CN113174611B - Self-supporting Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode and preparation method thereof - Google Patents
Self-supporting Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-supporting Al 3 Ni 2 A Ni catalyzed hydrogen evolution electrode and a preparation method thereof belong to the technical field of hydrogen production by water electrolysis. The electrode of the catalytic hydrogen evolution electrode adopts low-cost metallic nickel and anhydrous AlCl 3 As a source of nickel and aluminum elements, al in molten salt is caused by molten salt electrolysis 3+ Reducing on the surface of the nickel matrix and alloying with nickel to form Al 3 Ni 2 Catalytic layer for preparing self-supporting Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode. The preparation method mainly comprises the following steps: (1) pretreatment of a nickel matrix; (2) Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 Coating to prepare Al 3 Ni 2 Ni electrode. The self-supporting catalytic hydrogen evolution electrode prepared by the preparation method has the advantages of good conductivity, stable use, high catalytic hydrogen evolution activity, simple preparation process, low cost and easy industrial large-scale popularization and application.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to a self-supporting hydrogen production deviceAl (aluminum alloy) 3 Ni 2 Ni catalyzed hydrogen evolution electrode and its preparation method.
Background
Energy is an important foundation for the development of the world and socioeconomic performance. With the progressive exhaustion of traditional fossil energy and the continuous aggravation of environmental pollution, the development and utilization of clean renewable energy has become a necessary choice for solving the energy crisis in all countries of the world. Hydrogen has the characteristics of high energy density and no pollution of reaction products, and is the most ideal energy carrier and substitute of fossil energy. Fossil fuel hydrogen production represented by methane steam reforming is the most economical hydrogen production method in industry at present, but the method still depends on fossil fuel and generates a large amount of carbon dioxide gas, and the energy crisis and the environmental problems caused by the energy crisis are not fundamentally solved.
Because the raw material used for producing hydrogen by electrolyzing water is water, the water is a renewable resource with rich earth content, is considered as the cleanest hydrogen production mode, and the purity of the produced hydrogen is higher. The electrodes adopted in the current industrial water electrolysis hydrogen production are mainly Rany Ni, low carbon steel and other materials, and have higher hydrogen evolution overpotential, so that higher electric energy loss is caused, and the large-scale industrial application of the water electrolysis hydrogen production is severely limited. Noble metal materials such as Pt and the like have high electrocatalytic hydrogen evolution activity, are optimal hydrogen evolution catalysts, but have low content in the crust, are expensive, and are difficult to popularize and apply in large scale. Therefore, research and development of the high-efficiency hydrogen evolution catalytic electrode is a key for developing the water electrolysis hydrogen production technology.
Among the non-noble metal electrode materials, ni-based materials exhibit higher hydrogen evolution catalytic activity. At present, ni-based catalytic materials are usually prepared by a solution hydrothermal synthesis method and a high-temperature solid-phase reduction method, the forms of the Ni-based catalytic materials are mostly powder, the Ni-based catalytic materials are required to be fully dispersed in a solvent, and then the Ni-based catalytic materials are fixed on a current collector by using binders such as Nafion solution, polyvinylidene fluoride organic solution and the like to prepare the cathode. The electrode has the following defects in the use process: (1) The catalyst has limited loading capacity, the binder can reduce the electron transmission capacity of the electrode material, and meanwhile, partial active sites of the catalyst can be coated by the binder, so that the catalytic performance of the catalyst is reduced; (2) In the electrolysis process, the active catalytic material is easy to fall off from the surface of the electrode, so that the stability of the hydrogen evolution catalytic electrode is poor; and (3) the electrode preparation process is complicated and the manufacturing cost is high.
Through searching, related patent documents disclose a preparation method for obtaining a hydrogen evolution electrode with relatively high electrode catalytic activity and stability, wherein the catalyst loading is improved, and the use of a binder is avoided or reduced. For example, chinese patent application No.: 201910824643.0, filing date: the invention is named as 2019, 9 and 2 days: a preparation method of a nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material. The preparation method in the application comprises the steps of firstly growing nickel hydroxide on the carbon cloth subjected to acid dipping modification treatment through a hydrothermal reaction, then carrying out phosphating treatment on the nickel hydroxide to obtain a nickel phosphide-carbon cloth three-dimensional self-supporting material, and then electrodepositing a nickel phosphorus alloy on the nickel phosphide-carbon cloth to prepare the nickel phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting electrode material with excellent hydrogen evolution performance without additional bonding and electrocatalytic. The electrode material prepared by the application can improve the catalytic activity and stability of the prepared electrode to a certain extent, but the preparation process is relatively complex and takes a long time.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects existing in the prior electrolytic water hydrogen evolution electrode preparation technology and provides a self-supporting Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode and its preparation method. Al with fine and uniform crystal grains grown on the surface of the nickel electrode and tightly combined with the nickel matrix is obtained by adopting a fused salt electrolysis method 3 Ni 2 Alloy plating to obtain Al with good catalytic activity 3 Ni 2 Ni hydrogen evolution electrode. Meanwhile, the preparation method mainly comprises the process of molten salt electrolysis, has simple process and lower cost, and is easy to popularize and apply industrially on a large scale.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the self-supporting Al of the invention 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode comprises the following steps:
(1) Pretreatment of a nickel matrix;
(2) Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 Coating to obtain Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode.
Further, in the step (2), al 3 Ni 2 The preparation method of the plating layer comprises the following steps: in the presence of AlCl 3 Performing constant potential electrolysis in the chloride molten salt, wherein the nickel matrix obtained in the step (1) is used as a working electrode, spectrally pure graphite is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode; after the electrolysis is finished, taking out the electrode, cooling, cleaning residual molten salt, and air-drying to obtain Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode.
Further, when electrolysis is carried out, the electrolysis process is carried out in a protective atmosphere of high-purity argon, and the electrolysis temperature is controlled to be 500-800 ℃; electrolytic potential relative to Ag + Ag is controlled to be-0.6 to-1.4V; the electrolysis time is 4-9 h.
Further, alCl in the adopted chloride molten salt 3 The molar content of (2) is 1% -10%.
Furthermore, the fused salt of chloride is one or two of lithium chloride, sodium chloride, potassium chloride, magnesium chloride and calcium chloride, and is dried in a vacuum oven for 40-48 hours at 250-300 ℃ before use; alCl 3 Is anhydrous AlCl without crystal water 3 。
In the step (1), the nickel substrate is nickel wires, nickel sheets, nickel screens or foam nickel, the nickel content is controlled to be more than 99.9%, and grease and oxide layers on the surface of the nickel substrate are removed, cleaned, air-dried and dried for standby before use.
Further, in the step (1), when the nickel matrix is nickel wire or nickel sheet, firstly, sequentially adopting 30-mesh, 60-mesh and 300-mesh sand paper to mechanically polish the nickel matrix so that the surface of the nickel matrix is metallic and then adopting deionized water to wash the nickel matrix clean; respectively ultrasonically cleaning in alkali liquor for 25-35 min, and ultrasonically cleaning in absolute ethyl alcohol for 15-25 min to remove grease on the surface of the nickel matrix; and finally, washing with deionized water, naturally air-drying, and storing in a vacuum drying oven for later use.
Furthermore, during cleaning, the alkali liquor adopts a mixed solution of sodium hydroxide and sodium carbonate.
Further, in the step (1), when the nickel matrix is pretreated, and the nickel matrix is nickel mesh or foam nickel, firstly, ultrasonic soaking is carried out in acetone for 35-45 min to carry out oil removal treatment; then ultrasonic cleaning is carried out on hydrochloric acid with the concentration of 3-5 mol/L for 10-20 min, and an oxide layer on the surface of the hydrochloric acid is removed; and finally, repeatedly washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH value is neutral, naturally airing, and then storing in a vacuum drying oven for standby.
The self-supporting Al of the invention 3 Ni 2 The Ni catalytic hydrogen evolution electrode is prepared by the preparation method and comprises a nickel matrix and Al plated on the surface of the nickel matrix 3 Ni 2 A catalytic layer.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The self-supporting Al of the invention 3 Ni 2 According to the preparation method of the Ni catalytic hydrogen evolution electrode, the whole preparation process is optimized, and particularly Al can be directly grown on the surface of nickel through molten salt electrolysis 3 Ni 2 Catalytic coating to obtain self-supporting Al 3 Ni 2 The Ni catalytic hydrogen evolution electrode does not need to use a binder, greatly improves the conductivity of the electrode, reduces the load transfer resistance in the process of the electrolytic water hydrogen evolution reaction, and has higher stability.
(2) The self-supporting Al of the invention 3 Ni 2 According to the preparation method of the Ni catalytic hydrogen evolution electrode, the bonding strength between the plating layer and the nickel matrix is further improved by optimizing the technological parameters of electrolysis, so that the falling-off phenomenon of the catalytic layer in the hydrogen evolution reaction process is effectively prevented, and the stability of the obtained electrode is greatly improved.
(3) The self-supporting Al of the invention 3 Ni 2 On one hand, the preparation method of the Ni-catalyzed hydrogen evolution electrode adopts low-cost nickel and anhydrous AlCl 3 As preparation of Al 3 Ni 2 The raw materials of the Ni catalytic hydrogen evolution electrode are beneficial to reducing the manufacturing cost of the electrode and improving the economic benefit. On the other hand, the electrode only comprises the step of molten salt electrolysis in the main preparation process, has simple process and lower cost, and is easy to popularize and apply industrially on a large scale.
(4) The self-supporting Al of the invention 3 Ni 2 Ni-catalyzed hydrogen evolution electrode comprising nickel-based Al obtained by molten salt electrolysis 3 Ni 2 The coating has a three-dimensional nano/micron structure, is well combined with a nickel matrix, is not easy to fall off in the use process, and meanwhile, the prepared Al 3 Ni 2 The Ni catalytic hydrogen evolution electrode has large specific surface area, more catalytic active points, excellent catalytic hydrogen evolution performance and good engineering application prospect.
Drawings
FIG. 1 shows the self-supporting electrode surface Al prepared in example 1 of the present invention 3 Ni 2 An X-ray diffraction pattern of the catalytic layer;
FIG. 2 shows the self-supporting electrode surface Al prepared in example 1 of the present invention 3 Ni 2 Scanning electron microscope pictures of the catalytic layer;
FIG. 3 is a self-supporting Al layer prepared in example 1 of the present invention 3 Ni 2 The test method is a linear potential scanning method, and the test conditions are as follows: the three electrodes are working electrodes, platinum sheets are auxiliary electrodes, saturated mercurous sulfate is a reference electrode, and the electrolyte adopts H with the mass concentration of 0.5mol/L 2 SO 4 Solution with scanning rate of 5 mV.s -1 Scanning range 0 to-0.9V (relative to standard hydrogen electrode);
FIG. 4 shows a free-standing Al composition prepared in example 1 of the present invention 3 Ni 2 A Tafil slope diagram of the Ni electrode, the nickel wire and the platinum wire electrode;
FIG. 5 shows a free-standing Al composition prepared in example 1 of the present invention 3 Ni 2 Electrochemical Impedance Spectroscopy (EIS) of Ni electrode and nickel wire electrode, still employing three electrode system at 0.5mol/L H 2 SO 4 In solution, measuring with a measuring range of 100KHz to 0.01Hz.
FIG. 6 is a self-supporting Al layer prepared in example 1 of the present invention 3 Ni 2 Timing potential graph of Ni electrode, test conditions: maintaining the cathode current density of 10 mA.cm -2 H at 0.5mol/L 2 SO 4 The solution was continuously electrolyzed for 36h.
Detailed Description
At present, ni-based catalytic materials are widely used for researching and developing high-efficiency hydrogen evolution catalytic electrodes. However, the hydrogen evolution electrode prepared by adopting the Ni-based material has some disadvantages. On the one hand, the form of Ni-based catalytic material used for preparing the electrode is mostly powder, and a non-conductive binder is needed to be fixed on a current collector, so that the prepared cathode catalytic hydrogen evolution activity is poor easily. On the other hand, in the use process of the electrode, the active catalytic material is easy to fall off from the surface of the electrode along with the occurrence of multiple electrolytic reactions, so that the stability of the hydrogen evolution catalytic electrode is poor, the service life is short, and the cost is high. Meanwhile, the conventional preparation process is complex and tedious, and the manufacturing cost is high. Therefore, the preparation method of the self-supporting hydrogen evolution electrode with good conductivity, large active area, high active component load and simple process is continuously explored, thereby being beneficial to promoting the large-scale industrial application of water electrolysis hydrogen production. The preparation method provided by the invention has the main advantages that the Al is obtained by adopting a fused salt electrolysis method 3 Ni 2 The alloy coating has uniform chemical composition, can be tightly combined with a nickel matrix, and is not easy to fall off in the use process. Meanwhile, the hydrogen evolution electrode has a nano/micron grain structure and excellent catalytic activity of electrolytic water hydrogen evolution reaction.
Specifically, the preparation method of the invention comprises the following steps:
(1) Pretreatment of a nickel matrix;
the nickel matrix adopts nickel wires, nickel sheets, nickel screens or foam nickel, and the nickel content is controlled to be more than 99.9%. When the nickel matrix is nickel wire or nickel sheet, firstly, 30 mesh, 60 mesh and 300 mesh sand paper is adopted to mechanically polish in turn, so that the surface of the nickel matrix is metallic and then washed clean by deionized water. And respectively ultrasonically cleaning the nickel matrix in alkali liquor for 25-35 min, and ultrasonically cleaning the nickel matrix in absolute ethyl alcohol for 15-25 min to remove grease on the surface of the nickel matrix. Wherein, the alkali liquor adopts a mixed solution of 8 percent of sodium hydroxide by mass and 3 percent of sodium carbonate by mass. And finally, washing with deionized water, naturally air-drying, and storing in a vacuum drying oven for later use.
When the nickel matrix is nickel screen or foam nickel, firstly, carrying out ultrasonic soaking in acetone for 35-45 min for degreasing treatment; then ultrasonic cleaning is carried out on hydrochloric acid with the concentration of 3-5 mol/L for 10-20 min, and an oxide layer on the surface of the hydrochloric acid is removed; and finally, repeatedly washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH value is neutral, naturally airing, and then storing in a vacuum drying oven for standby.
(2) Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 Coating to obtain Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode.
Al 3 Ni 2 The preparation method of the plating layer comprises the following steps: in the presence of AlCl 3 Constant potential electrolysis is carried out in the chloride molten salt, wherein AlCl is adopted in the chloride molten salt 3 The molar content of (2) is 1-10%, the nickel matrix obtained in the step (1) is used as a working electrode, the spectrum pure graphite is used as an auxiliary electrode, ag/AgCl is used as a reference electrode, and the nickel matrix is placed in chloride molten salt, and the electrolysis potential (relative to Ag) is controlled + Ag) is-0.6 to-1.4V, the electrolysis temperature is 500-800 ℃, and the continuous electrolysis is carried out for 4-9 h in the high-purity Ar atmosphere. After the electrolysis is finished, taking out the working electrode after the furnace temperature is cooled to room temperature, washing the surface residues of the working electrode with deionized water, and naturally air-drying to obtain Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode.
Deposited Al 3 Ni 2 The plating layer is critical to the performance of the finally obtained electrode, and in order to obtain the Ni-based self-supporting electrode with high catalytic activity and high stability, the technological parameters of the electrolysis process need to be strictly controlled so as to control the phase composition of the obtained alloy, thereby obtaining single Al with strong catalytic activity 3 Ni 2 On the one hand, the phase can ensure the bonding strength between the plating layer and the nickel matrix when being used for manufacturing the hydrogen evolution electrodeThe degree of the coating is effectively prevented from falling off; on the other hand, al obtained by molten salt electrolysis 3 Ni 2 The alloy coating has uniform chemical composition, is tightly combined with a nickel matrix, has a nano/micron grain structure, and the prepared electrode has good conductivity, large active area, high active component load and excellent electrolytic water hydrogen evolution reaction catalytic activity.
In addition, the fused salt of chloride used in the invention is one or two of lithium chloride, sodium chloride, potassium chloride, magnesium chloride and calcium chloride, and the fused salt of chloride is dried in a vacuum oven for 40-48 hours at 250-300 ℃ before use; alCl 3 Is anhydrous AlCl without crystal water 3 By using cheaper nickel and anhydrous AlCl 3 As preparation of Al 3 Ni 2 The raw materials of the Ni catalytic hydrogen evolution electrode are beneficial to reducing the manufacturing cost of the electrode and improving the economic benefit. Meanwhile, the main preparation process only comprises the step of molten salt electrolysis, and the method is simple in process, low in cost and easy to popularize and apply in a large scale.
The invention is further described below in connection with specific embodiments.
Example 1
Self-supporting Al of the present embodiment 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode comprises the following steps:
(1) Pretreatment of nickel substrates
Selecting nickel wires with the diameter of 1mm, firstly adopting 30-mesh, 60-mesh and 300-mesh sand paper to mechanically polish in sequence, and flushing the surfaces of the nickel wires with deionized water after the surfaces of the nickel wires are metallic; respectively ultrasonically cleaning in alkali liquor for 30min, and ultrasonically cleaning in absolute ethyl alcohol for 20min to remove grease on the surface of a substrate, wherein the alkali liquor is a mixed solution of 8% sodium hydroxide and 3% sodium carbonate in mass fraction; and finally, washing with deionized water, naturally air-drying, and storing in a vacuum drying oven for later use.
(2) Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 Preparation of Al coating 3 Ni 2 Ni electrode
Uniformly mixing the dried sodium chloride and potassium chloride according to a molar ratio of 1:1, and then packagingPutting into corundum crucible, heating to 700 deg.C under high purity Ar protection in tubular furnace to melt, adding 2mol% AlCl into the obtained chloride molten salt 3 The treated metallic nickel wire is used as a working electrode, the spectrum pure graphite is used as an auxiliary electrode, ag/AgCl is used as a reference electrode, and the electric potential is controlled to be-1.3V, and the continuous electrolysis is carried out for 5 hours in the high-purity Ar atmosphere. After the electrolysis is finished, taking out the working electrode after the furnace temperature is cooled to room temperature, washing the surface residues of the working electrode with deionized water, and naturally air-drying to obtain Al 3 Ni 2 Ni electrode.
(3)Al 3 Ni 2 Phase composition and micro morphology of Ni electrode
The prepared Al is subjected to X-ray diffractometer 3 Ni 2 The phase composition of the Ni electrode was analyzed, and the obtained diffraction pattern (XRD) was shown in FIG. 1; SSX-550 type scanning electron microscope pair prepared Al 3 Ni 2 The morphology of the Ni electrode was observed, and a Scanning Electron Microscope (SEM) photograph was obtained as shown in FIG. 2.
(4)Al 3 Ni 2 Catalytic hydrogen evolution performance test of Ni electrode
Test method of linear potential scanning is adopted to test metallic nickel wire, platinum wire and Al obtained in step (2) 3 Ni 2 The Ni electrode was subjected to performance test. The testing process adopts a three-electrode system: the three electrodes are working electrodes, platinum sheets are auxiliary electrodes, saturated mercurous sulfate is a reference electrode, and the electrolyte adopts H with the mass concentration of 0.5mol/L 2 SO 4 The solution was tested for its catalytic hydrogen evolution performance on an electrochemical workstation (PARSTAT 2273, USA) at a scan rate of 5 mV.s -1 The scan range was 0 to-0.9V (vs. standard hydrogen electrode), and the test results correspond to fig. 3 and 4.
(5)Al 3 Ni 2 Conductivity test of Ni electrode
A three-electrode system is adopted: nickel wire or Al obtained in step (2) 3 Ni 2 The Ni electrode is a working electrode, the platinum sheet is an auxiliary electrode, and the saturated mercurous sulfate is a reference electrode. The electrolyte adopts H with the mass concentration of 0.5mol/L 2 SO 4 Solutions were measured on an electrochemical workstation (PARSTAT 2273, USA)The conductivity was tested: the Electrochemical Impedance Spectroscopy (EIS) of the electrode was measured at a frequency range of 100KHz to 0.01Hz at a voltage of-75 mV (relative to a standard hydrogen electrode) with an amplitude of 5mV to characterize its conductivity, and the test results correspond to fig. 5.
(6)Al 3 Ni 2 Stability test of Ni electrode
A three-electrode system is adopted: al obtained in the step (2) 3 Ni 2 The Ni electrode is a working electrode, the platinum sheet is an auxiliary electrode, and the saturated mercurous sulfate is a reference electrode. The electrolyte adopts H with the mass concentration of 0.5mol/L 2 SO 4 Solutions recorded on electrochemical workstation (PARSTAT 2273, USA) at 10mA.cm -2 The time-dependent potential profile of the current density is used to characterize the stability of the electrode, and the test results correspond to fig. 6.
Example 2
Self-supporting Al of the present embodiment 3 Ni 2 The preparation procedure of the Ni-catalyzed hydrogen evolution electrode was essentially as in example 1, with the main differences: in the embodiment, the nickel substrate adopts a nickel sheet, and is ultrasonically cleaned in alkali liquor for 25min and in absolute ethyl alcohol for 25min during pretreatment operation.
Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 In the plating process, lithium chloride is adopted as chloride molten salt, a vacuum drying oven is used for 48 hours at the temperature of 250 ℃, and AlCl with the molar content of 1% is added 3 When electrolysis is performed, the electrolysis potential is controlled (relative to Ag + Ag) is-1.4V, the electrolysis temperature is 500 ℃, and the electrolysis duration is 4 hours.
Al on the hydrogen evolution electrode prepared by the method 3 Ni 2 The structural characterization and performance of the catalytic layer were the same as in example 1, and the results were substantially the same as in example 1.
Example 3
Self-supporting Al of the present embodiment 3 Ni 2 The preparation procedure of the Ni-catalyzed hydrogen evolution electrode was essentially as in example 1, with the main differences: in the embodiment, the nickel substrate adopts a nickel sheet, and is ultrasonically cleaned in alkali liquor for 35min and in absolute ethyl alcohol for 15min during pretreatment operation.
Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 In the plating process, magnesium chloride and calcium chloride are adopted as chloride fused salt, and the vacuum drying oven is carried out for 40 hours at the temperature of 250-300 ℃, and then AlCl with the molar content of 10% is added 3 When electrolysis is performed, the electrolysis potential is controlled (relative to Ag + Ag) is-0.6V, the electrolysis temperature is 800 ℃, and the electrolysis duration is 9h.
Al on the hydrogen evolution electrode prepared by the method 3 Ni 2 The structural characterization and performance of the catalytic layer were the same as in example 1, and the results were substantially the same as in example 1.
Example 4
Self-supporting Al of the present embodiment 3 Ni 2 The preparation procedure of the Ni-catalyzed hydrogen evolution electrode was essentially as in example 1, with the main differences: in the embodiment, a nickel substrate adopts a nickel screen, and when the pretreatment operation is performed, the nickel substrate is firstly subjected to ultrasonic soaking in acetone for 30min for degreasing treatment; then ultrasonic cleaning is carried out for 15min in 4mol/L hydrochloric acid, and an oxide layer on the surface of the hydrochloric acid is removed; and finally, repeatedly washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH value is neutral, naturally airing, and then storing in a vacuum drying oven for standby.
Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 In the plating process, potassium chloride is adopted as chloride molten salt, a vacuum drying oven is used for 45 hours at the temperature of 280 ℃, and AlCl with the molar content of 6% is added 3 When electrolysis is performed, the electrolysis potential is controlled (relative to Ag + Ag) is-1.0V, the electrolysis temperature is 700 ℃, and the electrolysis duration is 6h.
Al on the hydrogen evolution electrode prepared by the method 3 Ni 2 The structural characterization and performance of the catalytic layer were the same as in example 1, and the results were substantially the same as in example 1.
Example 5
Self-supporting Al of the present embodiment 3 Ni 2 The preparation procedure of the Ni-catalyzed hydrogen evolution electrode was essentially as in example 4, with the main differences: in the embodiment, the nickel matrix adopts foam nickel, and when the pretreatment operation is carried out, the nickel matrix is firstly immersed in acetone for 45min in an ultrasonic manner to carry out oil removal treatment; then ultrasonic cleaning is carried out for 10min in 5mol/L hydrochloric acid, and an oxide layer on the surface of the hydrochloric acid is removed; finally sequentially using absolute ethyl alcoholAnd repeatedly washing with deionized water for several times until the pH is neutral, naturally air-drying, and then storing in a vacuum drying oven for standby.
Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 In the plating process, calcium chloride is adopted as chloride fused salt, a vacuum drying box is used for 47 hours at the temperature of 250-300 ℃, and AlCl with the molar content of 8% is added 3 When electrolysis is performed, the electrolysis potential is controlled (relative to Ag + Ag) is-0.8V, the electrolysis temperature is 600 ℃, and the electrolysis duration is 5h.
Al on the hydrogen evolution electrode prepared by the method 3 Ni 2 The structural characterization and performance of the catalytic layer were the same as in example 1, and the results were substantially the same as in example 1.
Example 6
Self-supporting Al of the present embodiment 3 Ni 2 The preparation procedure of the Ni-catalyzed hydrogen evolution electrode was essentially as in example 4, with the main differences: in the embodiment, the nickel matrix adopts foam nickel, and when the pretreatment operation is carried out, the nickel matrix is firstly immersed in acetone for 35min in an ultrasonic manner to carry out oil removal treatment; then ultrasonically cleaning the surface of the substrate for 20min in 3mol/L hydrochloric acid to remove an oxide layer on the surface of the substrate; and finally, repeatedly washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH value is neutral, naturally airing, and then storing in a vacuum drying oven for standby.
Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 In the plating process, sodium chloride and calcium chloride are adopted as chloride fused salt, and the vacuum drying oven is used for 44 hours at the temperature of 250-300 ℃, and then AlCl with the molar content of 4% is added 3 When electrolysis is performed, the electrolysis potential is controlled (relative to Ag + Ag) is-0.9V, the electrolysis temperature is 550 ℃, and the electrolysis duration is 7h.
Al on the hydrogen evolution electrode prepared by the method 3 Ni 2 The structural characterization and performance of the catalytic layer were the same as in example 1, and the results were substantially the same as in example 1.
Although the present invention has been described above with reference to the embodiments and the drawings, the scope of the present invention is not limited to the disclosure of the embodiments and the drawings. The above-described embodiments are intended to be illustrative only and not limiting, and many alternatives, modifications and variations may be made by those skilled in the art without departing from the spirit of the invention and scope of the appended claims, which are to be considered as within the scope of the invention.
Claims (8)
1. Self-supporting Al 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode is characterized by comprising the following steps of: the method comprises the following steps:
(1) Pretreatment of a nickel matrix;
(2) Molten salt electrolytic deposition of Al on nickel substrate surface 3 Ni 2 Coating to obtain Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode;
Al 3 Ni 2 the preparation method of the plating layer comprises the following steps: in the presence of AlCl 3 Performing constant potential electrolysis in the chloride molten salt, wherein the nickel matrix obtained in the step (1) is used as a working electrode, spectrally pure graphite is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode; when electrolysis is carried out, the electrolysis process is carried out in a protective atmosphere of high-purity argon, and the electrolysis temperature is controlled to be 500-800 ℃; electrolytic potential relative to Ag + Ag is controlled to be-0.6 to-1.4V; the electrolysis time is 4-9 h; after the electrolysis is finished, taking out the electrode, cooling, cleaning residual molten salt, and air-drying to obtain Al 3 Ni 2 Ni catalyzed hydrogen evolution electrode.
2. A self-supporting Al according to claim 1 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode is characterized by comprising the following steps of: alCl in the adopted chloride molten salt 3 The molar content of (2) is 1% -10%.
3. A self-supporting Al according to claim 2 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode is characterized by comprising the following steps of: the fused salt of chloride is one or two of lithium chloride, sodium chloride, potassium chloride, magnesium chloride and calcium chloride, and is dried in a vacuum oven for 40-48 h at 250-300 ℃ before use; alCl 3 Is anhydrous AlCl without crystal water 3 。
4. A self-supporting Al according to any one of claims 1-2 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode is characterized by comprising the following steps of: in the step (1), the nickel matrix adopts nickel wires, nickel sheets, nickel screens or foam nickel, the nickel content is controlled to be more than 99.9%, and grease and an oxide layer on the surface of the nickel matrix are removed before use, and the nickel matrix is cleaned, air-dried and dried for standby.
5. A self-supporting Al according to claim 4 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode is characterized by comprising the following steps of: in the step (1), when the nickel matrix is nickel wires or nickel sheets, firstly, sequentially adopting 30-mesh, 60-mesh and 300-mesh sand paper to mechanically polish the nickel matrix so that the surface of the nickel matrix is metallic and then adopting deionized water to wash the nickel matrix clean; respectively ultrasonically cleaning in alkali liquor for 25-35 min, and ultrasonically cleaning in absolute ethyl alcohol for 15-25 min to remove grease on the surface of the nickel matrix; and finally, washing with deionized water, naturally air-drying, and storing in a vacuum drying oven for later use.
6. A self-supporting Al according to claim 5 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode is characterized by comprising the following steps of: during cleaning, the alkali liquor adopts a mixed solution of sodium hydroxide and sodium carbonate.
7. A self-supporting Al according to claim 4 3 Ni 2 The preparation method of the Ni catalytic hydrogen evolution electrode is characterized by comprising the following steps of: in the step (1), when the nickel matrix is nickel mesh or foam nickel, firstly, carrying out ultrasonic soaking in acetone for 35-45 min for degreasing treatment; then ultrasonic cleaning is carried out on the mixture for 10 to 20 minutes in 3 to 5mol/L hydrochloric acid, and an oxide layer on the surface of the mixture is removed; and finally, repeatedly washing with absolute ethyl alcohol and deionized water for a plurality of times until the pH value is neutral, naturally airing, and then storing in a vacuum drying oven for standby.
8. Self-supporting Al 3 Ni 2 The Ni catalytic hydrogen evolution electrode is characterized in that: by means of e.g. weightsThe process according to any one of claims 1 to 7, which comprises a nickel substrate and Al plated on the surface of the nickel substrate 3 Ni 2 A catalytic layer.
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