CN112002912A - Preparation method of nitrogen-doped carbon paper oxygen reduction reaction catalyst - Google Patents
Preparation method of nitrogen-doped carbon paper oxygen reduction reaction catalyst Download PDFInfo
- Publication number
- CN112002912A CN112002912A CN202010916585.7A CN202010916585A CN112002912A CN 112002912 A CN112002912 A CN 112002912A CN 202010916585 A CN202010916585 A CN 202010916585A CN 112002912 A CN112002912 A CN 112002912A
- Authority
- CN
- China
- Prior art keywords
- carbon paper
- reduction reaction
- oxygen reduction
- nitrogen
- reaction catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
Abstract
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst, which comprises the following steps of firstly, mixing concentrated sulfuric acid and concentrated nitric acid to prepare mixed acid, placing carbon paper in the mixed acid, pretreating under ultrasonic oscillation, washing and drying; step two, the carbon paper after pretreatment is used as a cathode and contains Co2+、Fe2+、Fe3+Or Mn2+Electrodepositing a metal simple substance on the carbon paper in an ionic electrolyte solution, washing and drying; transferring the carbon paper deposited with the metal simple substance to a tubular furnace, and carrying out heat treatment in an ammonia atmosphere to realize the doping of nitrogen atoms to the carbon paper to obtain nitrogen-doped carbon paper oxygenAnd (3) a reduction reaction catalyst. The preparation method has the advantages of low cost and simple and convenient operation, and the catalyst prepared by the preparation method has good catalytic performance of oxygen reduction reaction and can be directly used as an electrode to be applied to the fields of fuel cells, metal air cells and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst.
Background
The development of clean and sustainable energy storage and conversion technology is a requirement for solving the problems of energy crisis, climate warming, environmental pollution and the like. Fuel cells have high efficiency, good safety, high energy density, and environmental friendliness, and are considered to be the most promising alternatives to fossil fuels for applications in the fields of portable power sources, vehicles, and the like. During discharge of the fuel cell, a reduction reaction process occurs in which oxygen gas obtains electrons at the cathode. The oxygen reduction reaction is a kinetic retardation process and needs to be promoted by a catalyst to be effectively carried out.
Under current state of the art, platinum based catalysts are effective oxygen reduction catalysts. The platinum-based catalyst has the defects of poor stability and poor tolerance to methanol fuel; platinum is a precious metal, and the earth crust has low reserves and high price, which limits the scale use of the platinum-based catalyst in fuel cells. Therefore, the development of a non-noble metal oxygen reduction reaction catalyst with low price and good performance is the key for large-scale use of fuel cells.
Among many non-noble metal catalysts for oxygen reduction reaction, nitrogen-doped carbon catalysts have received great attention in the industry because of their low cost and good catalytic performance. Researches show that the nitrogen-doped carbon material has a catalytic effect on oxygen reduction reaction, mainly directly generates water by a high-efficiency four-electron reaction way, and is an ideal oxygen reduction reaction catalyst. The improvement of the catalytic activity of the nitrogen-doped carbon material comes from the fact that nitrogen atoms have electron-withdrawing performance, so that the surrounding carbon atoms can be positively charged, and the fracture of O ═ O double bonds is promoted.
The typical preparation method of the nitrogen-doped carbon material catalyst is that transition metal ions, organic nitrogen-containing compounds and carbon black materials are mixed and then placed in a tubular furnace, and heat treatment is carried out at different temperatures and in different atmospheres, so that the doping of nitrogen atoms to carbon black is realized. The carbon black material used herein includes general carbon black, carbon nanotubes, graphene, and the like. The traditional nitrogen-doped carbon material catalyst is in a powder form, and when the catalyst is prepared into an electrode, the powder material and certain binder emulsion are required to be uniformly mixed to obtain slurry, and then the slurry is coated on conductive substrate materials such as a stainless steel mesh, foamed nickel, carbon paper and the like. The disadvantage of this preparation method is that the substrate occupies most of the volume of the electrode, and the electrode space utilization rate is low; the use of the binder reduces the conductivity of the electrode and influences the performance of the catalyst; the powder catalyst may be dropped off on the substrate, reducing the life of the electrode.
Disclosure of Invention
The method aims to solve the problems that a platinum-based catalyst is expensive, and the problems that the space utilization rate of a powder nitrogen-doped carbon material catalyst is low, a binder is used and the catalyst falls off in the preparation of an electrode. The invention provides a preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst, wherein nitrogen atoms are doped into carbon paper in the method to obtain the nitrogen-doped carbon paper oxygen reduction reaction catalyst. Because the active site of the catalyst is generated in situ on the carbon paper, the nitrogen-doped carbon paper can be directly used as a fuel cell electrode, has the performances of catalysis, conductivity and support, has low price and overcomes the defects of the preparation of a powder catalyst electrode.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst comprises the following steps:
the method comprises the following steps: and (4) pretreating the carbon paper. Mixing concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 1: 5-5: 1 to prepare mixed acid, placing carbon paper in the mixed acid, treating the carbon paper for 1-10 hours at 20-80 ℃ under ultrasonic oscillation, taking out the carbon paper, soaking and cleaning the carbon paper by using deionized water, and drying the carbon paper for 2-8 hours at 50-120 ℃.
Preferably, the concentrated sulfuric acid has a concentration of 1.84g/cm3The concentration of the concentrated nitric acid is 1.4g/cm3。
Preferably, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 1.
Step two: and electrodepositing the metal simple substance. With a catalyst containing Co2+、Fe2+、Fe3+And Mn2+The water solution of any ion in the ions is electrolyte; taking the carbon paper treated in the first step as a cathode, and performing electrodeposition at a voltage of-0.5 to-3.0V for 10 to 300 seconds; and soaking and cleaning the deposited carbon paper in deionized water, cleaning the carbon paper in ethanol and acetone, and drying the carbon paper by cold air.
Said Co-containing2+The electrolyte is prepared by dissolving cobalt dichloride or cobalt nitrate in deionized water; said Fe-containing2+The electrolyte is prepared by dissolving iron dichloride in deionized water; said Fe-containing3+The electrolyte is prepared by dissolving ferric trichloride or ferric nitrate in deionized water; said Mn being contained2+The ionic electrolyte is prepared by dissolving manganese dichloride or manganese nitrate in deionized water; the concentration of metal ions is 0.01-1.0 mol/L, and the temperature of the electrolyte is 10-50 ℃.
Preferably, the voltage for electrodeposition is-2.0V and the deposition time is 50 seconds.
Preferably, the metal ion concentration is 0.1mol/L and the electrolyte temperature is 25 ℃.
Step three: and (6) heat treatment. Transferring the carbon paper treated in the second step into a tubular furnace for heat treatment; and introducing ammonia gas in the heat treatment process, wherein the heat treatment temperature is 500-900 ℃, the heat treatment time is 0.5-4 hours, and naturally cooling to room temperature to obtain the nitrogen-doped carbon paper oxygen reduction reaction catalyst.
Preferably, the heat treatment temperature in the third step is 700 ℃, and the heat treatment time is 2 hours.
In the first step, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 1.
The catalyst prepared by the method has higher current density and higher concentration of catalytic active sites for oxygen reduction reaction; Co-N-OCP inAn oxygen reduction current density at 0.50V (vs. RHE) of 3.00mA/cm2(ii) a The output voltage of the assembled zinc-air battery at 1600s is 1.26V respectively.
Compared with the prior art, the invention has the beneficial effects that:
the raw materials are easy to obtain, the preparation process is simple, and the obtained catalyst is low in cost.
And (II) the obtained catalyst has good catalytic activity of oxygen reduction reaction.
And (III) the obtained catalyst can be directly assembled in a battery as an electrode, so that the use of a conductive substrate and a binder is avoided, and the defects existing in the preparation of the electrode by using a powder catalyst are avoided.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of the catalyst obtained in example 1 of the present invention;
FIG. 3 is a linear potential scanning curve of the products obtained in comparative examples 1 and 2 and example 1 of the present invention;
FIG. 4 is a linear potential scanning curve of the products obtained in comparative examples 1 and 3 and example 2;
FIG. 5 is a linear potential scanning curve of the products obtained in comparative examples 1 and 4 and example 3;
FIG. 6 is a constant current discharge curve diagram of a zinc-air battery assembled by catalysts obtained in examples 1, 2 and 3 of the present invention and comparative example 1.
Detailed Description
The present invention will be further illustrated below with reference to specific examples and comparative examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1:
a preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst comprises the following steps:
the method comprises the following steps: carbon paper pretreatmentAnd (6) processing. Concentrated sulfuric acid (1.84 g/cm)3) And concentrated nitric acid (1.4 g/cm)3) Mixing and preparing mixed acid according to the volume ratio of 1:1, placing carbon paper in the mixed acid, treating for 3 hours at 50 ℃ under ultrasonic oscillation, taking out the carbon paper, soaking and cleaning the carbon paper by using deionized water, and drying for 8 hours at 100 ℃.
Step two: and electrodepositing a cobalt simple substance. Dissolving cobalt dichloride in deionized water to prepare Co2+The ion concentration of the electrolyte is 0.1mol/L, and the temperature of the electrolyte is controlled to be 25 ℃. And (4) taking the carbon paper treated in the step one as a cathode, and performing electrodeposition at a voltage of-2.0V for 50 seconds. And soaking and cleaning the deposited carbon paper in deionized water, cleaning the carbon paper in ethanol and acetone, and drying the carbon paper by cold air.
Step three: and (6) heat treatment. And D, transferring the carbon paper subjected to the electrodeposition treatment in the step two into a tube furnace for heat treatment. And introducing ammonia gas in the heat treatment process, wherein the heat treatment temperature is 700 ℃, the heat treatment time is 2 hours, and naturally cooling to room temperature to obtain the nitrogen-doped carbon paper oxygen reduction reaction catalyst marked as Co-N-OCP.
The Co-N-OCP prepared in example 1 was subjected to electron microscope scanning and X-ray diffraction, and the specific results were as follows:
FIG. 1 is a scanning electron micrograph of the Co-N-OCP catalyst obtained in example 1 at different magnifications, which shows that particles are deposited on the carbon fibers of the carbon paper. FIG. 2 is an X-ray diffraction pattern of the Co-N-OCP catalyst obtained in example 1, and a diffraction peak of elemental cobalt can be retrieved, which shows that particles deposited on carbon fibers of carbon paper are elemental cobalt.
Example 2:
a preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst comprises the following steps:
the method comprises the following steps: and (4) pretreating the carbon paper. Concentrated sulfuric acid (1.84 g/cm)3) And concentrated nitric acid (1.4 g/cm)3) Mixing and preparing mixed acid according to the volume ratio of 1:1, placing carbon paper in the mixed acid, treating for 3 hours at 50 ℃ under ultrasonic oscillation, taking out the carbon paper, soaking and cleaning the carbon paper by using deionized water, and drying for 8 hours at 100 ℃.
Step two: and electrodepositing the elementary substance of iron. Dissolving ferric trichloride in deionized water to prepare Fe3+Ion concentration of0.1mol/L electrolyte, and the temperature of the electrolyte is controlled to be 25 ℃. And (4) taking the carbon paper treated in the step one as a cathode, and performing electrodeposition at a voltage of-2.0V for 50 seconds. And soaking and cleaning the deposited carbon paper in deionized water, cleaning the carbon paper in ethanol and acetone, and drying the carbon paper by cold air.
Step three: and (6) heat treatment. And D, transferring the carbon paper subjected to the electrodeposition treatment in the step two into a tube furnace for heat treatment. And introducing ammonia gas in the heat treatment process, wherein the heat treatment temperature is 700 ℃, the heat treatment time is 2 hours, and naturally cooling to room temperature to obtain the nitrogen-doped carbon paper oxygen reduction reaction catalyst marked as Fe-N-OCP.
Example 3:
a preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst comprises the following steps:
the method comprises the following steps: and (4) pretreating the carbon paper. Concentrated sulfuric acid (1.84 g/cm)3) And concentrated nitric acid (1.4 g/cm)3) Mixing and preparing mixed acid according to the volume ratio of 1:1, placing carbon paper in the mixed acid, treating for 3 hours at 50 ℃ under ultrasonic oscillation, taking out the carbon paper, soaking and cleaning the carbon paper by using deionized water, and drying for 8 hours at 100 ℃.
Step two: and electrodepositing a manganese simple substance. Dissolving manganese dichloride in deionized water to prepare Mn2+The ion concentration of the electrolyte is 0.1mol/L, and the temperature of the electrolyte is controlled to be 25 ℃. And (4) taking the carbon paper treated in the step one as a cathode, and performing electrodeposition at a voltage of-2.0V for 50 seconds. And soaking and cleaning the deposited carbon paper in deionized water, cleaning the carbon paper in ethanol and acetone, and drying the carbon paper by cold air.
Step three: and (6) heat treatment. And D, transferring the carbon paper subjected to the electrodeposition treatment in the step two into a tube furnace for heat treatment. And introducing ammonia gas in the heat treatment process, wherein the heat treatment temperature is 700 ℃, the heat treatment time is 2 hours, and naturally cooling to room temperature to obtain the nitrogen-doped carbon paper oxygen reduction reaction catalyst marked as Mn-N-OCP.
Comparative example 1:
the method comprises the following steps: and (4) pretreating the carbon paper. Concentrated sulfuric acid (1.84 g/cm)3) And concentrated nitric acid (1.4 g/cm)3) Mixing the raw materials according to a volume ratio of 1:1 to prepare mixed acid, placing the carbon paper in the mixed acid, and treating the paper at 50 ℃ under ultrasonic vibrationCleaning for 3 hours, soaking and cleaning with deionized water, and drying at 100 ℃ for 8 hours.
Step two: and (6) heat treatment. And C, transferring the carbon paper pretreated in the step I into a tube furnace for heat treatment. And introducing ammonia gas in the heat treatment process, wherein the heat treatment temperature is 700 ℃, the heat treatment time is 2 hours, and naturally cooling to room temperature to obtain the product labeled as N-OCP.
Comparative example 2:
the method comprises the following steps: and (4) pretreating the carbon paper. Concentrated sulfuric acid (1.84 g/cm)3) And concentrated nitric acid (1.4 g/cm)3) Mixing and preparing mixed acid according to the volume ratio of 1:1, placing the carbon paper in the mixed acid, treating for 3 hours at 50 ℃ under ultrasonic oscillation, soaking and cleaning with deionized water, and drying for 8 hours at 100 ℃.
Step two: and electrodepositing a cobalt simple substance. Dissolving cobalt dichloride in deionized water to prepare Co2+The ion concentration of the electrolyte is 0.1mol/L, and the temperature of the electrolyte is controlled to be 25 ℃. And (4) taking the carbon paper treated in the step one as a cathode, and performing electrodeposition at a voltage of-2.0V for 50 seconds. And soaking and cleaning the deposited carbon paper in deionized water, cleaning the carbon paper in ethanol and acetone, and drying the carbon paper by cold air. The resulting product was labeled as Co-OCP.
Comparative example 3:
the method comprises the following steps: and (4) pretreating the carbon paper. Concentrated sulfuric acid (1.84 g/cm)3) And concentrated nitric acid (1.4 g/cm)3) Mixing and preparing mixed acid according to the volume ratio of 1:1, placing carbon paper in the mixed acid, treating for 3 hours at 50 ℃ under ultrasonic oscillation, taking out the carbon paper, soaking and cleaning the carbon paper by using deionized water, and drying for 8 hours at 100 ℃.
Step two: and electrodepositing the elementary substance of iron. Dissolving ferric trichloride in deionized water to prepare Fe3+The ion concentration of the electrolyte is 0.1mol/L, and the temperature of the electrolyte is controlled to be 25 ℃. And (4) taking the carbon paper treated in the step one as a cathode, and performing electrodeposition at a voltage of-2.0V for 50 seconds. And soaking and cleaning the deposited carbon paper in deionized water, cleaning the carbon paper in ethanol and acetone, and drying the carbon paper by cold air. The resulting product was labeled as Fe-OCP.
Comparative example 4:
the method comprises the following steps: and (4) pretreating the carbon paper. Concentrated sulfuric acid (1.84 g/cm)3) And concentrated nitric acid (1.4 g/cm)3) Mixing and preparing mixed acid according to the volume ratio of 1:1, placing carbon paper in the mixed acid, treating for 3 hours at 50 ℃ under ultrasonic oscillation, taking out the carbon paper, soaking and cleaning the carbon paper by using deionized water, and drying for 8 hours at 100 ℃.
Step two: and electrodepositing a manganese simple substance. Dissolving manganese dichloride in deionized water to prepare Mn2+The ion concentration of the electrolyte is 0.1mol/L, and the temperature of the electrolyte is controlled to be 25 ℃. And (4) taking the carbon paper treated in the step one as a cathode, and performing electrodeposition at a voltage of-2.0V for 50 seconds. And soaking and cleaning the deposited carbon paper in deionized water, cleaning the carbon paper in ethanol and acetone, and drying the carbon paper by cold air. The resulting product was labeled Mn-OCP.
The catalysts Co-N-OCP, Fe-N-OCP and Mn-N-OCP obtained in example 1, example 2 and example 3 and the products N-OCP, Co-OCP, Fe-OCP and Mn-OCP obtained in comparative example 1, comparative example 2, comparative example 3 and comparative example 4 are subjected to relevant performance tests, and the specific test results are as follows:
FIG. 3 is a graph showing the linear potential scanning curves of N-OCP and Co-OCP obtained in comparative examples 1 and 2, and Co-N-OCP obtained in example 1; FIG. 4 is a graph showing the linear potential scanning curves of N-OCP, Fe-OCP obtained in comparative examples 1 and 3, and Fe-N-OCP obtained in example 2; FIG. 5 is a graph showing the linear potential scanning curves of the products N-OCP and Mn-OCP obtained in comparative examples 1 and 4, and the catalyst Mn-N-OCP obtained in example 3; the electrochemical test conditions were: at 25 ℃ in 0.1M KOH saturated with oxygen, the scanning rate was 5mV/s and the electrode speed was 1600 rpm.
The initial oxygen reduction potentials of the product N-OCP of comparative example 1 and the product Co-OCP of comparative example 2 were 0.77V and 0.83V (vs. RHE), respectively, and the initial oxygen reduction potential of the catalyst Co-N-OCP of inventive example 1 was 0.86V; the oxygen reduction current densities of N-OCP, Co-OCP and Co-N-OCP at 0.50V (vs. RHE) are 2.14, 1.99 and 3.00mA/cm in sequence2. Comparative example 3 the initial oxygen reduction potential of the product Fe-OCP was 0.84V (vs. RHE), and the initial oxygen reduction potential of the catalyst Fe-N-OCP of inventive example 2 was 0.86V (vs. RHE); the oxygen reduction current densities of the Fe-OCP and the Fe-N-OCP at 0.50V (vs. RHE) are 1.93 and 2.78mA/cm in sequence2. Comparative example 4 Mn-O productThe initial oxygen reduction potential of CP was 0.81V (vs. RHE), and the initial oxygen reduction potential of catalyst Mn-N-OCP of inventive example 3 was 0.84V (vs. RHE); the oxygen reduction current densities of Mn-OCP and Mn-N-OCP at 0.50V (vs. RHE) are 1.71 and 2.62mA/cm in sequence2. The catalysts Co-N-OCP, Fe-N-OCP and Mn-N-OCP obtained in the embodiment of the invention have more corrected initial oxygen reduction potential and higher current density, which shows that the catalysts have higher catalytic activity of oxygen reduction reaction.
FIG. 6 shows the constant current discharge curves of the zinc-air batteries assembled by the catalysts Co-N-OCP, Fe-N-OCP, Mn-N-OCP and N-OCP obtained in the examples 1, 2, 3 and 1 of the invention, and the test conditions are as follows: pure zinc sheet as negative electrode, catalyst carbon paper as positive electrode, electrolyte at 25 deg.C of 6.0M KOH solution, pure oxygen gas introduced, and discharge current density of 5mA/cm2. The output voltages of the four batteries at 1600s are respectively 1.26V, 1.25V, 1.21V and 1.03V, which shows that the catalysts Co-N-OCP, Fe-N-OCP and Mn-N-OCP obtained by the embodiment of the invention have good practical working performance.
The above embodiments are only used for illustrating the technical solutions of the present patent, and not for limiting the same; although the present patent is described in detail with reference to the foregoing embodiments, those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments can be modified, or some technical features can be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present patent.
Claims (10)
1. A preparation method of a nitrogen-doped carbon paper oxygen reduction reaction catalyst is characterized by comprising the following steps:
step one, pretreating carbon paper: mixing concentrated sulfuric acid and concentrated nitric acid in proportion to prepare mixed acid; treating for 1-10 hours under ultrasonic oscillation at 20-80 ℃, taking out the carbon paper, soaking and cleaning with deionized water, and drying for 2-8 hours at 50-120 ℃;
step two, electrodepositing a metal simple substance: to contain Co2+、Fe2+、Fe3+And Mn2+The aqueous solution of any ion in the ions is electrolyte; taking the carbon paper treated in the first step as a cathode, and performing electrodeposition at a voltage of-0.5 to-3.0V for 10 to 300 seconds; soaking and cleaning the deposited carbon paper in deionized water, cleaning in ethanol and acetone, and drying by cold air;
step three, heat treatment: transferring the carbon paper treated in the second step into a tubular furnace for heat treatment; and introducing ammonia gas in the heat treatment process, wherein the heat treatment temperature is 500-900 ℃, the heat treatment time is 0.5-4 hours, and naturally cooling to room temperature to obtain the nitrogen-doped carbon paper oxygen reduction reaction catalyst.
2. The method of claim 1, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: the concentration of the concentrated sulfuric acid is 1.84g/cm3The concentration of the concentrated nitric acid is 1.4g/cm3。
3. The method of claim 1, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: in the first step, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 5-5: 1.
4. The method of claim 1, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: said Co-containing2 +、Fe2+、Fe3+And Mn2+The ionic electrolyte is prepared by dissolving cobalt dichloride, cobalt nitrate, ferric trichloride, ferric dichloride, ferric nitrate, manganous dichloride or manganous nitrate corresponding to ions in deionized water respectively.
5. The method of claim 1, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: the concentration of metal ions is 0.01-1.0 mol/L, and the temperature of the electrolyte is 10-50 ℃.
6. The method of claim 1, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: the voltage for electrodeposition was-2.0V and the deposition time was 50 seconds.
7. The method of claim 1, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: in the third step, the heat treatment temperature is 700 ℃, and the heat treatment time is 2 hours.
8. The method of claim 3, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: in the first step, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 1.
9. The method of claim 5, wherein the nitrogen-doped carbon paper oxygen reduction reaction catalyst is prepared by the following steps: the metal ion concentration is 0.1mol/L, and the electrolyte temperature is 25 ℃.
10. A nitrogen-doped carbon paper oxygen reduction reaction catalyst prepared by the method of any one of claims 1-9, wherein: the catalyst has higher current density and higher concentration of catalytic active sites for oxygen reduction reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010916585.7A CN112002912A (en) | 2020-09-03 | 2020-09-03 | Preparation method of nitrogen-doped carbon paper oxygen reduction reaction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010916585.7A CN112002912A (en) | 2020-09-03 | 2020-09-03 | Preparation method of nitrogen-doped carbon paper oxygen reduction reaction catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112002912A true CN112002912A (en) | 2020-11-27 |
Family
ID=73465352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010916585.7A Pending CN112002912A (en) | 2020-09-03 | 2020-09-03 | Preparation method of nitrogen-doped carbon paper oxygen reduction reaction catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112002912A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196984A (en) * | 2022-01-20 | 2022-03-18 | 辽宁大学 | Constant-current electrodeposited copper-based catalyst on carbon paper, preparation method thereof and application of catalyst in electrocatalysis of 4-ethynylaniline |
| CN114614025A (en) * | 2020-12-09 | 2022-06-10 | 天津大学 | Structure and manufacturing method of high-performance manganese nitride oxygen reduction catalyst |
| CN114614028A (en) * | 2020-12-09 | 2022-06-10 | 天津大学 | Method for in-situ synthesis of manganese nitride oxygen reduction catalyst by calcining nitrogen-containing organic matter |
| CN116145175A (en) * | 2023-02-22 | 2023-05-23 | 兰州大学 | Electrocatalyst, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602086A (en) * | 2016-11-23 | 2017-04-26 | 北京化工大学 | Self-supporting oxygen reduction/oxygen evolution double-effect oxygen electrode catalyst and preparation method therefor |
| CN108923030A (en) * | 2018-06-29 | 2018-11-30 | 大连理工大学 | A kind of cobalt nitride/porous carbon sheet/carbon cloth self-supporting lithium sulfur battery anode material preparation method |
| CN109585862A (en) * | 2018-11-07 | 2019-04-05 | 三峡大学 | A kind of preparation method of difunctional cobalt and nitrogen, oxygen doping carbon In-situ reaction electrode |
| CN109746007A (en) * | 2018-12-25 | 2019-05-14 | 中山大学 | A kind of functionalization transition metal phosphide-oxide composite nano materials and the preparation method and application thereof |
| CN110433829A (en) * | 2019-07-31 | 2019-11-12 | 广西师范大学 | A kind of MoO2-NiSxThe agent of/CC Electrocatalytic Activity for Hydrogen Evolution Reaction and preparation method |
| CN111235614A (en) * | 2020-01-17 | 2020-06-05 | 天津大学 | Preparation method and application of multifunctional self-supporting electrode with nitrogen-doped carbon wrapping structure |
-
2020
- 2020-09-03 CN CN202010916585.7A patent/CN112002912A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602086A (en) * | 2016-11-23 | 2017-04-26 | 北京化工大学 | Self-supporting oxygen reduction/oxygen evolution double-effect oxygen electrode catalyst and preparation method therefor |
| CN108923030A (en) * | 2018-06-29 | 2018-11-30 | 大连理工大学 | A kind of cobalt nitride/porous carbon sheet/carbon cloth self-supporting lithium sulfur battery anode material preparation method |
| CN109585862A (en) * | 2018-11-07 | 2019-04-05 | 三峡大学 | A kind of preparation method of difunctional cobalt and nitrogen, oxygen doping carbon In-situ reaction electrode |
| CN109746007A (en) * | 2018-12-25 | 2019-05-14 | 中山大学 | A kind of functionalization transition metal phosphide-oxide composite nano materials and the preparation method and application thereof |
| CN110433829A (en) * | 2019-07-31 | 2019-11-12 | 广西师范大学 | A kind of MoO2-NiSxThe agent of/CC Electrocatalytic Activity for Hydrogen Evolution Reaction and preparation method |
| CN111235614A (en) * | 2020-01-17 | 2020-06-05 | 天津大学 | Preparation method and application of multifunctional self-supporting electrode with nitrogen-doped carbon wrapping structure |
Non-Patent Citations (1)
| Title |
|---|
| YANG XIANG ETAL.: "Constructing flexible and self-standing electrocatalyst for oxygen reduction reaction by in situ doping nitrogen atoms into carbon cloth", 《APPLIED SURFACE SCIENCE》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114614025A (en) * | 2020-12-09 | 2022-06-10 | 天津大学 | Structure and manufacturing method of high-performance manganese nitride oxygen reduction catalyst |
| CN114614028A (en) * | 2020-12-09 | 2022-06-10 | 天津大学 | Method for in-situ synthesis of manganese nitride oxygen reduction catalyst by calcining nitrogen-containing organic matter |
| CN114614028B (en) * | 2020-12-09 | 2023-09-05 | 天津大学 | Method for in-situ synthesis of manganese oxide reduction catalyst by calcining nitrogen-containing organic matter |
| CN114614025B (en) * | 2020-12-09 | 2023-09-05 | 天津大学 | Structure and manufacturing method of manganese oxide reduction catalyst |
| CN114196984A (en) * | 2022-01-20 | 2022-03-18 | 辽宁大学 | Constant-current electrodeposited copper-based catalyst on carbon paper, preparation method thereof and application of catalyst in electrocatalysis of 4-ethynylaniline |
| CN114196984B (en) * | 2022-01-20 | 2023-12-08 | 辽宁大学 | Constant-current electrodeposited copper-based catalyst on carbon paper, preparation method thereof and application thereof in electrocatalytic 4-ethynylaniline |
| CN116145175A (en) * | 2023-02-22 | 2023-05-23 | 兰州大学 | Electrocatalyst, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112002912A (en) | Preparation method of nitrogen-doped carbon paper oxygen reduction reaction catalyst | |
| CN108336374B (en) | High-performance ternary Fe-Co-Ni Co-doped nitrogen-containing carbon material and preparation method and application thereof | |
| CN103413951A (en) | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof | |
| CN107394217A (en) | A kind of nitrating, p-doped biomass carbon material synthetic method and its application in terms of microorganism fuel cell cathode | |
| CN105854918A (en) | Composite material of nanoscale cobalt based particles and nitrogen doped carbon, synthetic method and application | |
| CN104624190A (en) | Cobalt-based transition metal oxygen reduction catalyst, preparation method and application thereof | |
| CN112652780B (en) | Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst | |
| CN110124707B (en) | Spiral ultralow platinum loading Mo2C catalyst and preparation method and application thereof | |
| CN113215617A (en) | Copper nanowire-loaded CoNi nanosheet electrocatalyst and preparation method and application thereof | |
| CN112103520A (en) | Anode catalyst of alcohol fuel cell | |
| Kadier et al. | None-platinum electrode catalysts and membranes for highly efficient and inexpensive H2 production in microbial electrolysis cells (MECs): A review | |
| CN112142037A (en) | Cobalt and nitrogen doped carbon nano tube and preparation method and application thereof | |
| CN110504456A (en) | It is a kind of based on nitrogen oxygen doping ball/piece porous carbon materials oxygen reduction electrode and its preparation method and application | |
| CN114583191A (en) | Method for preparing anode catalyst of direct methanol fuel cell by electrodeposition | |
| CN112968184A (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN107138172B (en) | Preparation method of electrode catalytic material and application of electrode catalytic material in glucose fuel cell | |
| CN103316679A (en) | Preparation method of ordered mesoporous non-noble metal-nitrogen-graphitized carbon material | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN113629260A (en) | Cobalt and nitrogen co-doped carbon nanosheet material and preparation and application thereof | |
| CN114892197B (en) | Electrocatalysis synthesis of H2O2Catalyst, preparation method and application thereof | |
| Rao et al. | N-doped macroporous carbon loading Mo2C as cathode electrocatalyst of hybrid neutral-alkaline microbial electrolysis cells for H2 generation | |
| CN114744224B (en) | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire | |
| CN114293203B (en) | Preparation method of nitrogen-phosphorus co-doped graphene/cobalt phosphide nano-sheet array catalyst | |
| CN113174609B (en) | Preparation method and application of ultrahigh-performance hydrogen evolution water electrolysis catalyst | |
| CN113839058A (en) | Carbon-based oxygen reduction reaction catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201127 |
|
| RJ01 | Rejection of invention patent application after publication |