CN109585861B - Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode - Google Patents

Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode Download PDF

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CN109585861B
CN109585861B CN201811320265.4A CN201811320265A CN109585861B CN 109585861 B CN109585861 B CN 109585861B CN 201811320265 A CN201811320265 A CN 201811320265A CN 109585861 B CN109585861 B CN 109585861B
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nitrogen
cobalt
doped carbon
electrodeposition
cobalt monoxide
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CN109585861A (en
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黄妞
杨柳
闫术芳
丁玉岳
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China Three Gorges University CTGU
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a preparation method of a bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode, which comprises the steps of preparing a flaky cobaltosic oxide array in-situ electrode by utilizing electrodeposition and air atmosphere annealing, growing polyaniline on the surface of the cobaltosic oxide by using an electrodeposition or chemical bath alternating reaction method, and then carrying out annealing reaction in a protective atmosphere, wherein the polyaniline forms a nitrogen-doped carbon material in the protective atmosphere, and simultaneously, the cobaltosic oxide is reduced into the cobalt monoxide. The product obtained by the technical scheme of the invention has excellent electrocatalytic Oxygen Reduction Reaction (ORR) performance due to the construction of various high electrocatalytic active sites, including nitrogen-doped active sites in carbon materials and other lattice defects and cobalt monoxide caused by the nitrogen-doped active sites; the cobalt monoxide has better performance of an electrocatalytic Oxygen Evolution Reaction (OER); in addition, the interface formed by the cobalt oxide, the carbon material and the strong interface coupling effect also has excellent electrocatalytic oxygen evolution reaction and oxygen reduction reaction performances.

Description

Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode
Technical Field
The invention relates to an in-situ electrode and preparation thereof, belonging to the field of energy storage and conversion materials and devices.
Background
The Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) dual-functional electrocatalyst with excellent performance plays an important role in fuel cells and novel metal air cells, directly determines the performance and cost of devices, and the electrocatalyst with the dual functions of catalyzing the OER and ORR reactions is a hot spot of controversial research in various countries. Currently, platinum and its alloys and the like are industrially used catalysts having good catalytic ORR. However, platinum is expensive and tends to form inert platinum oxide on the surface for long-term operation in an alkaline environment, and further platinum is susceptible to poisoning by fuel oxidizing molecules, such as methanol, and thus its performance is drastically reduced. Yttrium oxide and ruthenium oxide are commonly used as anodes in the production of oxygen by electrolysis of water due to their good electrocatalytic effect on OER. However, yttrium and ruthenium are rare metal materials and expensive, and their overpotentials for catalyzing the OER reaction are generally greater than 300mV, and the practical performance needs to be improved. Therefore, the invention aims to prepare the low-cost and high-efficiency bifunctional electrocatalyst, namely the compound of the cobalt monoxide and the nitrogen-doped carbon, wherein the cobalt monoxide has the function of catalyzing OER and ORR reactions, the nitrogen-doped carbon has the function of catalyzing the ORR reactions, and the overall conductivity of the composite material is improved, so that the electron transport is accelerated, and the catalytic reaction speed is improved. In addition, the cobalt monoxide can also improve the inherent catalytic capability of the composite material interface due to the strong interface coupling effect with the carbon material, such as the generation of Co-N bonds.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode, which has the advantages of low equipment requirement, low cost of required raw materials, easy control of reaction conditions, simple production process, good consistency of formed products, small environmental pollution, etc., can be used for dual-functional electrocatalysts of OER and ORR, and has great significance for batch production of in-situ electrodes.
Therefore, the invention provides a method for preparing a porous cobaltosic oxide array electrode by electrodeposition-annealing, then depositing polyaniline and annealing in a protective atmosphere to prepare a strong interface coupling cobalt monoxide and nitrogen-doped carbon composite in-situ electrode, which comprises the following steps:
firstly, dissolving cobalt nitrate in deionized water under the condition of stirring at room temperature, wherein the concentration of the cobalt nitrate is 50-200 mM; then, growing a sheet-shaped cobalt hydroxide array on the conductive substrate by an electrodeposition method in the cobalt nitrate aqueous solution, wherein the electrodeposition time is 90-360 s, and the potential of the working electrode relative to the saturated calomel electrode is-0.9-1.2V; and finally, annealing in the air to prepare the in-situ porous flaky cobaltosic oxide array, wherein the temperature is 300-500 ℃, and the reaction time is 0.5-2 h. The conductive substrate comprises any one of carbon cloth, graphite paper, copper foam or nickel. The reaction principle of the step is that nitrate radical is electrolyzed and reduced in water to generate hydroxyl radical, and the hydroxyl radical further reacts with cobalt ions to generate cobalt hydroxide;
(1)NO3 -+e-+H2O→NO2↑+2OH-；
or NO3 -+3e-+2H2O→NO↑+4OH-；
(2)Co2++2OH-→Co(OH)2。
Since the electron gain and loss in the electrodeposition reaction determine the reaction progress, the diffraction of the film layer obtained in this way is better than that of hydrothermal and sol-gel methods, and the film is more uniform. For example, in the case of carbon paper, cobalt hydroxide is uniformly grown on each carbon fiber and graphite sheet in the carbon paper. Wherein each cobalt hydroxide nanosheet forming the cobalt hydroxide array is generally a single crystal, and then is annealed and sintered in the air, and cobaltous hydroxide gradually loses water and undergoes a deoxidation reaction to generate cobaltosic oxide. The process is rapidly carried out by selecting the temperature of 300-500 ℃, so that each cobalt hydroxide single crystal nanosheet sheet is converted into polycrystalline cobaltosic oxide particles, pores are formed between cobaltosic oxide and cobaltosic oxide particles while the sheet shape is maintained, uniform loading of subsequent precursor liquid is facilitated, and more heterogeneous interfaces of cobalt oxide and carbon are facilitated to be formed.
Depositing polyaniline on the substrate with cobaltosic oxide array, and then carrying out Ar gas or N2Annealing reaction in gas at 600-900 ℃ for 0.5-4 h.
The polyaniline deposition method comprises two types of electrodeposition and chemical bath; the polyaniline electrodeposition is carried out in a mixed solution of aniline and sodium sulfate; the chemical bath is alternately soaked in an aniline monomer aqueous solution and an ammonium persulfate aqueous solution for 10-60 times.
The concentration of the aniline is 0.02-0.08M, and the concentration of the sodium sulfate is 0.1-0.4M.
In the electrodeposition process, the anode current is 0.5-4 mA, and the deposition time is 600-3600 s.
The concentration of aniline monomer aqueous solution in the chemical bath is 30-70mmol, and the biological concentration of ammonium persulfate aqueous solution is 10-20 mmol.
Ar gas or N2Annealing reaction is carried out in gas at the temperature of 600-900 ℃, and the annealing reaction time is 0.5-4 h.
In the technical scheme of the invention, polyaniline originally has higher polymerization degree and forms carbon after carbonization, the carbon has high graphitization degree and strong conductivity, and is beneficial to promoting catalytic reaction, and the polyaniline forms nitrogen-doped carbon material under protective atmosphere and simultaneously enables the carbon material to be formedReducing the cobaltosic oxide into cobaltous oxide; n element contained in the polyaniline can be doped into a carbon skeleton or form graphitized nitrogen or pyrrole nitrogen or pyridine nitrogen on the surface in the process of forming the carbon material, and the OER and ORR catalytic performance is good; ③ if ammonia and other nitrogen-containing micromolecules released in the process of converting polyaniline into carbon material, the cobaltosic oxide can be reduced into cobalt monoxide, and Co-N is formed between atoms and carbon material interface after atom rearrangementx-a C bond.
Drawings
FIG. 1 OER-ORR Linear voltammetric Scan (LSV) of the sample prepared in example 1.
FIG. 2 OER-ORR Linear voltammetric Scan (LSV) of the sample prepared in example 2.
FIG. 3 OER-ORR Linear voltammetric Scan (LSV) of the sample prepared in example 3.
FIG. 4 OER-ORR linear voltammetric scan (LSV) of the sample prepared in example 4.
FIG. 5 OER-ORR Linear voltammetric Scan (LSV) of the sample prepared in example 5.
FIG. 6 OER-ORR linear voltammetric scan (LSV) of the sample prepared in example 6.
FIG. 7 OER-ORR linear voltammetric scan (LSV) of the sample prepared in example 7.
FIG. 8 OER-ORR linear voltammetric scan (LSV) of the sample prepared in example 8.
FIG. 9 OER-ORR linear voltammetric scan (LSV) of the sample prepared in example 9.
FIG. 10 OER-ORR linear voltammetric scan (LSV) of the sample prepared in example 10.
FIG. 11 OER-ORR Linear voltammetric Scan (LSV) of the sample prepared in example 11.
FIG. 12 OER-ORR linear voltammetric scan (LSV) of the sample prepared in example 12.
FIG. 13 SEM image of cobaltosic oxide array prepared in example 1.
Fig. 14 SEM image of the in-situ co and n-doped carbon composite electrode prepared in example 1.
Fig. 15 SEM image of the cobalt oxide and nitrogen-doped carbon in-situ composite electrode prepared in example 7.
Fig. 16 XRD pattern of the in-situ co-doped co and n-doped carbon composite electrode prepared in example 1.
Detailed Description
The method for testing the OER and ORR performance LSV in the embodiment of the invention comprises the following steps: the cobalt oxide and nitrogen-doped carbon in-situ composite electrode is used as a working electrode, a carbon rod is used as a counter electrode, a saturated Hg/HgO electrode is used as a reference electrode, the electrolyte is 0.1M KOH aqueous solution, and the scanning speed is 10 mV/s. The OER and ORR tests were conducted with oxygen, the working electrode was not rotated and oxygen was allowed to saturate spontaneously in KOH aqueous solution without magneton agitation. The electrodeposition method comprises the following steps: the conductive substrate is used as a working electrode, the carbon rod is used as a counter electrode, and the saturated calomel electrode is used as a reference electrode.
Example 1:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. Taking a 16.6mmol ammonium persulfate solution as an A solution and a 50mmol aniline solution as a B solution, repeatedly and alternately soaking the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in an A, B solution for 10 times, washing with deionized water, and drying on a hot table at 80 ℃ for 10 min. And (3) putting the dried carbon paper into a tubular furnace, reacting for 4 hours at 600 ℃ under Ar airflow, naturally cooling to room temperature, and taking out.
FIG. 1 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 1. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.751V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach-4.05 mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.840V。
Fig. 13 is an SEM image of the porous flake cobaltosic oxide array in-situ electrode prepared in example 1. It is known from the figure that porous flakes, which were originally composed of cobaltosic oxide nanoparticles, were grown on a carbon paper substrate composed of carbon fibers without being loaded and sintered by precursor liquid.
Fig. 14 is an SEM image of the electrode prepared in example 1. It can be seen from the figure that after the polyaniline prepared by the composite chemical bath is annealed and sintered, the polyaniline is carbonized into a carbon sheet film to cover the electrode surface, and the original cobalt oxide sheet array is converted into nano particles.
Fig. 16 is an XRD pattern of the cobalt monoxide and nitrogen-doped carbon in-situ composite electrode prepared in example 1. It is known from the figure that the sintered electrode without supporting precursor liquid is formed by growing cobaltosic oxide on a carbon paper substrate. When the cobaltosic oxide array was loaded with the precursor solution and sintered, the cobaltosic oxide phase peak almost disappeared and a new cobaltosic oxide peak appeared.
Example 2:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. Taking a 16.6mmol ammonium persulfate solution as an A solution and a 50mmol aniline solution as a B solution, repeatedly and alternately soaking the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in an A, B solution for 10 times, washing with deionized water, and drying on a hot table at 80 ℃ for 10 min. Drying, placing into a tubular furnace, reacting at 600 ℃ for 1h under Ar gas flow, then heating to 900 ℃ for reaction for 30min, naturally cooling to room temperature, and taking out.
FIG. 2 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 2. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.833V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 3.08mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.942V。
Example 3:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. Taking a 16.6mmol ammonium persulfate solution as an A solution and a 50mmol aniline solution as a B solution, repeatedly and alternately soaking the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in an A, B solution for 20 times, washing with deionized water, and drying on a hot bench at 80 ℃ for 10 min. And (3) putting the dried carbon paper into a tubular furnace, reacting for 1h at 600 ℃, then heating to 900 ℃ for reacting for 30min, naturally cooling to room temperature, and taking out.
FIG. 3 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 3. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.833V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach-1.95 mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.948V。
Example 4:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. Taking a 16.6mmol ammonium persulfate solution as an A solution and a 50mmol aniline solution as a B solution, repeatedly and alternately soaking the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in an A, B solution for 20 times, washing with deionized water, and drying on a hot bench at 80 ℃ for 10 min. Drying, putting into a tube furnace, reacting for 4h at 600 ℃ under Ar gas flow, naturally cooling to room temperature, and taking out.
FIG. 4 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 4. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.758V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 3.17mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.893V。
Example 5:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. Taking a 16.6mmol ammonium persulfate solution as an A solution and a 50mmol aniline solution as a B solution, repeatedly and alternately soaking the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in an A, B solution for 30 times, washing with deionized water, and drying on a hot bench at 80 ℃ for 10 min. Drying, placing into a tubular furnace, reacting at 600 ℃ for 1h under Ar gas flow, then heating to 900 ℃ for reaction for 30min, naturally cooling to room temperature, and taking out.
FIG. 5 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 5. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.842V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 2.438mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.963V。
Example 6:
electrodeposition was carried out in a cobalt nitrate hexahydrate solution at a concentration of 150mM, a voltage of-1.0V and a time of 90s at room temperature. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. Taking 16.6mmol ammonium persulfate solution as A solution and 50mmol aniline solution as B solution, repeatedly and alternately soaking the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper for 30 times, washing with deionized water, and drying on a hot table at 80 ℃ for 10 min. Drying, putting into a tube furnace, reacting for 4h at 600 ℃ under Ar gas flow, naturally cooling to room temperature, and taking out.
FIG. 6 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 6. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.770V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 3.44mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.910V。
Example 7:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. And then carrying out electrodeposition on the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in a mixed solution of aniline and sodium sulfate, wherein the concentration of the aniline is 0.05M, the concentration of the sodium sulfate is 0.2M, the current is 0.5mA, and the time is 1800 s. Then repeatedly washing with deionized water, and drying at 80 deg.C for 10 min. Drying, putting into a tube furnace, reacting for 4h at 600 ℃ under Ar gas flow, naturally cooling to room temperature, and taking out.
FIG. 7 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 7. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.787V, O in alkaline aqueous solutionHalf-wave potential corresponding to RR reaction is E1/2The limiting current density can reach 3.87mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.986V。
Fig. 15 is an SEM image of the cobalt oxide and nitrogen-doped carbon in-situ composite electrode prepared in example 7. It can be seen from the figure that after the polyaniline subjected to composite electrodeposition is sintered, the polyaniline is carbonized into a carbon film to be covered on the surface of the original sheet array structure.
Example 8:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. And then carrying out electrodeposition on the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in a mixed solution of aniline and sodium sulfate, wherein the concentration of the aniline is 0.05M, the concentration of the sodium sulfate is 0.2M, the current is 1mA, and the time is 1800 s. Then repeatedly washing with deionized water, and drying at 80 deg.C for 10 min. Drying, putting into a tube furnace, reacting for 4h at 600 ℃ under Ar gas flow, naturally cooling to room temperature, and taking out.
FIG. 8 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 8. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.760V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 3.94mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.859V。
Example 9:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. And then carrying out electrodeposition on the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in a mixed solution of aniline and sodium sulfate, wherein the concentration of the aniline is 0.05M, the concentration of the sodium sulfate is 0.2M, the current is 2mA, and the time is 1200 s. Then repeatedly washing with deionized water, and drying at 80 deg.C for 10 min. Drying, placing into a tubular furnace, reacting at 600 ℃ for 1h under Ar gas flow, then heating to 900 ℃ for reaction for 30min, naturally cooling to room temperature, and taking out.
FIG. 9 is a graph of the OER, ORR linear voltammetric scan (LSV) of the electrode prepared in example 9. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.838V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 2.83mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.958V。
Example 10:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. And then carrying out electrodeposition on the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in a mixed solution of aniline and sodium sulfate, wherein the concentration of the aniline is 0.05M, the concentration of the sodium sulfate is 0.2M, the current is 2mA, and the time is 1200 s. Then repeatedly washing with deionized water, and drying at 80 deg.C for 10 min. Drying, putting into a tube furnace, reacting for 4h at 600 ℃ under Ar gas flow, naturally cooling to room temperature, and taking out.
FIG. 10 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 10. The current density when the electrode passes through is 10mA/cm2In the meantime, the OER reaction in the alkaline aqueous solution produces oxygenCorresponding potential is E100.782V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 3.54mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.920V。
Example 11:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. And then carrying out electrodeposition on the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in a mixed solution of aniline and sodium sulfate, wherein the concentration of the aniline is 0.05M, the concentration of the sodium sulfate is 0.2M, the current is 4mA, and the time is 600 s. Then repeatedly washing with deionized water, and drying at 80 deg.C for 10 min. Drying, putting into a tube furnace, reacting for 4h at 600 ℃ under Ar gas flow, naturally cooling to room temperature, and taking out.
FIG. 11 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 11. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.812V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach-4.29 mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.960V。
Example 12:
and (3) carrying out electrodeposition on the carbon paper in a cobalt nitrate hexahydrate solution at room temperature, wherein the concentration of the cobalt nitrate hexahydrate is 150mM, the voltage is-1.0V, and the time is 90 s. And then repeatedly washing the carbon paper with deionized water on a hot table at 80 ℃ for drying for 10min, putting the carbon paper with the deposit into a tubular furnace, reacting for 30min at 400 ℃ under Air flow, naturally cooling to room temperature, and taking out to obtain the porous flaky cobaltosic oxide array in-situ electrode growing on the carbon paper. And then carrying out electrodeposition on the porous flaky cobaltosic oxide array in-situ electrode grown on the carbon paper in a mixed solution of aniline and sodium sulfate, wherein the concentration of the aniline is 0.05M, the concentration of the sodium sulfate is 0.2M, the current is 4mA, and the time is 600 s. Then repeatedly washing with deionized water, and drying at 80 deg.C for 10 min. Drying, placing into a tubular furnace, reacting at 600 ℃ for 1h under Ar gas flow, then heating to 900 ℃ for reaction for 30min, naturally cooling to room temperature, and taking out.
FIG. 12 is a graph of the OER, ORR linear voltammetric scans (LSV) of the electrodes prepared in example 12. The current density when the electrode passes through is 10mA/cm2When the potential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is E100.836V, half-wave potential corresponding to ORR reaction in alkaline aqueous solution is E1/2The limiting current density can reach 1.91mA/cm under the condition of no stirring2，ΔE＝E10-E1/2＝0.933V。

Claims (7)

1. A preparation method of a bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode is characterized by comprising the following steps:
(1) dissolving cobalt nitrate in deionized water, growing a flaky cobalt hydroxide array on a conductive substrate by electrodeposition, and annealing the cobalt hydroxide array in air to form a porous flaky cobaltosic oxide array, wherein the electrodeposition time is 90-360 s, the potential of a working electrode relative to a saturated calomel electrode is-0.9-1.2V, the annealing temperature in the air is 300-500 ℃, and the annealing reaction time is 0.5-2 h;
(2) depositing polyaniline on the substrate with cobaltosic oxide array, and then carrying out Ar gas or N2Performing annealing reaction in gas to prepare the bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode, wherein the polyaniline deposition method is chemical bath deposition; the chemical bath is characterized in that the aniline monomer aqueous solution and the ammonium persulfate aqueous solution are alternately soaked for 10-60 times, the mass of the aniline monomer aqueous solution in the chemical bath is 30-70mmol, and the mass of the ammonium persulfate aqueous solution in the chemical bath is 10-20 mmol.
2. The method for preparing a bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode according to claim 1, wherein the concentration of the cobalt nitrate aqueous solution is 50-200 mM.
3. The method for preparing the bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode according to claim 1, wherein the conductive substrate comprises any one of carbon cloth, graphite paper, copper foam or nickel.
4. The method for preparing the bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode according to claim 1, wherein the polyaniline deposition method further comprises electrodeposition; the polyaniline electrodeposition is carried out in a mixed solution of aniline and sodium sulfate.
5. The method for preparing the bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode according to claim 4, wherein the aniline concentration is 0.02-0.08M, and the sodium sulfate concentration is 0.1-0.4M.
6. The method for preparing the bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode according to claim 4, wherein in the polyaniline electrodeposition process, the anode current is 0.5-4 mA, and the deposition time is 600-3600 s.
7. The method for preparing the bifunctional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode according to claim 1, wherein Ar gas or N is used2Annealing reaction is carried out in gas at the temperature of 600-900 ℃, and the annealing reaction time is 0.5-4 h.
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JP2012164492A (en) * 2011-02-04 2012-08-30 Tokyo Institute Of Technology Air electrode catalyst for fuel cell and method for producing the same
CN103682343A (en) * 2013-12-27 2014-03-26 北京大学 Cobalt stannide/polyaniline composite material, and preparation method and application thereof
CN107381658A (en) * 2017-07-12 2017-11-24 北京化工大学 A kind of topological preparation method of ultra-thin porous two-dimensional layer transition metal oxide nano-slice array material
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CN103682343A (en) * 2013-12-27 2014-03-26 北京大学 Cobalt stannide/polyaniline composite material, and preparation method and application thereof
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