Manufacturing method of boron-doped high-entropy electrolytic cell anode

Abstract

The invention provides a manufacturing method of a boron-doped high-entropy electrolytic cell anode, and relates to the technical field of anode manufacturing, and the manufacturing method comprises the following steps: compounding a high-entropy oxide containing five transition metal elements of iron, cobalt, nickel, vanadium and chromium with a boron source, synthesizing a boron-doped precursor in one step through solvothermal, and annealing to synthesize a boron-doped high-entropy catalyst; the boron-doped high-entropy catalyst is prepared into slurry, the surface of a nickel felt substrate is uniformly coated with the slurry by adopting a high-pressure gas-assisted spraying process, a compact catalyst layer is formed after constant-temperature drying, and finally the composite high-entropy anode is prepared. Compared with a traditional precious metal-based anode, the anode reaction overpotential is remarkably reduced through the high-entropy multi-metal synergistic effect and the coupling effect of boron doping. The preparation process has the material cost advantage and large-scale production adaptability, and an innovative solution is provided for efficient development of alkaline water electrolysis hydrogen production equipment.

Description

Technical Field

[0001] The invention relates to the technical field of anode manufacturing, in particular to a method for manufacturing a boron-doped high-entropy electrolytic cell anode. Background Art

[0002] As the pace of global energy transformation accelerates, the demand for hydrogen energy, as a clean and efficient secondary energy source, is showing a rapid growth trend. As a representative of sustainable hydrogen production technology, water electrolysis has gradually become the focus of scientific research and industrialization. Among the many water electrolysis technologies, alkaline electrolyzers are currently widely used in industrial production due to their maturity and reliability. However, the anode materials of existing alkaline electrolyzers mostly rely on precious metal catalysts (such as RuO2, IrO2, etc.), which have significant limitations in cost, catalytic activity and long-term stability.

[0003] Specifically, although nickel-based catalysts have attracted attention due to their low cost, their electrolysis efficiency and stability are still difficult to meet actual needs; and although precious metal catalysts have excellent performance, their high cost seriously restricts their large-scale promotion and application. Therefore, the development of an anode material that combines low cost and high performance has become an important direction for promoting breakthrough developments in alkaline electrolyzer technology. This is not only related to the economic feasibility of the hydrogen energy industry, but will also directly affect the progress and effectiveness of future energy transformation.

[0004] In recent years, with the rapid development of materials science, high-entropy oxides (HEOs) have gradually become a research hotspot in the field of energy catalysis due to their unique multi-component synergistic effect and excellent physical and chemical stability. HEOs form a single solid solution phase structure through the combination of multiple metal oxides and the entropy stabilization effect, showing excellent thermal stability, chemical corrosion resistance and mechanical strength. These characteristics give them significant advantages in extreme environments, especially in the anode catalytic reaction of alkaline electrolyzers, where HEOs are considered to have great application potential.

[0005] However, although high entropy oxides have shown certain catalytic activity and stability at the theoretical and experimental levels, they still face many challenges in anode applications. First, the catalytic activity of existing high entropy oxide catalysts is still insufficient to meet industrial needs, especially in terms of electrolysis efficiency and overpotential control at high current density, there is still a lot of room for improvement. Secondly, the long-term stability of high entropy oxides still needs to be further optimized, especially the problem of structural stability under highly alkaline environments and strong oxidizing conditions has not been completely solved. In addition, existing preparation processes such as impregnation and sintering methods make it difficult to achieve uniform distribution and efficient utilization of catalysts, resulting in insufficient exposure of active sites, thereby limiting the full play of their catalytic performance.

[0006] In response to the above problems, researchers are exploring a variety of innovative preparation methods to significantly improve the activity and stability of high-entropy oxide catalysts. For example, by introducing highly active metal components (such as Ni, Fe, Co, etc.) through doping or composite modification, the electronic structure of the catalyst can be effectively optimized, thereby improving its catalytic activity; through nanostructure design (such as nanoparticles, nanowires, nanosheets, etc.), the number and exposure rate of active sites can be significantly increased, while enhancing the anti-agglomeration ability of the catalyst. In addition, new preparation processes such as co-precipitation method, sol-gel method, atomic layer deposition (ALD), etc. can achieve uniform distribution and precise regulation of the catalyst, thereby significantly improving its utilization rate and stability.

[0007] It should be noted that the preparation cost and large-scale production of high-entropy oxides are still the key bottlenecks restricting their commercial applications. Currently, researchers are trying to reduce the production cost of high-entropy oxides by selecting low-cost raw materials, simplifying the preparation process, and developing large-scale production technologies. For example, using industrial waste or cheap metal oxides as raw materials and combining with efficient synthesis methods is expected to achieve the economic production of high-entropy oxides. In summary, developing a high-entropy oxide material and its preparation method that can significantly improve the activity and stability of anode catalysts while reducing production costs has become an important research direction to promote the commercialization of alkaline electrolyzer technology. Summary of the Invention

[0008] In view of the above prior art, the present invention proposes a method for fabricating a boron-doped high-entropy electrolyzer anode.

[0009] A method for fabricating a boron-doped high-entropy electrolyzer anode provided by the present invention includes: synthesizing a boron-doped high-entropy catalyst in one step by solvothermal method using metal salts containing five transition metal elements of iron, cobalt, nickel, vanadium, and chromium and a boron source; Formulating the boron-doped high-entropy catalyst with a binder and a dispersant into a slurry, and uniformly coating the slurry onto the surface of a nickel felt substrate by a high-pressure gas-assisted spraying process, and forming a dense catalytic layer after drying at a constant temperature, and finally obtaining a composite high-entropy anode.

[0010] Preferably, the thickness of the nickel felt substrate is 0.1 - 0.3 mm, and the area is 1 - 4 cm 2 .

[0011] Preferably, the binder is Form B ionomer, and the mass ratio of Form B ionomer in the slurry is 20 - 30%.

[0012] Preferably, the dispersant is at least one of deionized water, ethanol, and isopropanol.

[0013] Preferably, the loading of the boron-doped high-entropy catalyst is 0.8-1.2 mg / cm 2 .

[0014] Preferably, the temperature of the constant-temperature drying is 60-90 °C.

[0015] Preferably, in the spraying process, the nozzle diameter of the spraying equipment is 0.3 mm and the pressure is 0.4 MPa.

[0016] Preferably, the boron-doped high-entropy catalyst is specifically prepared by the following steps: Step 1: Uniformly disperse iron salt, cobalt salt, nickel salt, vanadium salt, chromium salt and boric acid in a fixed molar ratio in a mixed solvent of oleylamine and octadecene to obtain a mixed solution; Step 2: After subjecting the mixed solution to programmed heating treatment, wash the sample with heptane and vacuum dry to obtain a precursor powder; Step 3: Anneal the precursor powder in air to obtain a boron-doped high-entropy catalyst.

[0017] Preferably, the molar ratio of the iron salt, cobalt salt, nickel salt, vanadium salt, chromium salt and boric acid is 1:4:1:0.2:1:2; the volume ratio of the oleylamine and octadecene is 1:2.

[0018] Preferably, the temperature of the programmed heating treatment is 250-280 °C, and the holding time is 1-2 h; the time of the vacuum drying is 12-24 h; the temperature of the annealing treatment is 350-450 °C, and the time is 1.5-2 h.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a method for manufacturing an anode of a boron-doped high-entropy electrolytic cell, which uses a high-entropy oxide composed of inexpensive transition metal elements such as boron-doped iron, cobalt, nickel, vanadium, and chromium as the main component of the catalyst, avoiding the high cost problem of traditional noble metal catalysts. At the same time, the boron doping process is simple and low-cost. Compared with the traditional multi-stage synthesis process, in the solvothermal synthesis, in a closed reaction system, various reactants can fully contact, mix and react under the mediation of the solvent, achieving high-efficiency material conversion in a short time. All reaction steps are completed in the same system, and the reactants are uniformly dispersed in the solvent in the form of molecules or ions, ensuring the full mixing and interaction of boron elements with metal elements such as iron, cobalt, nickel, vanadium, and chromium at the atomic or molecular level. The obtained high-entropy oxide catalyst has a highly uniform microstructure and composition distribution, ensuring the consistency and stability of the catalyst performance. More importantly, the entire manufacturing process is simplified, making the production process easier to control and manage, which is conducive to achieving stable and uniform product output in large-scale industrial production.

[0020] In addition, through boron doping technology, the present invention significantly improves the anodic activity and stability of the catalyst. The introduction of boron element optimizes the electronic structure of the catalyst, enhances its catalytic activity for anodic reactions, and significantly improves the electrolysis efficiency. Compared with traditional noble metal-based anodes, the present invention significantly reduces the anodic reaction overpotential through the coupling effect of high-entropy multi-metal synergistic effect and boron doping. This preparation process has both material cost advantages and adaptability to large-scale production, providing an innovative solution for the efficient development of alkaline water electrolysis hydrogen production equipment. Description of the Drawings

[0021] Figure 1 It is a transmission electron microscope test diagram of the boron-doped high-entropy catalyst obtained in Example 1 of the present invention.

[0022] Figure 2 It is an X-ray diffraction test diagram of the boron-doped high-entropy catalyst obtained in Example 1 of the present invention.

[0023] Figure 3 It is an X-ray photoelectron spectroscopy test diagram of the boron-doped high-entropy catalyst obtained in Example 1 of the present invention.

[0024] Figure 4 It is a comparison diagram of the performance test curves of the composite high-entropy anode obtained in Example 1 of the present invention and the commercial RuO2 anode.

[0025] Figure 5 It is a comparison diagram of the performance test curves of the alkaline electrolytic cell assembled with the composite high-entropy anode obtained in Example 1 of the present invention and the commercial RuO2 anode.

[0026] Figure 6 It is a physical display diagram of the composite high-entropy anode obtained in Example 1 of the present invention.

[0027] Figure 7 It is a comparison diagram of the performance test curves of the composite high-entropy anode obtained in Example 1 of the present invention and the anodes obtained in Comparative Examples 1-3.

[0028] Figure 8 It is a comparison diagram of the performance test curves of the alkaline electrolytic cell assembled with the composite high-entropy anode obtained in Example 1 of the present invention and the anodes obtained in Comparative Examples 1-3. Detailed Embodiments

[0029] In order to make the technical means, creative features, achieved purposes and functions of the present invention easy to understand, the present invention will be further described below in conjunction with specific embodiments.

[0030] Example 1: A method for manufacturing an anode of a boron-doped high-entropy electrolytic cell: Preparation of boron-doped high-entropy catalyst: Step 1: Weigh 0.353 g of iron(III) acetylacetonate (Fe(acac)3), 1.028 g of cobalt(III) acetylacetonate (Co(acac)3), 0.257 g of nickel(II) acetylacetonate (Ni(acac)2), 0.069 g of vanadium(II) acetylacetonate (V(acac)2), and 0.349 g of chromium(III) acetylacetonate (Cr(acac)3), with a molar ratio of 1:4:1:0.2:1:2; another 0.1237 g of boric acid (H3BO3) is weighed as the boron source; add the above raw materials into a three-necked flask containing 5 ml of oleylamine and 10 ml of octadecene, and ultrasonically disperse for 30 min to form a homogeneous mixed solution; Step 2: Heat the mixed solution to 280 °C at a rate of 7 °C / min and keep it for 1.5 h; after the reaction, add 20 ml of heptane for dilution, centrifuge to collect the precipitate, wash it with heptane three times, and dry it in vacuum at 60 °C for 18 h to obtain the precursor powder; Step 3: Place the precursor powder in a tube furnace, heat it to 400 °C in air at a rate of 2 °C / min, anneal for 2 h, and after natural cooling, obtain a black powder-like boron-doped high-entropy catalyst (denoted as HEO-B1).

[0031] The morphology and structure of HEO-B1 were characterized in detail by transmission electron microscopy (TEM). The test images show (see Figure 1 ), the catalyst particles are nano-scale flakes. Although there is slight agglomeration, the overall dispersion is good. Its high specific surface area helps to expose a large number of active sites, thereby enhancing the catalytic reaction activity. In addition, the observed bending of the lattice fringes indicates local lattice distortion, which is mainly attributed to the multi-element solid solution effect of elements such as Fe, Co, Ni, Cr, and V in the high-entropy alloy. The radius differences of these metal atoms are up to 12%. Nevertheless, the overall morphology of the catalyst remains uniform and no obvious phase separation phenomenon appears. The X-ray diffraction (XRD, see Figure 2 The test results show that the diffraction peaks correspond to the oxide phases of Fe, Co, and Ni, but the characteristic diffraction peaks of borides are not detected, which confirms that boron doping does not form borides and further verifies the structural characteristics of high-entropy oxides.

[0032] X-ray photoelectron spectroscopy (XPS, see Figure 3 Analysis confirmed the presence of boron doping. The test results show that the binding energy of the B 1s peak is located at 191.2 eV, between boron oxide (B2O3, 192 - 193 eV) and metal borides (such as NiB, 188.5 eV), indicating that boron exists in the form of a partially oxidized solid solution state in the catalyst, forming a B-O-M (M is metal) bonding mode.

[0033] For each transition metal element, its 2p 3 / 2There is a clear corresponding relationship between the peak position and the oxidation state. Taking iron (Fe) as an example, the binding energy of Fe 3+ is located at 710.5 - 712.0 eV, mainly corresponding to high-valence oxides such as Fe2O3 and FeOOH; the binding energy of Fe 2+ ranges from 708.0 - 709.5 eV and is usually associated with FeO or partially oxidized Fe3O4 (magnetite). The coexistence of Fe 3+ and Fe 2+ forms a mixed valence state, which is beneficial to the optimization of active sites. Fe 3+ , as the active site for the anodic oxygen evolution reaction, participates in the adsorption process of *OH → *O, while Fe 2+ maintains charge balance through the redox cycle of Fe 2+ ↔ Fe 3+ . For cobalt (Co), the binding energy of Co 3+ is 780.5 - 782.0 eV and mainly exists in hydroxyoxides (CoOOH) or spinel-structured Co3O4; the binding energy of Co 2+ is in the range of 778.5 - 780.0 eV, corresponding to low-valence phases such as CoO or Co(OH)2. The dynamic balance between Co 3+ and Co 2+ plays a key role in the OER process. The partial reduction of Co 3+ to Co 2+ helps to form a CoOOH / CoO heterojunction, thereby effectively reducing the energy barrier for OOH formation. For nickel (Ni), the binding energy of Ni 3+ ranges from 855.5 - 857.0 eV, showing high-valence compounds such as NiOOH or Ni2O3; the binding energy of Ni 2+ is 853.5 - 855.0 eV and is related to NiO or Ni(OH)2. Ni 3+ is stabilized through the charge transfer of the B - O - Ni bond (B→O→Ni), thus enhancing the structural stability of the catalyst. For vanadium (V), the binding energy of V 4+ is located at 515.5 - 517.0 eV, clearly pointing to the VO2 phase, which may be in the rutile or monoclinic phase structure. The d¹ electron state of V 4+ is prone to hybridization with the O 2p orbital, resulting in a decrease in the formation energy of oxygen vacancies and thus increasing the density of active sites. For chromium (Cr), the binding energy of Cr 3+ is 576.0 - 577.5 eV, corresponding to stable oxides (Cr2O3) or hydroxides (Cr(OH)3); while the binding energy of Cr 2+ ranges from 574.0 - 575.5 eV, indicating that B doping may lead to a local reduction environment, but Cr 2+ is easily oxidized to Cr3+ , which may cause structural stress.

[0034] Overall, the boron-doped high-entropy oxide catalyst significantly improves the anodic catalytic activity and stability through the synergistic effect of the valence states of various metal elements, providing strong support for the commercial application of alkaline electrolyzer technology.

[0035] Catalytic slurry preparation and coating: Take 5 mg of the boron-doped high-entropy catalyst and mix it with 0.25 g of Form B ionomer, add a dispersant composed of 5 ml of deionized water and 5 ml of isopropanol, and ultrasonically disperse it at room temperature for 1 h to obtain a uniform slurry with a solid content of 24.5%.

[0036] Preheat a nickel felt substrate with a thickness of 0.2 mm and an area of 2 cm 2 to 90 °C, and use a high-pressure gas-assisted spraying device (nozzle diameter of 0.3 mm, pressure of 0.4 MPa) for spraying. The spraying distance is 10 cm, and repeat it multiple times to control the catalyst loading to 1.0 mg / cm 2 . After the spraying treatment, the obtained composite high-entropy anode has a uniform coating, and the physical display is as Figure 6 shown.

[0037] Example 2: A method for fabricating an anode of a boron-doped high-entropy electrolyzer: Preparation of boron-doped high-entropy catalyst: Step 1: Weigh 0.353 g of iron(III) acetylacetonate (Fe(acac)3), 1.028 g of cobalt(II) acetylacetonate (Co(acac)3), 0.257 g of nickel(II) acetylacetonate (Ni(acac)2), 0.069 g of vanadium(II) acetylacetonate (V(acac)2), and 0.349 g of chromium(III) acetylacetonate (Cr(acac)3), with a molar ratio of 1:4:1:0.2:1:2; another 0.1237 g of boric acid (H3BO3) is weighed as the boron source; add the above raw materials into a three-necked flask containing 5 ml of oleylamine and 10 ml of octadecene, and ultrasonically disperse for 30 min to form a homogeneous mixed solution; Step 2: Heat the mixed solution to 250 °C at a rate of 7 °C / min and hold for 2 h; after the reaction, add 20 ml of heptane for dilution, centrifuge to collect the precipitate, and wash it 3 times with heptane, and dry it in vacuum at 60 °C for 12 h to obtain the precursor powder; Step 3: Place the precursor powder in a tubular furnace, heat it to 350 °C in air at a rate of 2 °C / min, anneal for 1.8 h, and cool it naturally to obtain a black powder-like boron-doped high-entropy catalyst.

[0038] Catalytic slurry preparation and coating: Take 5 mg of the boron-doped high-entropy catalyst and mix it with 0.25 g of Form B ionomer. Add a dispersant composed of 5 ml of deionized water and 5 ml of ethanol, and ultrasonically disperse it at room temperature for 1 h to obtain a uniform slurry with a solid content of 20%.

[0039] Preheat a nickel felt substrate with a thickness of 0.1 mm and an area of 4 cm 2 to 60 °C, and spray it using a high-pressure gas-assisted spraying device (nozzle diameter: 0.3 mm, pressure: 0.4 MPa). The spraying distance is 10 cm, and repeat it multiple times. Control the catalyst loading to be 0.8 mg / cm 2 to obtain a composite high-entropy anode.

[0040] Example 3: A method for fabricating a boron-doped high-entropy electrolytic cell anode: Preparation of boron-doped high-entropy catalyst: Step 1: Weigh 0.353 g of iron(III) acetylacetonate (Fe(acac)3), 1.028 g of cobalt(II) acetylacetonate (Co(acac)3), 0.257 g of nickel(II) acetylacetonate (Ni(acac)2), 0.069 g of vanadium(II) acetylacetonate (V(acac)2), and 0.349 g of chromium(III) acetylacetonate (Cr(acac)3), with a molar ratio of 1:4:1:0.2:1:2; another 0.1237 g of boric acid (H3BO3) is weighed as the boron source; add the above raw materials into a three-necked flask containing 5 ml of oleylamine and 10 ml of octadecene, and ultrasonically disperse for 30 min to form a homogeneous mixed solution; Step 2: Heat the mixed solution to 270 °C at a rate of 7 °C / min and keep it for 1 h; after the reaction, add 20 ml of heptane for dilution, centrifuge to collect the precipitate, and wash it with heptane 3 times, then vacuum dry at 60 °C for 24 h to obtain the precursor powder; Step 3: Place the precursor powder in a tubular furnace, heat it to 450 °C in air at a rate of 2 °C / min, anneal for 1.5 h, and cool it naturally to obtain a black powder-like boron-doped high-entropy catalyst.

[0041] Preparation and coating of catalytic slurry: Take 5 mg of the boron-doped high-entropy catalyst and mix it with 0.25 g of Form B ionomer (sulfonated polyether ether ketone, sulfonation degree 35%). Add a dispersant composed of 5 ml of ethanol and 5 ml of isopropanol, and ultrasonically disperse it at room temperature for 1 h to obtain a uniform slurry with a solid content of 30%.

[0042] Preheat a nickel felt substrate with a thickness of 0.3 mm and an area of 1 cm² to 80 °C, and spray it using a high-pressure gas-assisted spraying device (nozzle diameter: 0.3 mm, pressure: 0.4 MPa). The spraying distance is 10 cm, and repeat it multiple times. Control the catalyst loading to be 1.2 mg / cm² to obtain a composite high-entropy anode.

[0043] Comparative Example 1: Large-scale preparation of boron-doped high-entropy catalyst: The difference from Example 1 is that the masses of iron acetylacetonate (Fe(acac)3), cobalt acetylacetonate (Co(acac)3), nickel acetylacetonate (Ni(acac)3), vanadium acetylacetonate (V(acac)2), chromium acetylacetonate (Cr(acac)3) and boric acid (H3BO3) are 2 times those of Example 1. At the same time, 7 ml of oleylamine and 14 ml of octadecene are used, and finally a black powdery boron-doped high-entropy catalyst (denoted as HEO-B2) is obtained.

[0044] The single-anode performance test of the obtained HEO-B2 (see Figure 7 ), and the performance test after assembling it into an electrolytic cell as the anode (see Figure 8 ). The results show that its performance is highly consistent with that of HEO-B1.

[0045] Comparative Example 2: Large-scale preparation of boron-doped high-entropy catalyst: The difference from Example 1 is that the masses of iron acetylacetonate (Fe(acac)3), cobalt acetylacetonate (Co(acac)3), nickel acetylacetonate (Ni(acac)2), vanadium acetylacetonate (V(acac)2), chromium acetylacetonate (Cr(acac)3) and boric acid (H3BO3) are 3 times those of Example 1. At the same time, 10 ml of oleylamine and 20 ml of octadecene are used, and finally a black powdery boron-doped high-entropy catalyst (denoted as HEO-B3) is obtained.

[0046] The single-anode performance test of the obtained HEO-B3 (see Figure 7 ), and the performance test after assembling it into an electrolytic cell as the anode (see Figure 8 ). The results show that its performance is highly consistent with that of HEO-B1.

[0047] Comparative Example 3: Large-scale preparation of boron-doped high-entropy catalyst: The difference from Example 1 is that the masses of iron acetylacetonate (Fe(acac)3), cobalt acetylacetonate (Co(acac)3), nickel acetylacetonate (Ni(acac)2), vanadium acetylacetonate (V(acac)2), chromium acetylacetonate (Cr(acac)3) and boric acid (H3BO3) are 5 times those of Example 1. At the same time, 13 ml of oleylamine and 26 ml of octadecene are used, and finally a black powdery boron-doped high-entropy catalyst (denoted as HEO-B5) is obtained.

[0048] The single-anode performance test of the obtained HEO-B5 (see Figure 7 ), and the performance test after assembling it into an electrolytic cell as the anode (see Figure 8 ). The results show that its performance is highly consistent with that of HEO-B1.

[0049] The above are only the embodiments of the present invention, and thus do not limit the patent scope of the present invention. Any equivalent solutions made by using the content of the specification of the present invention and directly or indirectly applied in other related technical fields shall similarly be within the patent protection scope of the present invention.

Claims

1. A manufacturing method of a boron-doped high-entropy electrolytic cell anode, characterized in that, Including: A boron-doped high-entropy catalyst is synthesized in one step by solvothermal method from metal salts containing five transition metal elements of iron, cobalt, nickel, vanadium, and chromium and a boron source; The boron-doped high-entropy catalyst, a binder, and a dispersant are formulated into a slurry, which is uniformly coated on the surface of a nickel felt substrate by a high-pressure gas-assisted spraying process, and a dense catalytic layer is formed after drying at a constant temperature, and finally a composite high-entropy anode is prepared.

2. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 1, characterized in that, The thickness of the nickel felt substrate is 0.1 - 0.3 mm, and the area is 1 - 4 cm 2 .

3. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 1 or 2, characterized in that, The binder is Form B ionomer (sulfonated polyether ether ketone, sulfonation degree 35%), and the mass ratio of Form B ionomer in the slurry is 20-30%.

4. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 1 or 2, characterized in that, The dispersant is at least one of deionized water, ethanol, and isopropanol.

5. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 1 or 2, characterized in that, The loading of the boron-doped high-entropy catalyst is 0.8-1.2 mg / cm 2 .

6. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 1 or 2, characterized in that, The temperature of the constant temperature drying is 60 - 90 o °C.

7. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 1 or 2, characterized in that, In the spraying process, the nozzle diameter of the spraying equipment is 0.3 mm, and the pressure is 0.4 MPa.

8. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 1 or 2, characterized in that, The boron-doped high-entropy catalyst is specifically prepared by the following steps: Step 1: A fixed molar ratio of iron salt, cobalt salt, nickel salt, vanadium salt, chromium salt, and boric acid are uniformly dispersed in a mixed solvent of oleylamine and 1-octadecene to obtain a mixed solution; Step 2: After the mixed solution is treated by programmed heating, the sample is washed with heptane and dried in vacuum to obtain a precursor powder; Step 3: The precursor powder is annealed in air to obtain a boron-doped high-entropy catalyst.

9. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 8, characterized in that, The molar ratio of the iron salt, cobalt salt, nickel salt, vanadium salt, chromium salt, and boric acid is 1:4:1:0.2:1:2; the volume ratio of oleylamine and 1-octadecene is 1:

2.

10. The manufacturing method of the boron-doped high-entropy electrolytic cell anode according to claim 8, characterized in that, The temperature of the programmed heat treatment is 250 - 280 o °C, and the heat preservation time is 1 - 2 h; the time of the vacuum drying is 12 - 24 h; the temperature of the annealing treatment is 350 - 450 o °C, and the time is 1.5 - 2 h.

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