CN110707337B - Preparation method and application of carbon-based non-noble metal oxygen reduction catalyst - Google Patents
Preparation method and application of carbon-based non-noble metal oxygen reduction catalyst Download PDFInfo
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- CN110707337B CN110707337B CN201910929770.7A CN201910929770A CN110707337B CN 110707337 B CN110707337 B CN 110707337B CN 201910929770 A CN201910929770 A CN 201910929770A CN 110707337 B CN110707337 B CN 110707337B
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the field of energy materials, and particularly relates to a carbon-based non-noble metal oxygen reduction catalyst and a preparation method thereof, and further relates to an electrocatalysis application of the catalyst in a cathode oxygen reduction reaction of a fuel cell. The method is characterized in that the polypyrrole doped with ferrocyanide is prepared by adopting an anion doping method, sublimed sulfur is added in the pyrolysis process, heteroatom sulfur is further introduced, and the sulfur and nitrogen co-doped carbon-based non-noble metal oxygen reduction catalyst is prepared. The oxygen reduction catalyst of the invention shows high-efficiency oxygen reduction electrochemical performance and stability, the half-wave potential of the oxygen reduction electrochemical reaction of the preferable oxygen reduction catalyst is (0.89V vs. RHE), which is superior to commercial platinum carbon (0.84V vs. RHE), and the electrochemical stability of the preferable oxygen reduction catalyst is greatly superior to commercial platinum carbon; assembled into a zinc-air battery with the maximum output power of 94mW/cm2Better than 20 wt% commercial platinum carbon (maximum output power 78 mW/cm)2)。
Description
Technical Field
The invention belongs to the field of energy materials, and particularly relates to a carbon-based non-noble metal oxygen reduction catalyst and a preparation method thereof, and further relates to an electrocatalysis application of the catalyst in a cathode oxygen reduction reaction of a fuel cell.
Background
With the rapid consumption of traditional fossil fuels, it becomes more urgent to explore clean and renewable energy technologies to solve the problems of energy shortage and environmental pollution. Among all energy storage and conversion systems, fuel cells are called "green energy for the 21 st century" because of their advantages of high energy density, light weight, abundant sources of materials, no pollution, etc. The anode of the fuel cell mainly generates oxidation reaction (H) of hydrogen gas2→2H++2e－HOR), the reaction is relatively simple and a fast kinetic process; the cathode mainly generates the reduction reaction of oxygen (1/2O)2+2H+→H2O, ORR), generally need to be carried out at a higher overpotential, and its slow kinetics severely limit the energy conversion efficiency of the fuel cell. Platinum (Pt) catalysts with good molecular adsorption and dissociation characteristics are currently the most desirable and currently the only commercially available oxygen reduction catalyst material. However, since platinum metal is expensive, it is used in a large amount in a fuel cell (the amount of Pt supported on the cathode side is generally 0.4 mg. cm)－2) So that the catalyst cost accounts for more than about 50% of the total cell cost. Dependence of fuel cells on platinum-based catalysts is resistanceWhich hinders the bottleneck of its large-scale commercial application. In addition, the Pt-based oxygen reduction catalyst has problems of poor stability and being easily poisoned by trace amount of carbon monoxide that may be carried in hydrogen gas. Therefore, the oxygen reduction reaction catalyst with high development efficiency, good stability and low cost replaces a platinum-based catalyst, is a research hotspot in the field and also has important practical application value.
Currently, research on non-platinum based oxygen reduction catalysts has focused primarily on transition metal oxides, transition metal-containing nitrogen-doped carbon materials, and fully non-metallic heteroatom-doped carbon materials. The catalyst has the characteristics of rich raw material sources, low price, methanol permeation resistance and the like, can reach the activity equivalent to that of Pt under the acidic or alkaline condition, and is considered to have the possibility of replacing noble metal Pt as an oxygen reduction catalyst. Of these, pyrolytic Fe/N-C as a non-noble metal ORR catalyst has shown great application potential in recent years and is currently the most promising oxygen reduction catalyst to replace Pt. The synthesis method of the Fe/N-C catalyst has various types, for example, a macrocyclic iron compound and an organic metal framework complex are directly used for pyrolysis, the synthesis efficiency is high, the structure is stable, and the control of the content of effective iron is more rigid because the Fe/N coordination structure and the proportion of a precursor of the catalyst are fixed. The method can also be used for one-pot pyrolysis of small molecular iron compounds and nitrogen-containing compounds, the precursor material source is wide, the structural design is flexible and various, the effective iron load can be improved, but the experimental condition variables are numerous, and the multi-factor process regulation and control is complex and time-consuming.
Disclosure of Invention
Aiming at the defects of the prior art and the requirements of research and application in the field, the invention provides a preparation method and application of a Fe/N-C catalyst which is low in price, simple in preparation process and high in activity and stability.
The preparation method of the oxygen reduction catalyst comprises the following step of preparing polypyrrole as a catalyst precursor by adopting an anion doping method. According to a cationic free radical mechanism of pyrrole polymerization, a polypyrrole chain segment contains a large amount of positive charges, iron-containing anion ferrocyanide is doped into the polypyrrole chain segment through electrostatic action, active sites can be effectively prevented from being aggregated in a pyrolysis process, and the active sites inside can be protected by an externally coated carbon material. And further introducing heteroatom S in a mode of adding sublimed sulfur in the pyrolysis process to prepare the sulfur and nitrogen co-doped carbon-based non-noble metal oxygen reduction catalyst. The catalyst has high-efficiency oxygen reduction catalytic performance, and can be applied to air electrode catalysts of hydrogen-oxygen fuel cells, zinc-air fuel cells, magnesium-air fuel cells and aluminum-air fuel cells.
A preparation method of a carbon-based non-noble metal oxygen reduction catalyst comprises the following steps:
step 1: preparation of sodium ferrocyanide-doped polypyrrole: adding 0-0.024mol (0-11.626g) of sodium ferrocyanide decahydrate, 0.016mol (3.648g) of ammonium persulfate and 200mL of distilled water into a 500mL three-neck flask under the protection of nitrogen, maintaining the system temperature at 0 ℃ and a fixed stirring speed in a cold machine for dissolving for 10min, dissolving 0.012mol (840 mu L) of pyrrole in 50mL of absolute ethyl alcohol, transferring into a separating funnel, slowly dripping into the three-neck flask, continuously stirring for 6h to obtain a black product, carrying out suction filtration, washing with distilled water for multiple times in the process, and drying in a vacuum drying oven at 60 ℃ for 24h to obtain the sodium ferrocyanide doped polypyrrole.
Step 2: preparation of carbon-based oxygen reduction catalyst: 100mg of sodium ferrocyanide doped polypyrrole and 0-500mg of sublimed sulfur are taken, and a proper amount of absolute ethyl alcohol is used as a wetting agent to be ground and mixed in a mortar until the mixture is uniform. And then placing the obtained product in a clean porcelain boat, placing the porcelain boat in a high-temperature tube furnace, under the protection of nitrogen, firstly raising the temperature to 800-1000 ℃ by a program of 5 ℃/min, maintaining for 2h, and then lowering the temperature to 25 ℃ by a program of 10 ℃/min to obtain the doped carbon material.
The invention discloses application of a carbon-based non-noble metal oxygen reduction catalyst, and the oxygen reduction catalyst is applied to an air electrode catalyst of a hydrogen-oxygen fuel cell, a zinc-air fuel cell, a magnesium-air fuel cell or an aluminum-air fuel cell.
The preparation method of the air electrode comprises the following steps: ethanol and 5% Nafion solution are mixed according to the volume ratio (10-25): 1 obtaining a mixed solution, and compounding carbon baseUltrasonically dispersing the assembled oxygen reduction catalyst into the mixed solution, spraying the mixed solution on a carbon paper or carbon cloth electrode, and drying to obtain the air electrode, wherein the loading capacity of the catalyst is 1mg/cm2。
The invention has the beneficial effects that: (1) polypyrrole doped with ferrous cyanide anions is used as a precursor of the carbon-based oxygen reduction catalyst for the first time, and sulfur doping is carried out on the polypyrrole by adding sublimed sulfur in the pyrolysis process to obtain the oxygen reduction catalyst with a microporous and mesoporous combined hierarchical pore structure; the special assembly structure realizes the uniform dispersion and stable loading of the catalytic active sites, and is very beneficial to the diffusion and rapid transportation of oxygen, thereby accelerating the dynamic process of the oxygen reduction catalytic reaction. (2) The oxygen reduction catalyst of the invention shows high-efficiency oxygen reduction electrochemical performance and stability, the half-wave potential of the oxygen reduction electrochemical reaction of the preferable oxygen reduction catalyst is (0.89V vs. RHE), which is superior to commercial platinum carbon (0.84V), and the electrochemical stability of the preferable oxygen reduction catalyst is greatly superior to the commercial platinum carbon; assembled into a zinc-air battery with the maximum output power of 94mW/cm2Better than 20 wt% commercial platinum carbon (maximum output power 78 mW/cm)2)。
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a scanning electron micrograph of polypyrrole prepared in example 1;
FIG. 2 is a SEM photograph of the C-based oxygen reduction catalyst prepared in example 2;
FIG. 3 is a cyclic voltammogram of the carboxy reduction catalyst prepared in example 3;
FIG. 4 is a linear scan plot of the carboxy reduction catalyst prepared in example 3;
FIG. 5 is a linear scan plot of the carbon-based oxygen reduction catalyst prepared in example 3 at different rotational speeds;
FIG. 6 is a current-time curve of the carboxy reduction catalyst prepared in example 3;
fig. 7 is an open circuit voltage curve of the zinc-air fuel cell made in example 4;
fig. 8 is a polarization curve of the zinc-air fuel cell made in example 4;
Detailed Description
Example 1: preparation of sodium ferrocyanide-doped polypyrrole: adding 0.024mol (11.626g) of sodium ferrocyanide decahydrate, 0.016mol (3.648g) of ammonium persulfate and 200mL of distilled water into a 500mL three-neck flask under the protection of nitrogen, maintaining the system temperature at 0 ℃ and a fixed stirring speed in a cold machine to dissolve for 10min, dissolving 0.012mol (840 mu L) of pyrrole in 50mL of absolute ethyl alcohol, transferring the solution into a separating funnel to be slowly dripped into the three-neck flask, continuously stirring for 6h to obtain a black product, carrying out suction filtration, washing with distilled water for multiple times in the process, and drying in a vacuum drying oven at 60 ℃ for 24h to obtain the sodium ferrocyanide doped polypyrrole. FIG. 1 is a scanning electron micrograph of the polypyrrole obtained.
Example 2: preparation of carbon-based oxygen reduction catalyst: 100mg of sodium ferrocyanide doped polypyrrole and 300mg of sublimed sulfur are taken, and a proper amount of absolute ethyl alcohol is used as a wetting agent to be ground and mixed in a mortar until the mixture is uniform. And then placing the obtained product in a clean porcelain boat, placing the porcelain boat in a high-temperature tube furnace, under the protection of nitrogen, firstly raising the temperature to 900 ℃ by a program of 5 ℃/min, maintaining for 2 hours, then lowering the temperature to 25 ℃ by a program of 10 ℃/min, and obtaining a doped carbon material which is named as Fe/3S/N-C, wherein figure 2 is a scanning electron microscope photo of the prepared corresponding carbon material.
Example 3: manufacturing an oxygen reduction working electrode: 5 mg of the above synthesized sample was dispersed in 800. mu.l of a Nafion isopropyl alcohol solution with a volume fraction of 3%, the material was uniformly dispersed by sonication, 10. mu.l was dropped on a dried rotating disk electrode (diameter 5mm), and after natural drying, the electrochemical catalytic performance of the sample was tested. FIG. 3 is a cyclic voltammogram of the oxygen reduction catalyst obtained in this example at saturated N2Under the condition of 0.1M KOH electrolyte solution, a cyclic voltammogram is similar to a rectangle in a voltage range of 0.2-1.0V, and no obvious reduction peak exists. Relatively speaking, at saturation O2The obvious characteristic peak of Oxygen Reduction Reaction (ORR) appears under the condition of 0.1M KOH electrolyte solution, which shows that the material has remarkable electrocatalytic activity for the oxygen reduction reaction, and the voltage of the reduction peak is equal to 0.87V. FIG. 4 shows the oxygen reduction catalyst obtained in the present exampleSaturated O2The catalyst exhibited a higher half-wave potential (0.84V) than 20 wt% commercial platinum carbon, indicating that the catalyst had better catalytic activity than commercial platinum carbon, in an electrolyte solution (0.1M KOH) and a linear scan curve at 1600rmp rpm with a half-wave potential of 0.89V. FIG. 5 shows the oxygen reduction catalyst obtained in this example in the presence of saturated O2The electron transfer number of the linear scanning curve in the electrolyte solution (0.1M KOH) and at different rotating speeds is about 4 calculated by the corresponding Koutecky-levich equation, belongs to a reaction path with four dominant electrons, and shows high-efficiency ORR catalytic activity. Fig. 6 is a current-time curve of the oxygen reduction catalyst obtained in this example, which shows superior stability to commercial platinum carbon. After 10000s hold, there is still 97% current hold, much higher than commercial platinum carbon (62% current hold).
Example 4: preparing an air electrode: mixing a 5% Nafion solution, ultrapure water and ethanol according to a volume ratio of 3: 30: 70 obtaining a mixed solution, ultrasonically dispersing the prepared oxygen reduction catalyst into the mixed solution, then spraying the mixed solution on a carbon paper or carbon cloth electrode, and drying to obtain the air electrode, wherein the loading capacity of the catalyst is 1mg/cm2. For comparison, an air electrode was fabricated by the same procedure with 20 wt% of commercial platinum carbon as a catalyst. The manufactured air electrode is used as a cathode, a zinc sheet is used as an anode, 6M KOH solution is used as electrolyte to form a zinc-air fuel cell, and the open-circuit voltage and the polarization curve of the cell are obtained by testing at normal temperature and normal pressure. Fig. 7 shows the open circuit voltage of the zinc-air fuel cell fabricated in this example, which is 1.51V, which is greater than that of a cell (1.48V) using 20 wt% commercial platinum carbon as ORR catalyst under the same conditions. FIG. 8 is a polarization curve of the zinc-air fuel cell fabricated in this example, calculated to correspond to a maximum power density of 94mW/cm2More than a single cell (78 mW/cm) using 20 wt% of commercial platinum carbon as ORR catalyst under the same condition2)。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention can be smoothly implemented by those skilled in the art in the light of the accompanying drawings and the above description; however, those skilled in the art should, upon attaining an understanding of the present disclosure, appreciate that many changes, modifications, and equivalents may be made to the invention without departing from the spirit and scope of the invention; meanwhile, any changes, modifications, evolutions, etc. of the equivalent changes made to the above embodiments according to the implementation technology of the present invention are within the protection scope of the technical solution of the present invention.
Claims (3)
1. A preparation method of a carbon-based non-noble metal oxygen reduction catalyst is characterized in that the catalyst is prepared by firstly preparing ferrocyanide doped polypyrrole by adopting an anion doping method, and then adding sublimed sulfur to the polypyrrole under the protection of inert gas for pyrolysis;
the preparation method of the carbon-based non-noble metal oxygen reduction catalyst comprises the following specific steps:
(1) preparation of sodium ferrocyanide-doped polypyrrole: adding sodium ferrocyanide decahydrate more than or equal to 0.024mol, 0.016mol ammonium persulfate and 200mL distilled water into a 500mL three-neck flask under the protection of nitrogen, maintaining the system temperature at 0 ℃ and a fixed stirring speed in a refrigerator to dissolve for 10min, dissolving 0.012mol pyrrole in 50mL absolute ethyl alcohol, transferring into a separating funnel, slowly dripping into the three-neck flask, continuously stirring for 6h to obtain a black product, carrying out suction filtration, washing with distilled water for multiple times in the process, and drying in a vacuum drying oven at 60 ℃ for 24h to obtain the sodium ferrocyanide doped polypyrrole;
(2) preparing a carbon-based non-noble metal oxygen reduction catalyst: taking sublimed sulfur of more than 0mg and less than or equal to 500mg and polypyrrole doped with 100mg of sodium ferrocyanide, grinding and mixing the sublimed sulfur and the polypyrrole in a mortar by using a proper amount of absolute ethyl alcohol as a wetting agent until the mixture is uniform, then placing the obtained product in a clean porcelain boat, placing the porcelain boat in a high-temperature tubular furnace, under the protection of nitrogen, firstly raising the temperature to 800-1000 ℃ by a program of 5 ℃/min, maintaining the temperature for 2h, and then reducing the temperature to 25 ℃ by a program of 10 ℃/min to obtain the carbon-based non-noble metal oxygen reduction catalyst.
2. A carbon-based non-noble metal oxygen reduction catalyst prepared by the preparation method of claim 1, which is characterized in that the molar weight of the added sodium ferrocyanide decahydrate is more than 0 time and less than or equal to 1.5 times of the molar weight of pyrrole monomer, the mass of the added sublimed sulfur is more than 0 time and less than or equal to 5 times of the mass of pyrrole, and the pyrolysis temperature is 800-1000 ℃ under the protection of inert gas.
3. Use of the carbon-based non-noble metal oxygen reduction catalyst prepared by the preparation method according to claim 1, wherein the catalyst is applied to an air electrode catalyst of a hydrogen-oxygen fuel cell, a zinc-air fuel cell, a magnesium-air fuel cell or an aluminum-air fuel cell.
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| CN114430047B (en) * | 2020-09-24 | 2024-04-02 | 中国石油化工股份有限公司 | Carbon material, platinum-carbon catalyst, and preparation method and application thereof |
| CN112397732A (en) * | 2020-11-13 | 2021-02-23 | 上海海事大学 | ORR catalyst material and preparation method and application thereof |
| CN113130924B (en) * | 2021-04-20 | 2022-09-06 | 中国科学技术大学 | Metal-air battery catalyst, preparation method and application thereof |
| CN114142049A (en) * | 2021-11-26 | 2022-03-04 | 武汉科思特仪器股份有限公司 | Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst |
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