High-corrosion-resistance high-performance cathode catalyst material and preparation method thereof

Abstract

The application discloses a kind of high corrosion resistance high-performance cathode catalyst materials, it is related to energy technology field, catalyst material includes: iron powder 30-50 parts, nickel powder 30-50 parts, phosphorus powder 16 parts, carbon powder 4-10 parts and platinum powder 0-4 parts.The application further discloses a kind of preparation method of high corrosion resistance high-performance cathode catalyst materials.The catalyst prepared by the application has high activity, high selectivity, high stability, high corrosion resistance, and the catalyst is not easy to fail during work, can be stable for a long time, especially suitable for oilfield high salt, high sulfur produced water environment, large-scale suitable for electrolytic water hydrogen production technology field, under the premise of ensuring high corrosion resistance and high catalytic activity, reduce the preparation cost of catalyst, realize economic benefit maximization.

Description

Technical Field

[0001] This invention relates to the field of energy technology, specifically to a highly corrosion-resistant and high-performance cathode catalyst material and its preparation method. Background Technology

[0002] Against the backdrop of global energy transition and environmental protection, hydrogen energy, as a clean and efficient secondary energy source, has received widespread attention. Hydrogen can be produced through various pathways, among which water electrolysis is considered one of the most promising technologies due to its clean and pollution-free nature. In particular, produced water from oilfields, generated during oil extraction, has a complex composition, containing large amounts of minerals, salts, and organic matter, which can cause significant environmental pollution. Effectively utilizing this produced water for hydrogen production can not only achieve wastewater resource utilization but also reduce environmental pollution, thus having significant economic and social implications. However, the high salinity and corrosiveness of produced water from oilfields place extremely high demands on water electrolysis equipment. Existing water electrolysis equipment and materials often exhibit poor durability and stability under such conditions, easily leading to corrosion and failure, thereby affecting hydrogen production efficiency and equipment lifespan. To address this, we propose a highly corrosion-resistant and high-performance cathode catalyst material and its preparation method. Summary of the Invention

[0003] To address the aforementioned technical problems, this paper provides a highly corrosion-resistant and high-performance cathode catalyst material and its preparation method. This technical solution solves the problems of poor durability and stability mentioned above.

[0004] To achieve the above objectives, the technical solution adopted in this invention is as follows: a high corrosion-resistant and high-performance cathode catalyst material, wherein the catalyst material comprises, by molar mass, 30-50 parts of iron powder, 30-50 parts of nickel powder, 16 parts of phosphorus powder, 4-10 parts of carbon powder and 0-4 parts of platinum powder.

[0005] Preferably, the iron powder preparation step is carried out by reducing iron oxide with solid and gaseous reducing agents. Under high temperature conditions, hydrogen reacts chemically with iron oxide to remove oxygen from the iron oxide and obtain reduced iron powder. Nickel powder is prepared using a reduction method. The preparation steps include preparing a nickel sulfate solution, adding potassium oxalate, dissolving it in water (potassium oxalate has low solubility in cold water, so it is completely dissolved by heating), filtering the nickel oxalate precipitate, washing it three times with water and twice with ethanol, without heat drying, taking the nickel oxalate, heating it, and the nickel oxide generated by the decomposition of nickel oxalate reacts with carbon monoxide to produce nickel and carbon dioxide. After cooling, the powder is poured onto filter paper, reacting with air to generate heat, thus obtaining nickel powder.

[0006] Preferably, the phosphorus powder is based on a reduction method, in which a reducing agent is used to reduce phosphorus in a phosphorus-containing compound to obtain phosphorus powder; Toner is prepared by polymerization. The preparation steps involve ultrasonically dispersing and uniformly mixing resin monomers, pigments, dispersants and other reagents, adding water and dispersants, stirring thoroughly to form a homogeneous solution, carrying out a polymerization reaction to polymerize the monomers into a polymer, washing the polymerized product to remove unreacted monomers and impurities, separating the polymer from the solution by filtration, removing water, and obtaining toner. Platinum powder is prepared by reduction.

[0007] A method for preparing a highly corrosion-resistant and high-performance cathode catalyst material, comprising the following steps: S1. Prepare materials using a molar mass fractionator, including 30-50 parts iron powder, 30-50 parts nickel powder, 16 parts phosphorus powder, 4-10 parts carbon powder, and 0-4 parts platinum powder; S2. Weigh the materials and mix them according to the proportion to obtain a uniform powder mixture; S3. Place the powder mixture in a high-energy ball mill, set the ball mill speed to 100r / min-300r / min, and continue ball milling for 8h-12h to mix and activate the powder. During the ball milling process, add ethanol and isopropanol as dispersion media to prevent powder agglomeration. S4. Load the ball-milled powder mixture into a mold and use cold pressing technology to press the powder into shape with a pressure of 100MPa-300MPa to form a preliminary catalyst preform. Repeat the cold pressing process multiple times. S5. Place the cold-pressed blank in a vacuum sintering furnace, raise the temperature to 1100℃-1200℃, maintain this temperature for 1h-7h, wait for sintering to be completed, slowly cool to room temperature, take it out, and perform plasma spraying sintering treatment on the titanium electrode plate to obtain the water electrolysis catalytic cathode electrode. S6. Test the cathode electrode.

[0008] Preferably, in step S2, the material is placed in the reaction vessel and stirred for 30 minutes; in step S3, the prepared uniform powder mixture is transferred to the grinding jar of a high-energy ball mill, and the parameters of the ball mill are set, with the rotation speed set between 100 r / min and 300 r / min and the milling time set to 8-12 hours. The ball mill is then started, and after 1 hour of milling, ethanol is added to the high-energy ball mill for stirring. Stirring continues, and after 2 hours of milling, isopropanol is added to the high-energy ball mill for stirring. Stirring continues until the stirring is complete.

[0009] Preferably, in step S4, the powder mixture after being fully ball-milled by the high-energy ball mill is taken out from the grinding jar and transferred to a transfer container. The mold is then thoroughly cleaned and inspected. The powder mixture is loaded into the mold, and the mold is shaken to distribute the powder evenly in all corners of the cavity. Cold pressing is then performed. The cold pressing technology is based on the fact that when the material is subjected to high pressure, the particles move closer to each other and are squeezed, overcoming the gaps and friction factors between them, thereby causing displacement and gradually arranging them tightly, ultimately achieving molding.

[0010] Preferably, in step S5, the parameters inside the vacuum sintering furnace are set in advance before sintering. After the setting is completed, the temperature is in a slow rising stage until the temperature rises to the preset temperature range, and then sintering is carried out.

[0011] Preferably, in step S5, plasma spraying involves wiping the surface of the titanium electrode plate with an organic solvent to remove any oil, grease, and other organic contaminants that may be present on the surface. Ultrasonic cleaning is then used to further clean the electrode plate surface. Sandpaper is used to polish the surface of the titanium electrode plate. The equipment is inspected and adjusted, and the plasma gas and flow rate are set. A suitable ion gas is selected, and the temperature, energy, and stability characteristics of the plasma arc are controlled by adjusting the gas flow rate. The pretreated catalyst material is loaded into the hopper of the plasma spraying equipment's feeding system. The feeding system of the plasma spraying equipment is then started, allowing the catalyst material to be delivered to the plasma spray gun at a set rate for spraying.

[0012] Preferably, in step S6, the prepared cathode sample is placed in a simulated oilfield produced water environment for corrosion resistance testing. The test conditions are: immersion in an aqueous solution containing sodium ions, potassium ions, calcium ions, magnesium ions, chloride ions, sulfate ions, and bicarbonate ions at 60°C for 100 hours, and observation of the corrosion on the catalyst surface; hydrogen production efficiency is tested in a laboratory reactor under atmospheric pressure, with a steam flow rate of 5 mL / min-20 mL / min and a reaction temperature of 20°C-60°C, to test the hydrogen production rate of the catalyst.

[0013] Preferably, in step S5, the vacuum sintering furnace body adopts a double-layer structure, with the outer shell made of metal and the inner layer made of graphite and ceramic fiber materials.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: The catalyst prepared by this invention has high activity, high selectivity, high stability, and high corrosion resistance. The catalyst is not prone to failure during operation and can operate stably for a long time. It is especially suitable for the high-salt and high-sulfur produced water environment of oil fields. It can be widely applied in the field of water electrolysis hydrogen production technology. While ensuring high corrosion resistance and high catalytic activity, the preparation cost of the catalyst is reduced, thereby maximizing economic benefits. Attached Figure Description

[0015] Figure 1 This is a flowchart illustrating the preparation process of the cathode catalyst material of this invention. Figure 2 Fe in Embodiment 1 of the present invention 40 Ni 40 P 10 C 10 Electrode LSV test line chart; Figure 3 Fe in Embodiment 1 of the present invention 40 Ni 40 P 10 C 10 Electrode LSV test diagram; Figure 4 Fe in Example 3 of the present invention 40 Ni 37 Pt3P 16 C4 electrode diagram; Figure 5 Fe in Example 3 of the present invention 40 Ni 37 Pt3P 16 SEM image of C4 electrode; Figure 6 Fe in Example 3 of the present invention 40 Ni 37 Pt3P 16 Stability plots of C4 at different voltages; Figure 7 Fe in Embodiment 2 of the present invention 40 Ni 40 P 10 C 10 Electrode LSV test line chart; Figure 8 Fe in Embodiment 2 of the present invention 40 Ni 40 P 10 C 10 Electrode LSV test diagram. Detailed Implementation

[0016] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0017] Reference Figure 1 As shown, a high corrosion-resistant and high-performance cathode catalyst material comprises, by molar mass parts: 30-50 parts iron powder, 30-50 parts nickel powder, 16 parts phosphorus powder, 4-10 parts carbon powder, and 0-4 parts platinum powder.

[0018] The iron powder preparation process involves reducing iron oxides using solid and gaseous reducing agents. Under high temperature conditions, hydrogen reacts chemically with iron oxide to remove oxygen from the iron oxide, thus obtaining reduced iron powder. Nickel powder is prepared using a reduction method. The preparation steps include preparing a nickel sulfate solution, adding potassium oxalate, dissolving it in water (potassium oxalate has low solubility in cold water, so it is completely dissolved by heating), filtering the nickel oxalate precipitate, washing it three times with water and twice with ethanol, without heat drying, taking the nickel oxalate, heating it, and the nickel oxide generated by the decomposition of nickel oxalate reacts with carbon monoxide to produce nickel and carbon dioxide. After cooling, the powder is poured onto filter paper, reacting with air to generate heat, thus obtaining nickel powder.

[0019] This application employs a multi-step preparation process involving chemical precipitation, decomposition, and reduction. In particular, it emphasizes the removal and control of impurities at each stage. For example, impurities in the solution are removed through multiple washings during the formation of nickel oxalate precipitate, and other difficult-to-remove impurity elements are avoided during the subsequent reduction of nickel oxide with carbon monoxide. This ensures that the final nickel powder has a high purity level, and high-purity nickel powder has important applications in many fields with strict requirements for material composition.

[0020] Phosphorus powder is produced using a reduction method, in which a reducing agent is used to reduce phosphorus in phosphorus-containing compounds to obtain phosphorus powder. Toner is prepared by polymerization. The preparation steps involve ultrasonically dispersing and uniformly mixing resin monomers, pigments, dispersants and other reagents, adding water and dispersants, stirring thoroughly to form a homogeneous solution, carrying out a polymerization reaction to polymerize the monomers into a polymer, washing the polymerized product to remove unreacted monomers and impurities, separating the polymer from the solution by filtration, removing water, and obtaining toner. Platinum powder is prepared by reduction.

[0021] The high corrosion-resistant and high-performance cathode catalytic material prepared by this invention utilizes high-throughput computation to screen elements with excellent corrosion resistance and catalytic activity. Based on the operating conditions of oilfield produced water, iron and nickel are preferred as the main alloying elements. Iron is a fundamental element in the alloy, enhancing the overall structural stability and increasing the strength and toughness of the material. A high proportion of iron significantly improves the electrode's resistance to erosion corrosion under high-speed water flow. Nickel, on the other hand, exhibits excellent corrosion resistance, especially in chloride and high-salt environments. Nickel can form a dense nickel oxide layer, effectively preventing further corrosion of the electrode material in the high-salt and high-chlorine environment of produced water, thus ensuring electrode activity. By adding nickel, phosphorus, and carbon to form an alloy with iron, the problem of iron's inherent tendency to corrode in brine is effectively solved. The addition of platinum significantly improves the corrosion resistance of the catalyst. Carbon in the alloy can form carbides with iron, increasing the material's strength and hardness, further enhancing the electrode's resistance to erosion corrosion. Platinum also enhances the overall hydrogen evolution activity of the alloy catalyst. Furthermore, platinum possesses extremely high corrosion and oxidation resistance, exhibiting excellent stability and corrosion resistance in high-salt environments. Through theoretical calculations and experimental verification, the optimal proportions of each element in the catalytic material were determined: iron 30%–50%, nickel 30%–50%, phosphorus 16%, carbon 4%–10%, and platinum 0%–4%. Within these proportions, the catalytic material not only exhibits excellent performance but also high economic efficiency, making it suitable for industrial applications. This also yields the electrode catalyst material with the best performance: Fe. 40 Ni 37 Pt3P 16 C4. Furthermore, after prolonged operation, nanoparticle noble metal catalysts undergo sintering and growth, leading to a significant decrease in electrode performance. However, the noble metal alloy in this invention is more stable than pure noble metals and is less prone to nanoparticle aggregation and growth. The electrode material exhibits strong resistance to sintering. Experimental verification shows that the prepared catalyst does not exhibit significant changes in performance or microstructure after prolonged operation. Due to the low amount of noble metal used, the economic benefits are significant. This invention can significantly reduce production costs and improve economic efficiency in industrial applications. At the same time, the high stability and long lifespan of the catalyst reduce the need for frequent catalyst replacement, further saving operating and maintenance costs and meeting the needs of large-scale oil and gas field produced water electrolysis for hydrogen production.

[0022] A method for preparing a highly corrosion-resistant and high-performance cathode catalyst material, comprising the following steps: S1. Prepare materials, including 30-50 parts iron powder, 30-50 parts nickel powder, 16 parts phosphorus powder, 4-10 parts carbon powder and 0-4 parts platinum powder; S2. Weigh the materials and mix them according to the proportion to obtain a uniform powder mixture; S3. Place the powder mixture in a high-energy ball mill, set the ball mill speed to 100r / min-300r / min, and continue ball milling for 8h-12h to mix and activate the powder. During the ball milling process, add ethanol and isopropanol as dispersion media to prevent powder agglomeration. S4. Load the ball-milled powder mixture into a mold and use cold pressing technology to press the powder into shape with a pressure of 100MPa-300MPa to form a preliminary catalyst preform. Repeat the cold pressing process multiple times. S5. Place the cold-pressed blank in a vacuum sintering furnace, raise the temperature to 1100℃-1200℃, maintain this temperature for 1h-7h, wait for sintering to be completed, slowly cool to room temperature, take it out, and perform plasma spraying on the prepared catalyst on the titanium electrode plate to obtain the electrolytic water catalytic cathode electrode. S6. Test the cathode electrode.

[0023] By carefully selecting iron powder, nickel powder, phosphorus powder, carbon powder, and platinum powder, and determining specific proportions to prepare the materials, a multi-element synergistic effect can be achieved, thereby endowing the catalyst with rich and adjustable performance characteristics. Iron and nickel powders are often used as active components or carriers of catalysts. The combination of the two can provide different electronic structures and active sites, which is beneficial for adsorbing and activating reactants in the process of water electrolysis and enhancing the catalytic reaction. The addition of phosphorus powder may change the crystal structure or surface chemical properties of the material, further optimizing the chemical environment around the active sites and improving catalytic activity. Carbon powder can disperse other active ingredients and prevent agglomeration. On the other hand, its good conductivity helps electron transfer and improves the overall electrocatalytic efficiency. Although the amount of platinum powder can be flexibly adjusted from 0 to 4 parts, even a small amount can significantly improve the catalytic effect of the entire catalyst due to its excellent catalytic performance. It can also work in combination with other components to achieve multi-component synergy and make the catalyst performance reach a better state. Strictly adhering to the proportions for weighing and mixing raw materials is crucial to ensure uniform distribution of various powder components at the microscopic level. This avoids localized enrichment or deficiency of components and is essential for the subsequent formation of a stable and consistent catalyst. Only a homogeneous powder mixture can guarantee similar physicochemical properties in each part of the material during subsequent ball milling, pressing, and sintering processes. This ensures that the final electrode exhibits uniform catalytic performance across all parts, avoiding localized differences in catalytic effects caused by uneven composition and improving the overall working efficiency and lifespan of the electrode.

[0024] Placing the powder mixture in a high-energy ball mill and ball milling it at a specific speed and duration can effectively break down and refine the powder particles, increasing the specific surface area of ​​the particles. A larger specific surface area means that more active sites can be exposed to participate in the catalytic reaction, thereby improving the activity of the catalyst. At the same time, adding ethanol and isopropanol as dispersion media during the ball milling process can effectively prevent powder agglomeration, so that the powder particles maintain a good dispersion state during the refining process, further ensuring the uniformity of the material and the full utilization of the active sites. Moreover, well-dispersed powder is easier to compact in the subsequent molding process, which helps to improve the density and quality of the green body. In a vacuum sintering furnace, the green body is heated to 1100℃-1200℃ and held for a certain period of time. The vacuum environment can effectively prevent the material from reacting chemically with oxygen and nitrogen in the air at high temperatures, prevent the active ingredients from being oxidized or generating impurity phases, and maintain the purity and original composition characteristics of the material to the greatest extent. Testing the cathode electrode allows for a comprehensive and accurate understanding of its various performance indicators, such as catalytic activity, stability, conductivity, and surface morphology. Through testing, potential problems in the electrode preparation process can be identified in a timely manner, such as uneven material mixing, defects in the molding process, and weak coating adhesion. This enables targeted optimization and improvement of the preparation process, ensuring that the electrolytic cathode electrode for water electrolysis has reliable performance and meets the needs of industrial production or scientific research experiments for efficient and stable water electrolysis.

[0025] In step S2, the material is placed in the reaction vessel and stirred for 30 minutes. In step S3, the prepared uniform powder mixture is transferred to the grinding jar of a high-energy ball mill. The parameters of the ball mill are set, with the rotation speed set between 100 r / min and 300 r / min and the milling time set to 8-12 hours. The ball mill is then started. After milling for 1 hour, ethanol is added to the high-energy ball mill for stirring. Stirring continues. After milling for 2 hours, isopropanol is added to the high-energy ball mill for stirring. Stirring continues until the stirring is complete.

[0026] This application places various materials in a reaction vessel and stirs them for 30 minutes, which allows powders of different components to come into full contact and mix in a relatively short time. Under the mechanical action of stirring, powder particles that may have accumulated or been unevenly dispersed are redistributed, effectively avoiding local component imbalances caused by material accumulation. This ensures that the entire powder mixture reaches a uniform state from the macroscopic to the microscopic level, which is crucial for subsequent processes. Uniform raw material mixing is the foundation for ensuring stable performance of the final catalyst and consistent catalytic effects throughout. For example, if the mixture is not sufficiently stirred, different parts of the material will undergo different physicochemical changes due to differences in composition during subsequent ball milling activation, molding, and sintering processes. This results in the final electrode exhibiting inconsistent catalytic performance in different areas, affecting the overall water electrolysis catalytic effect.

[0027] In step S4, the powder mixture, after being fully ball-milled in a high-energy ball mill, is removed from the grinding jar and transferred to a transfer container. The mold is then thoroughly cleaned and inspected. The powder mixture is loaded into the mold, and the mold is shaken to ensure that the powder is evenly distributed throughout the cavity. Cold pressing is then performed. Cold pressing technology is based on the fact that when the material is subjected to high pressure, the particles move closer to each other and are squeezed together, overcoming the gaps and friction factors between them, thereby causing displacement and gradually aligning them tightly, ultimately achieving the desired shape.

[0028] This application involves loading the powder mixture into a mold and then shaking the mold to ensure the powder is evenly distributed throughout the cavity. This operation is crucial for the quality of the final green body. During cold pressing, if the powder is not evenly distributed in the cavity, there may be areas where the powder is too thick or where there are gaps that are not filled. In areas where the powder is too thick, the forces between the particles may be too great under pressure, which can easily lead to excessively high density and uneven internal stress in the green body, potentially causing cracking later. In contrast, areas with gaps cannot be fully compacted, resulting in inconsistent overall density of the green body, affecting its mechanical properties and its activity as a catalyst. By shaking the mold to ensure even powder distribution, it is possible to ensure that during cold pressing, the powder particles throughout the cavity approach and compress each other in the expected manner under pressure, overcoming gaps and friction, displacing evenly and arranging themselves tightly. This results in a green body with uniform density, dense structure, and consistent properties throughout, which is beneficial for subsequent processing and stable performance during the water electrolysis catalysis process.

[0029] In step S5, the parameters inside the vacuum sintering furnace are set in advance before sintering. After the settings are completed, the temperature slowly rises until it reaches the preset temperature range, at which point sintering is carried out.

[0030] In step S5, plasma spraying involves wiping the surface of the titanium electrode plate with an organic solvent to remove any oil, grease, and other organic contaminants. Ultrasonic cleaning is then used to further clean the electrode plate surface. Sandpaper is then used to polish the surface. The equipment is inspected and adjusted, and the plasma gas and flow rate are set. A suitable ion gas is selected, and the temperature, energy, and stability of the plasma arc are controlled by adjusting the gas flow rate. The pretreated catalyst material is loaded into the hopper of the plasma spraying equipment's feeding system. The feeding system is then started, allowing the catalyst material to be delivered to the plasma spray gun at the set rate for spraying.

[0031] This application uses sandpaper to polish the surface of the titanium electrode plate, which alters the surface roughness to a suitable level. After polishing, a microscopic uneven structure is formed on the electrode plate surface. This microscopic roughness increases the actual contact area, which is beneficial for improving the adhesion between the catalyst coating and the electrode plate. During plasma spraying, the molten catalyst material can be better embedded in these microscopic uneven structures, much like piecing together... Figure 1 The two materials are well-matched, which makes the adhesion between the coating and the electrode plate stronger and less likely to peel off during subsequent use, thus ensuring that the electrode can play a stable catalytic role for a long time. A comprehensive inspection and debugging of the plasma spraying equipment is crucial to ensuring spraying quality and process safety. Checking the tightness of all connections in the spray gun components prevents air and material leaks during spraying, ensuring stable plasma arc generation and proper catalyst delivery. Inspecting the electrodes for wear prevents plasma arc instability caused by electrode issues, which could affect material melting and atomization. Confirming the feeding system is unobstructed ensures the catalyst material is delivered evenly to the spray gun at the set rate, preventing uneven spraying.

[0032] In step S6, the prepared cathode sample was placed in a simulated oilfield produced water environment for corrosion resistance testing. The test conditions were: immersion in an aqueous solution containing sodium, potassium, calcium, magnesium, chloride, sulfate, and bicarbonate ions at 60°C for 100 hours, and observation of the corrosion on the catalyst surface. Hydrogen production efficiency was tested in a laboratory reactor under atmospheric pressure, with a steam flow rate of 5 mL / min-20 mL / min and a reaction temperature of 20°C-60°C, to test the hydrogen production rate of the catalyst.

[0033] In step S5, the vacuum sintering furnace body adopts a double-layer structure, with the outer shell made of metal and the inner layer made of graphite and ceramic fiber materials.

[0034] Example 1 Fe 40 Ni40 P 16 C 10 Electrode material preparation and application Weigh out equimolar amounts of 40 mol% iron powder, 40 mol% nickel powder, 10 mol% phosphorus powder, and 10 mol% carbon powder. Mix the raw materials in proportion to obtain a homogeneous powder mixture. Place the powder mixture in a high-energy ball mill and set the ball mill speed to 300 r / min for 10 hours to ensure uniform mixing and full activation of the powder. During the ball milling process, add an appropriate amount of ethanol or isopropanol as a dispersion medium to prevent powder agglomeration. Load the ball-milled powder mixture into a mold and use cold pressing technology to press the powder into shape at a pressure of 200 MPa to form a preliminary catalyst blank. To ensure the uniformity and density of the blank, repeat the cold pressing process three times. Place the cold-pressed blank in a vacuum sintering furnace and heat the furnace to 1100℃ at a heating rate of 5℃ / h, and maintain this temperature for 4 hours to achieve densification of the blank. After sintering, slowly cool to room temperature at a cooling rate of 10℃ / h and remove the dense Fe. 40 Ni 40 P 16 C 10 Alloy billet, with the prepared Fe 40 Ni 40 P 16 C 10 The catalyst was plasma-sprayed onto a Ti electrode plate to obtain Fe. 40 Ni 40 P 16 C 10 Catalytic cathode electrode; The prepared electrode samples were placed in a simulated oilfield produced water environment for corrosion resistance testing. The specific test conditions were as follows: soaking in an aqueous solution containing Na+: 38913 mg / l, K+: 1056 mg / l, Ca2+: 5008 mg / l, Mg2+: 2021 mg / l, Cl-: 72896 mg / l, SO42-: 631 mg / l, and HCO3-: 576 mg / l at 60°C for 100 h. No corrosion was observed on the catalyst surface. Electrochemical tests were performed on the above electrodes in a three-electrode system, with a current reaching 10 mA / cm². 2 The overpotential was 177 mV, and the current reached 50 mA / cm. 2 The overpotential is 236 mV, and the electrode exhibits excellent stability during the 100-hour test.

[0035] Hydrogen production efficiency was tested in a laboratory reactor under the following conditions: atmospheric pressure, water vapor flow rate of 10 mL / min, and reaction temperature of 60℃. The hydrogen production rate of the catalyst was found to reach 82%.

[0036] Example 2 Fe 40 Ni 40 P 16 Preparation and Application of C4 Electrode Materials Weigh out equimolar amounts of 40 mol% iron powder, 40 mol% nickel powder, 16 mol% phosphorus powder, and 4 mol% carbon powder. Mix the raw materials in proportion to obtain a homogeneous powder mixture. Place the powder mixture in a high-energy ball mill and set the ball mill speed to 300 r / min for 10 hours to ensure uniform mixing and full activation of the powder. During the ball milling process, add an appropriate amount of ethanol or isopropanol as a dispersion medium to prevent powder agglomeration. Load the ball-milled powder mixture into a mold and use cold pressing technology to press the powder into shape at a pressure of 200 MPa to form a preliminary catalyst blank. To ensure the uniformity and density of the blank, repeat the cold pressing process three times. Place the cold-pressed blank in a vacuum sintering furnace and heat the furnace to 1100℃ at a heating rate of 5℃ / h, and maintain this temperature for 4 hours to achieve densification of the blank. After sintering, slowly cool to room temperature at a cooling rate of 10℃ / h and remove the dense Fe. 40 Ni 40 P 16 C4 alloy billet, with prepared Fe 40 Ni 40 P 16 C4 catalyst was plasma-sprayed onto a Ti electrode plate to obtain Fe. 40 Ni 40 P 16 C4 catalytic cathode electrode; The prepared electrode samples were placed in a simulated oilfield produced water environment for corrosion resistance testing. The specific test conditions were as follows: soaking in an aqueous solution containing Na+: 38913 mg / l, K+: 1056 mg / l, Ca2+: 5008 mg / l, Mg2+: 2021 mg / l, Cl-: 72896 mg / l, SO42-: 631 mg / l, and HCO3-: 576 mg / l at 60°C for 100 hours. No corrosion was observed on the catalyst surface.

[0037] Electrochemical tests were performed on the above electrodes in a three-electrode system. The overpotential was 137 mV when the current reached 10 mA / cm², and 50 mA / cm² when the current reached 50 mA / cm². 2 The overpotential is 194 mV, and the electrode exhibits excellent stability during the 100-hour test.

[0038] Hydrogen production efficiency was tested in a laboratory reactor under the following conditions: atmospheric pressure, water vapor flow rate of 10 mL / min, and reaction temperature of 60℃. The hydrogen production rate of the catalyst was found to reach 85%.

[0039] Example 3 Fe 40 Ni 37 Pt3P 16 Preparation and Application of C4 Electrode Materials Weigh out equimolar amounts of 40 mol% iron powder, 40 mol% nickel powder, 10 mol% phosphorus powder, 10 mol% carbon powder, and 3 mol% platinum powder. Mix the raw materials in proportion to obtain a homogeneous powder mixture. Place the powder mixture in a high-energy ball mill and set the ball mill speed to 500 r / min for 24 h to ensure uniform mixing and full activation of the powder. During the ball milling process, add an appropriate amount of ethanol or isopropanol every 3 h as a dispersion medium to prevent powder agglomeration. Load the ball-milled powder mixture into a mold and use cold pressing technology to press the powder into shape at a pressure of 300 MPa to form a preliminary catalyst blank. To ensure the uniformity and density of the blank, repeat the cold pressing process three times. Place the cold-pressed blank in a vacuum sintering furnace and heat the furnace to 1200℃ at a heating rate of 5℃ / h, and maintain this temperature for 4 h to achieve densification of the blank. After sintering, slowly cool to room temperature at a cooling rate of 5℃ / h and remove the dense Fe. 40 Ni 37 Pt3P 16 C4 alloy billet, with prepared Fe 40 Ni 37 Pt3P 16 C4 catalyst was plasma-sprayed onto a Ti electrode plate to obtain Fe. 40 Ni 40 P 16 C 10 Catalytic cathode electrode; The prepared electrode samples were placed in a simulated oilfield produced water environment for corrosion resistance testing. The specific test conditions were as follows: soaking in an aqueous solution containing Na+: 38913 mg / l, K+: 1056 mg / l, Ca2+: 10727 mg / l, Mg2+: 3142 mg / l, Cl-: 119760 mg / l, SO42-: 500 mg / l, and HCO3-: 464 mg / l at 60°C for 100 hours. No corrosion was observed on the catalyst surface. The overpotential at a current of 10 mA / cm2 was 109 mV, and the overpotential at a current of 50 mA / cm2 was 173 mV. The electrode showed excellent stability during the 300-hour test, indicating that the introduction of the noble metal Pt into the cathode electrode catalyst reduced the overpotential.

[0040] Hydrogen production efficiency was tested in a laboratory reactor under the following conditions: atmospheric pressure, water vapor flow rate of 10 mL / min, and reaction temperature of 60℃. The hydrogen production rate of the catalyst was found to reach 90%.

[0041] Example 4 Fe was prepared according to the above technical solution. 40 Ni 37 Pt3P 16 C4 catalyst was tested for corrosion resistance and hydrogen production efficiency. The test results showed that, in a simulated oilfield produced water environment, Fe... 40 Ni 37 Pt3P 16 C4 material showed no obvious corrosion within 100 hours at 60℃, and the hydrogen production efficiency reached 85%.

[0042] Example 5 Adjusting the ball milling time to 8 hours while keeping the other steps unchanged, the test results showed that the catalyst's corrosion resistance decreased slightly, but the hydrogen production efficiency remained above 80%.

[0043] Example 6 When the sintering temperature was lowered to 1100℃ while the other steps remained unchanged, the test results showed that the density and corrosion resistance of the catalyst were slightly reduced, but the hydrogen production efficiency could still reach 75%.

[0044] Example 7 The temperature of the sintering furnace was raised to 1200℃ and held for 1h, 3h, 5h and 7h respectively before being slowly cooled to room temperature. The test results showed that when the temperature was held for less than 2h, 2.5h and 3h respectively, the catalyst concentration was low, the corrosion resistance was poor and the hydrogen production efficiency was less than 50%. When the temperature was held for more than 5h and then slowly cooled to room temperature, the density and corrosion resistance of the catalyst were slightly reduced, but the hydrogen production efficiency could still reach 70%.

[0045] In the description of this patent, it should be understood that the terms "appropriate amount", "multiple times", "slowly", etc., indicating the quantity or speed are only for the convenience of describing this patent and simplifying the description, and do not indicate or imply that the referred solution must have a specific quantity, and therefore should not be construed as a limitation on this patent.

[0046] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A high corrosion-resistant, high-performance cathode catalyst material, characterized in that, The catalyst materials, by molar mass parts, include: 30-50 parts iron powder, 30-50 parts nickel powder, 16 parts phosphorus powder, 4-10 parts carbon powder, and 0-4 parts platinum powder.

2. The high corrosion resistance and high performance cathode catalyst material according to claim 1, characterized in that, The iron powder preparation process involves reducing iron oxides using solid and gaseous reducing agents. Under high temperature conditions, hydrogen reacts chemically with iron oxide to remove oxygen from the iron oxide, thus obtaining reduced iron powder. Nickel powder is prepared using a reduction method. The preparation steps include preparing a nickel sulfate solution, adding potassium oxalate, dissolving it in water (potassium oxalate has low solubility in cold water, so it is completely dissolved by heating), filtering the nickel oxalate precipitate, washing it three times with water and twice with ethanol, without heat drying, taking the nickel oxalate, heating it, and the nickel oxide generated by the decomposition of nickel oxalate reacts with carbon monoxide to produce nickel and carbon dioxide. After cooling, the powder is poured onto filter paper, reacting with air to generate heat, thus obtaining nickel powder.

3. The high corrosion resistance and high performance cathode catalyst material according to claim 1, characterized in that, Phosphorus powder is produced using a reduction method, in which a reducing agent is used to reduce phosphorus in phosphorus-containing compounds to obtain phosphorus powder. Toner is prepared by polymerization. The preparation steps involve ultrasonically dispersing and uniformly mixing resin monomers, pigments, dispersants and other reagents, adding water and dispersants, stirring thoroughly to form a homogeneous solution, carrying out a polymerization reaction to polymerize the monomers into a polymer, washing the polymerized product to remove unreacted monomers and impurities, separating the polymer from the solution by filtration, removing water, and obtaining toner. Platinum powder is prepared by reduction.

4. A method for preparing a highly corrosion-resistant and high-performance cathode catalyst material, characterized in that, The preparation steps are as follows: S1. Prepare materials by mass fractions, including 30-50 parts iron powder, 30-50 parts nickel powder, 16 parts phosphorus powder, 4-10 parts carbon powder, and 0-4 parts platinum powder; S2. Weigh the materials and mix them according to the proportion to obtain a uniform powder mixture; S3. Place the powder mixture in a high-energy ball mill, set the ball mill speed to 100r / min-300r / min, and continue ball milling for 8h-12h to mix and activate the powder. During the ball milling process, add ethanol and isopropanol as dispersion media to prevent powder agglomeration. S4. Load the ball-milled powder mixture into a mold and use cold pressing technology to press the powder into shape with a pressure of 100MPa-300MPa to form a preliminary catalyst preform. Repeat the cold pressing process multiple times. S5. Place the cold-pressed blank in a vacuum sintering furnace, raise the temperature to 1100℃-1200℃, maintain this temperature for 1h-7h, wait for sintering to be completed, slowly cool to room temperature, take it out, and perform plasma spraying on the prepared catalyst on the titanium electrode plate to obtain the electrolytic water catalytic cathode electrode. S6. Test the cathode electrode.

5. The method for preparing a high corrosion-resistant, high-performance cathode catalyst material according to claim 4, characterized in that, In step S2, the material is placed in the reaction vessel and stirred for 30 minutes. In step S3, the prepared uniform powder mixture is transferred to the grinding jar of a high-energy ball mill. The parameters of the ball mill are set, with the rotation speed set between 100 r / min and 300 r / min and the milling time set to 8-12 hours. The ball mill is then started. After milling for 1 hour, ethanol is added to the high-energy ball mill for stirring. Stirring continues. After milling for 2 hours, isopropanol is added to the high-energy ball mill for stirring. Stirring continues until the stirring is complete.

6. The method for preparing a high corrosion-resistant, high-performance cathode catalyst material according to claim 4, characterized in that, In step S4, the powder mixture, after being fully ball-milled in a high-energy ball mill, is removed from the grinding jar and transferred to a transfer container. The mold is then thoroughly cleaned and inspected. The powder mixture is loaded into the mold, and the mold is shaken to ensure that the powder is evenly distributed throughout the cavity. Cold pressing is then performed. Cold pressing technology is based on the fact that when the material is subjected to high pressure, the particles move closer to each other and are squeezed together, overcoming the gaps and friction factors between them, thereby causing displacement and gradually aligning them tightly, ultimately achieving the desired shape.

7. The method for preparing a high corrosion-resistant, high-performance cathode catalyst material according to claim 4, characterized in that, In step S5, the parameters inside the vacuum sintering furnace are set in advance before sintering. After the settings are completed, the temperature slowly rises until it reaches the preset temperature range, at which point sintering is carried out.

8. The method for preparing a high corrosion-resistant, high-performance cathode catalyst material according to claim 4, characterized in that, In step S5, plasma spraying involves wiping the surface of the titanium electrode plate with an organic solvent to remove any oil, grease, and other organic contaminants. Ultrasonic cleaning is then used to further clean the electrode plate surface. Sandpaper is then used to polish the surface. The equipment is inspected and adjusted, and the plasma gas and flow rate are set. A suitable ion gas is selected, and the temperature, energy, and stability of the plasma arc are controlled by adjusting the gas flow rate. The pretreated catalyst material is loaded into the hopper of the plasma spraying equipment's feeding system. The feeding system is then started, allowing the catalyst material to be delivered to the plasma spray gun at the set rate for spraying.

9. The method for preparing a high corrosion-resistant, high-performance cathode catalyst material according to claim 4, characterized in that, In step S6, the prepared cathode sample was placed in a simulated oilfield produced water environment for corrosion resistance testing. The test conditions were: immersion in an aqueous solution containing sodium, potassium, calcium, magnesium, chloride, sulfate, and bicarbonate ions at 60°C for 100 hours, and observation of the corrosion on the catalyst surface. Hydrogen production efficiency was tested in a laboratory reactor under atmospheric pressure, with a steam flow rate of 5 mL / min-20 mL / min and a reaction temperature of 20°C-60°C, to test the hydrogen production rate of the catalyst.

10. The method for preparing a high corrosion-resistant, high-performance cathode catalyst material according to claim 4, characterized in that, In step S5, the vacuum sintering furnace body adopts a double-layer structure, with the outer shell made of metal and the inner layer made of graphite and ceramic fiber materials.

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