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CN-121992426-A - High-activity/stability alkaline water electrolysis hydrogen production electrode and preparation method thereof

CN121992426ACN 121992426 ACN121992426 ACN 121992426ACN-121992426-A

Abstract

Aiming at the field of electrode construction in the alkaline water electrolysis hydrogen production industry, the catalytic electrode prepared by the prior method has the problems of poor activity, poor stability and the like. The invention discloses a preparation method of an alkaline water hydrogen evolution electrode with a flat and compact surface morphology. The preparation method comprises the specific processes of (1) preparing a compact catalyst precursor on the surface of a current collector in a pulse electroplating mode, (2) performing densification treatment, (3) constructing an active material catalytic layer by electrochemical ultrashort pulse, and (4) performing secondary annealing to finally prepare the high-activity and high-stability electrolytic water gassing catalytic electrode.

Inventors

  • Request for anonymity
  • ZHANG LING
  • WU WANGYANG

Assignees

  • 张伶
  • 重庆大学

Dates

Publication Date
20260508
Application Date
20241107

Claims (7)

  1. 1. A high-activity/stability alkaline water electrolysis hydrogen production electrode and a preparation method thereof. The invention is realized by (1) preparing a layer of compact catalyst on the surface of a current collector by a pulse electroplating mode, (2) performing densification treatment, (3) constructing an active material catalytic layer by electrochemical ultrashort pulse, and (4) performing rapid annealing in air to finally prepare the high-activity and high-stability electrolytic water gassing catalytic electrode.
  2. 2. The pulse plating structured dense and flat electrolytic water gassing electrode according to claim 1, characterized by comprising the steps of: (1) Preparing a catalytic layer precursor with a flat morphology by adopting a pulse electroplating mode; (2) Densification treatment; (3) Constructing an active substance catalytic layer by electrochemical ultrashort pulse; (4) And (5) carrying out secondary annealing to obtain the compact catalytic layer.
  3. 3. The method for constructing the compact and flat electrolytic water gassing electrode by pulse plating according to claim 1 or 2, wherein the pulse plating in the step (1) has plating parameters of cathode current density of-40 to-400 mA/cm 2 , cathode time of 0.01-0.07 s, anode current density of 10-50 mA/cm 2 , anode time of 0.01-0.07 s, and repeated electrodeposition of 6000-12000 times.
  4. 4. The method for manufacturing the dense and flat electrolytic water gassing electrode by pulse plating according to claim 1 or 2, wherein the densification treatment in the step (2) is to raise the temperature of the prepared catalytic electrode precursor to 600-900 ℃ at 5-10 ℃ per min in a reducing atmosphere, and after the catalytic electrode precursor is maintained for a period of time, slowly lowering the temperature at a rate of 5-20 ℃ per min.
  5. 5. The method for constructing the compact and flat electrolytic water gassing electrode by pulse plating according to claim 1 or 2, wherein the step (3) of constructing the active material catalytic layer by electrochemical ultrashort pulse is to immerse the electrode after densification in electrolyte and construct a transition metal active layer on the surface of the catalytic layer by adopting a secondary electrodeposition mode.
  6. 6. The method for constructing the compact and flat electrolytic water gassing electrode by pulse plating according to claim 1 or 2, wherein the rapid annealing in the air in the step (4) adopts a secondary annealing mode to improve the density and mechanical strength of the catalytic layer.
  7. 7. A high activity/stability alkaline water electrolytic hydrogen-producing electrode as claimed in claim 1 or 2 or 3, wherein said current collector is nickel woven mesh nickel diagonal draw net, nickel felt, cobalt woven net, cobalt diagonal draw net one or more of cobalt felt, iron woven mesh, iron inclined pull mesh, iron felt, stainless steel woven mesh, stainless steel inclined pull mesh, stainless steel felt, titanium woven mesh, titanium inclined pull mesh and titanium felt.

Description

High-activity/stability alkaline water electrolysis hydrogen production electrode and preparation method thereof 1. Technical field: the invention relates to a high-activity/stability alkaline water electrolysis hydrogen production electrode and a preparation method thereof, in particular to a technology capable of preparing large-area catalytic electrodes in batches. 2. The background technology is as follows: Development of clean, efficient, renewable alternative energy sources is a global problem to be solved. Among the alternative clean energy sources, hydrogen energy has the characteristics of wide sources, high energy density, no pollution, zero carbon emission and the like, and is considered as the clean energy source with the most development potential in the 21 st century. The main sources of the hydrogen energy in the present stage are natural gas reforming hydrogen production, coal gasification hydrogen production, naCl electrolysis hydrogen production and alkaline water electrolysis water hydrogen production. In a plurality of hydrogen production methods, the industrial application of the alkaline water electrolysis water hydrogen production technology utilizing renewable energy sources has important scientific and social significance for promoting the development of hydrogen energy economy. The hydrogen bond energy in the water molecules is up to 498.7kJ/mol, and the speed of hydrogen production by alkaline water electrolysis is limited by the reaction speed of a cathode and an anode. Thus, the development of high performance electrolyzed water gassing electrodes is extremely important for hydrogen production processes. The traditional electrolytic water gassing electrode is mainly a noble metal-based electrocatalyst, such as Pt/C, ruO 2, irO 2 and the like, has high activity, but is expensive and has unsatisfactory stability. This results in high cost of hydrogen production by water electrolysis and difficulty in industrialization. Therefore, the development of the non-noble metal-based electrolyzed water gas-evolving catalytic electrode with high activity and high stability is a key for realizing the industrial application of the electrolyzed water hydrogen production technology. Among all non-noble metal hydrogen evolution catalytic electrodes, the gas evolution electrode formed by the interface of metal and oxide has excellent water electrolysis performance. However, the conventional alkaline water electrolysis gassing electrode is prepared mainly by the following two methods. The first is to prepare catalyst powder and then adhere the catalyst powder to a current collector through Nafion and other adhesives to prepare the electrolytic water gassing electrode. N, P co-doped graphene coated CoP is prepared as Dapeng Cao and used as a catalyst for preparing hydrogen by water electrolysis. Patent number CN 115463676A discloses preparation and application of a graphene oxide supported Ru-CoP based aerogel electrolyzed water catalyst. Patent number CN 114232138A discloses the preparation and application of an iron-cobalt-phosphorus-nitrogen doped carbon nanofiber water electrolysis catalyst. The second method is to directly prepare an electrolytic water gassing electrode on a current collector by a hydrothermal method. And preparing the electrolytic water gassing electrode with a communicating pore canal structure by a NaOH in-situ etching method. Patent number CN 113684494A discloses a ternary transition metal electrolytic water hydrogen evolution catalyst composite material prepared by adopting a hydrothermal method and a preparation method thereof. Patent number CN 114411188A discloses a method for growing cobalt-based nanowire array on porous conductive substrate, increasing specific surface area of electrode material, and using the electrode material as hydrogen-producing electrode by alkaline water electrolysis after electrochemical activity treatment. However, the conventional catalytic electrode has the problems of poor binding force between the catalytic layer and the current collector and low structural strength of the catalytic layer, so that the conventional catalytic electrode has poor activity and poor stability, and is difficult to apply to industrial production. Therefore, the alkaline water electrolysis industry is in urgent need of high-activity and high-stability electrolysis water gas-evolving catalytic electrode. In the patent, an electrolytic water gassing catalytic electrode with the surface of the catalytic layer communicated with each other is prepared by adopting a method of combining pulse electrodeposition with oxidation etching. And electrodepositing metal ions in the solution onto the surface of the electrode through pulse electrodeposition to form a catalytic layer precursor, improving the mechanical strength of the catalytic layer on the surface of the catalytic electrode through densification treatment, and finally preparing the catalytic layer with high mechanic