CN110504456B - Oxygen reduction electrode based on nitrogen-oxygen doped ball/sheet porous carbon material and preparation method and application thereof - Google Patents
Oxygen reduction electrode based on nitrogen-oxygen doped ball/sheet porous carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an oxygen reduction electrode based on a nitrogen-oxygen doped ball/sheet porous carbon material, and a preparation method and application thereof, wherein the method comprises the following steps: the method comprises the steps of taking hexabromobenzene and pyridine as raw materials, adopting a solvothermal method to directly carry out in-situ dehalogenation polymerization reaction in one step to prepare a crude product of the nitrogen-oxygen doped ball/sheet porous carbon material, adopting temperature programming carbonization under the protection of inert gas, cooling and grinding to obtain the nitrogen-oxygen doped ball/sheet porous carbon material. The nitrogen-oxygen doped sphere/sheet porous carbon material is stable in structure and good in conductivity (the material resistance is only 15.96m omega, and the conductivity is 8.11 x 10) ‑4 Omega.m) and a plurality of catalytic active sites, can be used for preparing an oxygen reduction electrode of a fuel cell, can be used in the fuel cell and shows good electrochemical performance; due to the simple synthesis process, environmental friendliness and excellent electrochemical performance of the method, the low-cost large-scale preparation of the nitrogen-oxygen doped sphere/sheet porous carbon material can be realized, so that the method has good application prospect and industrialization potential.
Description
Technical Field
The invention relates to an oxygen reduction electrode based on a nitrogen-oxygen doped sphere/sheet porous carbon material, and a preparation method and application thereof, and belongs to the field of inorganic functional materials.
Background
With the increasing exhaustion of fossil energy and the increasing severity of environmental deterioration, the development of efficient and safe clean energy and technology is urgent. Clean and renewable energy technologies, such as fuel cells, are important technologies that are expected to address current energy and environmental challenges. Wherein electrocatalysts are the core of the above renewable energy technology. Currently, the best oxygen-reducing electrocatalysts to be recognized are still platinum-based catalysts, based on their excellent oxygen-reducing catalytic ability and high current density. But its commercial large-scale application is limited due to the high price of platinum-based materials and the poor resistance to methanol and CO poisoning.
In order to solve the problems of the above electrocatalysts, the non-metal catalysts have been widely noticed by researchers due to their similar excellent oxygen reduction activity, higher methanol and CO poisoning resistance. Among them, the heteroatom-doped nanostructured carbon material (such as carbon nanotube, graphene, porous carbon, carbon quantum dot, etc.) has the advantages of various structures, abundant resources, good conductivity, large specific surface area, strong corrosion resistance, environmental friendliness, unique surface properties, etc., and is considered to be the most promising substitute for noble metal catalysts.
For example, CN105186010B provides a preparation method of a nitrogen-doped carbon-oxygen reduction catalyst with a hierarchical pore structure, belonging to the technical field of fuel cells. According to the invention, firstly, a freeze drying method is adopted to prepare eutectic salt with a three-dimensional macroporous structure, then, the eutectic salt is used as a template, a nitrogen-containing precursor is doped, ammonium persulfate is used as an oxidant, ferric salt is used as a cocatalyst, an oxidative polymerization method is adopted to initiate oxidative polymerization of the nitrogen-containing precursor on the surface of the eutectic salt, and finally, high-temperature pyrolysis is carried out and the eutectic salt is removed. The nitrogen-doped carbon-oxygen reduction catalyst with the hierarchical porous structure prepared by the method can effectively avoid the pyrolysis loss, structural collapse and sintering of a nitrogen-containing polymer precursor in the high-temperature carbonization process, improve the yield of the catalyst and the nitrogen doping efficiency, can generate a large number of micropores, mesopores and macropores, and improve the mass transfer efficiency of oxygen and water. However, the method is complex to operate, low in doping amount and low in yield, so that large-scale popularization and application cannot be realized.
CN105609793A specifically relates to an iron-nitrogen doped graphene porous material with dual sites catalyzing oxygen reduction, and a preparation method and application thereof. The porous material is formed by embedding graphite carbon-coated iron carbide into a nitrogen-doped porous graphene band network structure. Preparing graphene oxide solution, adding a proper amount of conductive polymer pyrrole, carrying out hydrothermal treatment to obtain uniform hydrogel, carrying out oxidative polymerization on the hydrogel by using ferric iron, dispersing the hydrogel in fresh ferric iron solution to complete adsorption, carrying out drying and high-temperature carbonization heat treatment, and finally removing inactive and free iron phase in a reaction system by using dilute acid to obtain the final iron-nitrogen doped graphene porous material. However, the preparation method of the iron-nitrogen doped graphene porous material prepared by the method is complicated, and the entering of metal atoms influences the cycling stability of the material, so that the method cannot be applied to industrial production.
The patent of CN105186010A discloses a method for preparing a nitrogen-doped carbon-oxygen reduction catalyst by using eutectic salt as a template and then performing high-temperature heat-release, wherein the prepared nitrogen-doped carbon material with a hierarchical pore structure has abundant pore structures, but the method uses various raw materials, and has high cost and complex process.
The patent of CN107282081A discloses a method for synthesizing a fluffy porous nitrogen-doped carbon-oxygen reduction catalyst by using a carbon source, a nitrogen source, zinc chloride, basic magnesium carbonate pentahydrate and the like as a reducing agent and providing heteroatoms, wherein the method has a wide application range, but the process is relatively complex, and the prepared oxygen reduction catalyst has general performance and cannot meet the requirements of production and life on the oxygen reduction catalyst.
The single heteroatom doped carbon material and the multiple heteroatom doping become research focuses of researchers, but the synthesis of the carbon material capable of accurately regulating and controlling the doping amount and the doping type of the multiple heteroatoms still remains the difficulty of research and study. When doping atoms are introduced into the carbon material, the traditional method achieves the doping effect by a physical blending mode or a post-treatment mode, the two modes have low doping efficiency, the doping is uneven, only edge doping can be carried out, the performance of the carbon material is unstable, and the performance of the carbon material is further influenced. There is a need for further improvements in this regard.
Disclosure of Invention
The technical problem to be solved by the embodiment of the invention is to provide an oxygen reduction electrode based on a nitrogen-oxygen doped sphere/sheet porous carbon material, and a preparation method and application thereof.
The technical scheme of the first aspect of the invention comprises the following steps:
(1) the preparation method of the nitrogen-oxygen doped hierarchical porous carbon material comprises the following steps:
s1: carrying out a closed reaction on hexabromobenzene and pyridine at high temperature and high pressure; the closed reaction is an in-situ dehalogenation polymerization reaction.
S2: after the reaction is finished, releasing pressure to normal pressure, naturally cooling to room temperature, washing with deionized water and petroleum ether until the upper layer liquid is transparent, and drying the solid obtained after washing to obtain a dried sample;
s3: carrying out high-temperature roasting treatment on the dried sample under the protection of inert gas, thereby obtaining the nitrogen-oxygen doped hierarchical porous carbon material;
(2) a method of oxygen reduction electrode preparation, the method comprising the steps of:
A. grinding and polishing a glassy carbon electrode in alumina water slurry with the particle size of 0.05-1.0 mu m, then ultrasonically washing the glassy carbon electrode in acetone, absolute ethyl alcohol and high-purity water for 20-40 seconds in sequence, and drying the glassy carbon electrode by blowing with nitrogen to obtain a pretreated glassy carbon electrode;
B. dispersing the nitrogen-oxygen doped sphere/sheet porous carbon material and Nafion solution in a mixed solution of ethanol water, and then performing ultrasonic dispersion for 5-15 minutes to obtain a uniformly mixed solution; and dripping the uniformly mixed solution on the pretreated glassy carbon electrode for multiple times, and drying at room temperature to obtain the oxygen reduction electrode.
Wherein, in the method for manufacturing an oxygen reduction electrode according to the present invention, in the step (a), the amounts of the acetone, the absolute ethyl alcohol, the high purity water and the Nafion are not particularly limited, which can be suitably determined and selected by those skilled in the art of electrode manufacturing, and will not be described in detail herein; the acetone, the absolute ethyl alcohol and the Nafion are all common raw materials in the preparation field, can be obtained commercially through various channels, and are not described in detail herein.
In the method for preparing the nitrogen-oxygen doped sphere/sheet porous carbon material, in step S1, the reaction pressure is 2 to 8MPa, and may be, for example, 2MPa, 4MPa, 6MPa or 8 MPa.
In the method for preparing the nitrogen-oxygen doped sphere/sheet porous carbon material of the present invention, in step S1, the reaction time is 2 to 10 hours, and for example, may be 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours.
In the method for preparing the oxynitride-doped sphere/sheet porous carbon material, in step S1, the molar ratio of hexabromobenzene to pyridine is 0.01 to 0.03, and may be, for example, 1:100, 1:90, 1:80, 1:70, 1:60 or 1: 50.
In the preparation method of the nitrogen-oxygen doped ball/sheet porous carbon material of the present invention, in step S1, the reaction temperature is 140-.
In the method for preparing the nitrogen-oxygen doped sphere/sheet porous carbon material, in step S2, the obtained solid may be washed with petroleum ether, and the number of washing times may be 2-4.
In the method for preparing the nitrogen-oxygen doped sphere/sheet porous carbon material, in step S2, the vacuum drying temperature is 60-100 ℃, for example, 60 ℃, 80 ℃ or 100 ℃; the drying time is 8 to 12 hours, and may be, for example, 8 hours, 10 hours, or 12 hours.
In the preparation method of the nitrogen-oxygen doped ball/sheet porous carbon material of the present invention, in step S3, the temperature of the high temperature treatment is 800-.
In the method for preparing the nitrogen-oxygen doped sphere/sheet porous carbon material of the present invention, in step S3, the high temperature treatment time is 1 to 3 hours, for example, 1 hour, 2 hours or 3 hours.
In the method for preparing the nitrogen-oxygen doped sphere/sheet porous carbon material, in step S3, the inert gas is nitrogen or argon.
In summary, the high-temperature baking treatment in step 3 is to place the dried sample in the temperature range and inert gas for 1-3 hours, so as to obtain the nitrogen-oxygen doped sphere/sheet porous carbon material of the present invention.
The present inventors have found that when such a preparation method is used, a nitrogen-oxygen doped sphere/sheet porous carbon material with excellent electrical properties can be obtained, which all result in significant performance degradation when certain process parameters are changed.
The nitrogen-oxygen doped hierarchical porous carbon material prepared in the step (1) has excellent electrical properties and relatively small material resistance, so that the nitrogen-oxygen doped hierarchical porous carbon material can be applied to the field of lithium battery cathode materials and has good application prospects and industrialization potentials. The nitrogen-oxygen doped hierarchical porous carbon material can also be used for assembling lithium batteries.
The inventor finds that the cathode material containing the nitrogen-oxygen doped sphere/sheet porous carbon material has good electrochemical performance, such as the excellent performances of corrected oxygen reduction peak potential (-0.118V Vs.Ag/AgCl), half-wave potential (-0.1V Vs.Ag/AgCl), long cycle life, low cost, environmental friendliness and the like, so that the cathode material can be applied to the field of fuel cell electrode materials.
Based on the above research results, a second aspect of the present invention is directed to providing an oxygen reduction electrode obtained by the above method.
As described above, the oxygen reduction electrode has various excellent electrochemical properties, so that it can be applied to a fuel cell, thereby obtaining a fuel cell having excellent properties.
As described above, the present invention provides an oxygen reduction electrode based on a nitrogen-oxygen doped sphere/sheet porous carbon material, a preparation method thereof, a use thereof, and an oxygen reduction electrode comprising the same, wherein the nitrogen-oxygen doped sphere/sheet porous carbon material has excellent performance, can be used for preparing an oxygen reduction electrode of a fuel cell, can be used in the fuel cell, exhibits good electrochemical performance, and has great application potential and industrial value in the electrochemical field.
According to the nitrogen-oxygen doped sphere/sheet porous carbon material, the heteroatom-doped carbon sphere and carbon nanosheet porous channel composite structure increases the active sites of the material and improves the stability of the material. The material has low preparation cost, and the synthesis method has excellent oxygen reduction (ORR) performance when being used as a fuel cell electrode material, thereby having good industrial production prospect.
The invention adopts a solvothermal method to directly prepare a crude product of the nitrogen-oxygen doped ball/sheet porous carbon material through one-step in-situ dehalogenation polymerization reaction, adopts temperature programming carbonization under the protection of inert gas, and grinds the product after cooling to obtain the nitrogen-oxygen doped ball/sheet porous carbon material. The nitrogen-oxygen doped sphere/sheet porous carbon material is stable in structure and good in conductivity (the material resistance is only 15.96m omega, and the conductivity is 8.11 x 10) -4 Omega m), has a plurality of catalytic active sites, can be used for preparing an oxygen reduction electrode of a fuel cell, can be used in the fuel cell and shows good electrochemical performance; due to the simple synthesis process, environmental friendliness and excellent electrochemical performance of the method, the low-cost large-scale preparation of the nitrogen-oxygen doped sphere/sheet porous carbon material can be realized, so that the method has good application prospect and industrialization potential.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
The four small figures in fig. 1 are a Scanning Electron Microscope (SEM) image, a Transmission Electron Microscope (TEM) image and a High Resolution (HRTEM) image of the spherical and sheet-like materials, and an element distribution map (EDS) of the nitrogen-oxygen doped spherical/sheet porous carbon material prepared in example 1 of the present invention, from left to right, from top to bottom, in that order.
FIG. 2 is a Raman diagram of a nitrogen-oxygen doped sphere/sheet porous carbon material according to example 1 of the present invention;
FIG. 3 is a nitrogen adsorption graph of a nitrogen-oxygen doped sphere/sheet porous carbon material according to example 1 of the present invention;
FIG. 4 is a graph showing the pore size distribution of the N-doped sphere/sheet porous carbon material of example 1 of the present invention;
FIG. 5 is a XPS high resolution C1s spectrum of a nitrogen-oxygen doped sphere/sheet porous carbon material of example 1 of the present invention;
FIG. 6 is a XPS high resolution N1s spectrum of a nitrogen-oxygen doped sphere/sheet porous carbon material using example 1 of the present invention;
FIG. 7 is a XPS high resolution O1s spectrum of a nitrogen-oxygen doped sphere/sheet porous carbon material using example 1 of the present invention;
FIG. 8 is a CV curve of oxygen reduction electrode prepared by using the N-doped ball/sheet porous carbon material of example 1 of the present invention, with a sweep rate of 10mV/s, for oxygen reduction in an argon/oxygen saturated state;
FIG. 9 is a graph of the linear scan of oxygen reduction at different rotational speeds of an oxygen reduction electrode made using the nitrogen-oxygen doped sphere/sheet porous carbon material of example 1 of the present invention, with a scan rate of 10mV/s, in an oxygen saturated state;
FIG. 10 is a Koutecky-Levich diagram of an oxygen reduction electrode made using the nitrogen-oxygen doped sphere/sheet porous carbon material of example 1 of the present invention;
FIG. 11 is a graph comparing methanol poisoning resistance tests of oxygen reduction electrodes made using nitrogen oxygen doped ball/sheet porous carbon material of example 1 of the present invention with 20% Pt/C catalyst;
FIG. 12 is a graph showing the stability test of an oxygen reduction electrode fabricated using the nitrogen-oxygen-doped sphere/sheet porous carbon material of example 1 of the present invention;
FIG. 13 is a CV curve of oxygen reduction electrode prepared using the nitrogen-oxygen doped sphere/sheet porous carbon materials of examples 1 and 2-3 of the present invention at a sweep rate of 10mV/s for oxygen reduction in an oxygen saturated state;
FIG. 14 is a CV curve of oxygen reduction electrode prepared using the nitrogen-oxygen doped sphere/sheet porous carbon materials of examples 1 and 4-5 of the present invention, with a sweep rate of 10mV/s, for oxygen reduction in an oxygen saturated state.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
1. Preparation method of nitrogen-oxygen doped ball/sheet porous carbon material
Example 1
S1: carrying out closed reaction on hexabromobenzene and pyridine at the reaction pressure of 3MPa and the temperature of 200 ℃ for 6 hours; wherein the mass ratio of hexabromobenzene to pyridine is 1: 80;
s2: after the reaction is finished, releasing pressure to normal pressure, naturally cooling to room temperature, fully washing the obtained solid with petroleum ether for 3 times, and performing vacuum drying at 40 ℃ for 10 hours to obtain a dried sample;
s3: and (3) treating the dried sample at a high temperature of 1000 ℃ for 2 hours under the protection of nitrogen, thereby obtaining the nitrogen-oxygen doped sphere/sheet porous carbon material which is named as P1.
Examples 2 to 3: examination of reaction ratio in step S1
The procedures were unchanged except for replacing the mass of the reacted hexabromobenzene in the step S1 with 2g and 6g, respectively, so that examples 2-3 were sequentially carried out, and the obtained oxynitride-doped sphere/sheet porous carbon materials were sequentially named as P2 and P3.
Examples 4 to 6: examination of high temperature processing temperature in step S3
The procedures were not changed except for replacing the high-temperature treatment temperature in step S3 with 900 ℃ and 1100 ℃, respectively, so that examples 4 to 5 were sequentially carried out, and the resulting nitrogen-oxygen-doped sphere/sheet porous carbon materials were sequentially named P4 and P5.
2. Preparation of oxygen reduction electrode of nitrogen-oxygen doped ball/sheet porous carbon material
Example 7: the preparation method of the oxygen reduction electrode comprises the following steps
(A) Firstly, grinding and polishing a glassy carbon electrode in alumina water slurry with the particle size of 1.0 mu m, then ultrasonically washing the glassy carbon electrode in acetone, absolute ethyl alcohol and high-purity water for 20-40 seconds in sequence, drying the glassy carbon electrode by using nitrogen, and then repeating the steps in the alumina water slurry with the particle size of 0.05 mu m to obtain a pretreated glassy carbon electrode;
(B) weighing a certain amount of the nitrogen-oxygen doped sphere/sheet porous carbon material and Nafion solution, dispersing in a mixed solution of ethanol water, and then carrying out ultrasonic dispersion for 5-15 minutes to obtain a uniformly mixed solution; and dripping the uniformly mixed solution on the pretreated glassy carbon electrode for multiple times, and drying at room temperature to obtain the oxygen reduction electrode. Wherein the mass of the nitrogen-oxygen doped ball/sheet porous carbon material is 4.00mg, and the mass of the nitrogen-oxygen doped ball/sheet porous carbon material is 0.8mL of ionized water, 0.2mL of absolute ethyl alcohol and 20 mu L of Nafion.
3. Test of nitrogen-oxygen doped ball/sheet porous carbon material electrode
The nitrogen-oxygen doped ball/sheet porous carbon material electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum sheet is used as a counter electrode, and the oxygen reduction performance of the nitrogen-oxygen doped ball/sheet porous carbon material electrode is tested by Autolab at 25 ℃ in a potential window of 0-minus 1.0V in 0.1M KOH electrolyte solution. Test results show that the nitrogen-oxygen doped ball/sheet porous carbon material electrode has an oxygen reduction peak potential of-0.118V (Vs.Ag/AgCl) and a half-wave potential of-0.1V (Vs.Ag/AgCl). The relative current density of the nitrogen-oxygen doped ball/sheet porous carbon material electrode has no obvious attenuation after continuous testing for 24 hours, and the final retention value is still nearly about 100%, which indicates that the composite material P1 has excellent cycling stability.
Microscopic characterization
The nitrogen-oxygen doped sphere/sheet porous carbon material P1 obtained in example 1 was subjected to microscopic characterization by a plurality of different means, and the results are as follows:
1. the four small images in fig. 1 are a Scanning Electron Microscope (SEM) image, a Transmission Electron Microscope (TEM) image and a High Resolution (HRTEM) image of the nitrogen-oxygen doped sphere/sheet porous carbon material prepared in example 1 of the present invention, and an element distribution map (EDS) from left to right, from top to bottom.
The material is seen to be a flaky and spherical composite material from an SEM image, and the material is seen to be composed of folded graphene sheets and microspheres from a TEM image; it can also be seen from HRTEM that the material has a rich pore structure. It can be seen from EDS that the material has only nitrogen, carbon and oxygen elements present and is uniformly distributed in the material.
2. Calculating I of the Material from the Raman plot of FIG. 2 D /I G When the graphite content is 0.92, the graphitization degree in the P1 is higher, and the graphitization degree is high, the conductivity of the material is good; but also has certain defects, and the defects provide more active sites for electrocatalysis.
3. From the nitrogen adsorption curve of fig. 3 it can be seen that the adsorption curve belongs to the typical ii adsorption curve and possesses a hysteresis loop of type H3, which is mutually verified with fig. 4.
4. From the pore size distribution diagram of fig. 4, it can be obtained that P1 has microporous, mesoporous, and macroporous compositions. The existence of mesopores and micropores increases the number of active sites for catalytic reaction.
5. From the XPS high resolution C1s spectrum of fig. 5, it can be seen that the bond energy is 284.8eV, C — C bond, 285.6eV, C — N bond, 286.3eV, C — O bond, and 290.0eV, COOR; wherein the carbon content is 94.39%.
6. From the XPS high resolution N1s spectrum of FIG. 6, the bond energies were 401.2eV for pyridine nitrogen bond, 402.5eV for quaternary amine nitrogen bond, 406.7eV for pyridine oxide nitrogen bond, 406.7eV for N-O x A functional group; the heteroatom nitrogen is 3.73%, and the presence of these functional groups provides more active sites for the reaction.
7. From the XPS high resolution O1s spectrum of fig. 7, it is found that the bond energy is C ═ O bond at 532.2eV, C — O bond at 533.2eV, COOR at 534.0eV, and heteroatom oxygen content is 1.75%;
electrochemical performance test
1. FIG. 8 is a CV curve of P1 electrode vs. oxygen reduction at argon/oxygen saturation with a sweep rate of 10 mV/s. Wherein, two closed rings from top to bottom are CV curves of an argon saturation state and an oxygen saturation state respectively. As can be seen from the graph, the CV curve of the P1 electrode in the argon saturation state is approximately rectangular, no reduction peak appears, and only the capacitance behavior is exhibited. But under the oxygen saturation state, an obvious reduction peak appears, and the potential of the reduction peak is-0.118V, which indicates that the composite material P1 has good response to oxygen.
2. FIG. 9 is a graph of the linear sweep of the P1 electrode at oxygen saturation for oxygen reduction at various rotational speeds, with a sweep rate of 10 mV/s. Wherein, the rotation speeds from top to bottom at the leftmost are respectively 400, 625, 900, 1225, 1600, 2025 and 2500 rpm.
As can be seen from the figure, the oxygen reduction current density has no obvious change along with the increase of the rotating speed in the voltage range of-0.17 to 0V, and the oxygen reduction current is mainly controlled by dynamics in the voltage range. And in the voltage range of-1V to-0.17V, the oxygen reduction current density is increased along with the increase of the rotating speed, which shows that the oxygen reduction current density is mainly controlled by diffusion in the voltage range.
3. FIG. 10 is a graph of the P1 electrode calculated for a material with substantially 4 electron transfer according to the LSV curve using the Koutecky-Levich equation.
4. Figure 11 is a comparison of the methanol poisoning resistance test of the P1 electrode with a 20% Pt/C catalyst. Wherein, at the leftmost side, the P1 electrode and the 20% Pt/C electrode are respectively arranged from top to bottom. As can be seen from the figure, when 3mol/L methanol aqueous solution is added at 300s, the current density of the P1 electrode is basically kept unchanged, and the current density of 20% Pt/C is changed obviously. This demonstrates that composite P1 has better resistance to methanol poisoning than the 20% Pt/C already commercialized.
5. Fig. 12 is a stability test chart of the P1 electrode. The cycling stability is the cycling stability tested by a chronoamperometry method, and the test conditions are as follows: at O 2 The test was carried out in a saturated 0.1mol/L KOH aqueous solution at 1600rpm for 24h at-0.25V. As can be seen from the graph, the relative current density of the P1 electrode has no obvious attenuation after continuous testing for 24h, and the final retention value is still nearly 100% or so, which indicates that the composite material P1 has excellent cycling stability.
Characterization of electrical properties of other materials
1. FIG. 13 is a CV curve of oxygen reduction electrode prepared using the nitrogen-oxygen doped sphere/sheet porous carbon materials of examples 1 and 2-3 of the present invention, with a sweep rate of 10mV/s, for oxygen reduction in an oxygen saturated state. As can be seen from the figure, the peak potential and the initial potential of the P1 electrode are positive compared with those of the P2 electrode and the P3 electrode, which indicates that the composite material P1 has excellent oxygen reduction performance.
FIG. 14 is a CV curve of oxygen reduction electrode prepared using the nitrogen-oxygen doped sphere/sheet porous carbon materials of examples 1 and 4-5 of the present invention, with a sweep rate of 10mV/s, for oxygen reduction in an oxygen saturated state. As can be seen from the figure, the peak potential and the initial potential of the P1 electrode are positive compared with those of the P4 electrode and the P5 electrode, which indicates that the composite material P1 has excellent oxygen reduction performance.
As described above, the invention provides a nitrogen-oxygen doped sphere/sheet porous carbon material, a preparation method and application thereof, and an oxygen reduction electrode prepared from the nitrogen-oxygen doped sphere/sheet porous carbon material.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (5)
1. A preparation method of an oxygen reduction electrode based on a nitrogen-oxygen doped spherical and flaky porous carbon material is characterized by comprising the following steps:
(1) the preparation method of the nitrogen-oxygen doped hierarchical porous carbon material comprises the following steps:
s1: carrying out a closed reaction on hexabromobenzene and pyridine at high temperature and high pressure;
s2: after the reaction is finished, releasing pressure to normal pressure, naturally cooling to room temperature, washing with deionized water and petroleum ether until the upper layer liquid is transparent, and drying the solid obtained after washing to obtain a dried sample;
s3: carrying out high-temperature roasting treatment on the dried sample under the protection of inert gas to obtain the nitrogen-oxygen doped hierarchical porous carbon material which is a spherical and flaky composite material;
(2) a method of oxygen reduction electrode preparation, the method comprising the steps of:
A. grinding and polishing a glassy carbon electrode in alumina water slurry with the particle size of 0.05-1.0 mu m, then ultrasonically washing the glassy carbon electrode in acetone, absolute ethyl alcohol and high-purity water for 20-40 seconds in sequence, and drying the glassy carbon electrode by blowing with nitrogen to obtain a pretreated glassy carbon electrode;
B. dispersing the nitrogen-oxygen doped hierarchical porous carbon material and the Nafion solution in a mixed solution of ethanol water, and then performing ultrasonic dispersion for 5-15 minutes to obtain a uniformly mixed solution; dripping the uniformly mixed solution on the pretreated glassy carbon electrode for multiple times, and drying at room temperature to obtain an oxygen reduction electrode;
the molar ratio of hexabromobenzene to pyridine is 0.0125;
in step S3, the temperature of the high-temperature treatment is 1000 ℃;
in step S1, the reaction pressure is 2-8MPa, and the reaction time is 2-10 hours;
in step S1, the reaction temperature is 140-260 ℃.
2. The method for preparing an oxygen reduction electrode based on a nitrogen-oxygen doped spherical and flaky porous carbon material according to claim 1, wherein: in step S2, the drying temperature is 60-100 deg.C and the drying time is 8-12 hours.
3. The method for preparing an oxygen reduction electrode based on a nitrogen-oxygen doped spherical and flaky porous carbon material according to claim 1, wherein: in step S3, the high temperature treatment time is 1 to 3 hours.
4. An oxygen reduction electrode obtained by the production method according to any one of claims 1 to 3.
5. A fuel cell comprising the oxygen-reducing electrode of claim 4.
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