CN110408950B - Electrolytic water cathode based on microscopic blasting process and preparation method thereof - Google Patents
Electrolytic water cathode based on microscopic blasting process and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electrolytic water cathode based on a microscopic blasting process and a preparation method thereof, belonging to the technical field of hydrogen production by electrolytic water. The invention discloses an electrolytic water cathode, which comprises a metal substrate and a porous metal target component which is coated on the metal substrate and is integrated with the metal substrate. The invention also discloses a preparation method of the electrolytic water cathode, which comprises the steps of spraying the yolk structure composite metal particles on the cleaned conductive substrate in a plasma thermal spraying mode, and then selectively corroding to form metal nano particles on the metal substrate and remove residual non-target components to obtain the electrolytic water cathode. The method has simple process, and can greatly improve the catalytic performance of the electrode compared with the traditional process.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to an electrolytic water cathode based on a microscopic blasting process and a preparation method thereof.
Background
Hydrogen energy has become a scientific and social focus in recent years as a highly efficient clean energy source. At present, the hydrogen energy industry presents a high-speed development situation on the global scale, and the hydrogen energy industry comprises a whole industrial chain of hydrogen production, storage, transportation, handling and utilization. The hydrogen preparation is also concerned as the upstream end of the hydrogen energy industry chain, especially with the effective integration of electricity-abandoning resources and nuclear power resources, the hydrogen with low cost can be obtained by alkaline water electrolysis hydrogen production in the future, and powerful support can be provided for the development of hydrogen fuel cell automobiles for the downstream end.
The biggest technical problem of alkaline water electrolysis hydrogen production at present is that the electric energy consumption is too high under the condition of unit hydrogen production quantity. From the distribution analysis of the electric energy consumption in the water electrolysis process, the electric energy consumption is mainly reflected in the overpotential of the cathode and anode reactions. The electrode overpotential is expressed on one hand in the intrinsic catalytic performance of the electrode catalyst and on the other hand in the number of effective catalytic active sites on the electrode surface. At present, in the industry, the cathode of the electrolyzed water is mainly made of nickel-based metal materials, on one hand, due to the alkali liquor corrosion resistance of nickel, on the other hand, the nickel has good hydrogen evolution catalytic activity. The preparation method of the nickel-based electrode mainly comprises electroplating, plasma thermal spraying, powder sintering and the like, wherein the plasma thermal spraying is to spray metal nickel powder on a metal substrate by high-temperature melting. Due to the close contact between the molten metal and a large number of gaps among nickel powder, the nickel-based electrode obtained by plasma thermal spraying has good electrolysis durability and certain catalytic activity, but the electrode still does not meet the high requirement of further reducing the electric energy consumption of the electrolysis water.
Disclosure of Invention
The invention aims to provide an electrolytic water cathode based on a microscopic blasting process and a preparation method thereof, which are used for further greatly reducing the energy consumption of electrolytic water.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an electrolytic water cathode based on a microscopic blasting process, comprising: the porous metal target component is coated on the surface of the metal substrate and is integrated with the metal substrate.
Further, the metal substrate is selected from one of nickel mesh, nickel foam, nickel sheet, stainless steel mesh, iron foam, stainless steel sheet, copper mesh, copper foam, copper sheet, cobalt mesh, cobalt foam and cobalt sheet.
Further, the porous metal target component is composed of metal nanoparticles, and the diameter of each metal nanoparticle is 5-1000 nanometers.
The invention also provides a preparation method of the electrolytic water cathode based on the microscopic blasting process, which comprises the following steps:
s1, cleaning a metal substrate;
s2, spraying yolk structure composite metal particles on the cleaned metal substrate;
and S3, soaking the metal substrate processed in the step S2 in a selective corrosion solution for selective corrosion to obtain a metal substrate coated with metal nano particles on the surface, and washing and drying to obtain the electrolytic water cathode.
Further, in step S2, the diameter of the yolk structure composite metal particle is 5 to 200 micrometers, the yolk structure composite metal particle includes a surface layer metal target component and an inner layer non-target component, the surface layer metal target component is one of nickel, titanium and nickel-molybdenum alloy, the inner layer non-target component is one of aluminum, zinc, copper, carbon, polystyrene and silicon, and the mass fraction of the surface layer metal target component in the yolk structure composite metal particle is 40 to 90%.
Further, the cleaning treatment in step S1 is specifically to place the metal substrate in an acetone solution for ultrasonic cleaning for 10-30 minutes, and then clean with ethanol until the grease layer on the surface of the metal substrate is removed; and then, placing the metal substrate in a hydrochloric acid solution with the concentration of 1-6 mol/L for 5-25 minutes by ultrasonic treatment, standing for 10-30 minutes, and then cleaning with distilled water until a surface oxide layer of the metal substrate is removed.
Further, in the step S2, the spraying is specifically to spray the yolk structure composite metal particles onto the surface of the metal substrate after the cleaning treatment by using a plasma thermal spraying method under a protective atmosphere of argon and hydrogen.
Further, in the step S3, the soaking time is 20-30 hours, and the selective etching solution comprises the following components in percentage by mass: 15-40% of sodium hydroxide, 5-20% of ammonium persulfate and the balance of water.
Compared with the prior art, the invention has the following advantages and effects: the invention provides a high-performance electrolytic water cathode obtained by means of plasma thermal spraying through a microscopic blasting process. In the plasma thermal spraying process, the inner layer non-target component with lower gasification temperature is gasified at high temperature and expands in volume, so that the molten state surface layer metal target component which is difficult to gasify in the yolk structure composite metal particles generates a micro blasting effect, the electrochemical surface area of the porous metal target component on the surface of the metal substrate is effectively improved, and the effective catalytic active sites are increased. The method has simple process, and can greatly improve the catalytic performance of the electrode compared with the traditional process.
Drawings
FIG. 1 is a scanning electron microscope picture of the cathode surface of the electrolyzed water of example 1 of the present invention;
FIG. 2 is a plot of a three-electrode electrolytic water linear voltammetric sweep of examples 1-3 of the present invention and comparative examples;
FIG. 3 is a scanning electron microscope picture of the cathode surface of the electrolyzed water of the comparative example of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The invention provides an electrolytic water cathode based on a microscopic blasting process, which comprises a metal substrate and a porous metal target component, wherein the porous metal target component is coated on the surface of the metal substrate and is integrated with the metal substrate.
The metal substrate is an electrically conductive and corrosion-resistant metal substrate, preferably one of a nickel mesh, a foamed nickel, a nickel sheet, a stainless steel mesh, a foamed iron, a stainless steel sheet, a copper mesh, a foamed copper, a copper sheet, a cobalt mesh, a foamed cobalt and a cobalt sheet, and more preferably one of a nickel mesh, a foamed nickel and a nickel sheet.
The porous metal target component is preferably metal nanoparticles, and the diameter of the metal nanoparticles is 5-1000 nanometers.
The invention also provides a preparation method of the electrolyzed water anode based on the corrosion process, which comprises the following steps:
s1, cleaning a metal substrate;
s2, spraying yolk structure composite metal particles on the cleaned metal substrate;
and S3, soaking the metal substrate processed in the step S2 in a selective corrosion solution for selective corrosion to obtain a metal substrate coated with metal nano particles on the surface, and washing and drying to obtain the electrolytic water cathode.
Specifically, the metal substrate is firstly placed in an acetone solution for ultrasonic cleaning for 10-30 minutes, and then repeatedly cleaned by ethanol to remove a grease layer on the surface of the metal; and then, placing the metal substrate in a hydrochloric acid solution with the concentration of 1-6 mol/L for 5-25 minutes by ultrasonic treatment, standing for 10-30 minutes, repeatedly washing with distilled water, and removing an oxide layer on the surface of the metal to obtain the cleaned metal substrate.
After cleaning the metal substrate, spraying the yolk structure composite metal particles on the surface of the cleaned metal substrate by adopting a plasma thermal spraying method under the protective atmosphere of argon and hydrogen; the diameter of the yolk structure composite metal particle is preferably 5-200 microns, the yolk structure composite metal particle comprises a surface metal target component and an inner layer non-target component, the gasification temperature of the surface metal target component is different from that of the inner layer component, the surface metal target component is a metal component with a higher gasification temperature, preferably one of nickel, titanium and nickel-molybdenum alloys, the inner layer non-target component is a material with a lower gasification temperature, preferably one of aluminum, zinc, copper, carbon, polystyrene and silicon, and the mass fraction of the surface metal target component in the yolk structure composite metal particle is preferably 40-90%. In the process of spraying the yolk structure composite metal particles on the metal substrate by adopting a plasma thermal spraying method, the surface metal target component of the yolk structure composite metal particles is difficult to gasify and is in a molten state, and the inner layer non-target component is gasified and then expands in volume to support and explode the molten surface metal target component, so that the electrochemical surface area of the porous target component on the surface of the metal substrate is effectively improved, and the effective catalytic active sites are increased.
And after the spraying is finished, selectively corroding the metal substrate, removing residual non-target components on the substrate after the spraying, so as to form metal nano particles on the conductive substrate, and then washing and drying the obtained metal substrate coated with the metal nano particles to obtain the electrolytic water cathode. In the invention, the selective corrosion mode preferably adopts the mode that the metal substrate after the spraying treatment is placed in the selective corrosion solution to be soaked for 24 hours; the selective corrosion liquid in the invention preferably comprises the following components in percentage by mass: 15-40% of sodium hydroxide, 5-20% of ammonium persulfate and the balance of water. The purpose of the selective etching is, on the one hand, to remove the non-target components remaining on the substrate after spraying, leaving the porous metal target components completely exposed. In the invention, the washing is preferably repeated washing treatment by using distilled water, and the drying is preferably natural drying.
In order to further understand the present invention, the following will explain the present invention in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
(1) Cleaning a metal nickel screen: placing the metal nickel net in an acetone solution for ultrasonic cleaning for 20 minutes, and repeatedly cleaning with ethanol to remove a metal surface grease layer; then, the metal substrate is placed in a hydrochloric acid solution with the concentration of 4mol/L for 10 minutes by ultrasonic treatment, is kept stand for 15 minutes, and is repeatedly washed by distilled water to remove an oxide layer on the surface of the metal.
(2) Spraying yolk structure nickel-zinc particles (nickel is a surface layer metal target component, and zinc is an inner layer non-target component) on the cleaned metal nickel net in a plasma thermal spraying mode: and spraying yolk structure nickel-zinc particles with the particle diameter of 100 microns and the nickel component mass fraction of 50% on the surface of the cleaned metal nickel screen by adopting a plasma thermal spraying method under the protective atmosphere of argon and hydrogen.
(3) And (3) placing the metal nickel mesh subjected to the plasma thermal spraying treatment in a mixed aqueous solution of sodium hydroxide with the mass fraction of 30% and ammonium persulfate with the mass fraction of 10% for soaking for 24 hours, repeatedly washing with distilled water, and drying to obtain the electrolytic water cathode.
(4) Analyzing the surface structure of the cathode of the electrolytic water based on the microscopic blasting process:
FIG. 1 shows the SEM pictures of the cathode surface of the electrolyzed water of this example under different magnifications. Wherein, FIG. 1a is a low-magnification scanning electron microscope image of the surface of the cathode of the electrolyzed water, FIG. 1b is a medium-magnification scanning electron microscope image of the surface of the cathode of the electrolyzed water, and FIG. 1c is a high-magnification scanning electron microscope image of the surface of the cathode of the electrolyzed water. From fig. 1, it can be seen that the surface of the metal nickel mesh is covered by porous metal nickel, and the porous metal nickel is composed of nickel nano-particles, and the average diameter of the particles is 20 nanometers. A large number of pores exist among the small nickel nano particles, so that the electrochemical surface area can be effectively improved, and the catalytic active sites can be increased.
(5) Electrolytic water cathode catalytic performance analysis based on the microscopic blasting process:
the hydrogen evolution performance of the electrolyzed water cathode obtained in the embodiment was tested by a linear voltammetry scan test method. The test uses a three-electrode system, the cathode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts potassium hydroxide solution with the mass of 1mol/L, the scanning rate is 5 millivolts per second, and the scanning range is-0.8 volt to-1.6 volts. The hydrogen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chenhua instruments ltd) and the test results corresponded to fig. 2 and table 1, where silver/silver chloride was a silver/silver chloride reference electrode filled with 3mol/L potassium chloride solution.
Example 2
(1) Cleaning a metal nickel screen: placing the metal nickel net in an acetone solution for ultrasonic cleaning for 20 minutes, and repeatedly cleaning with ethanol to remove a metal surface grease layer; then, the metal substrate is placed in a hydrochloric acid solution with the concentration of 4mol/L for 10 minutes by ultrasonic treatment, is kept stand for 15 minutes, and is repeatedly washed by distilled water to remove an oxide layer on the surface of the metal.
(2) Spraying yolk structure nickel-copper particles (nickel is a surface layer metal target component, and copper is an inner layer non-target component) on the cleaned metal nickel net in a plasma thermal spraying mode: and spraying yolk structure nickel-copper particles with the particle diameter of 120 microns and the nickel component mass fraction of 70% on the surface of the cleaned metal nickel screen by adopting a plasma thermal spraying method under the protective atmosphere of argon and hydrogen.
(3) And (3) placing the metal nickel mesh subjected to the plasma thermal spraying treatment in a mixed aqueous solution of sodium hydroxide with the mass fraction of 30% and ammonium persulfate with the mass fraction of 10% for soaking for 24 hours, repeatedly washing with distilled water, and drying to obtain the electrolytic water cathode.
(4) Electrolytic water cathode catalytic performance analysis based on the microscopic blasting process:
the hydrogen evolution performance of the electrolyzed water cathode obtained in the embodiment was tested by a linear voltammetry scan test method. The test uses a three-electrode system, the cathode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts potassium hydroxide solution with the mass of 1mol/L, the scanning rate is 5 millivolts per second, and the scanning range is-0.8 volt to-1.6 volts. The hydrogen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chenhua instruments ltd) and the test results corresponded to fig. 2 and table 1.
Example 3
(1) Cleaning the stainless steel net: placing the stainless steel net in an acetone solution for ultrasonic cleaning for 20 minutes, and repeatedly cleaning with ethanol to remove the grease layer on the surface of the metal; then, the metal substrate is placed in a hydrochloric acid solution with the concentration of 4mol/L for 10 minutes by ultrasonic treatment, is kept stand for 15 minutes, and is repeatedly washed by distilled water to remove an oxide layer on the surface of the metal.
(2) Spraying yolk structure nickel-aluminum particles (nickel is a surface component, and aluminum is an inner component) on the cleaned stainless steel mesh in a plasma thermal spraying manner: and spraying yolk structure nickel-copper particles with the particle diameter of 160 microns and the nickel component mass fraction of 50% on the surface of the cleaned stainless steel mesh by adopting a plasma thermal spraying method under the protective atmosphere of argon and hydrogen.
(3) And (3) placing the stainless steel mesh subjected to the plasma thermal spraying treatment in a mixed aqueous solution of sodium hydroxide with the mass fraction of 30% and ammonium persulfate with the mass fraction of 10% for soaking for 24 hours, repeatedly washing with distilled water, and drying to obtain the electrolytic water cathode.
(4) Electrolytic water cathode catalytic performance analysis based on the microscopic blasting process:
the hydrogen evolution performance of the electrolyzed water cathode obtained in the embodiment was tested by a linear voltammetry scan test method. The test uses a three-electrode system, the cathode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts potassium hydroxide solution with the mass of 1mol/L, the scanning rate is 5 millivolts per second, and the scanning range is-0.8 volt to-1.6 volts. The hydrogen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chenhua instruments ltd) and the test results corresponded to fig. 2 and table 1.
Comparative example
The present comparative example provides a method of preparing an electrolyzed water cathode based on a conventional thermal spray process.
(1) Cleaning a metal nickel screen:
placing the metal nickel net in an acetone solution for ultrasonic cleaning for 20 minutes, and repeatedly cleaning with ethanol to remove a metal surface grease layer; then, the metal substrate is placed in a hydrochloric acid solution with the concentration of 4mol/L for 10 minutes by ultrasonic treatment, is kept stand for 15 minutes, and is repeatedly washed by distilled water to remove an oxide layer on the surface of the metal.
(2) Spraying nickel and zinc mixed particles on the cleaned metal nickel net in a plasma thermal spraying mode:
and (2) spraying nickel particles and zinc particles (the mass fraction of the nickel particles in the mixed particles is 80%) with the particle diameters of 30 micrometers on the surface of the metal nickel mesh subjected to cleaning treatment by adopting a plasma thermal spraying method under the protective atmosphere of argon and hydrogen.
(3) Alkali washing the metal nickel net after the plasma thermal spraying treatment:
and (3) placing the metal nickel mesh subjected to the plasma thermal spraying treatment in a mixed aqueous solution of sodium hydroxide with the mass fraction of 30% and ammonium persulfate with the mass fraction of 10% for soaking for 24 hours, repeatedly washing with distilled water, and drying to obtain the cathode of the electrolytic water of the comparative example.
(4) The surface structure analysis of the cathode of the electrolytic water based on the traditional plasma thermal spraying process comprises the following steps:
FIG. 3 shows the scanning electron microscope images of the cathode surface of the electrolyzed water of the comparative example under different magnifications. Wherein, FIG. 3a is a low-magnification scanning electron microscope image of the surface of the comparative example electrolytic water cathode, FIG. 3b is a medium-magnification scanning electron microscope image of the surface of the comparative example electrolytic water cathode, and FIG. 3c is a high-magnification scanning electron microscope image of the surface of the comparative example electrolytic water cathode. As shown in FIG. 3, the surface of the metal nickel net is covered by the bulk metal nickel, the size of the bulk metal nickel is between 1 and 30 microns, the bulk metal nickel also has the porous characteristic, but the particle size of the pores is larger and is on average 100 nanometers.
(5) The electrolytic water cathode catalytic performance analysis based on the traditional plasma thermal spraying process comprises the following steps:
and (3) carrying out a hydrogen evolution performance test on the electrolyzed water cathode obtained in the comparative example by adopting a linear voltammetry scanning test method. The test uses a three-electrode system, the cathode of the electrolyzed water obtained in the comparative example is a working electrode, silver/silver chloride is a reference electrode, a platinum net is an auxiliary electrode, the electrolyte adopts 1mol/L potassium hydroxide solution, the scanning speed is 5 millivolts per second, and the scanning range is-0.8 volt to-1.6 volt. The hydrogen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chenhua instruments ltd) and the test results corresponded to fig. 2 and table 1.
Table 1: overpotential of different test electrodes under different current densities
In summary, with reference to table 1 and fig. 2, from the analysis of the data results of the three-electrode test, the electrolyzed water cathode based on the micro blasting process has significantly improved hydrogen evolution catalytic performance compared with the electrolyzed water cathode based on the conventional thermal spraying process, and particularly, under the condition of high current density (-200 milliampere per square centimeter), the overpotential of-380 millivolts at most is reduced, so that the hydrogen evolution power consumption under the condition of high gas yield can be greatly reduced. The microscopic blasting process can provide more nickel-based catalytic active sites compared with the traditional thermal spraying process on the premise of the same target component (nickel), and the overall catalytic performance of the electrode is improved.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. The electrolytic water cathode preparation method based on the microscopic blasting process is characterized by comprising the following steps of:
s1, cleaning a metal substrate;
s2, spraying yolk structure composite metal particles on a cleaned metal substrate, wherein the yolk structure composite metal particles comprise a surface layer metal target component and an inner layer non-target component, the surface layer metal target component is one of nickel, titanium and nickel-molybdenum alloy, and the inner layer non-target component is one of aluminum, zinc, copper, carbon, polystyrene and silicon;
and S3, soaking the metal substrate processed in the step S2 in a selective corrosion solution for selective corrosion to obtain a metal substrate coated with metal nano particles on the surface, and washing and drying to obtain the electrolytic water cathode.
2. The method for preparing the electrolytic water cathode based on the microscopic blasting process according to claim 1, wherein the method comprises the following steps: in the step S2, the diameter of the yolk structure composite metal particles is 5-200 microns, and the mass fraction of the surface layer metal target component in the yolk structure composite metal particles is 40-90%.
3. The method for preparing the electrolytic water cathode based on the microscopic blasting process according to claim 1, wherein the method comprises the following steps: the cleaning treatment in the step S1 is specifically that the metal substrate is placed in an acetone solution for ultrasonic cleaning for 10-30 minutes, and then is cleaned by ethanol until an oil layer on the surface of the metal substrate is removed; and then, placing the metal substrate in a hydrochloric acid solution with the concentration of 1-6 mol/L for 5-25 minutes by ultrasonic treatment, standing for 10-30 minutes, and then cleaning with distilled water until a surface oxide layer of the metal substrate is removed.
4. The method for preparing the electrolytic water cathode based on the microscopic blasting process according to claim 1, wherein the method comprises the following steps: in the step S2, the spraying is specifically to spray the yolk structure composite metal particles onto the surface of the cleaned metal substrate by using a plasma thermal spraying method under the protective atmosphere of argon and hydrogen.
5. The method for preparing the electrolytic water cathode based on the microscopic blasting process according to claim 1, wherein the method comprises the following steps: in the step S3, the soaking time is 20-30 h, and the selective corrosive liquid comprises the following components in percentage by mass: 15-40% of sodium hydroxide, 5-20% of ammonium persulfate and the balance of water.
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