Nickel-based catalytic electrode based on gallium as well as preparation method and application of nickel-based catalytic electrode

Abstract

The invention relates to a nickel-based catalytic electrode based on gallium and a preparation method and application thereof, and belongs to the technical field of metal gallium preparation and nickel-based anode catalysis, the nickel-based anode catalytic electrode specifically comprises a metal nickel substrate and a composite catalytic layer of a NiOOH active phase and a NiO active phase, and the composite catalytic layer of the NiOOH active phase and the NiO active phase is of a nanometer spherical structure. The electrode is prepared through an electrochemical deposition method, pre-deposition is carried out on the surface of a pretreated metal nickel substrate, and a precursor nickel layer is obtained; and in an alkaline electrolyte, carrying out electrochemical oxidation treatment on the obtained precursor nickel layer, and generating a composite catalytic layer on the surface of the precursor nickel layer in situ to obtain the nickel-based anode catalytic electrode. The nickel-based composite electrode is unique in structure and stable in property and has excellent oxygen evolution reaction catalytic activity in an alkaline system, the preparation process is simple, the energy-saving and consumption-reducing effects are remarkable, and application of a nickel-based catalytic electrode in the field of metal gallium electrodeposition can be promoted.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal gallium preparation and nickel-based anode catalysis, and specifically relates to a gallium-based nickel-based catalytic electrode and a preparation method and application thereof. Background Art

[0002] Gallium is a gray-blue or silvery-white metal with the element symbol Ga and an atomic weight of 69.723. Gallium has a very low melting point but a very high boiling point. Pure liquid gallium has a significant tendency to supercool and easily oxidizes in air, forming an oxide film. Gallium is a rare metal known as the "backbone of the electronics industry." Since the 1980s, with the gradual advancement of science and technology, the unique physical and chemical properties of gallium have attracted increasing attention from researchers. Its application is particularly widespread in the modern semiconductor industry, large-scale integrated circuits, aerospace, energy, magnetic materials, and medical and health care. The development of gallium's applications is also closely linked to the current economic development trends of low-carbon and green energy economies, and is closely connected to many industries of modern science and technology.

[0003] In recent years, with the rapid development of science and technology, the production and use of gallium have been increasing. Gallium is a rare metal and is often distributed in copper sulfide ores, bauxite and sphalerite. In addition, a small part exists in coal gangue and seawater. From associated minerals to metallic gallium, gallium metallurgy is currently mainly extracted through mother liquor from bauxite or high-aluminum fly ash smelting by-products, and the mainstream process is resin adsorption-electrodeposition combined technology. The specific process includes: after the gallium (III) ions in the mother liquor are adsorbed by the resin, an alkaline sulfide solution is used for elution to obtain a gallium-rich electrolyte, and then metallic gallium is prepared by electrodeposition reduction. However, this process faces two major bottlenecks:

[0004] 1) High oxygen evolution reaction (OER) overpotential: In alkaline electrolysis systems, the OER on the anode side involves a complex four-electron transfer process. The sluggish kinetics lead to high overpotential, significantly increasing energy consumption and production costs.

[0005] 2) Lack of cheap and efficient anode materials: Traditional anode materials (such as stainless steel, graphite, and precious metals) have very large limitations. For example, graphite is prone to physical disintegration and contamination of the electrolyte due to violent oxygen evolution, while the cost and electrocatalytic activity of stainless steel and precious metal electrodes cannot be taken into account at the same time. Although the precious metal platinum iridium oxide shows extremely high catalytic activity in oxygen evolution reaction, its high cost hinders its application in gallium electrolysis. Stainless steel electrodes are not only inactive; they are also easily corroded by sulfur, chlorine, and fluoride ions in the electrolyte during the oxygen evolution reaction, which greatly reduces their service life. In addition, the impurity ions (Fe 2+ and Fe 3+) will discharge cyclically on the anode and cathode, greatly inhibiting gallium deposition and reducing the Faraday efficiency during electrodeposition.

[0006] Therefore, in order to further enhance the ability of gallium metal to serve future industries, it is crucial to develop efficient and inexpensive anode materials for gallium electrowinning. Studies have found that nickel-based anodes exhibit excellent stability in alkaline environments and have significantly better corrosion resistance than stainless steel electrodes. However, their small intrinsic active surface area and insufficient catalytic sites for the oxygen evolution reaction limit the current density, making it difficult to meet the industrial needs of high efficiency and low energy consumption. Therefore, the development of new nickel-based anode materials with high catalytic activity, corrosion resistance and economy has become the key to promoting the development of gallium electrowinning technology and the large-scale development of the gallium metal industry. Especially in the context of the increasing production and use of gallium in recent years, the research and development of new, efficient and energy-saving nickel-based anode materials has even more important economic and scientific significance. Summary of the Invention

[0007] In response to the shortcomings of the existing technology, the present invention proposes a gallium-based nickel-based catalytic electrode, a preparation method and application thereof, and constructs a multi-level composite structure of nickel oxyhydroxide (NiOOH) and nickel oxide (NiO) on the surface of a nickel substrate through a two-step process of electrochemical deposition-electrochemical oxidation. This structure has abundant active sites and a high specific surface area, which can significantly reduce the OER overpotential. Due to the synergistic effect of NiOOH and NiO, the electron transmission path is optimized and the reaction kinetics are accelerated; at the same time, the composite oxide layer forms a stable passivation film in an alkaline sulfur-containing environment, which inhibits the corrosion of the nickel substrate and ion dissolution. The preparation method of the present invention is simple and controllable, does not require complex equipment, is suitable for large-scale production, and has very high economic benefits.

[0008] A gallium-based nickel-based catalytic electrode, specifically comprising a metallic nickel substrate and a composite catalytic layer of a NiOOH active phase and a NiO active phase;

[0009] A composite catalytic layer of NiOOH active phase and NiO active phase is provided on one surface of the nickel substrate;

[0010] The composite catalytic layer of the NiOOH active phase and the NiO active phase is a nano-spherical structure, and both the surface and the bulk of the composite catalytic layer contain controllable oxygen vacancy distribution.

[0011] The method for preparing the gallium-based nickel-based catalytic electrode specifically comprises the following steps:

[0012] (1) Pre-depositing a precursor nickel layer on the surface of a pretreated metal nickel substrate by electrochemical deposition;

[0013] (2) The obtained precursor nickel layer is subjected to electrochemical oxidation treatment in an alkaline electrolyte to in situ generate a composite catalytic layer of NiOOH active phase and NiO active phase on the surface of the precursor nickel layer to obtain a nickel-based anode catalytic electrode.

[0014] in:

[0015] In the step (1), the pretreatment process of the metal nickel substrate includes: ultrasonically cleaning the metal nickel substrate in 0.5 mol / L to 5 mol / L hydrochloric acid solution, anhydrous ethanol and deionized water in sequence for 5 minutes to 60 minutes.

[0016] In the step (1), the electrochemical deposition method is specifically a constant potential method, and the electrodeposition solution used is a NiSO4 solution with a concentration of 0.05 mol / L to 0.5 mol / L.

[0017] In the step (1), the deposition potential of the electrochemical deposition method is -1V to -6V, and the deposition time is 10min to 60min; during the electrochemical deposition process, the temperature is controlled at 25°C to 60°C, and the stirring speed is 100r / min to 500r / min.

[0018] In the step (2), the electrochemical oxidation specifically adopts constant potential oxidation, the oxidation potential is 0.3V to 0.6V (vs. SCE), and the oxidation time is 5min to 60min.

[0019] In the step (2), the alkaline electrolyte contains S 2- NaOH solution or KOH solution, the concentration of NaOH or KOH in the solution is 0.01mol / L~3mol / L, S in the solution 2- The content is 1g / L~15g / L.

[0020] The application of the gallium-based nickel-based catalytic electrode is specifically to use it as an active anode in the electroplating process of metal gallium in an alkaline system, the cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 - alkaline solution, the electrodeposition temperature is 30℃~80℃; compared with untreated pure nickel sheet or stainless steel substrate, 100mA / cm 2 The anode overpotential at industrial current density is reduced by 180mV to 390mV; compared with untreated pure nickel sheet and stainless steel electrode, 100mA / cm 2 The service life is increased by 3% to 15% under industrial current density.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. This invention uses a two-step electrochemical deposition-electrochemical oxidation process to construct a multi-level composite structure of nickel oxyhydroxide (NiOOH) and nickel oxide (NiO) containing oxygen vacancies on the surface of a nickel substrate. The synergistic effect of NiOOH and NiO optimizes electron transport pathways and accelerates reaction kinetics. Simultaneously, the composite oxide layer forms a stable passivation film in an alkaline, sulfur-containing environment, inhibiting corrosion and ion dissolution of the nickel substrate.

[0023] 2. The composite structure prepared by the present invention has abundant active sites and a high specific surface area, which can significantly reduce the overpotential of the oxygen evolution reaction and has very excellent corrosion resistance and stability;

[0024] 3. The preparation method of the present invention is simple and controllable, does not require complex equipment, is very suitable for large-scale production, and has high economic value. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Scanning electron microscope image of the gallium-based nickel-based catalytic electrode prepared in Example 1 of the present invention;

[0026] Figure 2 Transmission electron microscopy image of the gallium-based nickel-based catalytic electrode prepared in Example 1 of the present invention;

[0027] Figure 3 X-ray diffraction pattern of the gallium-based nickel-based catalytic electrode prepared in Example 1 of the present invention;

[0028] Figure 4 X-ray photoelectron spectrum of the gallium-based nickel-based catalytic electrode prepared in Example 1 of the present invention; wherein (a) is Ni 2p, (b) is O1s, and (c) is S2p;

[0029] Figure 5 Surface wetting angle of the gallium-based nickel-based catalytic electrode prepared in Example 1 of the present invention;

[0030] Figure 6 The contact angle in water of the gallium-based nickel-based catalytic electrode prepared in Example 1 of the present invention;

[0031] Figure 7 Raman spectrum of the gallium-based nickel-based catalytic electrode prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0032] Example 1

[0033] A method for preparing a gallium-based nickel-based catalytic electrode comprises the following steps:

[0034] (1) A nickel foam substrate (size: 20 mm × 10 mm × 1 mm) was ultrasonically cleaned in 3 mol / L hydrochloric acid, anhydrous ethanol, and deionized water for 30 min in sequence to remove surface oxides and organic impurities, thereby obtaining a pretreated nickel metal substrate.

[0035] Take 0.1mol / LNiSO4 as the electrodeposition solution, use clean foam nickel and carbon rod as the working electrode and counter electrode respectively, and pre-deposition is carried out on the surface of the pretreated metal nickel substrate by constant potential method at 30℃. The deposition potential is -5V, the deposition time is 10min, and the stirring speed is 300r / min to obtain the precursor nickel layer Ni / NF.

[0036] (2) The obtained precursor nickel layer Ni / NF was electrochemically oxidized in a 1 mol / L KOH solution containing 6 g / L Na2S: constant potential oxidation was adopted, the oxidation potential was 0.5 V (vs. SCE), and the oxidation time was 30 min. A composite catalytic layer of NiOOH active phase and NiO active phase was in situ generated on the surface of the precursor nickel layer to obtain a nickel-based anode catalytic electrode NiOOH / NiO(O v ) / NF. Scanning electron microscope image of nickel-based anode catalytic electrode Figure 1 As shown in the transmission electron microscopy images Figure 2 As shown, the X-ray diffraction pattern is Figure 3 As shown, the X-ray photoelectron spectrum is as follows Figure 4 As shown, Figure 4 (a) is Ni 2p, Figure 4 (b) is O1s, Figure 4 (c) is S2p. Schematic diagram of the surface wetting angle of nickel-based catalytic electrode Figure 5 The contact angle diagram in water is shown as Figure 6 As shown, the Raman spectrum is Figure 7 shown.

[0037] The structure of the prepared gallium-based nickel-based catalytic electrode specifically includes a metal nickel substrate and a composite catalytic layer of NiOOH active phase and NiO active phase arranged on one surface thereof. The composite catalytic layer of NiOOH active phase and NiO active phase is a nano-spherical structure, and the surface and bulk of the composite catalytic layer both contain controllable oxygen vacancy distribution.

[0038] The application of the gallium-based nickel-based catalytic electrode is specifically to use it as an active anode in the electroplating process of metal gallium in an alkaline system, the cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 -The electrodeposition temperature is 30°C. Due to the synergistic effect of nickel oxyhydroxide and nickel oxide rich in oxygen vacancies and the surface active structure with super hydrophilic and excellent hydrophobic properties, it exhibits excellent catalytic activity for oxygen evolution reaction. Compared with untreated pure nickel sheet or stainless steel substrate, 100mA / cm 2 The anodic overpotential at industrial current density is reduced by 180mV; compared with untreated pure nickel sheet and stainless steel electrode, 100mA / cm 2 The service life is increased by 3% under industrial current density.

[0039] Example 2

[0040] A method for preparing a gallium-based nickel-based catalytic electrode comprises the following steps:

[0041] (1) A nickel foam substrate (size: 20 mm × 10 mm × 1 mm) was ultrasonically cleaned in 3 mol / L hydrochloric acid solution, anhydrous ethanol, and deionized water for 30 min in sequence to remove surface oxides and organic impurities, thereby obtaining a pretreated nickel metal substrate.

[0042] Take 0.15mol / LNiSO4 as the electrodeposition solution, use clean foam nickel and carbon rod as the working electrode and counter electrode respectively, and pre-deposition is carried out on the surface of the pretreated metal nickel substrate by constant potential method at 50℃. The deposition potential is -3.6V, the deposition time is 20min, and the stirring speed is 400r / min to obtain the precursor nickel layer Ni / NF.

[0043] (2) The obtained precursor nickel layer Ni / NF was electrochemically oxidized in a 2 mol / L KOH solution containing 5 g / L Na2S: constant potential oxidation was adopted, the oxidation potential was 0.5 V (vs. SCE), and the oxidation time was 30 min. A composite catalytic layer of NiOOH active phase and NiO active phase was in situ generated on the surface of the precursor nickel layer to obtain a nickel-based anode catalytic electrode NiOOH / NiO(O v ) / NF.

[0044] The structure of the prepared gallium-based nickel-based catalytic electrode specifically includes a metal nickel substrate and a composite catalytic layer of NiOOH active phase and NiO active phase arranged on one surface thereof. The composite catalytic layer of NiOOH active phase and NiO active phase is a nano-spherical structure, and the surface and bulk of the composite catalytic layer both contain controllable oxygen vacancy distribution.

[0045] The application of the gallium-based nickel-based catalytic electrode is specifically to use it as an active anode in the electroplating process of metal gallium in an alkaline system, the cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 -The electrodeposition temperature is 40°C and the anodic overpotential is reduced by 200 mV compared to untreated pure nickel sheets or stainless steel substrates at industrial current density. The service life is increased by 5% at industrial current density compared to untreated pure nickel sheets and stainless steel electrodes.

[0046] Example 3

[0047] A method for preparing a gallium-based nickel-based catalytic electrode comprises the following steps:

[0048] (1) A nickel foam substrate (size: 20 mm × 10 mm × 1 mm) was ultrasonically cleaned in 3 mol / L hydrochloric acid solution, anhydrous ethanol, and deionized water for 30 min in sequence to remove surface oxides and organic impurities, thereby obtaining a pretreated nickel metal substrate.

[0049] Take 0.2mol / LNiSO4 as the electrodeposition solution, use clean foam nickel and carbon rod as the working electrode and counter electrode respectively, and pre-deposition is carried out on the surface of the pretreated metal nickel substrate by constant potential method at 40℃. The deposition potential is -1.4V, the deposition time is 40min, and the stirring speed is 100r / min to obtain the precursor nickel layer Ni / NF.

[0050] (2) The obtained precursor nickel layer Ni / NF was electrochemically oxidized in a 2 mol / L NaOH solution containing 4 g / L Na2S: constant potential oxidation was adopted, the oxidation potential was 0.43 V (vs. SCE), and the oxidation time was 40 min. A composite catalytic layer of NiOOH active phase and NiO active phase was in situ generated on the surface of the precursor nickel layer to obtain a nickel-based anode catalytic electrode NiOOH / NiO(O v ) / NF.

[0051] The structure of the prepared gallium-based nickel-based catalytic electrode specifically includes a metal nickel substrate and a composite catalytic layer of NiOOH active phase and NiO active phase arranged on one surface thereof. The composite catalytic layer of NiOOH active phase and NiO active phase is a nano-spherical structure, and the surface and bulk of the composite catalytic layer both contain controllable oxygen vacancy distribution.

[0052] The application of the gallium-based nickel-based catalytic electrode is specifically to use it as an active anode in the electroplating process of metal gallium in an alkaline system, the cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 - Alkaline solution, electrodeposition temperature is 50℃. Compared with untreated pure nickel sheet or stainless steel substrate, 100mA / cm 2 The anodic overpotential at industrial current density is reduced by 300mV; compared with untreated pure nickel sheet and stainless steel electrode, 100mA / cm 2 The service life is increased by 12% under industrial current density.

[0053] Example 4

[0054] A method for preparing a gallium-based nickel-based catalytic electrode comprises the following steps:

[0055] (1) A nickel foam substrate (size: 20 mm × 10 mm × 1 mm) was ultrasonically cleaned in 3 mol / L hydrochloric acid solution, anhydrous ethanol, and deionized water for 30 min in sequence to remove surface oxides and organic impurities, thereby obtaining a pretreated nickel metal substrate.

[0056] Take 0.24 mol / LNiSO4 as the electrodeposition solution, use clean foam nickel and carbon rod as the working electrode and counter electrode respectively, and pre-deposition is carried out on the surface of the pretreated metal nickel substrate by constant potential method at 40°C. The deposition potential is -1.4 V, the deposition time is 30 min, and the stirring speed is 300 r / min to obtain the precursor nickel layer Ni / NF.

[0057] (2) The obtained precursor nickel layer Ni / NF was electrochemically oxidized in a 3 mol / L NaOH solution containing 6 g / L Na2S: constant potential oxidation was adopted, the oxidation potential was 0.44 V (vs. SCE), and the oxidation time was 40 min. A composite catalytic layer of NiOOH active phase and NiO active phase was in situ generated on the surface of the precursor nickel layer, and a nickel-based anode catalytic electrode NiOOH / NiO(O v ) / NF.

[0058] The structure of the prepared gallium-based nickel-based catalytic electrode specifically includes a metal nickel substrate and a composite catalytic layer of NiOOH active phase and NiO active phase arranged on one surface thereof. The composite catalytic layer of NiOOH active phase and NiO active phase is a nano-spherical structure, and the surface and bulk of the composite catalytic layer both contain controllable oxygen vacancy distribution.

[0059] The application of the gallium-based nickel-based catalytic electrode is specifically to use it as an active anode in the electroplating process of metal gallium in an alkaline system, the cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 - Alkaline solution, electrodeposition temperature is 58 ° C. Compared with untreated pure nickel sheet or stainless steel substrate, 100mA / cm 2 The anodic overpotential at industrial current density is reduced by 350mV; compared with untreated pure nickel sheet and stainless steel electrode, 100mA / cm 2 The service life is increased by 15% under industrial current density.

[0060] Example 5

[0061] A method for preparing a gallium-based nickel-based catalytic electrode comprises the following steps:

[0062] (1) A nickel foam substrate (size: 20 mm × 10 mm × 1 mm) was ultrasonically cleaned in 3 mol / L hydrochloric acid solution, anhydrous ethanol, and deionized water for 30 min in sequence to remove surface oxides and organic impurities, thereby obtaining a pretreated nickel metal substrate.

[0063] Take 0.24 mol / LNiSO4 as the electrodeposition solution, use clean foam nickel and carbon rod as the working electrode and counter electrode respectively, and pre-deposition is carried out on the surface of the pretreated metal nickel substrate by constant potential method at 50°C. The deposition potential is -1.4 V, the deposition time is 30 min, and the stirring speed is 300 r / min to obtain the precursor nickel layer Ni / NF.

[0064] (2) The obtained precursor nickel layer Ni / NF was electrochemically oxidized in a 3 mol / L NaOH solution containing 8 g / L Na2S: constant potential oxidation was adopted, the oxidation potential was 0.44 V (vs. SCE), and the oxidation time was 30 min. A composite catalytic layer of NiOOH active phase and NiO active phase was in situ generated on the surface of the precursor nickel layer to obtain a nickel-based anode catalytic electrode NiOOH / NiO(O v ) / NF.

[0065] The structure of the prepared gallium-based nickel-based catalytic electrode specifically includes a metal nickel substrate and a composite catalytic layer of NiOOH active phase and NiO active phase arranged on one surface thereof. The composite catalytic layer of NiOOH active phase and NiO active phase is a nano-spherical structure, and the surface and bulk of the composite catalytic layer both contain controllable oxygen vacancy distribution.

[0066] The application of the gallium-based nickel-based catalytic electrode is specifically to use it as an active anode in the electroplating process of metal gallium in an alkaline system, the cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 - Alkaline solution, electrodeposition temperature is 50℃. Compared with untreated pure nickel sheet or stainless steel substrate, 100mA / cm 2 The anodic overpotential at industrial current density is reduced by 300mV; compared with untreated pure nickel sheet and stainless steel electrode, 100mA / cm 2 The service life is increased by 15% under industrial current density.

[0067] Example 6

[0068] A method for preparing a gallium-based nickel-based catalytic electrode comprises the following steps:

[0069] (1) A nickel foam substrate (size: 20 mm × 10 mm × 1 mm) was ultrasonically cleaned in 3 mol / L hydrochloric acid solution, anhydrous ethanol, and deionized water for 30 min in sequence to remove surface oxides and organic impurities, thereby obtaining a pretreated nickel metal substrate.

[0070] Take 0.1mol / LNiSO4 as the electrodeposition solution, use clean nickel foam and carbon rod as the working electrode and counter electrode respectively, and pre-deposition is carried out on the surface of the pretreated metal nickel substrate by constant potential method at 40℃. The deposition potential is -1.3V, the deposition time is 30min, and the stirring speed is 100r / min to obtain the precursor nickel layer Ni / NF.

[0071] (2) The obtained precursor nickel layer Ni / NF was electrochemically oxidized in a 1.8 mol / L NaOH solution containing 12 g / L Na2S: constant potential oxidation was adopted, the oxidation potential was 0.40 V (vs. SCE), and the oxidation time was 30 min. A composite catalytic layer of NiOOH active phase and NiO active phase was in situ generated on the surface of the precursor nickel layer to obtain a nickel-based anode catalytic electrode NiOOH / NiO(O v ) / NF.

[0072] The structure of the prepared gallium-based nickel-based catalytic electrode specifically includes a metal nickel substrate and a composite catalytic layer of NiOOH active phase and NiO active phase arranged on one surface thereof. The composite catalytic layer of NiOOH active phase and NiO active phase is a nano-spherical structure, and the surface and bulk of the composite catalytic layer both contain controllable oxygen vacancy distribution.

[0073] The application of the gallium-based nickel-based catalytic electrode is specifically to use it as an active anode in the electroplating process of metal gallium in an alkaline system, the cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 - Alkaline solution, electrodeposition temperature is 55℃. Compared with untreated pure nickel sheet or stainless steel substrate, 100mA / cm 2 The anodic overpotential at industrial current density is reduced by 310mV; compared with untreated pure nickel sheet and stainless steel electrode, 100mA / cm 2 The service life is increased by 10% under industrial current density.

[0074] The present invention has been described through the above embodiments. However, it should be understood that the above embodiments are for illustrative and illustrative purposes only and are not intended to limit the present invention to the described embodiments. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the above embodiments and that various variations and modifications may be made based on the teachings of the present invention, all of which fall within the scope of the present invention.

Claims

1. A gallium-based nickel-based catalytic electrode, characterized in that Specifically, it includes a metal nickel substrate, and a composite catalytic layer of NiOOH active phase and NiO active phase; A composite catalytic layer of NiOOH active phase and NiO active phase is provided on one surface of the nickel substrate; The composite catalytic layer of the NiOOH active phase and the NiO active phase is a nano-spherical structure, and both the surface and the bulk of the composite catalytic layer contain controllable oxygen vacancy distribution.

2. The method for preparing a gallium-based nickel-based catalytic electrode according to claim 1, characterized in that: The specific steps include: (1) Pre-depositing a precursor nickel layer on the surface of a pretreated metal nickel substrate by electrochemical deposition; (2) The obtained precursor nickel layer is subjected to electrochemical oxidation treatment in an alkaline electrolyte to in situ generate a composite catalytic layer of NiOOH active phase and NiO active phase on the surface of the precursor nickel layer to obtain a nickel-based anode catalytic electrode.

3. The method for preparing a gallium-based nickel-based catalytic electrode according to claim 2, characterized in that: In the step (1), the pretreatment process of the metal nickel substrate includes: ultrasonically cleaning the metal nickel substrate in 0.5 mol / L to 5 mol / L hydrochloric acid solution, anhydrous ethanol and deionized water for 5 minutes to 60 minutes in sequence.

4. The method for preparing a gallium-based nickel-based catalytic electrode according to claim 2, characterized in that: In the step (1), the electrochemical deposition method is specifically a constant potential method, and the electrodeposition solution used is a NiSO4 solution with a concentration of 0.05 mol / L to 0.5 mol / L.

5. The method for preparing a gallium-based nickel-based catalytic electrode according to claim 2, characterized in that: In the step (1), the deposition potential of the electrochemical deposition method is -1V to -6V, and the deposition time is 10min to 60min; during the electrochemical deposition process, the temperature is controlled at 25°C to 60°C, and the stirring speed is 100r / min to 500r / min.

6. The method for preparing a gallium-based nickel-based catalytic electrode according to claim 2, characterized in that: In the step (2), the electrochemical oxidation specifically adopts constant potential oxidation, the oxidation potential is 0.3V to 0.6V (vs. SCE), and the oxidation time is 5min to 60min.

7. The method for preparing a gallium-based nickel-based catalytic electrode according to claim 2, characterized in that: In the step (2), the alkaline electrolyte contains S 2- NaOH solution or KOH solution, the concentration of NaOH or KOH in the solution is 0.01mol / L~3mol / L, S in the solution 2- The content is 1g / L~15g / L.

8. The use of a gallium-based nickel-based catalytic electrode according to claim 1, characterized in that: Specifically, it is used as an active anode in the electroplating process of gallium in an alkaline system. The cathode is made of stainless steel or titanium plate, and the electrolyte is GaO2 - alkaline solution, the electrodeposition temperature is 30℃~80℃; compared with untreated pure nickel sheet or stainless steel substrate, 100mA / cm 2 The anode overpotential at industrial current density is reduced by 180mV to 390mV; compared with untreated pure nickel sheet and stainless steel electrode, 100mA / cm 2 The service life is increased by 3% to 15% under industrial current density.

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