CN114784293A - Spherical nickel oxide cobalt manganese electrode and preparation method and application thereof - Google Patents

Spherical nickel oxide cobalt manganese electrode and preparation method and application thereof Download PDF

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Publication number
CN114784293A
CN114784293A CN202210429041.7A CN202210429041A CN114784293A CN 114784293 A CN114784293 A CN 114784293A CN 202210429041 A CN202210429041 A CN 202210429041A CN 114784293 A CN114784293 A CN 114784293A
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cobalt
nickel
electrode
manganese
manganese oxide
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吕昌林
何敏仪
李红
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South China Normal University
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South China Normal University
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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
    • H01M4/8825—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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites

Abstract

The invention belongs to the technical field of synthesis of electrocatalytic materials, and particularly relates to a spherical nickel-cobalt-manganese oxide electrode (Ni)yCozMnmOx) And a preparation method and application thereof. The method takes water as a solvent, nickel-cobalt-manganese sulfate as a main component and sodium sulfate as an electrolyte to prepare an electrodeposition solution; immersing a substrate into an electrodeposition solution to be used as a working electrode, taking a titanium sheet as a counter electrode and taking a saturated calomel electrode as a reference electrode, and depositing spherical nickel-cobalt-manganese oxide on the substrate by cathodic deposition and anodic oxidation by using a cyclic voltammetry. And then, spherical nickel-cobalt-manganese oxide is used as a cathode, and a semiconductor material is used as a photo-anode to assemble the photocatalytic fuel cell for degrading organic pollutants.

Description

Spherical nickel oxide cobalt manganese electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of synthesis of electrocatalytic materials, and particularly relates to a spherical nickel oxide cobalt manganese electrode as well as a preparation method and application thereof.
Background
The preparation method mainly comprises an electrochemical deposition method, a microwave decomposition method, a magnetron sputtering method, a wet chemical method, an electrostatic spinning method, a sol-gel method and the like, wherein the wet chemical method and the sol-gel method generally need to prepare precursor substances firstly, and the nickel-cobalt-manganese oxide is obtained by roasting, the preparation method has a complex flow, and the obtained material has large particles; although the chemical vapor deposition method, the magnetron sputtering method and the electrostatic spinning method can realize the deposition of the nickel oxide, the cobalt oxide and the manganese oxide on the conductive substrate, the methods have complex operation, need special instruments and equipment and have high cost.
The electrochemical deposition method has the advantages of simple and controllable operation and low energy consumption, and the deposited material has the advantages of strong adhesive force, difficult falling, uniform distribution, controllable thickness and the like, so that the nickel-cobalt-manganese oxide nano film can be deposited; the electrochemical deposition method is to make charged ions in the electrodeposition liquid undergo chemical reaction under the action of an electric field, and then deposit the ions on a substrate, so as to prepare a deposition layer. The uniformity, thickness and material structure of the prepared deposition layer are not only related to the properties of charged particles in the prepared electrodeposition liquid, but also closely related to the range of potential intervals and deposition turns regulated and controlled in the deposition process.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, it is a primary object of the present invention to provide a spherical nickel cobalt manganese (Ni) oxideyCozMnmOx) The preparation method of the electrode is a method for realizing the deposition of nickel oxide, cobalt oxide and manganese oxide on a conductive substrate by utilizing an activated co-electrodeposition mode.
The invention also aims to provide the spherical nickel-cobalt-manganese oxide electrode prepared by the preparation method.
The invention further aims to provide application of the spherical nickel-cobalt-manganese oxide electrode.
The purpose of the invention is realized by the following technical scheme:
spherical nickel cobalt manganese (Ni) oxideyCozMnmOx) The preparation method of the electrode comprises the following steps:
(1) preparing an electrodeposition solution by using water as a solvent, nickel-cobalt-manganese sulfate as a main component and sodium sulfate as an electrolyte, and regulating the temperature of the electrodeposition solution to be 15-30 ℃; the concentration of nickel-cobalt-manganese sulfate in the electrodeposition solution is 0.1-10 mmol/L, and the concentration of sodium sulfate is 0.1 mol/L; the nickel cobalt manganese sulfate comprises the following components in a molar ratio of 8: 1: 1 of nickel sulfate, cobalt sulfate and manganese sulfate;
(2) immersing a substrate into the electrodeposition solution prepared in the step (1) to be used as a working electrode, taking a titanium sheet as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, controlling the potential interval and the number of deposition turns of the nickel-cobalt-manganese oxide deposition, and starting to activate the co-electrodeposition nickel-cobalt-manganese oxide;
(3) and (3) soaking the nickel-cobalt-manganese oxide prepared in the step (2) in deionized water for 10-30 min, taking out, and drying at constant temperature to obtain the spherical nickel-cobalt-manganese oxide electrode.
The size of the substrate in the step (2) is 0.5-3.0 cm2Specifically porous nickel foam, conductive glass, glassy carbon electrode, aluminum foil, graphite, nickel plate or platinum sheet.
The potential interval regulation range of the nickel oxide cobalt manganese deposition in the step (2) is-1.3V, and the number of deposition turns is 10-100 turns.
And (4) drying at constant temperature in the step (3) is drying at constant temperature of 35-45 ℃.
The spherical nickel-cobalt-manganese oxide electrode prepared by the preparation method has the chemical formula of NiyCozMnmOxWherein y is 0.8, z is 0.1, and m is 0.1.
The spherical nickel-cobalt-manganese oxide electrode is used as a cathode to construct a photocatalytic fuel cell and is applied to degradation of organic pollutants.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts an electrochemical codeposition method to prepare ternary metal oxide NiyCozMnmOxNi is prepared by taking nickel-cobalt-manganese sulfate as electrodeposition liquid instead of directly adding NaOH as a precipitatoryCozMnmOxThe oxide prepared by the electrodeposition method has the advantages of strong adhesive force, difficult falling, uniform distribution, controllable thickness and the like, simplifies the process flow and reduces the production cost.
(2) Compared with oxide electrodes with other shapes on the surface, the spherical ternary metal oxide obtained by electrochemical codeposition is more beneficial to the infiltration of electrolyte and the degradation of pollutants.
(3) With ternary metal oxide NiyCozMnmOxFor cathode, at 0.25mol L-1KMnO4Under the synergistic effect of the oxidant, the degradation efficiency of the BPA is greatly improved, and the degradation efficiency of the BPA can reach 39.7 percent.
Drawings
FIG. 1 shows the preparation of Ni by co-electrodeposition in example 1 of the present invention0.8Co0.1Mn0.1OxCurrent density-voltage curve of (a);
FIG. 2 is an SEM photograph of the co-electrodeposition product obtained in example 1 of the present invention;
FIG. 3 is a graph of BPA degradation efficiency, Ni, of a photocatalytic fuel cell constructed in example 2 of the present invention0.8Co0.1Mn0.1OxMeasurement curves of ITO as cathode and semiconductor as photo-anode;
fig. 4 is a graph of power density and current density versus cell voltage for a photocatalytic fuel cell in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. The present invention will be described in further detail with reference to specific examples. According to the design purpose of the invention, simple substitution of the same kind of substances and change of the size and shape, such as changing the size of the nickel cobalt manganese oxide (such as changing the size of a working electrode, a counter electrode and a reference electrode) prepared by the invention, changing the appearance of the electrode (such as changing the shape into a square or other shapes), simply changing the type, concentration or potential interval of deposition, deposition temperature and the like of the nickel cobalt manganese salt, all belong to the scope of the invention; the test methods used in the following examples are, unless otherwise specified, conventional methods known in the art; the materials, reagents and the like used are all commercially available reagents and materials unless otherwise specified.
Example 1 activation of Co-electrodeposition of spherical NiyCozMnmOxElectrode for electrochemical cell
(1) Preparing an electrodeposition solution by using deionized water as a solvent, nickel-cobalt-manganese sulfate (comprising nickel sulfate, cobalt sulfate and manganese sulfate) as a main component and sodium sulfate as a supporting electrolyte, and controlling the temperature of the electrodeposition solution to be 25 ℃; the concentrations of nickel sulfate, cobalt sulfate and manganese sulfate in the electrodeposition solution are respectively 5.0, 0.625 and 0.625mmol/L, and the concentration of sodium sulfate is 0.1 mol/L;
(2) immersing an ITO substrate into the prepared electrodeposition solution to be used as a working electrode, taking a titanium sheet as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, and controlling Ni0.8Co0.1Mn0.1OxThe potential interval of the deposition is-1.3V, the number of the deposition turns is 20, and the activation is started to carry out the co-electrodeposition of Ni0.8Co0.1Mn0.1Ox；
(3) Ni obtained in the step (2)0.8Co0.1Mn0.1OxSoaking in deionized water for 20min, taking out, and drying at constant temperature of 40 deg.C to obtain spherical Ni0.8Co0.1Mn0.1OxAnd an electrode.
This example prepares Ni by co-electrodeposition0.8Co0.1Mn0.1OxThe current density-voltage curve of (a) is shown in FIG. 1; the SEM spectra of the resulting co-electrodeposition products are shown in fig. 2.
Example 2 photocatalytic Fuel cell Performance
The assembled photocatalytic fuel cell is tested for performance, and the specific operation steps are as follows:
with CdS/TiO2Electrode as photoanode, spherical Ni prepared by activated co-electrodeposition on ITO as in example 10.8Co0.1Mn0.1OxThe electrode is used as a cathode, and 0.1mol/LNa is added into the anode pool2SO4As electrolyte, 1mmol/LBPA as anolyte, and 0.1mol/LNa added into the cathode cell2SO4Electrolyte solution, 0.25mol/LKMno4The two pools are connected by a saturated potassium chloride salt bridge as catholyte at 0.18 mW/cm-2Assembling a photocatalytic fuel cell under irradiation of visible light, and measuring the degradation rate and timeThe results of the graphs of the intervallic current density, the power and the voltage are shown in figures 3 and 4, the BPA degradation rate of the photocatalytic fuel cell for 120 minutes can reach 39.7 percent, and the short-circuit photocurrent density is 73.25 mu A cm-2The maximum power density at 0.38V was 9.59. mu.W.cm-2. This clearly indicates that the spherical Ni prepared by activated co-electrodeposition0.8Co0.1Mn0.1OxThe photocatalytic fuel cell constructed by taking ITO as a cathode has better degradation performance on BPA, and can more effectively realize the conversion of light energy and chemical energy to electric energy under the irradiation of visible light.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, and equivalents thereof are intended to be included within the scope of the present invention.

Claims (6)

1. A preparation method of a spherical nickel oxide cobalt manganese electrode is characterized by comprising the following steps:
(1) preparing an electrodeposition solution by using water as a solvent, nickel-cobalt-manganese sulfate as a main component and sodium sulfate as an electrolyte, and regulating the temperature of the electrodeposition solution to be 15-30 ℃; the concentration of nickel-cobalt-manganese sulfate in the electrodeposition solution is 0.1-10 mmol/L, and the concentration of sodium sulfate is 0.1 mol/L; the nickel cobalt manganese sulfate comprises the following components in a molar ratio of 8: 1: 1 nickel sulfate, cobalt sulfate and manganese sulfate;
(2) immersing a substrate into the electrodeposition solution prepared in the step (1) to be used as a working electrode, taking a titanium sheet as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, controlling the potential interval and the number of deposition turns of nickel-cobalt-manganese oxide deposition, and starting to activate and electrodeposit nickel-cobalt-manganese oxide;
(3) and (3) soaking the nickel-cobalt-manganese oxide prepared in the step (2) in deionized water for 10-30 min, taking out, and drying at constant temperature to obtain the spherical nickel-cobalt-manganese oxide electrode.
2. The method for preparing spherical nickel-cobalt-manganese oxide electrode according to claim 1The method is characterized in that: the size of the substrate in the step (2) is 0.5-3.0 cm2In particular to porous foam nickel, conductive glass, glassy carbon electrodes, aluminum foils, graphite, nickel plates or platinum sheets.
3. The method for preparing a spherical nickel-cobalt-manganese oxide electrode according to claim 1, wherein the method comprises the following steps: the potential interval regulation range of the nickel oxide cobalt manganese deposition in the step (2) is-1.3V, and the number of deposition turns is 10-100 turns.
4. The method for preparing a spherical nickel-cobalt-manganese oxide electrode according to claim 1, wherein the method comprises the following steps: and (3) drying at constant temperature, namely drying at constant temperature of 35-45 ℃.
5. A spherical nickel-cobalt-manganese oxide electrode produced by the production method according to any one of claims 1 to 4, characterized in that: the chemical formula of the spherical nickel oxide cobalt manganese electrode is NiyCozMnmOxWherein y is 0.8, z is 0.1, and m is 0.1.
6. The use of the spherical nickel cobalt manganese oxide electrode according to claim 5 as a cathode to construct a photocatalytic fuel cell for degrading organic pollutants.
CN202210429041.7A 2022-04-22 2022-04-22 Spherical nickel oxide cobalt manganese electrode and preparation method and application thereof Pending CN114784293A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116856023A (en) * 2023-09-04 2023-10-10 中石油深圳新能源研究院有限公司 Preparation method of battery connector, battery connector and battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116856023A (en) * 2023-09-04 2023-10-10 中石油深圳新能源研究院有限公司 Preparation method of battery connector, battery connector and battery

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