-32) g/100mL; the concentration of the zinc nitrate in the solution B is (6-30) g/100mL.
Preferably, the zinc nitrate is zinc nitrate hexahydrate.
Preferably, the reaction time of the solution C is 0.5 to 2 hours.
Preferably, feCl is added 3 The post-reaction time is 12 to 36 hours.
Preferably, the drying specifically comprises: drying at 80-100 deg.c for 12-24 hr.
Preferably, the high-temperature calcination specifically comprises: calcining at 800-1000 deg.c for 2-4 hr.
A hollow porous carbon material is prepared by the preparation method of the hollow porous carbon material and has a hollow concave dodecahedron structure.
A battery comprising a cathode prepared from the hollow porous carbon material; the battery is a zinc-air battery or a microbial fuel cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method of the hollow porous carbon material mainly adopts dimethyl imidazole, zinc nitrate and dopamine hydrochloride as raw materials, wherein a ZIF-8 frame structure formed by the dimethyl imidazole and the zinc nitrate cannot collapse in the pyrolysis process, a good frame structure is still kept, more active sites can be generated, the mass transfer capacity is increased, and Zn in a catalyst precursor is gasified in the pyrolysis process to generate a large number of micropores, so that the purpose of pore formation without using a template agent is achieved, the experimental operation steps are simplified, and the synthesis speed of the catalyst is accelerated. Dopamine hydrochloride can be polymerized under an alkaline condition, so that the formation of ZIF-8 can be delayed, a layer of carbon film is formed on the surface of dopamine, and the amino groups on the surface provide active sites for anchoring of a metal source and can well inhibit the aggregation of metallic iron.
(2) According to the preparation method of the hollow porous carbon material, the metal-doped hollow concave dodecahedron carbon material obtained by doping metal has highly dispersed metal atoms, and is doped in the carbon skeleton in a single-atom form, so that the active sites of the material are fully exposed, the structure has a high specific surface area, and the abundant multi-stage pore structures can effectively promote the material exchange efficiency in a solid-liquid phase interface and greatly improve the activity of oxygen reduction reaction.
(3) According to the preparation method of the hollow porous carbon material, the used solvent is water, the price is low, the preparation method is convenient and easy to obtain, the preparation method is environment-friendly, the environment-friendly synthesis concept is realized without harming human health, the synthesis process is simple and convenient, the operation is easy, the universality is realized, the experimental scale can be amplified in a certain degree in an equal proportion, and therefore, the yield can be increased under the condition of keeping the properties of the material in all aspects, and the industrial production is realized.
(4) The hollow porous carbon material prepared by the invention has obvious catalytic advantages when being used as an oxygen reduction reaction electrocatalyst, particularly as a cathode material of a zinc air battery and a microbial fuel cell, and is used as a high-performance cathode catalyst in the zinc air battery and the microbial fuel cell to replace a noble metal catalyst.
Drawings
Fig. 1 is a scanning electron microscope image of an iron-nitrogen co-doped hollow concave dodecahedron carbon material prepared in example 1 of the present invention.
Fig. 2 is a transmission electron microscope image and an iron element distribution diagram of the iron-nitrogen co-doped hollow concave dodecahedron carbon material prepared in embodiment 1 of the present invention.
FIG. 3 is a nitrogen desorption isotherm diagram of the iron-nitrogen-codoped hollow concave dodecahedron carbon material in example 1 of the present invention.
FIG. 4 is a pore size distribution diagram of the Fe-N co-doped hollow concave dodecahedron carbon material in example 1 of the present invention.
FIG. 5 is a graph showing the results of ORR performance tests comparing the iron-nitrogen co-doped hollow internally concave dodecahedral carbon material of example 1 of the present invention with 20% Pt/C.
FIG. 6 is a graph showing the results of performance tests on a zinc-air battery comparing 20% by weight Pt/C with an iron-nitrogen co-doped hollow concave dodecahedron carbon material in example 1 of the present invention.
FIG. 7 is a graph showing the results of performance tests on a microbial fuel cell in which the iron-nitrogen co-doped hollow dented dodecahedral carbon material was compared with 20% Pt/C in example 1 of the present invention.
FIG. 8 is an SEM image of an aza-doped irregular polyhedral carbon material prepared in example 5 of the present invention.
Fig. 9 is an SEM image of the nitrogen-doped self-derived carbon nanotube porous material prepared in example 6 of the present invention.
Fig. 10 is an SEM image of the iron-nitrogen co-doped self-derived carbon nanotube porous material prepared in example 7 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of an iron-nitrogen co-doped hollow concave dodecahedron carbon material (recorded as FeNC) specifically comprises the following steps:
dissolving 6.35g of dimethylimidazole in 40mL of water to form a solution A, dissolving 0.372g of zinc nitrate hexahydrate and 0.1g of dopamine hydrochloride in 5mL of water to form a solution B, adding the solution B into the solution A to form a solution C, stirring the solution C for 1h, and then adding 0.1mmol of anhydrous FeCl 3 Dissolving in 5mL of water to form a solution D, adding the solution D into the solution C, stirring for reaction for 12 hours, then centrifugally separating the solution to obtain a catalyst precursor, and drying in an oven at 80 ℃ for 12 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
The morphology of the FeNC catalyst obtained in this example was characterized by a scanning electron microscope, and the results are shown in fig. 1. The prepared FeNC catalyst is clearly seen in FIG. 1 as a hollow, concave dodecahedron structure. The microscopic morphology of the FeNC catalyst was studied by a transmission electron microscope, and the result is shown in fig. 2 (a), which clearly shows that the prepared carbon material is a hollow, concave dodecahedron-shaped ultrathin carbon layer structure. From (b) in fig. 2, it can be seen that iron is present in the catalyst in the form of a single atom. Fig. 3 and 4 are specific surface area and pore size analyses of the FeNC catalyst prepared by the above method using a fully automatic physical chemical adsorption apparatus. FIG. 3 shows nitrogen adsorption and desorption of FeNC catalyst materialIsotherm plot. Typical type IV adsorption isotherms and H4 hysteresis loops are mainly derived from capillary condensation in pore structures, and simultaneously indicate that a large number of micropores and mesopores exist in materials. The two pores play an important role in oxygen reduction reaction, wherein the micropores can enable oxygen molecules in the electrolyte to approach active reaction sites, and the mesopores can enhance mass transfer efficiency, provide sufficient oxygen and accelerate the process of ORR reaction. Fig. 4 is a pore size distribution diagram of a hollow, concave dodecahedron carbon material of FeNC, and it can be seen from fig. 4 that the pore size of the carbon material is mainly microporous and mesoporous, and the macropore is auxiliary, and the microporous and mesoporous can provide active sites, and the macropore provides channels, thereby effectively improving the ORR activity of the catalyst. FIG. 5 is a Linear Sweep Voltammogram (LSV) of ORR activity in 0.1M KOH for catalysts FeNC and PtC, from which it can be seen that FeNC has an initial potential of 1.01V higher than 1.00V for PtC, feNC has a half-wave potential of 0.886V higher than 0.867V for PtC, and a current density of 6.12mA cm -2 5.71mA cm higher than PtC -2 . FIG. 6 shows voltage and power density data of zinc-air cell assembled by using catalysts FeNC and PtC as cathode materials, wherein the open-circuit voltage of the FeNC-based zinc-air cell is 1.453V which is slightly higher than that of the PtC-based open-circuit voltage (1.446V), and the power density of the FeNC-based zinc-air cell is 460mW cm -2 Is much higher than 236mW cm of PtC group -2 The synthesized catalyst FeNC is proved to have good discharge performance in a zinc air battery. FIG. 7 shows voltage and power density data for a microbial fuel cell assembled from catalysts FeNC and PtC as cathode materials, wherein the open circuit voltage of the FeNC-based microbial fuel cell is 818mV higher than the open circuit voltage of the PtC-based microbial fuel cell (797 mV), and the power density of the FeNC-based microbial fuel cell is 3083 + -10 mW cm -2 2405 +/-44 mW cm far higher than PtC base -2 . A series of results show that the synthesized FeNC catalyst is expected to become the possibility of replacing PtC.
Example 2
A preparation method of a cobalt-nitrogen co-doped hollow concave dodecahedron carbon material (marked as CoNC) specifically comprises the following steps:
dissolving 6.35g of dimethylimidazole in 40mL of water to form a solution A, dissolving 0.372g of zinc nitrate hexahydrate and 0.1g of dopamine hydrochloride in 5mL of water to form a solution B, adding the solution B into the solution A to form a solution C, after the solution C is stirred for 1 hour, dissolving 0.2mmol of cobalt nitrate tetrahydrate in 5mL of water to form a solution D, adding the solution D into the solution C, stirring for 12 hours, then centrifugally separating the solution to obtain a catalyst precursor, and drying the catalyst precursor in an oven at 80 ℃ for 12 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Example 3
A preparation method of a nickel-nitrogen co-doped hollow concave dodecahedron carbon material (marked as NiNC) specifically comprises the following steps:
dissolving 6.35g of dimethylimidazole in 40mL of water to form a solution A, dissolving 0.372g of zinc nitrate hexahydrate and 0.1g of dopamine hydrochloride in 5mL of water to form a solution B, adding the solution B into the solution A to form a solution C, after stirring the solution C for 1h, dissolving 0.2mmol of nickel nitrate in 5mL of water to form a solution D, adding the solution C into the solution C, stirring for 12h, then centrifugally separating the solution to obtain a catalyst precursor, and drying the catalyst precursor in an oven at 80 ℃ for 12h. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Example 4
A preparation method of a nitrogen-doped hollow concave dodecahedron carbon material (recorded as NC) specifically comprises the following steps:
6.35g of dimethylimidazole was dissolved in 40mL of water to form solution A, 0.372g of zinc nitrate hexahydrate and 0.1g of dopamine hydrochloride were dissolved in 5mL of water to form solution B, which was added to A to form solution C, and stirred for 16h. And then, centrifugally separating the solution to obtain a catalyst precursor, and drying the catalyst precursor in an oven at 80 ℃ for 14 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Example 5
A preparation method of nitrogen-doped irregular polyhedral carbon material (marked as NC-2) specifically comprises the following steps:
12.7g of dimethylimidazole was dissolved in 40mL of water to form solution A, 0.744g of zinc nitrate hexahydrate and 0.1g of dopamine hydrochloride were dissolved in 5mL of water to form solution B, which was added to A to form solution C, and stirred for 16h. And then, centrifugally separating the solution to obtain a catalyst precursor, and drying the catalyst precursor in an oven at 80 ℃ for 14 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Fig. 8 is an SEM image of nitrogen-doped irregular polyhedral carbon material prepared in this example.
Example 6
A preparation method of nitrogen-doped self-derived carbon nanotube porous materials (marked as NC-CNTs) specifically comprises the following steps:
6.35g of dimethylimidazole was dissolved in 40mL of water to form solution A, 0.372g of zinc nitrate hexahydrate and 0.2g of dopamine hydrochloride were dissolved in 5mL of water to form solution B, which was added to A to form solution C, and stirred for 16h. And then, centrifugally separating the solution to obtain a catalyst precursor, and drying the catalyst precursor in an oven at 80 ℃ for 14 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Fig. 9 is an SEM image of the nitrogen-doped self-derived carbon nanotube porous material prepared in the present example.
Example 7
A preparation method of an iron-nitrogen co-doped self-derived carbon nanotube porous material (marked as FeNC-CNTs) specifically comprises the following steps:
dissolving 6.35g of dimethylimidazole in 40mL of water to form a solution A, dissolving 0.372g of zinc nitrate hexahydrate and 0.1g of dopamine hydrochloride in 5mL of water to form a solution B, adding the solution B into the solution A to form a solution C, stirring the solution C for 1h, and then adding 0.2mmol of anhydrous FeCl 3 Dissolving in 5mL of water to form a solution D, adding the solution D into the solution C, stirring for 12h, then carrying out centrifugal separation on the solution to obtain a catalyst precursor, and drying in an oven at 80 ℃ for 12h. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Fig. 10 is an SEM image of the iron-nitrogen co-doped self-derived carbon nanotube porous material prepared in this example.
Comparative example 1
A preparation method of an iron-nitrogen co-doped porous carbon material (marked as FeNC-PPy) specifically comprises the following steps:
6.35g of dimethylimidazole were dissolved in 40mL of water to form solution A, and 0.372g of nitric acid hexahydrateDissolving zinc and 0.1g pyrrole in 5mL water to form solution B, adding into A to form solution C, stirring C solution for 1.5h, adding 0.1mmol anhydrous FeCl 3 Dissolving in 5mL of water to form a solution D, adding the solution D into the solution C, stirring for 12h, then carrying out centrifugal separation on the solution to obtain a catalyst precursor, and drying in an oven at 80 ℃ for 16h. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Comparative example 2
A preparation method of an iron-nitrogen co-doped porous carbon material (recorded as FeNC-PANI) specifically comprises the following steps:
dissolving 6.35g of dimethylimidazole in 40mL of water to form solution A, dissolving 0.372g of zinc nitrate hexahydrate and 0.1g of aniline in 5mL of water to form solution B, adding the solution B into the solution A to form solution C, stirring the solution C for 1.5h, and then adding 0.1mmol of anhydrous FeCl 3 Dissolving in 5mL of water to form a solution D, adding the solution D into the solution C, stirring for 12 hours, then centrifugally separating the solution to obtain a catalyst precursor, and drying in an oven at 80 ℃ for 16 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Comparative example 3
A method for preparing a nitrogen-doped porous carbonaceous material (denoted as NC-NoP), comprising the steps of:
6.35g of dimethylimidazole was dissolved in 40mL of water to form solution A, 0.372g of zinc nitrate hexahydrate was dissolved in 5mL of water to form solution B, which was added to A to form solution C, and the mixture was stirred for 16 hours. And then, centrifugally separating the solution to obtain a catalyst precursor, and drying the catalyst precursor in an oven at 80 ℃ for 12 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Comparative example 4
A preparation method of an iron-nitrogen co-doped porous carbon material (recorded as FeNC-NoP) specifically comprises the following steps:
dissolving 6.35g of dimethylimidazole in 40mL of water to form a solution A, dissolving 0.372g of zinc nitrate hexahydrate in 5mL of water to form a solution B, adding the solution B into the solution A to form a solution C, stirring the solution C for 1h, and then adding 0.1mmol of anhydrous FeCl 3 Dissolved in 5mL of water to formAdding the solution D into the solution C, and stirring for 12 hours; and then, centrifugally separating the solution to obtain a catalyst precursor, and drying the catalyst precursor in an oven at 80 ℃ for 12 hours. And finally, performing high-temperature carbonization in a tubular furnace at 900 ℃ for 3h.
Porous carbon materials as shown in Table 1 were prepared by changing the types of nitrogen sources (dopamine hydrochloride, pyrrole, aniline) and the types of metals (iron salt, nickel salt, cobalt salt) in the medium catalyst (except for the variables described in example 1) by the controlled variable method using the experimental conditions of example 1 as basic experimental conditions (i.e., unless otherwise specified), and by performing comparative experiments, 11 kinds of carbon material catalysts were compared with the ORR activity performance in a 0.1M KOH solution of commercial 20% Pt/C, wherein the initial potential and half-wave potential results of each catalyst are summarized as shown in Table 1, for example.
TABLE 1 comparison of ORR data parameters for various examples, comparative examples and PtC under 0.1M KOH
Figure BDA0003823869170000081
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A method for producing a hollow porous carbon material, characterized by comprising the steps of:
dissolving dimethyl imidazole in water to form a solution A;
dissolving zinc nitrate and dopamine hydrochloride in water, uniformly stirring to form a solution B, and then adding the solution B into the solution A to form a solution C;
after the solution C is stirred for reaction, performing centrifugal separation to obtain a catalyst precursor;
and drying the catalyst precursor and then calcining at high temperature.
2. The method for producing a hollow porous carbon material according to claim 1, wherein the mass ratio of the dimethylimidazole to the zinc nitrate to the dopamine hydrochloride is: (3-13): (0.3-1.5): (0.1-0.3).
3. The method for producing a hollow porous carbon material according to claim 1, wherein the solution C is stirred to react, specifically: and adding metal salt after the solution C is stirred to react, and continuously stirring to react.
4. The method for producing a hollow porous carbon material according to claim 3, wherein the amount ratio of the metal salt to dopamine hydrochloride is 1g to 1g (1 to 8 mmol).
5. The method for producing a hollow porous carbon material according to claim 3, wherein the metal salt is anhydrous ferric chloride, nickel nitrate hexahydrate, or cobalt nitrate tetrahydrate.
6. The method for producing a hollow porous carbon material according to claim 1, wherein the concentration of dimethylimidazole in the solution A is (8 to 32) g/100mL; the concentration of the zinc nitrate in the solution B is (6-30) g/100mL.
7. The method for producing a hollow porous carbon material according to claim 1, wherein the drying specifically comprises: drying at 80-100 deg.c for 12-24 hr.
8. The method for producing a hollow porous carbon material according to claim 1, wherein the high-temperature calcination is specifically: calcining at 800-1000 deg.c for 2-4 hr.
9. A hollow porous carbon material produced by the method for producing a hollow porous carbon material according to any one of claims 1 to 8, characterized by having a hollow, concave dodecahedral structure.
10. A battery comprising a cathode, wherein the cathode is prepared from the hollow porous carbon material of claim 9; the battery is a zinc-air battery or a microbial fuel cell.
CN202211060022.8A 2022-08-31 2022-08-31 Hollow porous carbon material, preparation method thereof and battery Pending CN115472854A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211060022.8A CN115472854A (en) 2022-08-31 2022-08-31 Hollow porous carbon material, preparation method thereof and battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211060022.8A CN115472854A (en) 2022-08-31 2022-08-31 Hollow porous carbon material, preparation method thereof and battery

Publications (1)

Publication Number Publication Date
CN115472854A true CN115472854A (en) 2022-12-13

Family

ID=84368722

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211060022.8A Pending CN115472854A (en) 2022-08-31 2022-08-31 Hollow porous carbon material, preparation method thereof and battery

Country Status (1)

Country Link
CN (1) CN115472854A (en)

Similar Documents

Publication Publication Date Title
CN110752380A (en) ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof
CN104174424B (en) The preparation of the aerogel carried non noble metal oxygen reduction catalyst of a kind of nitrogen-doped graphene
CN108754531B (en) Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material
CN111342066B (en) Preparation method of transition metal-nitrogen-carbon nanotube co-doped active carbon oxygen reduction catalyst
WO2021232751A1 (en) Porous coo/cop nanotubes, preparation method therefor and use thereof
CN112652780B (en) Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst
CN113060719A (en) Wood-based carbon foam and preparation method thereof, cathode electrocatalyst, cathode and metal-air battery
CN112968184B (en) Electrocatalyst with sandwich structure and preparation method and application thereof
CN112635779A (en) Preparation method of MOF-derived high-activity Ni monatomic oxygen reduction electrocatalyst
CN112058268A (en) Preparation method of zeolite imidazolyl metal organic framework nanosheet for oxygen reduction reaction
CN111203264B (en) Iron-nickel-nitrogen co-doped carbon catalyst and preparation method and application thereof
CN114438516A (en) Preparation method of porous nickel-iron-based bimetallic organic framework electrocatalyst and application of porous nickel-iron-based bimetallic organic framework electrocatalyst in water oxidation reaction
CN113054209A (en) Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof
CN112490451A (en) Cu-CoNCNs catalyst derived from folic acid, preparation and application thereof
CN116742023A (en) Nitrogen-doped carbon nano-tube supported metal alloy nitrogen-doped carbon nano-sheet catalyst and preparation method and application thereof
CN115194144B (en) Preparation method of iron coordinated covalent triazine polymer derived nanocluster material
CN115241470A (en) Carbon nanotube cross-linked iron-nitrogen doped carbon skeleton catalyst and preparation method and application thereof
CN115472854A (en) Hollow porous carbon material, preparation method thereof and battery
CN113644281A (en) Bimetal doped carbon composite material and preparation method and application thereof
CN111313035A (en) Preparation method of air electrode catalyst of zinc-air battery
CN115125578B (en) Preparation method of B-S co-doped nickel-cobalt-based electrolytic water oxygen evolution catalyst
CN113889633B (en) Alloy catalyst and preparation method and application thereof
CN115101757B (en) High-activity carbon-based porous nano cage catalyst and preparation method and application thereof
CN113583248B (en) Highly-crosslinked phosphorus-doped one-dimensional amorphous metal organic framework nanowire network material and preparation method and application thereof
CN113122872B (en) Cobalt and nitrogen doped carbon nanotube/carbon electrocatalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination