CN109585861A - A kind of preparation method of difunctional cobalt black and nitrogen-doped carbon In-situ reaction electrode - Google Patents
A kind of preparation method of difunctional cobalt black and nitrogen-doped carbon In-situ reaction electrode Download PDFInfo
- Publication number
- CN109585861A CN109585861A CN201811320265.4A CN201811320265A CN109585861A CN 109585861 A CN109585861 A CN 109585861A CN 201811320265 A CN201811320265 A CN 201811320265A CN 109585861 A CN109585861 A CN 109585861A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- electrode
- nitrogen
- difunctional
- preparation
- 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.)
- Granted
Links
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
- H01M4/8803—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 present invention provides the preparation method of a kind of difunctional cobalt black and nitrogen-doped carbon In-situ reaction electrode; utilize electro-deposition and air atmosphere annealing preparation sheet cobaltosic oxide array original position electrode; electro-deposition or chemical bath alternation response the method annealing reaction under protective atmosphere after cobaltosic oxide surface grows polyaniline are used again; wherein polyaniline forms the carbon material of N doping under protective atmosphere, while cobaltosic oxide being made to be reduced to cobalt black.The product that technical solution of the present invention obtains, due to having constructed a variety of high electro-catalysis sites living, including in carbon material N doping active site and thus caused by other lattice defects and cobalt black, there is excellent electrocatalytic oxidation reduction reaction (ORR) performance；Cobalt black has preferable electrocatalytic oxidation evolution reaction (OER) performance；Furthermore the interface that cobalt black and carbon material and strong interface coupling effect are formed also has excellent electro-catalysis oxygen evolution reaction and oxygen reduction reaction performance.
Description
Technical field
The present invention relates to electrode in situ and its preparations, belong to energy stores and transition material and devices field.
Background technique
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional electrocatalyst haveing excellent performance in fuel cell and
Performer key player in novel metal air cell directly determines the performance and cost of device, has catalysis OER and ORR
The difunctional elctro-catalyst of reaction is the hot spot that various countries fall over each other research.Currently, platinum and its alloy etc. are industrially to be applied
The catalyst with good catalysis ORR.However, platinum expensive and long-term work surface is easily generated lazy under alkaline environment
Property platinum oxide, furthermore platinum is easily poisoned by oxidized molecule, such as methanol, performance thus can sharply decline.Yttrium oxide with
Ruthenium-oxide is because having the anode for being commonly used for being electrolysed in aquatic products oxygen to the good electro-catalysis effect of OER.However, yttrium, ruthenium are rare
Metal material, it is expensive, and they are catalyzed the overpotential that OER reacts and are generally higher than 300mV, if practical performance is needed to still need to mention
It rises.Thus, the present invention is directed to prepare a kind of cheap, efficient bifunctional electrocatalyst --- cobalt black and nitrogen-doped carbon
Compound, wherein cobalt black plays the function of catalysis OER and ORR reaction, and the carbon of N doping plays the function of catalysis ORR reaction
Can, and improve the effect of composite material overall conductivity accelerates electron transport and then improves catalytic.Furthermore an oxidation
Cobalt is due to the interface coupling effect strong with carbon material, such as generates Co-N key, can also improve the inherence at composite material interface and urge
Change ability.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of difunctional cobalt blacks and nitrogen-doped carbon In-situ reaction electrode
Preparation method, this method has that low equipment requirement, required low raw-material cost, reaction condition is easily controllable, production technology is simple
The advantages that list is formed by good product consistency, and environmental pollution is small, can be used for the bifunctional electrocatalyst of OER and ORR, for
The batch production of electrode in situ is of great importance.
For this purpose, the present invention provides a kind of electro-deposition-annealing to prepare porous cobaltosic oxide array electrode, redeposited polyphenyl
The method that the cobalt black and nitrogen-doped carbon composite in-situ electrode of strong interface coupling are prepared in amine and protective atmosphere annealing, including such as
Lower step:
Cobalt nitrate under the conditions of being stirred at room temperature, is dissolved in deionized water, wherein 50~200mM of nitric acid cobalt concentration by the first step；
Hydroxide flake cobalt array, wherein electro-deposition are grown in conductive substrates with the method for electro-deposition in this cobalt nitrate aqueous solution again
Time is 90~360s, and working electrode is -0.9~-1.2V relative to the current potential of saturated calomel electrode；Finally anneal in air
Original position porous flake cobaltosic oxide array is made, wherein temperature is 300~500 DEG C, and the reaction time is 0.5~2h.Described
Conductive substrates include any one in carbon cloth, graphite paper, foam copper or nickel.The reaction principle of the step be nitrate anion in water
Electroreduction is produced into hydroxyl, and hydroxyl is reacted with cobalt ions in turn generates cobalt hydroxide；
(1)NO3 -+e-+H2O→NO2↑+2OH-；
Or NO3 -+3e-+2H2O→NO↑+4OH-；
(2)Co2++2OH-→Co(OH)2。
Since receiving and losing electrons decide the progress of reaction, the diffraction of the film layer obtained in this way in electrodeposit reaction
Property is good compared with hydro-thermal, sol-gal process, and film is more evenly.Such as with carbon paper with example, on each carbon fiber, graphite flake in carbon paper
It uniformly grown cobalt hydroxide.The each cobalt hydroxide nanometer sheet for wherein constituting cobalt hydroxide array is generally a monocrystalline
Body is sintered using annealing in air, and gradually dehydration deoxygenation generates cobaltosic oxide to cobalt hydroxide.300~500 DEG C of selection
Purpose occur that this process faster so that each cobalt hydroxide single crystal nanoplate piece is changed into polycrystalline cobaltosic oxide
Grain, while keeping sheet, has hole between cobaltosic oxide and cobaltosic oxide particle, conducive to the uniform of subsequent preceding body liquid
Load, conducive to the heterogeneous interface for forming more cobalt blacks and carbon.
Second step, polyaniline deposited into above-mentioned growth have in the substrate of cobaltosic oxide array after in Ar gas or N2In gas
600~900 DEG C of 0.5~4h of annealing reaction of annealing reaction.
The polyaniline deposition method includes electro-deposition and two kinds of chemical bath；The polyaniline electro-deposition is in aniline
With electro-deposition is carried out in the mixed solution of sodium sulphate；Chemical bath is replaced in aniline monomer aqueous solution and ammonium persulfate aqueous solution
It impregnates, alternate frequency is 10~60.
The concentration of aniline is 0.02-0.08M, sodium sulfate concentration 0.1-0.4M.
In the electrodeposition process, anode current size is 0.5~4mA, 600~3600s of sedimentation time.
The concentration of aniline monomer aqueous solution is 30-70mmol, ammonium persulfate aqueous solution biological concentration in the chemical bath
For 10-20mmol.
The Ar gas or N2600~900 DEG C of annealing reactions in gas, annealing reaction time are 0.5~4h.
In technical solution of the present invention, the graphite of the carbon 1. formed after polyaniline degree of polymerization carbonization with higher originally
The highly conductive ability of change degree may advantageously facilitate by force the generation of catalysis reaction, and polyaniline forms the carbon materials of N doping under protective atmosphere
Material, while cobaltosic oxide being made to be reduced to cobalt black；2. the N element contained in polyaniline also can be in carbon material forming process
Middle incorporation carbon skeleton or surface, which form graphitization nitrogen or pyrroles's nitrogen, pyridine nitrogen, all has good OER and ORR catalytic performance；③
If the ammonia that polyaniline is discharged during being changed into carbon material its etc. nitrogenous small molecule cobaltosic oxide can be made to be reduced to one
Cobalt oxide forms Co-N with carbon material interface after atomic rearrangementx- C key.
Detailed description of the invention
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 1 embodiment 1 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 2 embodiment 2 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 3 embodiment 3 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 4 embodiment 4 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 5 embodiment 5 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 6 embodiment 6 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 7 embodiment 7 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 8 embodiment 8 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Fig. 9 embodiment 9 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Figure 10 embodiment 10 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Figure 11 embodiment 11 (LSV).
The linear voltammetric scan of the OER-ORR of sample prepared by Figure 12 embodiment 12 (LSV).
The SEM of cobaltosic oxide array prepared by Figure 13 embodiment 1 schemes.
The SEM of cobalt black prepared by Figure 14 embodiment 1 and nitrogen-doped carbon In-situ reaction electrode schemes.
The SEM of cobalt oxide prepared by Figure 15 embodiment 7 and nitrogen-doped carbon In-situ reaction electrode schemes.
The XRD diagram of cobalt black prepared by Figure 16 embodiment 1 and nitrogen-doped carbon In-situ reaction electrode.
Specific embodiment
OER, ORR performance LSV test method in inventive embodiments are as follows: be with cobalt oxide and nitrogen-doped carbon In-situ reaction electrode
Working electrode, using carbon-point be to electrode, to be saturated Hg/HgO electrode as reference electrode, electrolyte used are as follows: 0.1M KOH is water-soluble
Liquid, scanning speed 10mV/s.Oxygen is passed through in OER and ORR test, and working electrode is without spin and the stirring of unused magneton allows oxygen
It is saturated naturally in KOH aqueous solution.Electro-deposition method are as follows: using conductive substrates as working electrode, with carbon-point be to electrode, with saturation
Calomel electrode is reference electrode.
Embodiment 1:
At room temperature, in six aqueous solution of cobalt nitrate, electro-deposition is carried out to carbon paper, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Using 16.6mmol ammonium persulfate solution as solution A, 50mmol benzene
Amine aqueous solution is B solution, in A, B solution repeatedly by the cobaltosic oxide array original position electrode for the porous flake being grown on carbon paper
Alternate immersion 10 times, in 80 DEG C in thermal station dry 10min after being rinsed with deionized water.Carbon paper is put into tube furnace after drying, in Ar
Air-flow lower 600 DEG C of reactions 4h takes out after cooled to room temperature.
Fig. 1 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 1.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.751V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.089V, not stirring state limit inferior current density can reach~
4.05mA/cm2, Δ E=E10-E1/2=0.840V.
Figure 13 is the SEM figure of the cobaltosic oxide array original position electrode of porous flake prepared by embodiment 1.As seen from the figure not
Load and sintering by preceding body liquid, original cobaltosic oxide are that the porous flake of nano particle composition is grown in carbon fiber group
At carbon paper substrate on.
Figure 14 is the figure of electrode SEM prepared by embodiment 1.The polyaniline of preparation is bathed by composite chemical as seen from the figure and is moved back
After burning knot, polyaniline carbonization covers electrode surface at carbon laminar film, and original cobalt oxide sheet-like array is changed into nanometer
Grain.
Figure 16 is the XRD diagram of cobalt black and nitrogen-doped carbon In-situ reaction electrode prepared by embodiment 1.It does not bear as seen from the figure
Body liquid and the electrode being sintered are that cobaltosic oxide is grown in carbon paper substrate before carrying.When the array-supported preceding body liquid of cobaltosic oxide simultaneously
After sintering, the peak of cobaltosic oxide object phase almost disappears and the peak of new cobalt black occurs.
Embodiment 2:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Using 16.6mmol ammonium persulfate solution as solution A, 50mmol benzene
Amine aqueous solution is B solution, in A, B solution repeatedly by the cobaltosic oxide array original position electrode for the porous flake being grown on carbon paper
Alternate immersion 10 times, in 80 DEG C in thermal station dry 10min after being rinsed with deionized water.Tube furnace is put into after drying, in Ar air-flow
Lower 600 DEG C of reactions 1h then heats to 900 DEG C of reaction 30min, takes out after cooled to room temperature.
Fig. 2 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 2.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.833V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.109V, not stirring state limit inferior current density can reach~
3.08mA/cm2, Δ E=E10-E1/2=0.942V.
Embodiment 3:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide cobalt array original position electrode of porous flake on paper.Using 16.6mmol ammonium persulfate solution as solution A, 50mmol
Aniline solution is B solution, and the cobaltosic oxide array original position electrode for the porous flake being grown on carbon paper is anti-in A, B solution
Complex Alternating impregnates 20 times, in 80 DEG C in thermal station dry 10min after being rinsed with deionized water.Carbon paper is put into tube furnace after drying, and 600
DEG C reaction 1h then heat to 900 DEG C of reaction 30min, taken out after cooled to room temperature.
Fig. 3 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 3.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.833V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.115V, not stirring state limit inferior current density can reach~
1.95mA/cm2, Δ E=E10-E1/2=0.948V.
Embodiment 4:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide cobalt array original position electrode of porous flake on paper.Using 16.6mmol ammonium persulfate solution as solution A, 50mmol
Aniline solution is B solution, and the cobaltosic oxide array original position electrode for the porous flake being grown on carbon paper is anti-in A, B solution
Complex Alternating impregnates 20 times, in 80 DEG C in thermal station dry 10min after being rinsed with deionized water.Tube furnace is put into after drying, in Ar gas
600 DEG C of reaction 4h are flowed down, are taken out after cooled to room temperature.
Fig. 4 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 4.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.758V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.135V, not stirring state limit inferior current density can reach~
3.17mA/cm2, Δ E=E10-E1/2=0.893V.
Embodiment 5:
At room temperature, in six aqueous solution of cobalt nitrate, electro-deposition is carried out to carbon paper, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Using 16.6mmol ammonium persulfate solution as solution A, 50mmol benzene
Amine aqueous solution is B solution, in A, B solution repeatedly by the cobaltosic oxide array original position electrode for the porous flake being grown on carbon paper
Alternate immersion 30 times, in 80 DEG C in thermal station dry 10min after being rinsed with deionized water.Tube furnace is put into after drying, in Ar air-flow
Lower 600 DEG C of reactions 1h then heats to 900 DEG C of reaction 30min, takes out after cooled to room temperature.
Fig. 5 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 5.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.842V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.121V, not stirring state limit inferior current density can reach~
2.438mA/cm2, Δ E=E10-E1/2=0.963V.
Embodiment 6:
At room temperature, electro-deposition is carried out in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is 150mM, electricity
Pressure is -1.0V, time 90s.There to be the carbon paper of deposition in 80 DEG C in thermal station dry 10min with deionized water repeated flushing afterwards
Be put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, take out after cooled to room temperature obtain being grown on it is more on carbon paper
The cobaltosic oxide array original position electrode of hole sheet.Using 16.6mmol ammonium persulfate solution as solution A, 50mmol aniline solution is
B solution alternately and repeatedly impregnates the cobaltosic oxide array original position electrode for the porous flake being grown on carbon paper 30 times, spend from
In 80 DEG C in thermal station dry 10min after sub- water flushing.Tube furnace is put into after drying, 600 DEG C of reaction 4h, naturally cold under Ar air-flow
But to taking out after room temperature.
Fig. 6 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 6.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.770V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.140V, not stirring state limit inferior current density can reach~
3.44mA/cm2, Δ E=E10-E1/2=0.910V.
Embodiment 7:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Then three are aoxidized by the four of the porous flake being grown on carbon paper
Cobalt array original position electrode carries out electro-deposition in aniline and sodium sulphate mixed solution, and wherein concentration of aniline is 0.05M, and sodium sulphate is dense
Degree is 0.2M, electric current 0.5mA, time 1800s.Afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min.It is dry
Tube furnace is put into after dry, 600 DEG C of reaction 4h under Ar air-flow take out after cooled to room temperature.
Fig. 7 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 7.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.787V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.199V, not stirring state limit inferior current density can reach~
3.87mA/cm2, Δ E=E10-E1/2=0.986V.
Figure 15 is the SEM figure of cobalt oxide prepared by embodiment 7 and nitrogen-doped carbon In-situ reaction electrode.As seen from the figure by multiple
After closing the polyaniline of electro-deposition and sintering, polyaniline carbonization is covered on original sheet-like array body structure surface at carbon film.
Embodiment 8:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Then three are aoxidized by the four of the porous flake being grown on carbon paper
Cobalt array original position electrode carries out electro-deposition in aniline and sodium sulphate mixed solution, and wherein concentration of aniline is 0.05M, and sodium sulphate is dense
Degree is 0.2M, electric current 1mA, time 1800s.Afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min.It is dry
After be put into tube furnace, 600 DEG C of reaction 4h under Ar air-flow take out after cooled to room temperature.
Fig. 8 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 8.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.760V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.099V, not stirring state limit inferior current density can reach~
3.94mA/cm2, Δ E=E10-E1/2=0.859V.
Embodiment 9:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Then three are aoxidized by the four of the porous flake being grown on carbon paper
Cobalt array original position electrode carries out electro-deposition in aniline and sodium sulphate mixed solution, and wherein concentration of aniline is 0.05M, and sodium sulphate is dense
Degree is 0.2M, electric current 2mA, time 1200s.Afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min.It is dry
After be put into tube furnace, 600 DEG C of reaction 1h then heat to 900 DEG C of reaction 30min under Ar air-flow, take after cooled to room temperature
Out.
Fig. 9 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 9.As seen from the figure when electrode passes through
Current density be 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.838V, alkalinity are water-soluble
It is E that ORR, which reacts corresponding half wave potential, in liquid1/2=-0.120V, not stirring state limit inferior current density can reach~
2.83mA/cm2, Δ E=E10-E1/2=0.958V.
Embodiment 10:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Then three are aoxidized by the four of the porous flake being grown on carbon paper
Cobalt array original position electrode carries out electro-deposition in aniline and sodium sulphate mixed solution, and wherein concentration of aniline is 0.05M, and sodium sulphate is dense
Degree is 0.2M, electric current 2mA, time 1200s.Afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min.It is dry
After be put into tube furnace, 600 DEG C of reaction 4h under Ar air-flow take out after cooled to room temperature.
Figure 10 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 10.As seen from the figure when electrode is logical
The current density crossed is 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.782V, alkaline water
It is E that ORR, which reacts corresponding half wave potential, in solution1/2=-0.138V, not stirring state limit inferior current density can reach~
3.54mA/cm2, Δ E=E10-E1/2=0.920V.
Embodiment 11:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Then three are aoxidized by the four of the porous flake being grown on carbon paper
Cobalt array original position electrode carries out electro-deposition in aniline and sodium sulphate mixed solution, and wherein concentration of aniline is 0.05M, and sodium sulphate is dense
Degree is 0.2M, electric current 4mA, time 600s.Afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min.It is dry
After be put into tube furnace, 600 DEG C of reaction 4h under Ar air-flow take out after cooled to room temperature.
Figure 11 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 11.As seen from the figure when electrode is logical
The current density crossed is 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.812V, alkaline water
It is E that ORR, which reacts corresponding half wave potential, in solution1/2=-0.148V, not stirring state limit inferior current density can reach~
4.29mA/cm2, Δ E=E10-E1/2=0.960V.
Embodiment 12:
At room temperature, electro-deposition is carried out to carbon paper in six aqueous solution of cobalt nitrate, wherein six water concentration of cobalt nitrate is
150mM, voltage are -1.0V, time 90s.It is heavy by having afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min
Long-pending carbon paper is put into tube furnace, 400 DEG C of reaction 30min under Air air-flow, takes out after cooled to room temperature and obtains being grown on carbon
The cobaltosic oxide array original position electrode of porous flake on paper.Then three are aoxidized by the four of the porous flake being grown on carbon paper
Cobalt array original position electrode carries out electro-deposition in aniline and sodium sulphate mixed solution, and wherein concentration of aniline is 0.05M, and sodium sulphate is dense
Degree is 0.2M, electric current 4mA, time 600s.Afterwards with deionized water repeated flushing in 80 DEG C in thermal station dry 10min.It is dry
After be put into tube furnace, 600 DEG C of reaction 1h then heat to 900 DEG C of reaction 30min under Ar air-flow, take after cooled to room temperature
Out.
Figure 12 is the linear voltammetric scan of electrode OER, ORR (LSV) figure prepared by embodiment 12.As seen from the figure when electrode is logical
The current density crossed is 10mA/cm2When, it is E that OER reaction, which produces the corresponding current potential of oxygen, in alkaline aqueous solution10=0.836V, alkaline water
It is E that ORR, which reacts corresponding half wave potential, in solution1/2=-0.097V, not stirring state limit inferior current density can reach~
1.91mA/cm2, Δ E=E10-E1/2=0.933V.
Claims (10)
1. a kind of preparation method of difunctional cobalt black and nitrogen-doped carbon In-situ reaction electrode, which is characterized in that specific system
Preparation Method are as follows:
(1) cobalt nitrate is dissolved in deionized water, grows hydroxide flake cobalt array using being electrodeposited in conductive substrates, then will
Cobalt hydroxide array is annealed in air forms porous, sheet cobaltosic oxide array；
(2) in Ar gas or N after polyaniline deposited to above-mentioned growth having in the substrate of cobaltosic oxide array2Annealing reaction in gas,
Difunctional cobalt black and nitrogen-doped carbon In-situ reaction electrode can be prepared.
2. the preparation method of difunctional cobalt black according to claim 1 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, the cobalt nitrate aqueous solution concentration is 50 ~ 200 mM.
3. the preparation method of difunctional cobalt black according to claim 1 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, electrodeposition time is 90 ~ 360 s, and working electrode is -0.9 ~ -1.2 relative to the current potential of saturated calomel electrode
V。
4. the preparation method of difunctional cobalt black according to claim 1 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, the conductive substrates include any one in carbon cloth, graphite paper, foam copper or nickel.
5. the preparation method of difunctional cobalt black according to claim 1 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, the temperature annealed in the air is 300 ~ 500 DEG C, and the annealing reaction time is 0.5 ~ 2 h.
6. the preparation method of difunctional cobalt black according to claim 1 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, the polyaniline deposition method includes electro-deposition and two kinds of chemical bath；The polyaniline electro-deposition is in benzene
Electro-deposition is carried out in the mixed solution of amine and sodium sulphate；Chemical bath is handed in aniline monomer aqueous solution and ammonium persulfate aqueous solution
For immersion, alternate frequency is 10 ~ 60.
7. the preparation method of difunctional cobalt black according to claim 6 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, the concentration of aniline is 0.02-0.08 M, and sodium sulfate concentration is 0.1-0.4 M.
8. the preparation method of difunctional cobalt black according to claim 6 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, in electrodeposition process, anode current size is 0.5 ~ 4 mA, 600 ~ 3600 s of sedimentation time.
9. the preparation method of difunctional cobalt black according to claim 6 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, the concentration of aniline monomer aqueous solution is 30-70mmol in chemical bath, and ammonium persulfate aqueous solution biological concentration is 10-
20 mmol。
10. the preparation method of difunctional cobalt black according to claim 1 and nitrogen-doped carbon In-situ reaction electrode,
It is characterized in that, the Ar gas or N2600 ~ 900 DEG C of annealing reactions in gas, annealing reaction time are 0.5 ~ 4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811320265.4A CN109585861B (en) | 2018-11-07 | 2018-11-07 | Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811320265.4A CN109585861B (en) | 2018-11-07 | 2018-11-07 | Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109585861A true CN109585861A (en) | 2019-04-05 |
| CN109585861B CN109585861B (en) | 2022-03-04 |
Family
ID=65921742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811320265.4A Active CN109585861B (en) | 2018-11-07 | 2018-11-07 | Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109585861B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112018361A (en) * | 2020-08-31 | 2020-12-01 | 华中科技大学 | Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof |
| CN115000432A (en) * | 2022-06-06 | 2022-09-02 | 广东工业大学 | Cobalt oxide-loofah sponge derived nitrogen-doped carbon composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108183228A (en) * | 2018-01-05 | 2018-06-19 | 济南大学 | A kind of nitrogen-doped carbon nano-array/cobalt ferrite material |
-
2018
- 2018-11-07 CN CN201811320265.4A patent/CN109585861B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108183228A (en) * | 2018-01-05 | 2018-06-19 | 济南大学 | A kind of nitrogen-doped carbon nano-array/cobalt ferrite material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111235614B (en) * | 2020-01-17 | 2022-05-03 | 天津大学 | Preparation method and application of multifunctional self-supporting electrode with nitrogen-doped carbon wrapping structure |
| CN112018361A (en) * | 2020-08-31 | 2020-12-01 | 华中科技大学 | Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof |
| CN115000432A (en) * | 2022-06-06 | 2022-09-02 | 广东工业大学 | Cobalt oxide-loofah sponge derived nitrogen-doped carbon composite material and preparation method and application thereof |
| CN115000432B (en) * | 2022-06-06 | 2023-09-08 | 广东工业大学 | Cobalt oxide-luffa derivative nitrogen-doped carbon composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109585861B (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108543545B (en) | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications | |
| CN107523845B (en) | A kind of preparation method of carbon cloth load Ni-S-Se nano-chip arrays | |
| CN110465312A (en) | A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application | |
| CN109797405B (en) | Preparation method of cobalt sulfide and nitrogen-doped carbon composite array electrode | |
| CN109599565B (en) | Preparation method of difunctional cobalt and nitrogen-doped carbon composite in-situ electrode | |
| CN105140531A (en) | Three-dimensional anode material for hydrogen production by water electrolysis and preparation method of three-dimensional anode material | |
| CN112968185B (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN109852994B (en) | Co9S8Preparation method of nitrogen-doped carbon composite array electrode | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN108183228A (en) | A kind of nitrogen-doped carbon nano-array/cobalt ferrite material | |
| CN109860634B (en) | Method for manufacturing manganese cobalt oxide and nitrogen-doped carbon in-situ composite electrode | |
| CN109585861A (en) | A kind of preparation method of difunctional cobalt black and nitrogen-doped carbon In-situ reaction electrode | |
| CN108336374A (en) | Nitrogenous carbon material of a kind of high-performance ternary Fe-Co-Ni codopes and its preparation method and application | |
| CN109585856A (en) | A kind of preparation method of difunctional cobalt sulfide and sulphur, nitrogen-doped carbon In-situ reaction electrode | |
| CN110813361B (en) | Phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material and preparation method and application thereof | |
| CN109585862B (en) | Preparation method of dual-functional cobalt and nitrogen and oxygen doped carbon in-situ composite electrode | |
| CN109585860B (en) | Preparation method of sulfur-doped cobalt oxide and sulfur, nitrogen and oxygen-doped carbon in-situ composite electrode | |
| CN114784303A (en) | Preparation and application of copper polyphenol supramolecular network interface modified rare earth-based organic frame cathode material | |
| CN109939707A (en) | Two cobalt@nickel tungstate nucleocapsid heterojunction material of phosphatization and the preparation method and application thereof | |
| CN109546157B (en) | Preparation method of copper, cobalt nitride and carbon in-situ composite electrode | |
| CN115261915B (en) | Composite electrocatalyst containing cobalt and nickel and preparation method and application thereof | |
| Wang et al. | Carbon layer-protected self-supporting CoSe 2 nanowire arrays for durable hydrogen evolution reaction catalysts | |
| CN114150341A (en) | Transition metal selenide electrocatalytic material and preparation method and application thereof | |
| CN114672843B (en) | Nickel nitride/ruthenium/nitrogen doped coal activated carbon composite material and preparation method thereof | |
| Patil et al. | Binder-Free Synthesis of NiCo2S4 Nanowires Grown on Ni Foam as an Efficient Electrocatalyst for Oxygen Evolution Reaction |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |