CN113839058B - Carbon-based oxygen reduction reaction catalyst and preparation method thereof - Google Patents

Carbon-based oxygen reduction reaction catalyst and preparation method thereof Download PDF

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CN113839058B
CN113839058B CN202111116725.3A CN202111116725A CN113839058B CN 113839058 B CN113839058 B CN 113839058B CN 202111116725 A CN202111116725 A CN 202111116725A CN 113839058 B CN113839058 B CN 113839058B
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precursor
carbon
heat treatment
oxygen reduction
room temperature
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CN113839058A (en
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欧子豪
郭朝中
覃媛
徐川岚
刘建平
许欣如
刘瑶
高洁
姜莹
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Chongqing University of Arts and Sciences
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    • 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
    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract

The invention discloses a carbon-based oxygen reduction reaction catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: 1) Pre-carbonizing waste cosmetic cotton, and then carrying out acid washing, water washing and drying to obtain a pyrolytic polymer; 2) According to the mass ratio of (0.2-4) of the pyrolytic polymer to zinc salt and ammonium fluoride (0.1-2), zinc salt and ammonium fluoride are added into the pyrolytic polymer, then solvent is added into the pyrolytic polymer, and the pyrolytic polymer is ground uniformly and dried to obtain a precursor; 3) The precursor is put into a tube furnace, and is heated from room temperature to 800 ℃ to 1000 ℃ for heat treatment for 1 to 3 hours at the heating rate of 5 to 15 ℃ per minute under inert atmosphere, then is naturally cooled to room temperature, is taken out for pickling, washing and drying, is continuously put into the tube furnace, is heated from room temperature to 800 ℃ to 1000 ℃ for heat treatment for 1 to 3 hours at the heating rate of 5 to 15 ℃ per minute under inert atmosphere, and is taken out after the heat treatment is completed and is naturally cooled to room temperature, thus obtaining the catalyst. The carbon-based oxygen reduction reaction catalyst prepared by the method has high activity, good stability and outstanding battery performance.

Description

Carbon-based oxygen reduction reaction catalyst and preparation method thereof
Technical Field
The invention relates to an oxygen reduction reaction catalyst under a cathode of a fuel cell, in particular to a carbon-based oxygen reduction reaction catalyst and a preparation method thereof.
Background
The continuous consumption of traditional fossil fuels causes energy crisis and environmental pollution, so that advanced clean new energy technology is widely focused in academia. However, the Oxygen Reduction Reaction (ORR) under the cathode during discharge greatly limits the development of advanced energy conversion systems such as fuel cells and Metal Air Batteries (MABs) due to the characteristics of slow reaction kinetics, various reaction pathways, and the like. Currently, platinum-based catalysts are the most effective commercial ORR catalysts. But the wide application in fuel cells is limited due to the high price, poor stability, easy poisoning and the like. Therefore, developing a non-noble metal catalyst with high efficiency, low cost, stability to replace platinum-based noble metal catalysts is a significant challenge in the world today.
In recent years, carbon-based metal-free catalysts are favored by the scientific research world because of the characteristics of low cost, good conductivity, high stability and the like, and the oxygen reduction catalytic effect of the carbon-based metal-free catalysts is obviously improved after doping elements such as N, P, S, F and the like; in addition, the design and synthesis of a structure with layered porous and ultra-high specific surface area is also another important method for improving the catalytic activity. However, at present, the synthesis process of most catalysts is too complicated, so that the catalysts are difficult to produce on a large scale; in addition, the active structure with layered porous and superhigh specific surface area can be maintained while high-efficiency doping is also very difficult.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the carbon-based oxygen reduction reaction catalyst with low cost, simple process steps, large specific surface area and high activity by taking the waste cosmetic cotton as a carbon source and the preparation method thereof.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
a method for preparing a carbon-based oxygen reduction reaction catalyst, comprising the following steps:
1) Pre-carbonizing waste cosmetic cotton, and then carrying out acid washing, water washing and drying to obtain a pyrolytic polymer;
2) According to the mass ratio of (0.2-4) of the pyrolytic polymer to zinc salt and ammonium fluoride (0.1-2), zinc salt and ammonium fluoride are added into the pyrolytic polymer, then solvent is added into the pyrolytic polymer, and the pyrolytic polymer is ground uniformly and dried to obtain a precursor;
3) The precursor is put into a tube furnace, and is heated from room temperature to 800 ℃ to 1000 ℃ for heat treatment for 1 to 3 hours at the heating rate of 5 to 15 ℃ per minute under inert atmosphere, then is naturally cooled to room temperature, is taken out for pickling, washing and drying, is continuously put into the tube furnace, is heated from room temperature to 800 ℃ to 1000 ℃ for heat treatment for 1 to 3 hours at the heating rate of 5 to 15 ℃ per minute under inert atmosphere, and is taken out after the heat treatment is completed and is naturally cooled to room temperature, thus obtaining the catalyst.
Further, the temperature of the pre-carbonization treatment in the step 1) is 200-400 ℃, and the treatment time is 0.5-2h.
Further, the zinc salt in the step 2) is one or a combination of any several of zinc chloride, zinc sulfate or zinc nitrate.
Further, the solvent in the step 2) is methanol or ethanol.
Further, the pickling conditions in the step 1) and the step 3) are that the magnetic stirring is carried out for 6-10 hours in 0.4-0.6M sulfuric acid at 70-85 ℃.
The invention also provides a carbon-based oxygen reduction reaction catalyst which is of a N, F co-doped porous carbon-based structure and has a specific surface area of more than 2000m 2 .g -1 。
Compared with the prior art, the invention has the following technical effects:
1. waste cosmetic cotton is used as raw material, waste is utilized, and cost is saved.
2. The catalyst preparation flow is simple and convenient, and is easy for large-scale industrial production.
3. The catalyst prepared by the method has rich pore structures, and the structure can increase the diffusion rate of electrolyte and accelerate oxygen transmission, so that the catalyst has higher reaction activity; and the zinc salt and the ammonium fluoride can be used as dual activators to expose more N, F doping sites, so that the electrocatalytic performance of the catalyst is remarkably improved, and the catalyst can be assembled into a battery to provide higher power density and energy density than those of commercial Pt/C catalysts.
Drawings
FIG. 1 is a transmission electron microscope of a CF-Zn-F catalyst prepared in example 1 of the present invention;
FIG. 2 is a nitrogen adsorption-desorption isothermal graph of the CF-Zn-F catalyst prepared in example 1 according to the present invention, wherein the inner inset is a corresponding BJH pore size distribution graph;
FIG. 3 is an XRD scan of the CF-Zn-F catalyst prepared in example 1 of the invention;
FIG. 4 is a Raman plot of the CF-Zn-F, CF-Zn and CF-F catalysts prepared in example 1, comparative example 2, comparative example 3 of the present invention;
FIG. 5 shows the respective catalysts of CF-Zn-F, CF-Zn and CF-F prepared in example 1, comparative example 2 and comparative example 3 of the present invention in O 2 And N 2 CV curve in saturated 0.1M KOH solution.
FIG. 6 is an LSV curve of the CF-Zn-F, CF-Zn and CF-F catalysts prepared in example 1, comparative example 2, comparative example 3 of the present invention with a commercial Pt/C catalyst;
FIG. 7 is a statistical plot of the average hydrogen peroxide yields and average electron transfer numbers for the CF-Zn-F, CF-Zn and CF-F catalysts prepared in example 1, comparative example 2, comparative example 3 and commercial Pt/C catalysts of the present invention;
FIG. 8 is a LSV graph of catalysts prepared at various heat treatment temperatures for inventive example 1, comparative example 4, comparative example 5, and comparative example 6;
FIG. 9 is a LSV graph of the CF-Zn-F and commercial Pt/C catalysts prepared in example 1 of the present invention after scanning for 0 and 5000 cycles;
FIG. 10 is an anti-methanol poisoning graph of CF-Zn-F and commercial Pt/C catalysts prepared in example 1 of the present invention;
FIG. 11 is a graph showing the discharge polarization curves and corresponding power densities of zinc-air cells with CF-Zn-F and commercial Pt/C catalysts, respectively, as air electrodes, prepared in example 1 of the present invention;
FIG. 12 is an energy density plot of a zinc-air cell with CF-Zn-F and commercial Pt/C catalysts, respectively, prepared in example 1 of the present invention as air electrodes.
Detailed Description
The following examples illustrate the invention in further detail.
The invention provides a preparation method of a carbon-based oxygen reduction reaction catalyst, which specifically comprises the following steps:
1) Pre-carbonizing waste cosmetic cotton to remove grease inside to form a standard carbon material, cleaning the carbon material by acid washing, washing for multiple times to remove residual acid, and drying to obtain a pyrolyzed polymer;
2) According to the mass ratio of (0.2-4) of (0.1-2), zinc salt and ammonium fluoride are added into the pyrolyzed polymer, then solvent is added, grinding is carried out uniformly, and then drying is carried out to obtain a precursor, wherein the solvent is added only for ensuring that grinding is more complete, and the amount of the solvent is not particularly required;
3) And (3) placing the precursor into a tube furnace, heating from room temperature to 800-1000 ℃ for 1-3 hours at a heating rate of 5-15 ℃/min under inert atmosphere to form a N, F co-doped porous carbon-based structure, naturally cooling to room temperature, taking out unstable metal agglomerated substances in the material through acid washing, washing for multiple times to remove residual acid, drying, then continuously placing into the tube furnace, heating from room temperature to 800-1000 ℃ for 1-3 hours at a heating rate of 5-15 ℃/min under inert atmosphere to form a more stable N, F co-doped porous carbon-based structure, and taking out the catalyst after the heat treatment is completed and the material is naturally cooled to room temperature.
The invention also relates to the carbon-based oxygen reduction reaction catalyst prepared by the method, which is N, F co-doped porous carbon-based structure and has specific surface area of more than 2000m 2 .g -1 。
The drying referred to in this connection has no special requirements for temperature, but generally does not exceed 100 ℃.
In order to further describe the technical scheme of the present invention in detail, the following description is made with reference to specific embodiments.
Example 1
The embodiment provides a preparation method of a carbon-based oxygen reduction reaction catalyst, which specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 350 ℃ to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.5M sulfuric acid, magnetically stirring the waste cosmetic cotton for 8h in a water bath at 80 ℃, filtering the waste cosmetic cotton after washing the waste cosmetic cotton for a plurality of times to remove residual sulfuric acid, and drying the waste cosmetic cotton in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Zinc chloride (0.24 g) and ammonium fluoride (0.03 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, ethanol is added, and the mixture is ground uniformly and then dried to obtain a precursor;
3) Putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 950 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.5M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 80 ℃, removing unstable metal aggregate in the material, washing the precursor for multiple times to remove residual sulfuric acid, filtering the precursor, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 950 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst, namely CF-Zn-F.
FIG. 1 is a Transmission Electron Microscope (TEM) image of the CF-Zn-F catalyst prepared in this example; the TEM image shows that the catalyst is composed of disordered carbon structure and contains rich pore structure, and the structure can increase the diffusion rate of electrolyte and accelerate oxygen transmission, so that the catalyst has better performance.
FIG. 2 is a graph showing the isothermal adsorption-desorption of nitrogen in the CF-Zn-F catalyst prepared in this example, and the internal inset shows the corresponding BJH pore size distribution; it can be seen from the figure that the catalyst is at a relatively low N 2 Pressure (P/P) 0 <0.1 Shows a steep increase at higher N) 2 Pressure (P/P) 0 >0.4 A definite hysteresis loop was shown, a typical type I isotherm of coexistence of micropores and mesopores was reflected, and the specific surface area of the catalyst was measured to be 2251m 2 .g -1 Wherein the micropore area ratio is calculated to be up to 90.8%. Such an ultra-highThe BET specific surface area of (2) is attributed to the activation of zinc chloride, which is introduced into the carbon material, and after pyrolysis and etching, a large number of pores are generated, and the abundant microporous structure is beneficial to increasing the mass transfer capacity and finally improving the electrocatalytic performance.
FIG. 3 is an XRD scan of the CF-Zn-F catalyst prepared in this example; two peaks at approximately 23 ° and 44 ° were observed in the XRD pattern of the prepared catalyst, which were (002) and (101) planes of carbon, respectively, indicating that no zinc or zinc oxide particles were formed.
Comparative example 1
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 350 ℃ to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.5M sulfuric acid, magnetically stirring the waste cosmetic cotton for 8h in a water bath at 80 ℃, filtering the waste cosmetic cotton after washing the waste cosmetic cotton for a plurality of times to remove residual sulfuric acid, and drying the waste cosmetic cotton in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Taking 0.12g of the pyrolyzed polymer in the step 1), adding ethanol, grinding uniformly, and drying to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 950 ℃ at a heating rate of 10 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.5M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 80 ℃, washing the precursor for multiple times to remove residual sulfuric acid, filtering the precursor, drying the precursor in a baking oven at 60 ℃, putting the dried precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 950 ℃ at a heating rate of 10 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction catalyst, which is marked as CF.
Comparative example 2
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 350 ℃ to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.5M sulfuric acid, magnetically stirring the waste cosmetic cotton for 8h in a water bath at 80 ℃, filtering the waste cosmetic cotton after washing the waste cosmetic cotton for a plurality of times to remove residual sulfuric acid, and drying the waste cosmetic cotton in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Taking 0.12g of pyrolytic polymer and 0.24g of zinc chloride in the step 1), adding ethanol, grinding uniformly, and drying to obtain a precursor;
3) Putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 950 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.5M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 80 ℃, removing unstable metal agglomerated substances in the material, washing the precursor for multiple times to remove residual sulfuric acid, filtering the precursor, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 950 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst, namely CF-Zn.
Comparative example 3
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 350 ℃ to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.5M sulfuric acid, magnetically stirring the waste cosmetic cotton for 8h in a water bath at 80 ℃, filtering the waste cosmetic cotton after washing the waste cosmetic cotton for a plurality of times to remove residual sulfuric acid, and drying the waste cosmetic cotton in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Taking 0.12g of pyrolyzed polymer in the step 1) and 0.03g of ammonium fluoride, adding ethanol, grinding uniformly, and drying to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 950 ℃ at a heating rate of 10 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.5M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 80 ℃, washing the precursor for multiple times to remove residual sulfuric acid, filtering the precursor, drying the precursor in a baking oven at 60 ℃, putting the dried precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 950 ℃ at a heating rate of 10 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst, which is marked as CF-F.
Comparative example 4
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 350 ℃ to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.5M sulfuric acid, magnetically stirring the waste cosmetic cotton for 8h in a water bath at 80 ℃, filtering the waste cosmetic cotton after washing the waste cosmetic cotton for a plurality of times to remove residual sulfuric acid, and drying the waste cosmetic cotton in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Zinc chloride (0.24 g) and ammonium fluoride (0.03 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, ethanol is added, and the mixture is ground uniformly and then dried to obtain a precursor;
3) Putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 800 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.5M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 80 ℃, removing unstable metal agglomerated substances in the material, washing the precursor for multiple times to remove residual sulfuric acid, filtering the precursor, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 800 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst, namely CF-Zn-F-800.
Comparative example 5
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 350 ℃ to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.5M sulfuric acid, magnetically stirring the waste cosmetic cotton for 8h in a water bath at 80 ℃, filtering the waste cosmetic cotton after washing the waste cosmetic cotton for a plurality of times to remove residual sulfuric acid, and drying the waste cosmetic cotton in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Zinc chloride (0.24 g) and ammonium fluoride (0.03 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, ethanol is added, and the mixture is ground uniformly and then dried to obtain a precursor;
3) Putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 900 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.5M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 80 ℃, removing unstable metal agglomerated substances in the material, washing the precursor for multiple times to remove residual sulfuric acid, filtering the precursor, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 900 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst, namely CF-Zn-F-900.
Comparative example 6
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 350 ℃ to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.5M sulfuric acid, magnetically stirring the waste cosmetic cotton for 8h in a water bath at 80 ℃, filtering the waste cosmetic cotton after washing the waste cosmetic cotton for a plurality of times to remove residual sulfuric acid, and drying the waste cosmetic cotton in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Zinc chloride (0.24 g) and ammonium fluoride (0.03 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, ethanol is added, and the mixture is ground uniformly and then dried to obtain a precursor;
3) Putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 1000 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.5M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 80 ℃, removing unstable metal agglomerated substances in the material, washing the precursor for multiple times to remove residual sulfuric acid, filtering the precursor, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 1000 ℃ at the heating rate of 10 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst, namely CF-Zn-F-1000.
To illustrate the technical effects of the present invention in detail, the following electrochemical catalytic oxygen reduction reaction performance tests were performed on CF-Zn-F, CF-Zn, CF-F, CF-Zn-F-800, CF-Zn-F-900 and CF-Zn-F-1000 prepared in example 1 and comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5 and comparative example 6, respectively; the catalyst CF-Zn-F obtained in example 1 was assembled into a metal zinc-air fuel cell, and its cell performance was tested and compared with a commercial 20% pt/C catalyst.
All electrochemical data were tested using a CHI760E (Shanghai Chenhua instruments, inc., china) electrochemical workstation, using a three electrode system with a rotating ring-disk as the working electrode (RRDE, pin, U.S.) and a saturated mercury oxide electrode (Hg/HgO) as the reference electrode and a graphite rod as the counter electrode. All electrode potentials were exchanged with the Reversible Hydrogen Electrode (RHE). Cyclic voltammetric sweep (CV) measurements are at O 2 And N 2 A saturated 0.1M KOH solution was scanned at a scan rate of 50mV/s, while a linear voltammetric scan (LSV) was performed at a rotation rate of 400-2500rpm, with a scan rate of 10mV/s. The primary metal zinc-air battery comprises the following components: the metal zinc plate was the anode, the catalyst-loaded carbon paper was the air cathode, the nickel foam was the current collector, and the 6M KOH electrolyte.
Specific analyses are performed below in conjunction with FIGS. 4-10.
FIG. 4 shows the Raman spectra of the CF-Zn-F, CF-Zn and CF-F catalysts prepared in example 1, comparative example 2 and comparative example 3 of the present invention; it can be seen from the figure that CF and CF-Zn have the same I D /I G Indicating that zinc chloride activation alone does not significantly affect the degree of graphitization of the catalyst; while CF-Zn-F has the smallest I D /I G The zinc chloride and ammonium fluoride serving as dual activators can expose more N, F doping sites, so that the graphitization degree is improved.
FIG. 5 shows the CF-Zn-F, CF-Zn and CF-F catalysts prepared in example 1, comparative example 2, comparative example 3, respectively, of the present invention in O 2 And N 2 Cyclic voltammetric scan curve in saturated 0.1M KOH solution; from the drawings canIt is clear that CF-Zn-F (0.78V) has more corrected oxygen reduction peak potentials than CF (0.62V), CF-Zn (0.69V) and CF-F (0.68V) (vs. RHE), indicating that the prepared CF-Zn-F catalyst has higher reactivity.
FIG. 6 shows linear voltammetric scan curves for CF-Zn-F, CF-Zn and CF-F catalysts prepared in example 1, comparative example 2, comparative example 3 of the present invention versus commercial Pt/C catalysts; CF-Zn-F (0.83V, 6.27mA/cm in oxygen saturated 0.1M KOH at 1600rpm 2 ) And commercial Pt/C (0.85V, 5.80 mA/cm) 2 ) Equivalent, but stronger limiting current densities. Furthermore, it was superior to CF (0.68V, 3.25 mA/cm) 2 )、CF-Zn(0.73V，3.91mA/cm 2 ) And CF-F (0.72V, 4.46 mA/cm) 2 ) Much higher. These results indicate that activation of zinc chloride and doping of heteroatoms can significantly improve the electrocatalytic properties of CF, whereas the high ORR activity of CF-Zn-F benefits the dual activation effect.
FIG. 7 is a statistical plot of the average hydrogen peroxide yields and average electron transfer numbers for the CF-Zn-F, CF-Zn and CF-F catalysts prepared in example 1, comparative example 2, comparative example 3 and commercial Pt/C catalysts of the present invention; as can be seen from the figure, the average H of CF-Zn-F 2 O 2 The yield was 5.8%, well below CF (48.9%), CF-Zn (35.8%) and CF-F (12.7%), while the average number of electrons transported by CF-Zn-F was 3.88, comparable to Pt/C catalyst, well above CF (3.02), CF-Zn (3.28) and CF-F (3.74), indicating a near four electron reaction pathway for CF-Zn-F and a very high selectivity for oxygen reduction of water.
FIG. 8 shows linear voltammograms of catalysts prepared at different heat treatment temperatures for inventive example 1, comparative example 4, comparative example 5 and comparative example 6. In oxygen saturated 0.1M KOH, the CF-Zn-F, namely CF-Zn-F-950, had a higher half-wave potential and limiting current density than CF-Zn-F-800, CF-Zn-F-900 and CF-Zn-F-1000 at 1600rpm, indicating that the temperature could promote the generation of more active sites, but that too high a temperature would decompose the active sites, and thus the result indicated that the heat treatment at 950℃had the best catalytic effect.
Fig. 9 and 10 show long-cycle stability and methanol poisoning resistance experiments of the CF-Zn-F catalyst prepared in example 1 of the present invention and Pt/C catalyst. As can be seen from FIG. 9, after 5000 cycles of CV cycles, the half-wave potential of the Pt/C catalyst was attenuated by 22mV, while CF-Zn-F was attenuated by only 12mV, indicating that the synthesized CF-Zn-F catalyst had good stability; as can be seen from fig. 10, CF-Zn-F showed a negligible decay in current density compared to the sharp drop in current density after Pt/C injection of 3M methanol at 400 seconds and 700 seconds, reflecting its excellent methanol resistance.
Fig. 11 and 12 show discharge polarization curves and corresponding power density and energy density maps of zinc-air batteries using CF-Zn-F catalyst and Pt/C catalyst prepared in example 1 of the present invention as air electrodes, respectively. The maximum power density of the assembled cell using CF-Zn-F at the air cathode was 220.3mW/cm 2 Far higher than Pt/C (136.5 mW/cm) 2 ) Meanwhile, the zinc-air battery based on the CF-Zn-F electrocatalyst is at 50mA/cm 2 When providing
Figure BDA0003275604420000103
Is greater than Pt/C->
Figure BDA0003275604420000104
Slightly lower and the corresponding energy density is +.>
Figure BDA0003275604420000101
Greatly exceeds Pt/C->
Figure BDA0003275604420000102
Primary zinc air cell performance shows that CF-Zn-F electrocatalysts have considerable application potential in advanced energy conversion systems.
In order to fully explain the technical scheme of the invention, the invention also provides the following specific embodiments:
example 2
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 250 ℃ to remove grease inside to form a standard carbon material, then placing in 0.6M sulfuric acid, magnetically stirring for 6h in a water bath at 70 ℃, washing with water for many times, filtering, and drying in a baking oven at 70 ℃ to obtain a pyrolytic polymer;
2) Zinc sulfate (0.024 g) and ammonium fluoride (0.012 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, ethanol is added to be ground uniformly, and then the mixture is dried to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing argon for protection in the whole process, heating to 800 ℃ at a heating rate of 10 ℃/min for heat treatment for 3 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.6M sulfuric acid, magnetically stirring the precursor for 6 hours in a water bath at 70 ℃, filtering the precursor after washing for many times, drying the precursor in a baking oven at 70 ℃, putting the precursor into the tubular furnace again, introducing argon for protection in the whole process, heating to 1000 ℃ at a heating rate of 15 ℃/min for heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst.
Example 3
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 2 hours at 200 ℃ to remove grease inside to form a standard carbon material, then placing in 0.55M sulfuric acid, magnetically stirring for 9 hours in a water bath at 85 ℃, washing with water for many times, filtering, and drying in a drying oven at 55 ℃ to obtain a pyrolytic polymer;
2) Zinc sulfate (0.024 g) and ammonium fluoride (0.24 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, methanol is added to be ground uniformly, and then the mixture is dried to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 800 ℃ at a heating rate of 5 ℃/min for heat treatment for 3 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.55M sulfuric acid, magnetically stirring the precursor for 9 hours in a water bath at 85 ℃, filtering the precursor after washing for multiple times, drying the precursor in a drying oven at 55 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 800 ℃ at a heating rate of 5 ℃/min for heat treatment for 3 hours, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst.
Example 4
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing at 400 ℃ for 0.5h to remove oil in the waste cosmetic cotton and form a standard carbon material, then placing the waste cosmetic cotton in 0.4M sulfuric acid, magnetically stirring the waste cosmetic cotton for 10h in a water bath at 85 ℃, washing the waste cosmetic cotton for multiple times, filtering the waste cosmetic cotton, and drying the waste cosmetic cotton in a drying oven at 65 ℃ to obtain a pyrolyzed polymer;
2) Zinc nitrate (0.48 g) and ammonium fluoride (0.012 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, ethanol is added, and the mixture is ground uniformly and then dried to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 850 ℃ at a heating rate of 8 ℃/min, performing heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.4M sulfuric acid, magnetically stirring the precursor for 10 hours in a water bath at 85 ℃, washing the precursor with water for many times, filtering the precursor, drying the precursor in a drying oven at 65 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 1000 ℃ at a heating rate of 15 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst.
Example 5
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 300 ℃ to remove grease inside to form a standard carbon material, then placing in 0.45M sulfuric acid, magnetically stirring for 8h in a water bath at 75 ℃, filtering after washing for multiple times, and drying in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Zinc chloride (0.48 g) and ammonium fluoride (0.24 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, methanol is added to be ground uniformly, and then the mixture is dried to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 1000 ℃ at a heating rate of 15 ℃/min, performing heat treatment for 1h, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.45M sulfuric acid, magnetically stirring the precursor for 8h in a water bath at 75 ℃, filtering the precursor after washing the precursor for multiple times, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 950 ℃ at a heating rate of 10 ℃/min, performing heat treatment for 1h, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst.
Example 6
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing for 1h at 300 ℃ to remove grease inside to form a standard carbon material, then placing in 0.5M sulfuric acid, magnetically stirring for 8h in a water bath at 75 ℃, filtering after washing for multiple times, and drying in a baking oven at 60 ℃ to obtain a pyrolytic polymer;
2) Zinc chloride (0.12 g), zinc sulfate (0.24 g) and ammonium fluoride (0.12 g) are added into the pyrolyzed polymer (0.12 g) in the step 1) to be mixed, ethanol is added, and the mixture is ground uniformly and then dried to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 1000 ℃ at a heating rate of 15 ℃/min, performing heat treatment for 1h, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.45M sulfuric acid, magnetically stirring the precursor for 8h in a water bath at 75 ℃, filtering the precursor after washing the precursor for multiple times, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 950 ℃ at a heating rate of 15 ℃/min, performing heat treatment for 1h, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst.
Example 7
The preparation method of the carbon-based oxygen reduction reaction catalyst specifically comprises the following steps:
1) Placing the waste cosmetic cotton in a tubular furnace, pre-carbonizing at 300 ℃ for 1.5 hours to remove grease inside to form a standard carbon material, then placing in 0.45M sulfuric acid, magnetically stirring for 8 hours in a water bath at 75 ℃, washing for multiple times, filtering, and drying in a drying oven at 60 ℃ to obtain a pyrolyzed polymer;
2) Zinc sulfate (0.12 g), zinc nitrate (0.24 g) and ammonium fluoride (0.06 g) are added into the pyrolytic polymer (0.12 g) in the step 1) to be mixed, methanol is added to be ground uniformly, and then the mixture is dried to obtain a precursor;
3) And 2) putting the precursor in the step 2) into a tubular furnace, introducing nitrogen for protection in the whole process, heating to 1000 ℃ at a heating rate of 10 ℃/min, performing heat treatment for 3 hours, naturally cooling to room temperature after the heat treatment is finished, then putting the precursor into 0.45M sulfuric acid, magnetically stirring the precursor for 8 hours in a water bath at 75 ℃, filtering the precursor after washing the precursor for multiple times, drying the precursor in a baking oven at 60 ℃, putting the precursor into the tubular furnace again, introducing nitrogen for protection in the whole process, heating to 950 ℃ at a heating rate of 5 ℃/min, performing heat treatment for 1 hour, and naturally cooling to room temperature after the heat treatment is finished, thereby obtaining the carbon-based oxygen reduction reaction catalyst.

Claims (6)

1. A method for preparing a carbon-based oxygen reduction reaction catalyst, which is characterized by comprising the following steps:
1) Pre-carbonizing waste cosmetic cotton, and then carrying out acid washing, water washing and drying to obtain a pyrolytic polymer;
2) According to the mass ratio of (0.2-4) of the pyrolytic polymer to zinc salt and ammonium fluoride (0.1-2), zinc salt and ammonium fluoride are added into the pyrolytic polymer, then solvent is added into the pyrolytic polymer, and the pyrolytic polymer is ground uniformly and dried to obtain a precursor;
3) The precursor is put into a tube furnace, and is heated from room temperature to 800 ℃ to 1000 ℃ for heat treatment for 1 to 3 hours at the heating rate of 5 to 15 ℃ per minute under inert atmosphere, then is naturally cooled to room temperature, is taken out to be sequentially subjected to acid washing, water washing and drying, is continuously put into the tube furnace, is heated from room temperature to 800 ℃ to 1000 ℃ for heat treatment for 1 to 3 hours at the heating rate of 5 to 15 ℃ per minute under inert atmosphere, and is taken out after the heat treatment is completed and is naturally cooled to room temperature, thus obtaining the catalyst.
2. The method for preparing a carbon-based oxygen reduction catalyst according to claim 1, wherein the pre-carbonization treatment in step 1) is performed at a temperature of 200 to 400 ℃ for a treatment time of 0.5 to 2 hours.
3. The method for preparing a carbon-based oxygen reduction catalyst according to claim 1, wherein the zinc salt in the step 2) is one or a combination of any of zinc chloride, zinc sulfate and zinc nitrate.
4. The method for preparing a carbon-based oxygen reduction catalyst according to claim 1, wherein the solvent in the step 2) is methanol or ethanol.
5. The method for preparing a carbon-based oxygen reduction catalyst according to claim 1, wherein the conditions for acid washing in the step 1) and the step 3) are magnetic stirring in 0.4-0.6M sulfuric acid at 70-85 ℃ for 6-10 hours.
6. The carbon-based oxygen reduction reaction catalyst prepared by the method according to claim 1, wherein the catalyst has a N, F co-doped porous carbon-based structure and a specific surface area of more than 2000m 2 .g -1 。
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