An ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode and its preparation method
By spraying an iron salt solution onto a nickel-containing substrate and calcining it at high temperature to form a self-supporting iron-nickel catalytic electrode, the problems of high cost and poor stability of noble metal catalysts are solved, and efficient and low-cost large-area preparation and application are realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- MATERIAL INST OF CHINA ACADEMY OF ENG PHYSICS
- Filing Date
- 2026-02-06
- Publication Date
- 2026-05-26
AI Technical Summary
Existing AEM water electrolysis catalysts are mostly precious metals, which are expensive and have low stability. Synthetic nickel-iron catalysts pose safety risks and have agglomeration phenomena, making it difficult to spray them uniformly over a large area, resulting in poor stability of the catalytic electrode.
An iron salt solution was sprayed onto a nickel-containing substrate using ultrasonic spraying, and then calcined in a high-temperature furnace to form a self-supporting iron-nickel catalytic electrode. By controlling the spraying speed and temperature, a nickel-iron alloy nanostructure was formed, achieving large-area uniform coverage.
This non-precious metal catalyst achieves high raw material utilization and zero waste liquid, reduces preparation costs, improves the stability of the catalytic electrode and the efficiency of hydrogen production by water electrolysis, and is suitable for large-scale industrial applications.
Smart Images
Figure CN122082005A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrocatalytic materials technology, and in particular to an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode and its preparation method. Background Technology
[0002] Hydrogen energy is a new type of secondary energy that is abundant, green, low-carbon, and widely applicable. In recent years, membrane electrolysis (EM) water electrolysis technology has gradually become a research hotspot due to its advantages such as low cost, high current density, high purity, rapid response, and safety. AEM water electrolysis for hydrogen production has advantages such as simple equipment, safety, environmental friendliness, mild reaction conditions, and broad prospects for large-scale development. However, most existing AEM water electrolysis catalysts are precious metals such as iridium and ruthenium, which are expensive and have low stability.
[0003] The industry is actively seeking to develop non-precious metal catalysts, such as nickel-iron metal nanoparticles. However, the synthesis of nickel-iron metal nanoparticle catalysts requires reduction with sodium borohydride, releasing large amounts of hydrogen gas and posing extremely high safety risks. Furthermore, the particle size of the synthesized nickel-iron catalysts is difficult to control, leading to severe agglomeration during the preparation of the supported solution, making it difficult to uniformly coat the catalytic electrode. Simultaneously, powder catalysts require polymer binders to be loaded onto the diffusion layer to form the catalytic electrode, and their stability remains a significant challenge.
[0004] Therefore, how to develop a non-precious metal oxygen evolution catalytic electrode for AEM anode with high raw material utilization, zero waste liquid, and large-area fabrication is an urgent problem to be solved. Summary of the Invention
[0005] This invention aims to solve the problem of how to develop a non-precious metal oxygen evolution catalytic electrode for AEM anode with high raw material utilization, zero waste liquid, and large-area fabrication, and provides an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode and its preparation method.
[0006] To achieve the above-mentioned technical objectives, the technical solution provided by this invention is as follows: A method for preparing an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode includes the following steps: Step 1: Prepare iron salt solution: Dissolve a certain amount of iron salt solution in ethanol; Step 2: Spraying iron salt solution: Use ultrasonic spraying to spray iron salt solution onto the nickel-containing substrate; Step 3: Preparation of iron-nickel catalytic electrode: Place the nickel-containing substrate coated with iron salt in a high-temperature furnace and calcine it for a certain time under a hydrogen-argon atmosphere to obtain a self-supporting iron-nickel catalytic electrode.
[0007] Furthermore, in step 1, the iron salt solution contains iron salt and anhydrous ethanol solution at a weight percentage of 0.1w%~10w, and is ultrasonically stirred for 0.5-1h.
[0008] Furthermore, in step 2, the spraying speed is 0.01~50 mL / min, and the iron loading is 0.02 mg / cm³. 2 ~10 mg / cm 2 .
[0009] Furthermore, the high-temperature furnace is set to a temperature of 400~800℃ and a time of 0.1~6h.
[0010] During the thermal decomposition process in a tubular furnace, nickel in the nickel-containing substrate reacts with reduced iron to form a nickel-iron alloy nanostructure.
[0011] Furthermore, the nickel-containing substrate is one or more of the following: nickel foam, nickel felt, nickel mesh, nickel particle plate, nickel sheet, nickel-iron foam, nickel-cobalt foam, nickel-copper foam, nickel-chromium foam, nickel-molybdenum foam, nickel-iron alloy felt, nickel-cobalt alloy felt, nickel-copper alloy felt, nickel-molybdenum alloy felt, and nickel-chromium alloy felt.
[0012] The present invention also provides an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode. The surface of the self-supporting iron-nickel oxygen evolution catalytic electrode is composed of nano-spherical metal particles, which are uniformly covered on the surface of a nickel-containing substrate.
[0013] This invention also provides the application of an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode in anion exchange membrane water electrolysis for hydrogen production.
[0014] Furthermore, the temperature for electrolysis is 30~90°C. o C, the electrolysis current is 0.1~3A / cm 2 .
[0015] The present invention has the following beneficial effects: 1. A non-precious metal self-supporting iron-nickel oxygen evolution catalytic electrode was synthesized to replace the traditional precious metal iridium (ruthenium) oxide catalyst, reducing costs and significantly lowering the overpotential of water electrolysis for hydrogen production.
[0016] 2. In the synthesis of the self-supporting iron-nickel oxygen evolution catalytic electrode, the amount of iron salt used is extremely small, approximately 10-40 mmol / L, and no iron atom waste is discharged after the thermal decomposition reaction. This reduces the amount of raw materials used, maximizes atom utilization, and lowers synthesis costs.
[0017] 3. When synthesizing a self-supporting iron-nickel oxygen evolution catalytic electrode, the nickel-containing substrate can be scaled up arbitrarily, enabling the mass production of large-area catalytic electrodes. Attached Figure Description
[0018] Figure 1 SEM image of a self-supporting iron-nickel catalyst; Figure 2 Polarization curves for self-supported iron-nickel catalyst and ruthenium oxide (RuO2) catalyst; Figure 3 Polarization curves of the FeNi / nickel felt catalytic electrode at different alkaline temperatures; Figure 4 The FeNi / nickel felt catalytic electrode was used for stability testing in an AEM electrolyzer. Detailed Implementation
[0019] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0020] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0021] Example 1 First, 0.3 g of ferric chloride was dissolved in 15 mL of anhydrous ethanol to prepare a ferric chloride salt solution. The ferric chloride salt solution was then loaded into an ultrasonic spraying machine. A nickel felt substrate was placed on a heating stage, and the temperature was adjusted to 50°C. The spraying speed was then controlled to evenly spray the ferric chloride salt solution onto the nickel felt. After drying at room temperature, the substrate was placed in a tube furnace. Hydrogen and argon gases were introduced, and the tube furnace temperature was set to 500°C for 2 hours under a hydrogen and argon atmosphere. The substrate was then removed, yielding an anode oxygen evolution catalytic electrode with a surface covered by a self-supported iron-nickel catalyst. The cathode hydrogen evolution catalytic electrode had a Pt / C loading of 0.5 mg / cm³. 2 The diffusion layer electrode.
[0022] Prepare a 1M KOH alkaline solution, maintaining the solution temperature at 70℃. Install a self-supporting iron-nickel catalytic electrode in an AEM electrolytic cell and slowly apply current. After activation until the voltage stabilizes, measure the polarization curve to obtain the overpotential under different current densities, such as... Figure 1 The image shown is a SEM image of a self-supporting iron-nickel catalyst; as shown... Figure 2 As shown, the overpotential of the self-supported iron-nickel catalyst is significantly lower than that of the ruthenium oxide catalyst. This demonstrates that the self-supported iron-nickel catalyst can replace the ruthenium oxide noble metal catalyst in AEM water electrolysis for hydrogen production, thereby reducing the cost of AEM water electrolysis for hydrogen production.
[0023] Example 2 First, 0.5 g of ferric chloride was dissolved in 20 mL of anhydrous ethanol to prepare a ferric chloride salt solution. The ferric chloride salt solution was then loaded into an ultrasonic spraying machine. A nickel felt substrate was placed on a heating stage, and the temperature was adjusted to 50°C. The spraying speed was then controlled to evenly spray the ferric chloride salt solution onto the nickel felt. After drying at room temperature, the substrate was placed in a tube furnace. Hydrogen and argon gases were introduced, and the tube furnace temperature was set to 500°C for 2 hours under a hydrogen and argon atmosphere. The substrate was then removed, yielding a catalytic electrode with a surface covered by a self-supporting iron-nickel catalyst. The cathode hydrogen evolution catalytic electrode had a Pt / C loading of 0.5 mg / cm³. 2 The diffusion layer electrode.
[0024] Prepare a 1M KOH alkaline solution and set different temperature gradients. Install a self-supporting iron-nickel catalytic electrode in an AEM electrolytic cell and slowly apply current. After activation until the voltage stabilizes, measure the polarization curves to obtain the polarization curves at the corresponding temperatures, as shown below. Figure 3 As shown, the potential of the self-supporting iron-nickel catalyst gradually decreases with increasing temperature. The self-supporting iron-nickel catalyst can withstand the high-temperature environment of AEM electrolyzers in industrial use and does not fail under high-temperature conditions.
[0025] Example 3 Test conditions changed to a 50-degree water bath. o C, current density 1A / cm 2 The remaining steps are the same as in Example 1. Under the same conditions, the long-term operational stability of the fuel cell stack is examined, and the change in the stack voltage is tested, such as... Figure 4 As shown, the cell voltage remained at 1.8V after 100 hours of stable operation, with no significant attenuation.
[0026] Example 4: The iron salt was replaced with ferric nitrate, and the remaining steps were the same as in Example 1. The polarization curves showed no significant changes.
[0027] Comparative Example 1 Ethanol and deionized water were mixed at a volume ratio of 1:2, and RuO2 powder was added. Then, naphthol solution was added until the weight percentage of naphthol to RuO2 was 20 wt%. After ultrasonic dispersion, an anolyte was prepared. The anolyte was then sprayed onto one side of a nickel felt using an ultrasonic spraying machine to obtain an anode catalyst with a RuO2 loading of 3 mg / cm³. 2 The catalytic electrode.
[0028] Prepare a 1M KOH alkaline solution and maintain its temperature at 70℃. After the voltage stabilizes, measure the polarization curve to obtain the overpotential under different current densities, such as... Figure 2 As shown, the overpotential of the self-supported iron-nickel catalyst is significantly lower than that of the ruthenium oxide catalyst.
[0029] Comparative Example 2 First, a ferric chloride solution was prepared by dissolving 0.5g of ferric chloride in 20ml of anhydrous ethanol. The ferric chloride solution was then loaded into an ultrasonic spraying machine. A nickel felt substrate was placed on a heating stage, and the temperature was adjusted to 50℃. The spraying speed was then controlled to evenly spray the ferric chloride solution onto the nickel felt. After drying at room temperature, the substrate was placed in a tube furnace. Hydrogen and argon gases were introduced, and the tube furnace temperature was set to 500℃ for 2 hours under this atmosphere. The substrate was then removed, yielding a self-supporting iron-nickel catalytic electrode.
[0030] Prepare a 1M KOH alkaline solution, controlling the temperature of the solution within different ranges. After the voltage stabilizes, measure the polarization curve to obtain the potential under different temperature conditions, such as... Figure 3 As shown, the voltage of the iron-nickel catalyst decreases as the temperature of the alkaline solution increases. This indicates that the catalyst does not degrade with increasing temperature. This demonstrates that the catalyst can withstand the high-temperature environments of industrial applications.
[0031] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
[0032] The above detailed embodiments are a description of the present invention. It should not be considered that the specific embodiments of the present invention are limited to these descriptions. For those skilled in the art, several simple deductions and substitutions can be made without departing from the concept of the present invention, and all of these should be considered to fall within the protection scope of the present invention.
Claims
1. A method for preparing an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode, characterized in that, Includes the following steps: Step 1: Prepare iron salt solution: Dissolve a certain amount of iron salt solution in ethanol; Step 2: Spraying iron salt solution: Use ultrasonic spraying to spray iron salt solution onto the nickel-containing substrate; Step 3: Preparation of iron-nickel catalytic electrode: Place the nickel-containing substrate coated with iron salt in a high-temperature furnace and calcine it for a certain time under a hydrogen-argon atmosphere to obtain a self-supporting iron-nickel catalytic electrode.
2. The method for preparing an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode according to claim 1, characterized in that, In step 1, the iron salt solution contains iron salt and anhydrous ethanol solution at a weight percentage of 0.1w% to 10w, and is ultrasonically stirred for 0.5-1h.
3. The method for preparing an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode according to claim 1, characterized in that, In step 2, the spraying speed is 0.01~50 mL / min, and the iron loading is 0.02 mg / cm³. 2 ~10 mg / cm 2 .
4. The method for preparing an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode according to claim 1, characterized in that, The high-temperature furnace is set to a temperature of 400~800℃ and a time of 0.1~6 h.
5. The method for preparing an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode according to claim 1, characterized in that, The nickel-containing substrate is one or more of the following: nickel foam, nickel felt, nickel mesh, nickel particle plate, nickel sheet, nickel-iron foam, nickel-cobalt foam, nickel-copper foam, nickel-chromium foam, nickel-molybdenum foam, nickel-iron alloy felt, nickel-cobalt alloy felt, nickel-copper alloy felt, nickel-molybdenum alloy felt, and nickel-chromium alloy felt.
6. An ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode is prepared by any one of the methods described in claims 1-4.
7. The ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode according to claim 5, characterized in that, The surface of the self-supporting iron-nickel oxygen evolution catalytic electrode consists of nano-spherical metal particles that are uniformly covered on a nickel-containing substrate.
8. An application of an ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode as described in any one of claims 5-6 in anion exchange membrane water electrolysis for hydrogen production.
9. The application of the ultra-stable, high-performance self-supporting iron-nickel oxygen evolution catalytic electrode according to claim 8 in anion exchange membrane water electrolysis for hydrogen production, characterized in that, The electrolysis temperature is 30~90°C. o C, the electrolysis current is 0.1~3A / cm 2 .