CN112234213A - Preparation method and application of transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst - Google Patents
Preparation method and application of transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst Download PDFInfo
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- H—ELECTRICITY
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- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention discloses a preparation method and application of a transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst. The method comprises the following steps: (1) adding a transition metal salt and a carbon source into a dispersing agent and stirring to obtain a dispersing solution; (2) adding a sulfur source, a nitrogen source, a template agent and graphene into the dispersion liquid and stirring to obtain a mixed material; (3) heating and stirring the mixed material to remove the dispersant, drying, cooling and grinding to obtain fine particles; (4) calcining the particles in an inert atmosphere, cooling, washing, centrifuging and drying to obtain the transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst. The preparation method of the catalyst is simple, low in price and good in repeatability; the macroporous carbon electrocatalyst prepared by the invention has good oxygen reduction performance, can effectively reduce the overpotential of cathode oxygen reduction reaction, and when the electrocatalyst prepared by the invention is used for assembling a liquid electrolyte zinc-air battery, the open-circuit voltage and the constant current discharge time of the battery exceed the commercial Pt/C catalyst.
Description
Technical Field
The invention relates to the field of new energy material technology and electrochemical catalysis, in particular to a preparation method and application of a transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst.
Background
With the continuous development of society, the increasing energy demand of human beings leads to the rapid consumption of fossil fuels, meanwhile, the pollution caused by the combustion of fossil fuels leads to serious global environmental problems, and the exploration of clean and renewable energy technology is urgent for relieving the serious dependence of human beings on natural resources, so that scientists put a great deal of effort in the research and development of efficient, low-cost and environment-friendly energy conversion and storage systems. Among them, the Oxygen Reduction Reaction (ORR) is a cathode reaction that is commonly found in fuel cells and metal air cells, and catalysts used for the Oxygen Reduction Reaction (ORR) are mainly Pt and its alloys in consideration of activity and stability of the catalysts, but these noble metals are very rare in nature and expensive. The development of high-performance and low-cost oxygen reduction electrocatalysts is a key problem for promoting the development of novel energy sources and technologies thereof, and therefore, the development of novel oxygen reduction electrocatalysts becomes one of the hot topics of attention in the field.
Disclosure of Invention
The invention aims to provide a simple preparation method of a transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst, and the prepared electrocatalyst has a rich macroporous structure, a large specific surface area and good chemical stability, and can provide an enough reaction scene for an active site; the electrocatalyst has good conductivity and initial potential, and reduces the overpotential of oxygen reduction; the prepared transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst is assembled into a zinc-air battery, and the open-circuit voltage and the constant current discharge time of the battery exceed those of a commercial Pt/C catalyst.
The invention is realized by the following technical scheme:
a preparation method of a transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst is characterized by comprising the following steps:
(1) adding a transition metal salt and a carbon source into a dispersing agent and stirring to obtain a dispersion liquid;
(2) adding a sulfur source, a nitrogen source, a template agent and graphene into the dispersion liquid and stirring to obtain a mixed material; the sulfur source and the nitrogen source are the same substance;
(3) heating and stirring the mixed material to remove the dispersing agent, then drying, cooling and grinding to obtain fine particles;
(4) and calcining the particles under the protection of inert gas, cooling, washing, centrifuging and drying to obtain the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst.
Further, the transition metal salt in the step (1) is any one of cobalt chloride hexahydrate, ferric chloride hexahydrate and nickel chloride hexahydrate; the carbon source is amino acid; the dispersing agent is deionized water; the mass ratio of the transition metal salt to the amino acid is (0.5-1): 1; the mass-volume ratio of the carbon source to the dispersing agent is 3-10 mg/mL; the stirring is magnetic stirring, and the stirring time is 1-3 hours.
Further, the amino acid is any one of L-citrulline, L-cystine, L-methionine, L-arginine and D-glucosamine hydrochloride.
Further, in the step (2), the sulfur source and the nitrogen source are the same substance and are thiourea; the template agent is an inorganic salt template agent; the stirring is magnetic stirring, and the stirring time is 2-6 hours; the mass ratio of the thiourea to the inorganic salt template agent is 1: (20-30); the mass ratio of the thiourea to the graphene is 2: 1; the mass-volume ratio of the template agent to the dispersion liquid is 0.1-0.2 g/mL.
Further, the inorganic salt template agent is any one of sodium chloride, potassium chloride and sodium sulfate. The inorganic salt template has pore-forming effect to form macroporous electrocatalyst.
Further, in the step (3), the mixed material is stirred for 1-2 hours under the condition of oil bath at the temperature of 60-90 ℃ to remove the dispersing agent, and then is dried for 1-3 hours under vacuum at the temperature of 60-80 ℃, cooled to room temperature after drying, and ground after cooling to obtain fine particles.
Further, in the step (4), under the protection of inert gas, placing the particles in a tubular furnace for heating and calcining, heating to 600-900 ℃, keeping for 2-4 hours after heating, cooling to room temperature after calcining, then washing with deionized water, then performing centrifugal separation, and finally drying for 1-3 hours at 60-80 ℃ to obtain the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst.
The invention provides a method for preparing a transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst by using an inorganic salt template agent. According to the invention, the electrocatalytic activity can be obviously improved by introducing a trace amount of transition metal into the carbon material, the Co, Fe or Ni transition metal is coordinated with a compound containing S, N atoms, and the mixture is mixed with a carbon carrier and then calcined at high temperature under the protection of inert gas to obtain the oxygen reduction electrocatalyst with the synergistic action of the transition metal and S, N, so that a novel preparation method and a novel carrier material are searched while the cost of the oxygen reduction electrocatalyst is reduced.
The application of the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst is characterized in that the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst prepared by the preparation method is used in a zinc-air battery. The inventionThe prepared transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst has good oxygen reduction performance, the half-wave potential in 0.1M KOH solution is 812mV, and the half-wave potential of a commercial Pt/C catalyst is 802mV under the same condition, so that the overpotential of cathode oxygen reduction reaction is effectively reduced, and the Oxygen Reduction Reaction (ORR) process conforms to the 4-electron catalysis mechanism. The open-circuit voltage of the zinc-air battery assembled by the catalyst prepared by the invention is 1.465V and is 5mA cm-2Constant current discharge time at current density of 1400 minutes, while open circuit voltage of 1.432V at 5mA cm for a commercial Pt/C catalyst assembled zinc-air cell under the same conditions-2The constant current discharge time at current density lasted only 500 minutes.
The invention has the beneficial effects that:
(1) the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst is simple in preparation method, low in price and good in repeatability, and has important theoretical and practical significance for developing novel electrochemical catalysts and zinc-air batteries;
(2) when the electrocatalyst prepared by the invention is used for assembling the liquid electrolyte zinc-air battery, the open-circuit voltage and the constant current discharge time of the battery exceed the commercial Pt/C catalyst; according to the invention, transition metal salt and amino acid are mixed and stirred, thiourea is added to introduce nitrogen and sulfur elements, and inorganic salt is added to serve as a template, so that the reaction active sites and defects of the material are effectively increased; then calcining and carbonizing the mixture in inert atmosphere to form the macroporous carbon material prepared by an inorganic salt template method, thereby further improving the electrocatalytic performance of the material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are 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 obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is an oxygen reduction linear voltammetry (ORR-LSV) curve for two cobalt and sulfur nitrogen Co-doped macroporous carbon electrocatalysts (Co/S/N @ rGO) and a commercial Pt/C catalyst (model P822267) prepared in example 1 of the present invention;
FIG. 2 is an oxygen reduction linear voltammetry curve (ORR-LSV) of a cobalt and sulfur nitrogen Co-doped macroporous carbon electrocatalyst (Co/S/N @ rGO) prepared in example 1 of the present invention at different rotation speeds;
FIG. 3 shows the number of transferred electrons and H of cobalt and sulfur-nitrogen Co-doped macroporous carbon electrocatalyst (Co/S/N @ rGO) prepared in example 1 of the present invention obtained by a rotating ring disk-disk test2O2Yield;
FIG. 4 shows that the zinc-air cell assembled by cobalt and sulfur-nitrogen Co-doped macroporous carbon electrocatalyst (Co/S/N @ rGO) and commercial Pt/C catalyst (model P822267) prepared in example 1 of the invention is at 5mA cm-2And (5) a lower constant current discharge curve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a cobalt and sulfur-nitrogen co-doped macroporous carbon electrocatalyst comprises the following specific steps:
(1) adding 75.0mg of cobalt chloride hexahydrate and 100.0mg of D-glucosamine hydrochloride into 30.0mL of deionized water, and magnetically stirring for 2 hours to obtain a dispersion liquid;
(2) adding 100.0mg of thiourea, 3.0g of sodium chloride and 50.0mg of graphene into the dispersion liquid, and magnetically stirring for 2 hours to obtain a mixed material; the thiourea is used as a sulfur source and a nitrogen source at the same time;
(3) stirring the obtained mixed material for 1 hour under the condition of an oil bath at the temperature of 80 ℃ to remove deionized water, then putting the mixed material into a vacuum drying oven, drying the mixed material for 2 hours at the temperature of 60 ℃, cooling the dried mixed material to room temperature, cooling the dried mixed material, and grinding the cooled mixed material to obtain fine particles;
(4) under the protection of inert gas, putting the ground fine particles into a quartz boat, putting the quartz boat into a tube furnace, heating the furnace to 800 ℃ at the heating rate of 5 ℃/min, calcining the quartz boat for 2 hours at 800 ℃, cooling the quartz boat to room temperature after calcination, washing the quartz boat with deionized water, performing centrifugal separation, drying the precipitate for 3 hours at 60 ℃ after centrifugation, and obtaining 30.0mg of cobalt and sulfur nitrogen Co-doped macroporous carbon electrocatalyst (Co/S/N @ rGO).
Example 2
A preparation method of an iron and sulfur nitrogen co-doped macroporous carbon electrocatalyst comprises the following steps:
(1) adding 100.0mg of ferric chloride hexahydrate and 200.0mg of L-citrulline into 30.0mL of deionized water, and magnetically stirring for 3 hours to obtain a dispersion liquid;
(2) adding 200.0mg of thiourea, 4.0g of potassium chloride and 100.0mg of graphene into the dispersion liquid, and magnetically stirring for 5 hours to obtain a mixed material; the thiourea is used as a sulfur source and a nitrogen source at the same time;
(3) stirring the obtained mixed material for 2 hours under the condition of oil bath at 60 ℃ to remove deionized water, then putting the mixed material into a vacuum drying oven, drying the mixed material for 1 hour at 80 ℃, cooling the dried mixed material to room temperature, and grinding the dried mixed material after cooling to obtain fine particles;
(4) under the protection of inert gas, putting the ground fine particles into a quartz boat, putting the quartz boat into a tube furnace, heating the furnace to 900 ℃ at the heating rate of 10 ℃/min, calcining the quartz boat for 3 hours at 900 ℃, cooling the quartz boat to room temperature after calcining, washing the quartz boat with deionized water, performing centrifugal separation, drying the precipitate for 1 hour at 70 ℃ after centrifuging, and obtaining the 90.0mg iron and sulfur nitrogen co-doped macroporous carbon electrocatalyst (Fe/S/N @ rGO).
Example 3
A preparation method of a cobalt and sulfur-nitrogen co-doped macroporous carbon electrocatalyst comprises the following specific steps:
(1) adding 225.0mg of nickel chloride hexahydrate and 300.0mg of L-cystine into 30.0mL of deionized water, and magnetically stirring for 1 hour to obtain a dispersion liquid;
(2) adding 300.0mg of thiourea, 6.0g of sodium sulfate and 150.0mg of graphene into the dispersion liquid, and magnetically stirring for 6 hours to obtain a mixed material; the thiourea is used as a sulfur source and a nitrogen source at the same time;
(3) stirring the obtained mixed material for 1 hour under the condition of oil bath at the temperature of 90 ℃ to remove deionized water, then putting the mixed material into a vacuum drying oven, drying the mixed material for 2 hours at the temperature of 70 ℃, cooling the dried mixed material to room temperature, cooling the dried mixed material, and grinding the cooled mixed material to obtain fine particles;
(4) under the protection of inert gas, putting the ground fine particles into a quartz boat, putting the quartz boat into a tube furnace, heating the furnace to 600 ℃ at the heating rate of 3 ℃/min, calcining the quartz boat for 4 hours at 600 ℃, cooling the quartz boat to room temperature after calcining, washing the quartz boat with deionized water, performing centrifugal separation, drying the precipitate for 2 hours at 80 ℃ after centrifuging, and obtaining the nickel and sulfur nitrogen co-doped macroporous carbon electrocatalyst (Ni/S/N @ rGO) of 120.0 mg.
Example 4
1.0mg of the cobalt and sulfur-nitrogen Co-doped macroporous carbon electrocatalyst (Co/S/N @ rGO) prepared in example 1 and a commercial Pt/C catalyst (model P822267) were dispersed in 200. mu.l of ethanol and 9.8. mu.l of NaFion solution, ultrasonically mixed, 20. mu.l of slurry was applied to a rotating disk electrode, and after completely dried, the oxygen reduction linear voltammetry curve (ORR-LSV) was determined on an electrochemical workstation. The ORR-LSV curve is measured by taking a saturated Ag/AgCl electrode as a reference electrode, taking a Pt electrode as a counter electrode, sweeping the speed of 10mV/s and using 0.1M KOH as electrolyte. O is required before the ORR catalytic performance test2The saturation treatment (i.e. introducing oxygen at a flow rate of 50ml/min before the test to saturate the gas in the solution) is carried out, the ORR-LSV curve obtained by the test is shown in figure 1, and it can be clearly seen that in the solution of 0.1M KOH, the half-wave potential of the cobalt-sulfur-nitrogen Co-doped macroporous carbon electrocatalyst (Co/S/N @ rGO) prepared by the inorganic salt template method is 812mV, while the half-wave potential of the commercial Pt/C catalyst under the same condition is 802mV, which is shifted by 10mV, so that the overpotential of the Oxygen Reduction Reaction (ORR) is effectively reduced, and the performance is superior to that of the commercial Pt/C catalyst.
And then, an ORR-LSV curve of the cobalt and sulfur-nitrogen Co-doped macroporous carbon electrocatalyst (Co/S/N @ rGO) at different rotating speeds of 1600,1200,900,600,400 is tested, and the electrocatalyst is obtained by calculation through a K-L equation and accords with a 4 electron transfer mechanism as shown in figure 2. Electron transfer number and H obtained by testing with rotating ring disk electrode2O2The yield, as shown in FIG. 3, was consistent with the results obtained from the test of FIG. 2, while H was2O2The yield is very low, and the macroporous carbon electrocatalyst prepared by the inorganic salt template method is further verified to be an electrocatalyst conforming to a 4 electron transfer mechanism.
The catalyst (Co/S/N @ rGO) is used for assembling a liquid electrolyte zinc-air battery, and the open-circuit voltage of the battery is 1.465V; at 5mA cm-2The constant current discharge time was measured at the current density, and as shown in FIG. 4, it can be seen that the liquid electrolyte zinc-air battery assembled in example 1 of the present invention was 5mA cm-2Constant current discharge time at current density lasted 1400 minutes, while the open circuit voltage of a liquid electrolyte zinc-air cell assembled under the same conditions with a commercial Pt/C catalyst ((model P822267)) was 1.432V at 5mA cm-2The constant current discharge time at current density lasted only 500 minutes. Two liquid electrolyte zinc-air cells assembled in series using this catalyst (Co/S/N @ rGO) can be used to power a 3V diode. The preparation method of the electrocatalyst with the Oxygen Reduction Reaction (ORR) process conforming to the 4-electron catalysis mechanism is simple, low in cost, excellent in catalytic performance and good in repeatability, and has good theoretical and practical significance for developing novel electrocatalysts and zinc-air batteries.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (9)
1. A preparation method of a transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst is characterized by comprising the following steps:
(1) adding a transition metal salt and a carbon source into a dispersing agent and stirring to obtain a dispersion liquid;
(2) adding a sulfur source, a nitrogen source, a template agent and graphene into the dispersion liquid and stirring to obtain a mixed material; the sulfur source and the nitrogen source are the same substance;
(3) heating and stirring the mixed material to remove the dispersing agent, then drying, cooling and grinding to obtain fine particles;
(4) and calcining the particles under the protection of inert gas, cooling, washing, centrifuging and drying to obtain the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst.
2. The preparation method of the transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst according to claim 1, wherein the transition metal salt in step (1) is any one of cobalt chloride hexahydrate, ferric chloride hexahydrate and nickel chloride hexahydrate; the carbon source is amino acid; the dispersing agent is deionized water; the mass ratio of the transition metal salt to the amino acid is (0.5-1): 1; the mass-volume ratio of the carbon source to the dispersing agent is 3-10 mg/mL; the stirring is magnetic stirring, and the stirring time is 1-3 hours.
3. The method for preparing the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst according to claim 2, wherein the amino acid is any one of L-citrulline, L-cystine, L-methionine, L-arginine, and D-glucosamine hydrochloride.
4. The preparation method of the transition metal and sulfur-nitrogen co-doped macroporous carbon electrocatalyst according to claim 1, wherein the sulfur source and the nitrogen source in step (2) are the same substance and are thiourea; the template agent is an inorganic salt template agent; the stirring is magnetic stirring, and the stirring time is 2-6 hours; the mass ratio of the thiourea to the inorganic salt template agent is 1: (20-30); the mass ratio of the thiourea to the graphene is 2: 1; the mass-volume ratio of the template agent to the dispersion liquid is 0.1-0.2 g/mL.
5. The method for preparing a transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst according to claim 4, wherein the inorganic salt template agent is any one of sodium chloride, potassium chloride and sodium sulfate.
6. The preparation method of the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst as claimed in claim 1, wherein the step (3) is to stir the mixture for 1-2 hours at 60-90 ℃ in an oil bath to remove the dispersant, then to vacuum dry for 1-3 hours at 60-80 ℃, cool to room temperature after drying, and grind after cooling to obtain fine particles.
7. The preparation method of the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst as claimed in claim 1, wherein in the step (4), under the protection of inert gas, the particles are placed in a tubular furnace to be calcined at a temperature of 600 ℃ to 900 ℃ for 2-4 hours, and then cooled to room temperature after calcination, and then washed with deionized water, and then centrifugally separated, and finally dried at 60-80 ℃ for 1-3 hours to obtain the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst.
8. The preparation method of the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst according to claim 7, wherein the temperature rise rate is 3-10 ℃/min.
9. The application of the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst is characterized in that the transition metal and sulfur and nitrogen co-doped macroporous carbon electrocatalyst prepared by the preparation method in any one of claims 1 to 8 is used in a zinc-air battery.
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