CN112080761B - In-situ vanadium-doped nickel hydroxide electrode and preparation method and application thereof - Google Patents

In-situ vanadium-doped nickel hydroxide electrode and preparation method and application thereof Download PDF

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CN112080761B
CN112080761B CN202010993681.1A CN202010993681A CN112080761B CN 112080761 B CN112080761 B CN 112080761B CN 202010993681 A CN202010993681 A CN 202010993681A CN 112080761 B CN112080761 B CN 112080761B
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nickel hydroxide
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hydroxide electrode
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曹丽云
何丹阳
冯亮亮
黄剑锋
吴建鹏
李晓艺
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses an in-situ vanadium-doped nickel hydroxide electrode and a preparation method and application thereof.A final product directly synthesized by adopting a one-step hydrothermal method takes vanadium chloride as a vanadium source, hexamethylenetetramine as a morphology regulator and foamed nickel as a conductive substrate, thereby realizing the in-situ vanadium-doped beta-Ni (OH)2The preparation of the alkaline full-hydrolytic electrode introduces vanadium to improve the electrocatalytic performance, the preparation process is simple, the cost is low, the period is short, the process is easy to control, and the obtained in-situ vanadium-doped nickel hydroxide electrode is applied to the electrocatalytic reaction of full-hydrolytic hydrogen production and oxygen production, and shows good electrochemical activity and stability.

Description

In-situ vanadium-doped nickel hydroxide electrode and preparation method and application thereof
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to an in-situ vanadium-doped nickel hydroxide electrode and a preparation method and application thereof.
Background
This has raised particular attention due to the increasing climate warming and environmental concerns caused by fossil fuels. Therefore, it is an urgent task to find a clean alternative to renewable energy. Electrochemical water splitting is a reliable technology for storing and transporting peak excess electrical energy of wind and solar energy, and theoretical zero pollution can be realized only by generating hydrogen and oxygen. Currently, the most effective hydrogen and oxygen evolution electrocatalysts in commercial use are Pt-based materials and Ir/Ru-based oxides, respectively. However, these precious metals have greatly limited their widespread use due to their scarce reserves, high cost and their instability. Generally, strategies such as nano-fabrication, structure regulation, doping, and compounding with a conductive substrate are generally available for improving the performance of the catalyst. For this reason, it is necessary to develop a non-noble metal full-hydrolysis electrocatalyst with high activity and high stability, and it is also a great challenge.
The nickel hydroxide/foamed nickel has wide application in the fields of lithium ion batteries and supercapacitors because of its excellent electrochemical properties such as conductivity, stability and the like in alkaline solutions. However, transition metal hydroxides are believed to have a strong ability to cleave O and OH bonds, but convert these hydrogen-absorbing intermediates to H2There are disadvantages in the aspect. Therefore, the nickel hydroxide self-supporting electrode is constructed by doping, and then the efficient full-electrolysis water catalyst is developed. Particularly, vanadium and nickel belong to transition metal elements, and have high reserves in the earth crust and are easy to obtain; and the vanadium has flexible valence and good reaction activity. In addition, it is an effective method to prepare an electrocatalyst with a highly conductive three-dimensional porous foam metal as a hard template. Among them, nickel foam has been widely used as a self-supporting electrode for bulk water splitting, and its integrated structure eliminates the problem of interfacial resistance between the electrode and the catalyst, allows faster electron transport between the electrode-catalyst-electrolyte, and maintains its excellent mechanical stability. Therefore, it is very urgent to realize the synthesis of vanadium doped nickel hydroxide integrated electrodes synthesized in situ, and then to explore their performance as full water-splitting electrocatalysts.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an in-situ vanadium-doped nickel hydroxide electrode and a preparation method and application thereof, the preparation process is simple, the cost is low, the period is short, the process is easy to control, in-situ vanadium is introduced to improve the electrocatalytic performance, and the prepared in-situ vanadium-doped nickel hydroxide electrode shows good electrochemical activity and stability in the electrocatalytic reaction of full water hydrolysis under an alkaline condition.
In order to achieve the above object, the present invention provides a method for preparing an in-situ vanadium-doped nickel hydroxide electrode, comprising the following steps:
1) pretreating foamed nickel;
2) taking 0.06-0.11 mg of vanadium chloride and 0.21-0.35 mg of hexamethylenetetramine, simultaneously adding into 25-30 mL of ultrapure water, and uniformly stirring to obtain a solution A;
3) pouring the solution A into a reaction liner of a reaction kettle, putting the pretreated foamed nickel into an inner kettle of the reaction kettle, then installing the reaction liner into an outer kettle of the reaction kettle for fixation, putting the reaction kettle into a homogeneous phase reactor, and reacting at the temperature of 155-165 ℃ for 11-13 h at the rotating speed of 5-10 r/min;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product of the foamed nickel cooled after the reaction, and cleaning and drying to obtain the in-situ vanadium-doped nickel hydroxide electrode.
Preferably, the pretreatment of step 1) comprises: firstly, ultrasonically cleaning foamed nickel in an acetone solution for 5-15 min, then transferring the foamed nickel into hydrochloric acid with the concentration of 1-2 mol/L for ultrasonically cleaning for 5-10 min, finally alternately washing the foamed nickel for 3-4 times by using absolute ethyl alcohol and ultrapure water respectively, and drying the foamed nickel for 8-10 h in vacuum at the temperature of 30-40 ℃ for later use.
Preferably, the nickel foam is cut to 1.5cm by 4cm in the pretreatment.
Preferably, magnetic stirring is adopted in the step 2), the rotating speed of the magnetic stirring is 400-600 r/min, and the time is 30-40 min.
Preferably, the reaction lining in step 3) is a polyparaphenylene lining.
Preferably, the filling ratio of the solution A in the reaction lining in the step 3) is 50-60%.
Preferably, the step 4) is alternately cleaned by using ultrapure water and absolute ethyl alcohol.
Preferably, the drying temperature in the step 4) is 60-70 ℃, and the time is 6-8 h.
The invention also provides an in-situ vanadium-doped nickel hydroxide electrode prepared by the preparation method.
The invention also provides the application of the in-situ vanadium-doped nickel hydroxide electrode in the electrocatalytic reaction of full hydrolysis under the alkaline condition.
Compared with the prior art, the invention has the following beneficial effects:
1) compared with the preparation method, the invention adopts the final product directly synthesized by the one-step hydrothermal method, overcomes the defect of high temperature of the traditional calcining method, and has the characteristics of lower temperature, simple synthesis path, shorter period, low cost and easily controlled reaction conditions. In addition, the method is environment-friendly and can be popularized to large-scale production and application.
2) Doping is an effective method for adjusting the electronic structure of the catalyst, and accordingly, the adsorption energy of the material and the catalytic activity of the material are influenced. The transition metal vanadium has flexible valence state and good reaction activity; the earth crust has high reserves and is easy to obtain. Therefore, vanadium is introduced to improve the electrocatalytic performance of the electrode.
3) According to the invention, a morphology regulator hexamethylenetetramine is introduced, and parameters such as the ratio of the morphology regulator hexamethylenetetramine to the vanadium source, the reaction temperature, the reaction time, the reaction filling ratio and the like are strictly controlled, so that the control of the existing state of vanadium in the reaction is realized, the induction effect of the hexamethylenetetramine is fully utilized, and the in-situ vanadium-doped beta-Ni (OH) is realized2Preparing an electrode for alkaline full-hydrolysis.
4) The foamed nickel has a unique three-dimensional porous structure, so that the transmission rate of electrons between the catalyst and the electrolyte can be accelerated, and the mechanical stability of the integrated structure grown in situ can be improved, so that the integrated structure is firmer. In addition, the introduction of the conductive substrate can effectively make up the defect that the powder catalyst is easy to stack and curl in the test, thereby improving the in-situ vanadium-doped nickel hydroxide electrode (V-Ni (OH) prepared by the invention2NF) catalytic activity and stability.
5) When V-Ni (OH) is prepared by the present invention2the/NF self-supporting electrode shows good electrochemical activity and stability when applied to an alkaline full-electrolysis water catalyst. V-Ni (OH) to the present invention2the/NF self-supporting electrode respectively carries out HER and OER tests under alkaline (pH14) solution, when the current density reaches 10mA/cm2The required overpotential is 150-160 mV and 270-280 mV respectively. And, p-V-Ni (OH)2The NF electrode is subjected to long-time electrochemical hydrogen production and oxygen production i-t test in an alkaline medium, and the curve has no obvious fluctuation phenomenon, which shows that V-Ni (OH)2the/NF electrode has excellent alkaline electrochemical stability.
Drawings
FIG. 1 shows V-Ni (OH) prepared in example 1 of the present invention2X-ray diffraction (XRD) pattern of the/NF free-standing electrode;
FIG. 2 shows V-Ni (OH) prepared in example 1 of the present invention2Low power Scanning Electron Microscope (SEM) picture of NF self-supporting electrode;
FIG. 3 is V-Ni (OH) prepared in example 1 of the present invention2High power Scanning Electron Microscope (SEM) picture of NF self-supporting electrode;
FIG. 4 shows V-Ni (OH) prepared in example 1 of the present invention2A hydrogen production performance diagram (HER) of a Linear Sweep Voltammetry (LSV) curve of the NF self-supporting electrode under an alkaline condition;
FIG. 5 shows V-Ni (OH) prepared in example 1 of the present invention2Oxygen evolution performance plot (OER) of Linear Sweep Voltammetry (LSV) curve of/NF self-supporting electrodes in alkaline medium.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a preparation method of an in-situ vanadium-doped nickel hydroxide electrode, which comprises the following steps:
1) pretreating foamed nickel; preferably, the pre-treatment comprises: firstly, ultrasonically cleaning foamed nickel in an acetone solution for 5-15 min, then transferring the foamed nickel to a proper amount of hydrochloric acid with the concentration of 1-2 mol/L for ultrasonically cleaning for 5-10 min, finally alternately washing the foamed nickel for 3-4 times by using absolute ethyl alcohol and ultrapure water respectively, and drying the foamed nickel for 8-10 h in vacuum at the temperature of 30-40 ℃ for later use; preferably, the nickel foam is cut to 1.5cm × 4cm in the pretreatment;
2) taking 0.06-0.11 mg of vanadium chloride and 0.21-0.35 mg of hexamethylenetetramine, simultaneously adding into 25-30 mL of ultrapure water, and uniformly stirring to obtain a solution A; preferably, magnetic stirring is adopted for stirring, the rotating speed of the magnetic stirring is 400-600 r/min, and the time is 30-40 min;
3) pouring the solution A into a reaction liner of a reaction kettle, putting the pretreated foamed nickel into an inner kettle of the reaction kettle, then installing the reaction liner into an outer kettle of the reaction kettle for fixation, putting the reaction kettle into a homogeneous phase reactor, and reacting at the temperature of 155-165 ℃ for 11-13 h at the rotating speed of 5-10 r/min; preferably, the reaction lining is a poly-p-phenylene lining, and the filling ratio of the solution A in the reaction lining is 50-60%;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product of the foamed nickel cooled after the reaction, and cleaning and drying to obtain the in-situ vanadium-doped nickel hydroxide electrode. Preferably, the product nickel foam is alternately cleaned by adopting ultrapure water and absolute ethyl alcohol, the drying temperature is 60-70 ℃, and the drying time is 6-8 hours.
The in-situ vanadium-doped nickel hydroxide electrode prepared by the method has a xanthate microstructure, is applied to hydrogen production and oxygen production in full-hydrolysis electrocatalytic reaction under an alkaline condition, has good electrochemical activity and stability, is subjected to HER and OER tests respectively under an alkaline (pH14) solution, and has a current density of 10mA/cm2The required overpotential is 150-160 mV and 270-280 mV respectively. And, p-V-Ni (OH)2The NF electrode is subjected to long-time electrochemical hydrogen production and oxygen production i-t test in an alkaline medium, and the curve has no obvious fluctuation phenomenon, which shows that V-Ni (OH)2the/NF electrode has excellent alkaline electrochemical stability.
Example 1:
1) ultrasonically cleaning the cut foam nickel (1.5cm multiplied by 4cm) in an acetone solution for 5min, then transferring the foam nickel into 1mol/L hydrochloric acid for ultrasonic cleaning for 10min, finally alternately washing the foam nickel for 3 times by using absolute ethyl alcohol and ultrapure water respectively, and then drying the foam nickel for 8h in vacuum at 25 ℃ for later use;
2) taking 0.06mg of vanadium chloride and 0.21mg of hexamethylenetetramine, simultaneously adding the vanadium chloride and the hexamethylenetetramine into 25mL of ultrapure water, and stirring at the normal temperature at the rotating speed of 400r/min for 40min to obtain a solution A;
3) pouring the solution A into an inner liner of poly-p-phenylene, putting the treated foamed nickel into an inner kettle, then putting the inner liner into an outer kettle, fixing the inner liner in the outer kettle, putting the inner liner into a homogeneous phase reactor, and then reacting at 155 ℃ for 13 hours at the rotating speed of 5r/min, wherein the filling ratio is 50%;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product foamed nickel cooled after the reaction, alternately cleaning by using ultrapure water and absolute ethyl alcohol, and drying at the temperature of 60 ℃ for 8h to obtain the xanthate-shaped in-situ vanadium-doped nickel hydroxide self-supporting electrode.
The electrode prepared in example 1 was subjected to X-ray diffraction, low power and high power electron microscope scanning, respectively, as shown in FIGS. 1, 2 and 3, and the diffraction pattern thereof and Ni (OH) were observed in FIG. 12(PDF #14-0117) was completely agreed to prove that we succeeded in-situ synthesis of vanadium doped beta-Ni (OH) on foamed nickel substrate2And as seen from fig. 2 and fig. 3, the microstructure of the electrode is in a cocklebur shape, and the porous structure is favorable for full contact between the electrolyte and the electrode, so that the occurrence of catalytic reaction is accelerated, and the catalytic performance of the electrode is improved.
The electrode prepared in example 1 was subjected to HER and OER tests in alkaline (pH14) solution, see FIGS. 4 and 5, respectively, when the current density reached 10mA/cm2The desired HER overpotential is 155mV and OER overpotential is 280mV, for V-Ni (OH)2The NF electrode is subjected to long-time electrochemical hydrogen production and oxygen production i-t test in an alkaline medium, and the curve has no obvious fluctuation phenomenon, which shows that V-Ni (OH)2the/NF electrode has excellent alkaline electrochemical stability.
Example 2:
1) ultrasonically cleaning the cut foam nickel (1.5cm multiplied by 4cm) in an acetone solution for 10min, then transferring the foam nickel into 2mol/L hydrochloric acid for ultrasonic cleaning for 5min, finally alternately washing the foam nickel for 4 times by using absolute ethyl alcohol and ultrapure water respectively, and then drying the foam nickel for 9h in vacuum at 25 ℃ for later use;
2) taking 0.07mg of vanadium chloride and 0.24mg of hexamethylenetetramine, simultaneously adding the vanadium chloride and the hexamethylenetetramine into 26mL of ultrapure water, and stirring at the normal temperature at the rotating speed of 500r/min for 35min to obtain a solution A;
3) pouring the solution A into a lining of poly-p-phenylene, putting the treated foamed nickel into an inner kettle, then putting the lining into an outer kettle, fixing the lining, putting the inner kettle into a homogeneous reactor, and then reacting at 157 ℃ for 13h at the rotating speed of 6r/min, wherein the filling ratio is 52%;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product foamed nickel cooled after the reaction, alternately cleaning by using ultrapure water and absolute ethyl alcohol, and drying at the temperature of 62 ℃ for 8h to obtain the xanthate-shaped vanadium-doped nickel hydroxide self-supporting electrode.
Example 3:
1) ultrasonically cleaning cut foam nickel (1.5cm multiplied by 4cm) in an acetone solution for 15min, then transferring the foam nickel into 1mol/L hydrochloric acid for ultrasonic cleaning for 10min, finally alternately washing the foam nickel for 3 times by using absolute ethyl alcohol and ultrapure water respectively, and then drying the foam nickel for 10h in vacuum at 25 ℃ for later use;
2) taking 0.08mg of vanadium chloride and 0.27mg of hexamethylenetetramine, simultaneously adding into 27mL of ultrapure water, and stirring at the normal temperature at the rotating speed of 600r/min for 30min to obtain a solution A;
3) pouring the solution A into a lining of poly-p-phenylene, putting the treated foamed nickel into an inner kettle, then putting the lining into an outer kettle, fixing the lining, putting the inner kettle into a homogeneous reactor, and then reacting at 159 ℃ for 12 hours at a rotating speed of 7r/min, wherein the filling ratio is 54%;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product foamed nickel cooled after the reaction, alternately cleaning by using ultrapure water and absolute ethyl alcohol, and drying at the temperature of 64 ℃ for 7h to obtain the xanthate-shaped vanadium-doped nickel hydroxide self-supporting electrode.
Example 4:
1) ultrasonically cleaning the cut foam nickel (1.5cm multiplied by 4cm) in an acetone solution for 5min, then transferring the foam nickel into 2mol/L hydrochloric acid for ultrasonic cleaning for 5min, finally alternately washing the foam nickel for 4 times by respectively using absolute ethyl alcohol and ultrapure water, and then drying the foam nickel for 8h in vacuum at 25 ℃ for later use;
2) taking 0.09mg of vanadium chloride and 0.30mg of hexamethylenetetramine, simultaneously adding the vanadium chloride and the hexamethylenetetramine into 28mL of ultrapure water, and stirring at the normal temperature at the rotating speed of 400r/min for 40min to obtain a solution A;
3) pouring the solution A into a lining of poly-p-phenylene, putting the treated foamed nickel into an inner kettle, then putting the lining into an outer kettle, fixing the lining, putting the inner kettle into a homogeneous reactor, and then reacting for 12 hours at a rotating speed of 8r/min at a temperature of 161 ℃, wherein the filling ratio is 56%;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product foamed nickel cooled after the reaction, alternately cleaning by using ultrapure water and absolute ethyl alcohol, and drying at the temperature of 66 ℃ for 7h to obtain the xanthate-shaped vanadium-doped nickel hydroxide self-supporting electrode.
Example 5:
1) ultrasonically cleaning the cut foam nickel (1.5cm multiplied by 4cm) in an acetone solution for 10min, then transferring the foam nickel into 1mol/L hydrochloric acid for ultrasonic cleaning for 10min, finally alternately washing the foam nickel for 3 times by using absolute ethyl alcohol and ultrapure water respectively, and then drying the foam nickel for 9h in vacuum at 25 ℃ for later use;
2) taking 0.10mg of vanadium chloride and 0.32mg of hexamethylenetetramine, simultaneously adding into 29mL of ultrapure water, and stirring at normal temperature at the rotating speed of 500r/min for 35min to obtain a solution A;
3) pouring the solution A into a lining of poly-p-phenylene, putting the treated foamed nickel into an inner kettle, then putting the lining into an outer kettle, fixing the lining, putting the inner kettle into a homogeneous reactor, and then reacting for 11 hours at 163 ℃ at the rotating speed of 9r/min, wherein the filling ratio is 58%;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product foamed nickel cooled after the reaction, alternately cleaning by using ultrapure water and absolute ethyl alcohol, and drying at the temperature of 68 ℃ for 6 hours to obtain the xanthate-shaped vanadium-doped nickel hydroxide self-supporting electrode.
Example 6:
1) ultrasonically cleaning cut foam nickel (1.5cm multiplied by 4cm) in an acetone solution for 15min, then transferring the foam nickel into 2mol/L hydrochloric acid for ultrasonic cleaning for 5min, finally alternately washing the foam nickel for 4 times by using absolute ethyl alcohol and ultrapure water respectively, and then drying the foam nickel for 10h in vacuum at 25 ℃ for later use;
2) taking 0.11mg of vanadium chloride and 0.35mg of hexamethylenetetramine, simultaneously adding the vanadium chloride and the hexamethylenetetramine into 25-30 mL of ultrapure water, and stirring the mixture for 30min at the normal temperature at the rotating speed of 600r/min to obtain a solution A;
3) pouring the solution A into a lining of poly-p-phenylene, putting the treated foamed nickel into an inner kettle, then putting the lining into an outer kettle, fixing the lining, putting the inner kettle into a homogeneous reactor, and then reacting for 11 hours at 165 ℃ at the rotating speed of 10r/min, wherein the filling ratio is 60%;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product foamed nickel cooled after the reaction, alternately cleaning by using ultrapure water and absolute ethyl alcohol, and drying at the temperature of 70 ℃ for 6 hours to obtain the xanthate-shaped vanadium-doped nickel hydroxide self-supporting electrode.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of an in-situ vanadium-doped nickel hydroxide electrode is characterized by comprising the following steps:
1) pretreating foamed nickel;
2) taking 0.06-0.11 mg of vanadium chloride and 0.21-0.35 mg of hexamethylenetetramine, simultaneously adding into 25-30 mL of ultrapure water, and uniformly stirring to obtain a solution A;
3) pouring the solution A into a reaction inner liner of a reaction kettle, putting the pretreated foamed nickel into the inner liner of the reaction kettle, then fixing the reaction inner liner in an outer kettle of the reaction kettle, putting the reaction kettle into a homogeneous phase reactor, and reacting at the temperature of 155-165 ℃ for 11-13 h at the rotating speed of 5-10 r/min;
4) and after the reaction is finished, naturally cooling to room temperature, taking out the product of the foamed nickel cooled after the reaction, and cleaning and drying to obtain the in-situ vanadium-doped nickel hydroxide electrode.
2. The method for preparing the in-situ vanadium-doped nickel hydroxide electrode according to claim 1, wherein the pretreatment of the step 1) comprises the following steps: firstly, ultrasonically cleaning foamed nickel in an acetone solution for 5-15 min, then transferring the foamed nickel into hydrochloric acid with the concentration of 1-2 mol/L for ultrasonically cleaning for 5-10 min, finally alternately washing the foamed nickel for 3-4 times by using absolute ethyl alcohol and ultrapure water respectively, and drying the foamed nickel for 8-10 h in vacuum at the temperature of 30-40 ℃ for later use.
3. The method of claim 2, wherein the pre-treatment comprises cutting the nickel foam to 1.5cm x 4 cm.
4. The method for preparing the in-situ vanadium-doped nickel hydroxide electrode according to claim 1, wherein magnetic stirring is adopted in the step 2), the rotating speed of the magnetic stirring is 400-600 r/min, and the time is 30-40 min.
5. The method for preparing an in-situ vanadium-doped nickel hydroxide electrode according to claim 1, wherein the reaction lining in the step 3) is a polyparaphenylene lining.
6. The method for preparing the in-situ vanadium-doped nickel hydroxide electrode according to claim 5, wherein the filling ratio of the solution A in the reaction lining in the step 3) is 50-60%.
7. The method for preparing the in-situ vanadium-doped nickel hydroxide electrode according to claim 1, wherein the step 4) is performed by alternately cleaning with ultrapure water and absolute ethyl alcohol.
8. The method for preparing the in-situ vanadium-doped nickel hydroxide electrode according to claim 1, wherein the drying temperature in the step 4) is 60-70 ℃ and the drying time is 6-8 h.
9. An in-situ vanadium-doped nickel hydroxide electrode, which is characterized by being prepared by the preparation method of the in-situ vanadium-doped nickel hydroxide electrode according to any one of claims 1 to 8.
10. An in-situ vanadium doped nickel hydroxide electrode according to claim 9 for use in electrocatalytic reactions for total water splitting under alkaline conditions.
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