Preparation method of nickel alloy type electrolytic catalyst membrane by electrodeposition method
The catalyst preparation by nickel alloy-type electrodeposition method solves the problems of high cost of precious metal catalysts and poor performance of carbon-based catalysts, and achieves efficient and stable catalytic electrolysis of water in alkaline systems, significantly improving catalytic performance and stability.
Patent Information
- Application Number
- CN202510075138.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-17
- Publication Date
- 2025-04-11
AI Technical Summary
In the existing electrolytic hydrogen production technology, the scarcity and high cost of precious metal catalysts hinder the commercialization process of the technology, and carbon-based catalysts have problems of electrochemical inertia, poor catalytic activity and stability.
The catalyst was prepared by nickel alloy-type electrodeposition method, and the nickel mesh support was pretreated by using ultrasonic impregnation technology in an alkaline solution, followed by calcination and electrochemical deposition under a protective atmosphere to form a nickel-based alloy catalyst.
The prepared nickel-based alloy catalyst exhibits excellent hydrogen production performance and stability in the alkaline system. It promotes intermediate adsorption through bimetallic synergy, reduces solid-liquid interface resistance, improves charge transfer rate, and significantly improves the electrocatalytic HER reaction efficiency.
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Figure CN119800418A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of electrocatalysis, and in particular to a method for preparing a nickel alloy type electrolytic catalyst film by electrodeposition. Background Art
[0002] Under my country's "dual carbon" goal, clean, energy-dense, pollution-free green hydrogen energy is an effective strategy to solve global problems such as energy depletion and environmental pollution. Renewable energy water electrolysis to produce hydrogen has high conversion efficiency, hydrogen purity and commercial value, and is simple, efficient, environmentally friendly and has the characteristics of high purity of the resulting hydrogen. In the process of water electrolysis, the use of catalysts can effectively reduce electricity consumption. Precious metal catalysts such as Pt and Ir have excellent electrochemical hydrogen production performance. However, their rare content and high price make it difficult to meet large-scale applications, hindering the commercialization process of water electrolysis hydrogen production technology. The price of non-precious metals is significantly lower than that of Ir and Pt, and they have good hydrogen evolution performance. Therefore, the preparation of efficient, stable and low-cost hydrogen evolution catalysts that can operate stably under alkaline conditions is of great significance to the water electrolysis industry.
[0003] At present, the main preparation strategies of electrochemical catalysts in the world include alloying, metal doping, introducing defects, interface engineering, crystal phase regulation and nanostructuring. In fact, researchers have tried to develop cost-effective and promising electrocatalysts through different design methods, such as loading precious metal nanoparticles or alloys composed of other transition metals onto carbon-based materials, such as Pt, Ir, Rd, etc. Because carbon-based nanomaterials are environmentally friendly, abundant in reserves, low in cost, flexible and versatile, they have shown broad application prospects in the field of energy conversion in recent years. However, basic carbon materials such as carbon cloth are electrochemically inert, have poor catalytic activity, weak mechanical strength, poor stability, adhesion, etc., which are the reasons for the attenuation of the performance of carbon-based catalysts. It is usually necessary to modify these carbon-based materials to improve their electrocatalytic activity. By loading metals on carbon-based materials through structural design, new carbon-based catalysts with high catalytic activity can be prepared, or the synergistic effect between different metals can be utilized. Among them, bimetallic nanocatalysts usually show enhanced performance compared with single metals, which is directly related to the specific atomic arrangement of the two metal elements on the surface and near the surface. The alloy materials benefit from the synergistic effect between different metal atoms. Metal nanomaterials with multiple metal components can exhibit better catalytic performance than single-component metal nanomaterials.
[0004] Electrodeposition is a process that deposits a thin layer of material on a substrate by applying an electric current in an electrolyte solution. This method is widely used in various applications such as electroplating, electroforming and the production of nanostructured films. Its advantages are that electrodeposition can deposit a variety of materials, has good control over film thickness and uniformity, and can be performed at relatively low temperatures. It is also an economical and effective method for producing thin films and coatings. It can be widely used in industrial fields, from decorative electroplating to the production of functional nanostructured materials. Summary of the invention
[0005] In view of some shortcomings of the current water electrolysis technology, the main purpose of the present invention is to provide a research idea and preparation method for a nickel-based alloy catalyst prepared by an electrodeposition method. The product prepared by the present invention is environmentally friendly and pollution-free, has low cost, and has excellent water electrolysis hydrogen production performance. The obtained nickel-based alloy catalyst has a good structure and is corrosion-resistant. It is applied to the cathode reaction of water electrolysis hydrogen evolution, has high catalytic property, and has excellent high-concentration alkaline water electrolysis hydrogen production effect.
[0006] In order to solve the above technical problems, a technical solution adopted by the present invention is: a method for preparing a nickel alloy type electrolytic catalyst film by electrodeposition method, the steps of which include: A method for preparing a nickel alloy electrolytic catalyst film by electrodeposition method comprises the following steps: (1) A base nickel mesh is selected as a carrier, and the carrier is pretreated in an alkaline solution by ultrasonic immersion, and the carrier is assisted by ultrasonication. The carrier after ultrasonication is washed with deionized water and then dried; (2) dispersing a non-precious metal salt in the deionized water in step (1), then adding the carrier prepared above into the deionized water, immersing for a period of time, and then calcining under a first protective gas atmosphere to obtain a nickel-based precursor; (3) fully breaking up the nickel-manganese mixed reagent and mixing it in a mixed solution of water and ethanol, placing the substrate precursor obtained in step (2) in the mixed solution for ultrasonic impregnation treatment, and after the impregnation, calcining under a second protective gas atmosphere to obtain a nickel-based alloy catalyst precursor; (4) The nickel-based alloy catalyst precursor obtained in step (3) is electrochemically deposited in an electrochemical workstation three-electrode system to obtain a sample nickel-based catalyst.
[0007] In an embodiment of the present invention, in step (1), the ultrasonic power used is 100W~300W, and the alkaline solution is one of KOH or NaOH.
[0008] In an embodiment of the present invention, in step (1), the concentration of the alkali solution is 2 mol / L~8 mol / L, the ultrasonic frequency is 100~400W, and the ultrasonic time is 30~100 min.
[0009] In an embodiment of the present invention, in step S2, the calcination temperature is 300° C. to 600° C., and the calcination time is 3 to 6 hours.
[0010] In an embodiment of the present invention, the first protective atmosphere is one of nitrogen, argon or helium.
[0011] In an embodiment of the present invention, in step S2, the non-precious metal is one of manganese salt, iron salt, cobalt salt or nickel salt.
[0012] In an embodiment of the present invention, in step (3), the volume ratio of ethanol to water is 3:1-6:1, and the calcination rate is 1°C / min-5°C / min.
[0013] In an embodiment of the present invention, the second protective atmosphere is one of nitrogen, argon or helium.
[0014] In an embodiment of the present invention, in step (4), the current density of the electrochemical deposition is 400 mAcm -2 ~2000 mAcm -2 , lasting for 1~10 hours.
[0015] In an embodiment of the present invention, in step (4), the working electrode is a nickel-based alloy catalyst precursor, the reference electrode is a mercury oxide electrode, and the counter electrode is a platinum sheet electrode.
[0016] The beneficial effects of the present invention are as follows: the nickel-based alloy catalyst prepared by the present invention has excellent hydrogen production performance and good stability in an alkaline system. Compared with the existing single metal catalyst catalytic hydrogen production technology, the present invention can promote the adsorption of intermediates through the synergistic effect of bimetallic catalysts, so that the bimetallic catalyst has excellent HER electrocatalytic performance and exhibits lasting stability in a high-concentration alkaline solution system. On the other hand, the addition of other metals regulates the electronic structure of Ni, reduces the adsorption energy of metal Ni to hydrogen, can effectively reduce the solid-liquid interface resistance, and improve the charge transfer rate, thereby accelerating the electrocatalytic HER reaction process. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work, among which: Figure 1 This is a polarization curve diagram of the catalyst of Example 1 of the present invention during HER reaction in a high concentration alkaline solution.
[0018] Figure 2This is a photo illustration of the catalyst of Example 1 of the present invention. DETAILED DESCRIPTION
[0019] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0020] See also Figure 1-2 The embodiment of the present invention includes: a method for preparing a nickel alloy type electrolytic catalyst film by electrodeposition method, comprising the following steps: (1) A base nickel mesh is selected as a carrier, and the carrier is pretreated in an alkaline solution by ultrasonic immersion, and the carrier is assisted by ultrasonication. The carrier after ultrasonication is washed with deionized water and then dried; (2) dispersing a non-precious metal salt in the deionized water in step (1), then adding the carrier prepared above into the deionized water, immersing for a period of time, and then calcining under a first protective gas atmosphere to obtain a nickel-based precursor; (3) fully breaking up the nickel-manganese mixed reagent and mixing it in a mixed solution of water and ethanol, placing the substrate precursor obtained in step (2) in the mixed solution for ultrasonic impregnation treatment, and after the impregnation, calcining under a second protective gas atmosphere to obtain a nickel-based alloy catalyst precursor; (4) The nickel-based alloy catalyst precursor obtained in step (3) is electrochemically deposited in an electrochemical workstation three-electrode system to obtain a sample nickel-based catalyst.
[0021] Furthermore, in step (1), the ultrasonic power used is 100W~300W, and the alkaline solution is one of KOH or NaOH.
[0022] Furthermore, in step (1), the concentration of the alkali solution is 2 mol / L~8 mol / L, the ultrasonic frequency is 100~400W, and the ultrasonic time is 30~100 min.
[0023] Furthermore, in step S2, the calcination temperature is 300°C to 600°C, and the calcination time is 3 to 6 hours.
[0024] Furthermore, the first protective atmosphere is one of nitrogen, argon or helium.
[0025] Furthermore, in step S2, the non-precious metal is one of manganese salt, iron salt, cobalt salt or nickel salt.
[0026] Furthermore, in step (3), the volume ratio of ethanol to water is 3:1-6:1, and the calcination rate is 1°C / min-5°C / min.
[0027] Furthermore, the second protective atmosphere is one of nitrogen, argon or helium.
[0028] Furthermore, in step (4), the current density of the electrochemical deposition is 400 mAcm -2 ~2000 mA cm -2 , lasting for 1~10 hours.
[0029] Furthermore, in step (4), the working electrode is a nickel-based alloy catalyst precursor, the reference electrode is a mercury oxide electrode, and the counter electrode is a platinum sheet electrode. Example
[0030] Provided is a method for preparing a NiMn bimetallic catalyst, which is prepared by the following steps: dissolving 1 mol / L NaOH in deionized water, stirring until completely dissolved, adding an empty nickel mesh thereto, ultrasonically cleaning, and after the reaction temperature drops to room temperature, repeatedly rinsing with ethanol and water, and then immersing the cleaned nickel mesh in a 3 mol / L potassium permanganate solution, taking it out after ultrasonic treatment for 30 minutes, drying it at 80°C, and calcining it in air to obtain a NiMn catalyst precursor, and electro-depositing the NiMn catalyst precursor obtained above in a three-electrode system in a 1 M Ni(NO3)2+KOH solution, and drying the sample taken out after the deposition is completed. The prepared catalyst is named NiMn alloy catalyst. Figure 1 Figure 2 shows the polarization curves of nickel-based alloy catalysts undergoing electrolysis in alkaline solutions. (a) is the polarization curve of hydrogen evolution reaction with a single metal nickel-based catalyst, and (b) is the polarization curve of oxygen evolution reaction with a single metal nickel-based catalyst. Example
[0031] Provided is a method for preparing a NiFe bimetallic catalyst, which is prepared by the following steps: dissolving 1 mol / L NaOH in deionized water, stirring until completely dissolved, adding an empty nickel mesh thereto, cleaning it by ultrasonication, and after the reaction cools to room temperature, repeatedly rinsing it with ethanol and water, and then immersing the cleaned nickel mesh in a 3 mol / L ferric chloride solution, taking it out after ultrasonication for 30 minutes, drying it at 80°C, and calcining it in air to obtain a NiFe catalyst precursor, and electro-depositing the NiFe catalyst precursor obtained above in a three-electrode system in a 1 M Ni(NO3)2+KOH solution, and drying the sample taken out after the deposition is completed. The prepared catalyst is named NiFe alloy catalyst.
[0032] The beneficial effects of the method for preparing a nickel alloy type electrolytic catalyst membrane by electrodeposition method of the present invention are: the nickel-based alloy catalyst prepared by the present invention has excellent hydrogen production performance and good stability in an alkaline system. Compared with the existing single metal catalyst catalytic hydrogen production technology, the adsorption of intermediates can be promoted through the synergistic effect of bimetallic catalysts, so that the bimetallic catalyst has excellent HER electrocatalytic performance and exhibits long-lasting stability in a high concentration alkaline solution system. On the other hand, the addition of other metals regulates the electronic structure of Ni, reduces the adsorption energy of metal Ni to hydrogen, can effectively reduce the solid-liquid interface resistance, and increase the charge transfer rate, thereby accelerating the electrocatalytic HER reaction process.
[0033] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.
Claims
1. A method for preparing a nickel alloy electrolytic catalyst film by electrodeposition, characterized in that: The following steps are involved: (1) A base nickel mesh is selected as a carrier, and the carrier is pretreated in an alkaline solution by ultrasonic immersion, and the carrier is assisted by ultrasonication. The carrier after ultrasonication is washed with deionized water and then dried; (2) dispersing a non-precious metal salt in the deionized water in step (1), then adding the carrier prepared above into the deionized water, immersing for a period of time, and then calcining under a first protective gas atmosphere to obtain a nickel-based precursor; (3) fully breaking up the nickel-manganese mixed reagent and mixing it in a mixed solution of water and ethanol, placing the substrate precursor obtained in step (2) in the mixed solution for ultrasonic impregnation treatment, and after the impregnation, calcining under a second protective gas atmosphere to obtain a nickel-based alloy catalyst precursor; (4) The nickel-based alloy catalyst precursor obtained in step (3) is electrochemically deposited in an electrochemical workstation three-electrode system to obtain a sample named nickel-based alloy catalyst.
2. The method for preparing a nickel alloy type electrolytic catalyst film by electrodeposition according to claim 1, characterized in that: In step (1), the ultrasonic power used is 100W~300W, and the alkaline solution is one of KOH or NaOH.
3. The method for preparing a nickel alloy type electrolytic catalyst film by electrodeposition method according to claim 2, characterized in that: In step (1), the concentration of the alkali solution is 2 mol / L~8 mol / L, the ultrasonic frequency is 100~400W, and the ultrasonic time is 30~100min.
4. The method for preparing a nickel alloy electrolytic catalyst film by electrodeposition according to claim 1, characterized in that: In step S2, the calcination temperature is 300°C to 600°C, and the calcination time is 3 to 6 hours.
5. The method for preparing a nickel alloy type electrolytic catalyst film by electrodeposition method according to claim 4, characterized in that: The first protective atmosphere is one of nitrogen, argon or helium.
6. The method for preparing a nickel alloy electrolytic catalyst film by electrodeposition according to claim 1, characterized in that: In step S2, the non-precious metal is one of manganese salt, iron salt, cobalt salt or nickel salt.
7. The method for preparing a nickel alloy type electrolytic catalyst film by electrodeposition according to claim 1, characterized in that: In step (3), the volume ratio of ethanol to water is 3:1-6:1, and the calcination rate is 1°C / min-5°C / min.
8. The method for preparing a nickel alloy electrolytic catalyst film by electrodeposition according to claim 1, characterized in that: The second protective atmosphere is one of nitrogen, argon or helium.
9. The method for preparing a nickel alloy electrolytic catalyst film by electrodeposition according to claim 1, characterized in that: In step (4), the current density of electrochemical deposition is 400 mA cm-2~2000 mA cm-2, and the duration is 1~10 h.
10. The method for preparing a nickel alloy electrolytic catalyst film by electrodeposition according to claim 1, characterized in that: In step (4), the working electrode is a nickel-based alloy catalyst precursor, the reference electrode is a mercury oxide electrode, and the counter electrode is a platinum sheet electrode.