CN110408950A - A kind of electrolysis water cathode and preparation method thereof based on microcosmic blasting technology - Google Patents
A kind of electrolysis water cathode and preparation method thereof based on microcosmic blasting technology Download PDFInfo
- Publication number
- CN110408950A CN110408950A CN201910813406.4A CN201910813406A CN110408950A CN 110408950 A CN110408950 A CN 110408950A CN 201910813406 A CN201910813406 A CN 201910813406A CN 110408950 A CN110408950 A CN 110408950A
- Authority
- CN
- China
- Prior art keywords
- electrolysis water
- microcosmic
- metal
- nickel
- metallic substrates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of electrolysis water cathode and preparation method thereof based on microcosmic blasting technology, belongs to water electrolysis hydrogen production technical field.Electrolysis water cathode disclosed by the invention includes the porous metals target components that metallic substrates and cladding combine together on the metallic substrate and with metallic substrates.The invention also discloses the preparation methods of the electrolysis water cathode, this method sprays egg yolk structure composite metal particles by way of plasma thermal sprayed in the conductive substrates that cleaning treatment is crossed, then selective corrosion is carried out, to form metal nanoparticle on the metallic substrate, remaining non-target components is removed simultaneously, obtains electrolysis water cathode.The method of the present invention simple process can greatly improve electrode catalyst performance compared with traditional handicraft.
Description
Technical field
The present invention relates to water electrolysis hydrogen production technical field, especially a kind of electrolysis water cathode based on microcosmic blasting technology and
Preparation method.
Background technique
Hydrogen Energy becomes science and social hotspots as a kind of high-efficiency cleaning energy in recent years.Currently, Hydrogen Energy in global range
Industry shows the situation of high speed development, including hydrogen system, storage, fortune plus, with full industrial chain.Upstream as Hydrogen Energy industrial chain
End, hydrogen preparation are also concerned, especially as abandon electric resources, nuclear power resource effectively integrates, future passes through electrolyzed alkaline water
The available low-cost hydrogen of hydrogen manufacturing can provide strong support for the development of downstream hydrogen cell automobile.
Electrolyzed alkaline water hydrogen manufacturing technical problem maximum at present is that power consumption is excessively high under the conditions of system of unit hydrogen amount.From electricity
Power consumption distributional analysis during Xie Shui, power consumption are mainly reflected in cathode, anode reaction overpotential.Electrode overpotential one
Aspect is embodied in the intrinsic catalytic performance of electrode catalyst, is on the other hand embodied in the effective catalytic active site points of electrode surface
Mesh.Industrial at present, electrolysis water cathode mainly uses nickel-based metallic material, on the one hand due to the alkali resistant corrosion ability of nickel, separately
On the one hand having benefited from nickel itself has good catalytic activity for hydrogen evolution.The preparation method of these nickel base electrodes mainly have plating, etc.
Ion thermal spraying, powder sintered etc., wherein plasma thermal sprayed is to spray to metal nickel powder high-temperature fusion in metallic substrates.By
Be in close contact between molten condition metal and nickel by powder between a large amount of gap, nickel base electrode that plasma thermal sprayed obtains tool
There are good electrolysis durability and a certain catalytic activity, however this electrode is still not achieved and further decreases electrolytic water electric energy
The high request of consumption.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of electrolysis water cathodes and its system based on microcosmic blasting technology
Preparation Method, for electrolysis water power consumption to be further greatly reduced.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of electrolysis water cathode based on microcosmic blasting technology is, characterized by comprising: metallic substrates and porous metals mesh
Component is marked, the porous metals target components are coated on the metal substrate surface and combine together with the metallic substrates.
Further, the metallic substrates are selected from nickel screen, nickel foam, nickel sheet, stainless (steel) wire, foamed iron, stainless steel substrates, copper
One of net, foam copper, copper sheet, cobalt net, foam cobalt and cobalt piece.
Further, the porous metals target components are made of metal nanoparticle, the metal nanoparticle diameter
It is 5~1000 nanometers.
The present invention also provides a kind of preparation methods of electrolysis water cathode based on microcosmic blasting technology, include following step
It is rapid:
S1. by metallic substrates cleaning treatment；
S2. egg yolk structure composite metal particles are sprayed in the metallic substrates that cleaning treatment is crossed；
S3. it will be immersed in selective corrosion liquid by the metallic substrates of step S2 processing and carry out selective corrosion, obtained
Surface is coated with the metallic substrates of metal nanoparticle, and electrolysis water cathode is obtained after washing and drying.
Further, the diameter of egg yolk structure composite metal particles described in step S2 is 5~200 microns, the yolk
Structure composite metallic particles includes coating metal target components and internal layer non-target components, and the coating metal target components are
One of nickel, titanium, nickel-molybdenum alloy, the internal layer non-target components are one of aluminium, zinc, copper, carbon, polystyrene, silicon, institute
The mass fraction for stating coating metal target components in egg yolk structure composite metal particles is 40%~90%.
Further, it is clear to be specially placed in ultrasound in acetone soln by cleaning treatment described in step S1 for the metallic substrates
It washes 10~30 minutes, then is cleaned with ethyl alcohol to removing the metal substrate surface oil layer；Then the metallic substrates are placed in
Concentration is ultrasound 5~25 minutes in the hydrochloric acid solution of 1~6mol/L, and stands 10~30 minutes, then wash with distilled water to removing
Remove the surface oxide layer of the metallic substrates.
Further, spraying described in step S2 is specially under the protective atmosphere of argon gas and hydrogen, using plasma heat
The egg yolk structure composite metal particles are sprayed to the metal substrate surface that cleaning treatment is crossed by spraying method.
Further, soaking time described in step S3 is 20~30h, each component quality hundred in the selective corrosion liquid
Divide ratio are as follows: sodium hydroxide 15%~40%, ammonium persulfate 5%~20%, surplus are water.
Compared with prior art, the present invention having the following advantages that and effect: the invention proposes one kind by plasma heat
Spraying means obtain a kind of high-performance electrolysis water cathode by the thinking of microcosmic blasting technology.During plasma thermal sprayed, gas
Change the lower internal layer non-target components high-temperature gasification of temperature, volume expansion makes to be difficult to gasify in egg yolk structure composite metal particles
Molten state coating metal target components microcosmic blasting effect occurs, effectively increase metal substrate surface porous metals target group
Divide electrochemical surface area, increases effective active site.The method of the present invention simple process can be mentioned substantially compared with traditional handicraft
High electrode catalytic performance.
Detailed description of the invention
Fig. 1 is the electrolysis water cathode surface scanning electron microscopic picture of the embodiment of the present invention 1；
Fig. 2 is three electrolysis waterline voltammetric scan curve graphs of the embodiment of the present invention 1~3 and comparative example；
Fig. 3 is the electrolysis water cathode surface scanning electron microscopic picture of comparative example of the present invention.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
A kind of electrolysis water cathode based on microcosmic blasting technology provided by the invention includes metallic substrates and porous metals mesh
Component is marked, porous metals target components are coated on metal substrate surface and combine together with metallic substrates.
Metallic substrates are conductive and corrosion resistant metal substrate in the present invention, it is preferred to use nickel screen, nickel foam, nickel sheet, stainless
One of steel mesh, foamed iron, stainless steel substrates, copper mesh, foam copper, copper sheet, cobalt net, foam cobalt and cobalt piece, more preferably nickel screen,
One of nickel foam, nickel sheet.
The preferred metal nanoparticle of porous metals target components in the present invention, the diameter of metal nanoparticle are 5~1000
Nanometer.
The anode of electrolytic water preparation method based on etching process that the present invention also provides a kind of comprising the steps of:
S1. by metallic substrates cleaning treatment；
S2. egg yolk structure composite metal particles are sprayed in the metallic substrates that cleaning treatment is crossed；
S3. it will be immersed in selective corrosion liquid by the metallic substrates of step S2 processing and carry out selective corrosion, obtained
Surface is coated with the metallic substrates of metal nanoparticle, and electrolysis water cathode is obtained after washing and drying.
It is cleaned by ultrasonic 10~30 minutes specifically, metallic substrates are placed in acetone soln by the present invention first, then uses ethyl alcohol
It cleans repeatedly, removes metal surface oil layer；Then metallic substrates are placed in ultrasound in the hydrochloric acid solution that concentration is 1~6mol/L
5~25 minutes, and 10~30 minutes are stood, then cleaned repeatedly with distilled water, oxidation on metal surface layer is removed, cleaning treatment is obtained
The metallic substrates crossed.
After carrying out cleaning treatment to metallic substrates, using plasma thermal sprayed method, in the protective atmosphere of argon gas and hydrogen
It is lower that egg yolk structure composite metal particles are sprayed to the metal substrate surface that cleaning treatment is crossed；Mesolecithal structure composite gold of the present invention
The diameter of metal particles is preferably 5~200 microns, and egg yolk structure composite metal particles include that coating metal target components and internal layer are non-
Target components, the coating metal target components of egg yolk structure composite metal particles are different from interior layer component gasification temperature, surface layer gold
Belong to target components and select the higher metal component of gasification temperature, it is preferred to use one of nickel, titanium, nickel-molybdenum alloy, the non-mesh of internal layer
The lower material of component selection gasification temperature is marked as component, it is preferred to use one of aluminium, zinc, copper, carbon, polystyrene, silicon,
The mass fraction of coating metal target components is preferably 40%~90% in egg yolk structure composite metal particles.Using plasma heat
During spraying method sprays egg yolk structure composite metal particles on the metallic substrate, egg yolk structure composite metal particles table
Layer metal target component is not easy to gasify, in a molten state, after the gasification of internal layer non-target components, volume expansion, by molten state
The support of coating metal target components is quick-fried, effectively increases the porous target components electrochemical surface area of metal substrate surface, has increased
Imitate active site.
After the completion of spraying, which is subjected to selective corrosion, is removed after spraying remaining non-targeted in substrate
Component, so that metal nanoparticle is formed in conductive substrates, then, the Metal Substrate for being coated with metal nanoparticle that will be obtained
Bottom water is washed, is dried, and electrolysis water cathode is obtained.In the present invention, the mode of selective corrosion preferably uses will be after spray treatment
Metallic substrates, which are placed in selective corrosion liquid, impregnates for 24 hours；Each component mass percent is preferred in selective corrosion liquid in the present invention
Are as follows: sodium hydroxide 15%~40%, ammonium persulfate 5%~20%, surplus are water.The purpose of selective corrosion is on the one hand to
Non-target components remaining in substrate after spraying is removed, porous metals target components are fully exposed.Water in the present invention
It washes and is preferably handled using distilled water repeated flushing, it is dry preferably using natural drying.
For a further understanding of the present invention, below with reference to embodiment to provided by the invention a kind of based on microcosmic blasting technology
Electrolysis water cathode and preparation method thereof be described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
(1) metal nickel screen cleaning treatment: metal nickel screen is placed in acetone soln and is cleaned by ultrasonic 20 minutes, then is anti-with ethyl alcohol
Multiple cleaning, to remove metal surface oil layer；Then metallic substrates are placed in ultrasound 10 in the hydrochloric acid solution that concentration is 4mol/L
Minute, and 15 minutes are stood, then cleaned repeatedly with distilled water, to remove oxidation on metal surface layer.
(2) egg yolk structure nickel zinc particle is sprayed on the net in the metallic nickel that cleaning treatment is crossed by way of plasma thermal sprayed
(nickel is coating metal target components, and zinc is internal layer non-target components): being 100 microns by particle diameter, nickel constituent mass score
It is sprayed under the protective atmosphere of argon gas and hydrogen using plasma thermal sprayed method for 50% egg yolk structure nickel zinc particle
The metallic nickel net surface that cleaning treatment is crossed.
(3) by plasma thermal sprayed, treated that metal nickel screen is placed in 30% sodium hydroxide of mass fraction and mass fraction
It impregnates 24 hours in the mixed aqueous solution of 10% ammonium persulfate, then is handled with distilled water repeated flushing, obtain this hair after dry
Bright electrolysis water cathode.
(4) the electrolysis water cathode surface structural analysis based on microcosmic blasting technology:
Fig. 1 is illustrated under different amplification, the present embodiment electrolysis water cathode surface scanning electron microscopic picture.Wherein Fig. 1 a is
Electrolysis water cathode surface low range scanning electron microscope (SEM) photograph, Fig. 1 b are electrolysis water cathode surface moderate multiplying factor scanning electron microscope (SEM) photographs, and Fig. 1 c is electricity
Solve water cathode surface high magnification scanning electron microscope (SEM) photograph.It is porous by Fig. 1 it can be found that metallic nickel net surface is covered by porous-metal nickel
Metallic nickel is made of nano nickel particles, and average diameter of particles size is 20 nanometers.Exist between these small nano nickel particles big
Metering-orifice gap can effectively improve electrochemical surface area, increase active site.
(5) the electrolysis water cathode catalysis performance evaluation based on microcosmic blasting technology:
Hydrogen Evolution Performance test is carried out to the electrolysis water cathode that the present embodiment obtains using the test method of linear voltammetric scan.
Test uses three-electrode system, and the electrolysis water cathode that the present embodiment obtains is working electrode, and silver/silver chlorate is reference electrode, platinum
Net is auxiliary electrode, and electrolyte uses the potassium hydroxide solution of quality 1mol/L, and sweep speed is 5 millivolts of per second, scanning ranges
For -0.8 volt to -1.6 volts.(CHI660E, Shanghai Chen Hua Instrument Ltd.) tests it and analyses oxygen on electrochemical workstation
Can, test result corresponding diagram 2 and table 1, wherein silver/silver chlorate is the silver/silver chloride reference electricity for filling 3mol/L Klorvess Liquid
Pole.
Embodiment 2
(1) metal nickel screen cleaning treatment: metal nickel screen is placed in acetone soln and is cleaned by ultrasonic 20 minutes, then is anti-with ethyl alcohol
Multiple cleaning, to remove metal surface oil layer；Then metallic substrates are placed in ultrasound 10 in the hydrochloric acid solution that concentration is 4mol/L
Minute, and 15 minutes are stood, then cleaned repeatedly with distilled water, to remove oxidation on metal surface layer.
(2) egg yolk structure ambrose alloy particle is sprayed on the net in the metallic nickel that cleaning treatment is crossed by way of plasma thermal sprayed
(nickel is coating metal target components, and copper is internal layer non-target components): being 120 microns by particle diameter, nickel constituent mass score
It is sprayed under the protective atmosphere of argon gas and hydrogen using plasma thermal sprayed method for 70% egg yolk structure ambrose alloy particle
The metallic nickel net surface that cleaning treatment is crossed.
(3) by plasma thermal sprayed, treated that metal nickel screen is placed in 30% sodium hydroxide of mass fraction and mass fraction
It impregnates 24 hours in the mixed aqueous solution of 10% ammonium persulfate, then is handled with distilled water repeated flushing, obtain this hair after dry
Bright electrolysis water cathode.
(4) the electrolysis water cathode catalysis performance evaluation based on microcosmic blasting technology:
Hydrogen Evolution Performance test is carried out to the electrolysis water cathode that the present embodiment obtains using the test method of linear voltammetric scan.
Test uses three-electrode system, and the electrolysis water cathode that the present embodiment obtains is working electrode, and silver/silver chlorate is reference electrode, platinum
Net is auxiliary electrode, and electrolyte uses the potassium hydroxide solution of quality 1mol/L, and sweep speed is 5 millivolts of per second, scanning ranges
For -0.8 volt to -1.6 volts.(CHI660E, Shanghai Chen Hua Instrument Ltd.) tests it and analyses oxygen on electrochemical workstation
Can, test result corresponding diagram 2 and table 1.
Embodiment 3
(1) stainless (steel) wire cleaning treatment: stainless (steel) wire is placed in acetone soln and is cleaned by ultrasonic 20 minutes, then is anti-with ethyl alcohol
Multiple cleaning, to remove metal surface oil layer；Then metallic substrates are placed in ultrasound 10 in the hydrochloric acid solution that concentration is 4mol/L
Minute, and 15 minutes are stood, then cleaned repeatedly with distilled water, to remove oxidation on metal surface layer.
(2) egg yolk structure nickel alumina particles are sprayed on the stainless (steel) wire that cleaning treatment is crossed by way of plasma thermal sprayed
(nickel is surface layer component, and aluminium is interior layer component): being 160 microns by particle diameter, the yolk knot that nickel constituent mass score is 50%
Structure ambrose alloy particle sprays to cleaning treatment using plasma thermal sprayed method and crosses not under the protective atmosphere of argon gas and hydrogen
Rust steel mesh surface.
(3) by plasma thermal sprayed, treated that stainless (steel) wire is placed in 30% sodium hydroxide of mass fraction and mass fraction
It impregnates 24 hours in the mixed aqueous solution of 10% ammonium persulfate, then is handled with distilled water repeated flushing, obtain this hair after dry
Bright electrolysis water cathode.
(4) the electrolysis water cathode catalysis performance evaluation based on microcosmic blasting technology:
Hydrogen Evolution Performance test is carried out to the electrolysis water cathode that the present embodiment obtains using the test method of linear voltammetric scan.
Test uses three-electrode system, and the electrolysis water cathode that the present embodiment obtains is working electrode, and silver/silver chlorate is reference electrode, platinum
Net is auxiliary electrode, and electrolyte uses the potassium hydroxide solution of quality 1mol/L, and sweep speed is 5 millivolts of per second, scanning ranges
For -0.8 volt to -1.6 volts.(CHI660E, Shanghai Chen Hua Instrument Ltd.) tests it and analyses oxygen on electrochemical workstation
Can, test result corresponding diagram 2 and table 1.
Comparative example
This comparative example provides a kind of electrolysis water cathode preparation method based on traditional hot-spraying technique.
(1) metal nickel screen cleaning treatment:
Metal nickel screen is placed in acetone soln and is cleaned by ultrasonic 20 minutes, then is cleaned repeatedly with ethyl alcohol, to remove metal watch
Face oil layer；Then metallic substrates are placed in the hydrochloric acid solution that concentration is 4mol/L ultrasound 10 minutes, and stand 15 minutes, then
It is cleaned repeatedly with distilled water, to remove oxidation on metal surface layer.
(2) nickel, zinc hybrid particles are sprayed on the net in the metallic nickel that cleaning treatment is crossed by way of plasma thermal sprayed:
(note: in hybrid particles, the mass fraction of nickel particle is the nickel particle and zinc particle for being 30 microns for particle diameter
80%), under the protective atmosphere of argon gas and hydrogen, the metal nickel screen that cleaning treatment is crossed is sprayed to using plasma thermal sprayed method
Surface.
(3) alkali cleaning is carried out to the metal nickel screen after plasma thermal spraying treatment:
By plasma thermal sprayed, treated that metal nickel screen is placed in 30% sodium hydroxide of mass fraction, 10% mistake of mass fraction
It impregnates 24 hours in ammonium sulfate mixed aqueous solution, then is handled with distilled water repeated flushing, obtain comparative example electrolysis water after dry
Cathode.
(4) the electrolysis water cathode surface structural analysis based on conventional plasma hot-spraying technique:
It is illustrated under different amplification in Fig. 3, this comparative example electrolysis water cathode surface scanning electron microscopic picture.Wherein, scheme
3a is comparative example electrolysis water cathode surface low range scanning electron microscope (SEM) photograph, and Fig. 3 b is the scanning of comparative example electrolysis water cathode surface moderate multiplying factor
Electron microscope, Fig. 3 c are comparative example electrolysis water cathode surface high magnification scanning electron microscope (SEM) photographs.As shown in figure 3, metallic nickel net surface is by block
Shape metallic nickel is covered, and for reguline metal nickel size between 1~30 micron, reguline metal nickel also shows porosity characteristic, but structure
It is larger at the particle size of hole, it is average at 100 nanometers.
(5) the electrolysis water cathode catalysis performance evaluation based on conventional plasma hot-spraying technique:
Hydrogen Evolution Performance test is carried out to the electrolysis water cathode that this comparative example obtains using the test method of linear voltammetric scan.
Test uses three-electrode system, and the electrolysis water cathode that this comparative example obtains is working electrode, and silver/silver chlorate is reference electrode, platinum
Net is auxiliary electrode, and electrolyte uses the potassium hydroxide solution of 1mol/L, and sweep speed is 5 millivolts per second, scanning range is-
0.8 volt of extremely -1.6 volt.(CHI660E, Shanghai Chen Hua Instrument Ltd.) tests it and analyses oxygen performance on electrochemical workstation, surveys
Test result corresponding diagram 2 and table 1.
Table 1: overpotential of the difference test electrode under different current densities
In summary, it in conjunction with table 1 and Fig. 2, is analyzed from the data result of three electrode tests, the electricity based on microcosmic blasting technology
It solves water cathode and is improved compared with the electrolysis water cathode based on traditional hot-spraying technique with apparent catalytic activity of hydrogen evolution, especially in high electricity
Under current density (- 200 milliamperes every square centimeter), highest has -380 millivolts of overpotential to reduce, and can significantly reduce high yield tolerance
Under the conditions of liberation of hydrogen power consumption.Show under the premise of target components of the same race (nickel), the microcosmic more traditional hot-spraying technique of blasting technology can
To provide more nickel catalyst active sites, increase the catalytic performance of electrode entirety.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention, for this field skill
For art personnel, it is clear that invention is not limited to the details of the above exemplary embodiments, and without departing substantially from spirit of the invention or
In the case where essential characteristic, the present invention can be realized in other specific forms.Therefore, in all respects, should all incite somebody to action
Embodiment regards exemplary as, and is non-limiting, the scope of the present invention by appended claims rather than on state
Bright restriction, it is intended that including all changes that fall within the meaning and scope of the equivalent elements of the claims in the present invention
It is interior.Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, it is possible to understand that
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where not departing from the principle and spirit of the invention,
The scope of the present invention is defined by the appended.
Claims (8)
1. a kind of electrolysis water cathode based on microcosmic blasting technology is, characterized by comprising: metallic substrates and porous metals target
Component, the porous metals target components are coated on the metal substrate surface and combine together with the metallic substrates.
2. a kind of electrolysis water cathode based on microcosmic blasting technology according to claim 1, it is characterised in that: the metal
Substrate is selected from nickel screen, nickel foam, nickel sheet, stainless (steel) wire, foamed iron, stainless steel substrates, copper mesh, foam copper, copper sheet, cobalt net, foam
One of cobalt and cobalt piece.
3. a kind of electrolysis water cathode based on microcosmic blasting technology according to claim 1, which is characterized in that described porous
Metal target component is made of metal nanoparticle, and the metal nanoparticle diameter is 5~1000 nanometers.
4. a kind of electrolysis water cathode preparation method based on microcosmic blasting technology, which is characterized in that comprise the steps of:
S1. by metallic substrates cleaning treatment；
S2. egg yolk structure composite metal particles are sprayed in the metallic substrates that cleaning treatment is crossed；
S3. it will be immersed in selective corrosion liquid by the metallic substrates of step S2 processing and carry out selective corrosion, obtain surface
The metallic substrates of metal nanoparticle are coated with, electrolysis water cathode is obtained after washing and drying.
5. a kind of electrolysis water cathode preparation method based on microcosmic blasting technology according to claim 4, it is characterised in that:
The diameter of egg yolk structure composite metal particles described in step S2 is 5~200 microns, the egg yolk structure composite metal particles packet
Include coating metal target components and internal layer non-target components, the coating metal target components are nickel, titanium, one in nickel-molybdenum alloy
Kind, the internal layer non-target components is one of aluminium, zinc, copper, carbon, polystyrene, silicon, the egg yolk structure composition metal
The mass fraction of coating metal target components is 40%~90% in grain.
6. a kind of electrolysis water cathode preparation method based on microcosmic blasting technology according to claim 4, it is characterised in that:
Cleaning treatment described in step S1 is specially the metallic substrates to be placed in acetone soln to be cleaned by ultrasonic 10~30 minutes, then use
Ethyl alcohol is cleaned to removing the metal substrate surface oil layer；Then the metallic substrates are placed in concentration is 1~6mol/L's
Ultrasound 5~25 minutes in hydrochloric acid solution, and 10~30 minutes are stood, then wash with distilled water to the table for removing the metallic substrates
Face oxide layer.
7. a kind of electrolysis water cathode preparation method based on microcosmic blasting technology according to claim 4, it is characterised in that:
Spraying described in step S2 is specially under the protective atmosphere of argon gas and hydrogen, using plasma thermal sprayed method by the yolk
Structure composite metallic particles sprays to the metal substrate surface that cleaning treatment is crossed.
8. a kind of electrolysis water cathode preparation method based on microcosmic blasting technology according to claim 4, it is characterised in that:
Soaking time described in step S3 is 20~30h, each component mass percent in the selective corrosion liquid are as follows: sodium hydroxide
15%~40%, ammonium persulfate 5%~20%, surplus are water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910813406.4A CN110408950B (en) | 2019-08-30 | 2019-08-30 | Electrolytic water cathode based on microscopic blasting process and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910813406.4A CN110408950B (en) | 2019-08-30 | 2019-08-30 | Electrolytic water cathode based on microscopic blasting process and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110408950A true CN110408950A (en) | 2019-11-05 |
| CN110408950B CN110408950B (en) | 2021-04-27 |
Family
ID=68369366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910813406.4A Active CN110408950B (en) | 2019-08-30 | 2019-08-30 | Electrolytic water cathode based on microscopic blasting process and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110408950B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694928A (en) * | 2020-05-06 | 2021-11-26 | 中国科学院大连化学物理研究所 | Metal catalyst and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481787A (en) * | 2008-01-09 | 2009-07-15 | 私立中原大学 | Method and apparatus for forming compound film with porous coating |
| CN102560178A (en) * | 2012-02-20 | 2012-07-11 | 西安交通大学 | Method for preparing porous material |
| US20130052475A1 (en) * | 2011-08-23 | 2013-02-28 | Korea Institute Of Science And Technology | Method of fabricating porous film structure using dry processes and porous film structures fabricated by the same |
| CN105350015A (en) * | 2015-10-28 | 2016-02-24 | 派新（上海）能源技术有限公司 | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole |
| CN105728063A (en) * | 2016-03-23 | 2016-07-06 | 新奥科技发展有限公司 | Preparation method of metal substrate catalyst |
| CN106191916A (en) * | 2016-07-06 | 2016-12-07 | 天津市大陆制氢设备有限公司 | A kind of efficient porous Ni Mo hydrogen-precipitating electrode and preparation method thereof |
| CN106902821A (en) * | 2017-04-17 | 2017-06-30 | 高化学（江苏）化工新材料有限责任公司 | A kind of preparation method of the loaded catalyst of yolk type |
| CN108203799A (en) * | 2016-12-08 | 2018-06-26 | 沈阳黎明航空发动机(集团)有限责任公司 | A kind of resistance to marine corrosion thermal spraying abradable seal coating and preparation method thereof |
| CN108994290A (en) * | 2018-08-10 | 2018-12-14 | 上海交通大学 | A kind of core-shell structure magnesium-base hydrogen storage material and preparation method thereof |
| JP6455942B2 (en) * | 2014-07-04 | 2019-01-23 | アンヴァール株式会社 | Porous body and method for manufacturing the same, power storage device, transistor and solar cell |
| CN109373795A (en) * | 2018-11-14 | 2019-02-22 | 上海大学 | There is the method for the high heat transfer rate heat transfer pipe of porous structure liner using the preparation of high temperature elements vaporization technique |
| CN110014146A (en) * | 2019-05-22 | 2019-07-16 | 中国矿业大学 | A kind of nickel-molybdenum iron chromium-diamond alloy composite powder and its preparation method and application |
| CN110055477A (en) * | 2019-03-04 | 2019-07-26 | 天津大学 | A kind of nanoporous ni-based amorphous alloy material and its application in water electrolysis hydrogen production |
-
2019
- 2019-08-30 CN CN201910813406.4A patent/CN110408950B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481787A (en) * | 2008-01-09 | 2009-07-15 | 私立中原大学 | Method and apparatus for forming compound film with porous coating |
| US20130052475A1 (en) * | 2011-08-23 | 2013-02-28 | Korea Institute Of Science And Technology | Method of fabricating porous film structure using dry processes and porous film structures fabricated by the same |
| CN102560178A (en) * | 2012-02-20 | 2012-07-11 | 西安交通大学 | Method for preparing porous material |
| JP6455942B2 (en) * | 2014-07-04 | 2019-01-23 | アンヴァール株式会社 | Porous body and method for manufacturing the same, power storage device, transistor and solar cell |
| CN105350015A (en) * | 2015-10-28 | 2016-02-24 | 派新（上海）能源技术有限公司 | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole |
| CN105728063A (en) * | 2016-03-23 | 2016-07-06 | 新奥科技发展有限公司 | Preparation method of metal substrate catalyst |
| CN106191916A (en) * | 2016-07-06 | 2016-12-07 | 天津市大陆制氢设备有限公司 | A kind of efficient porous Ni Mo hydrogen-precipitating electrode and preparation method thereof |
| CN108203799A (en) * | 2016-12-08 | 2018-06-26 | 沈阳黎明航空发动机(集团)有限责任公司 | A kind of resistance to marine corrosion thermal spraying abradable seal coating and preparation method thereof |
| CN106902821A (en) * | 2017-04-17 | 2017-06-30 | 高化学（江苏）化工新材料有限责任公司 | A kind of preparation method of the loaded catalyst of yolk type |
| CN108994290A (en) * | 2018-08-10 | 2018-12-14 | 上海交通大学 | A kind of core-shell structure magnesium-base hydrogen storage material and preparation method thereof |
| CN109373795A (en) * | 2018-11-14 | 2019-02-22 | 上海大学 | There is the method for the high heat transfer rate heat transfer pipe of porous structure liner using the preparation of high temperature elements vaporization technique |
| CN110055477A (en) * | 2019-03-04 | 2019-07-26 | 天津大学 | A kind of nanoporous ni-based amorphous alloy material and its application in water electrolysis hydrogen production |
| CN110014146A (en) * | 2019-05-22 | 2019-07-16 | 中国矿业大学 | A kind of nickel-molybdenum iron chromium-diamond alloy composite powder and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| HAN, JIUHUI等: ""Vapor phase dealloying: A versatile approach for fabricating 3D porous materials"", 《ACTA MATERIALIA》 * |
| LU, ZHEN等: ""Three-dimensional bicontinuous nanoporous materials by vapor phase dealloying"", 《NATURE COMMUNICATIONS》 * |
| ZHONG, CHENGLIN等: ""Enhanced synergistic catalysis by a novel triple-phase interface design of NiO/Ru@Ni for the hydrogen evolution reaction"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 方秀梅 等: ""去合金化制备孔径可控纳米多孔金属研究进展"", 《中国材料进展》 * |
| 李俊 等: ""物理真空去合金法制备微米级多孔不锈钢"", 《金属学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694928A (en) * | 2020-05-06 | 2021-11-26 | 中国科学院大连化学物理研究所 | Metal catalyst and preparation method and application thereof |
| CN113694928B (en) * | 2020-05-06 | 2023-04-07 | 中国科学院大连化学物理研究所 | Metal catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110408950B (en) | 2021-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Electrodeposition mechanism and characterization of Ni–Mo alloy and its electrocatalytic performance for hydrogen evolution | |
| CN106191916A (en) | A kind of efficient porous Ni Mo hydrogen-precipitating electrode and preparation method thereof | |
| CN106967986B (en) | A kind of preparation method of the nickel hydroxide with hierarchical structure/compound hydrogen-precipitating electrode of nickel/graphene | |
| CN103952719B (en) | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof | |
| JP6426147B2 (en) | Metal porous body and method for producing metal porous body | |
| CN105350015A (en) | Composite hydrogen evolution negative pole with micropore hydrogen storage layer and preparing method for composite hydrogen evolution negative pole | |
| CN106048690B (en) | A kind of titanium-based titanium dioxide nanotube composite anode and preparation method thereof | |
| CN108767277A (en) | A kind of Fe-Pd bases nano-porous materials and preparation method thereof | |
| CN113604851A (en) | Super-hydrophobic coating without low surface energy substance modification on magnesium alloy surface and preparation method thereof | |
| WO2014165912A1 (en) | Coated composite anodes | |
| CN108239774A (en) | A kind of Ni-based hydrogen evolution electrode material and preparation method thereof | |
| CN105200421B (en) | A kind of method that laser fine fusion covering prepares hydrogen-precipitating electrode hydrogen storage layer | |
| CN110408950A (en) | A kind of electrolysis water cathode and preparation method thereof based on microcosmic blasting technology | |
| CN102899703A (en) | Silicate electrolyte and application of silicate electrolyte in magnesium alloy micro-arc oxidation film preparation | |
| CN101358363B (en) | Heat barrier composite plating and preparation technique thereof | |
| CN114921820B (en) | Cobalt-nickel based composite material, preparation method thereof, hydrogen evolution electrode based on cobalt-nickel based composite material and household appliance | |
| Huang et al. | Facile fabrication of an enhanced electrodeposited nickel electrode for alkaline hydrogen evolution reaction | |
| CN108772054A (en) | A kind of titanium dioxide-pucherite composite photocatalyst material and preparation method thereof | |
| CN108878905A (en) | A kind of copper magnetic collector and its preparation process and the magnetic lithium sky battery comprising it | |
| CN110265681B (en) | Composite electrode for catalyzing oxidation of sodium formate and preparation method and application thereof | |
| CN110607532A (en) | Preparation method of Co-Ni-P/fs-Si material for hydrogen evolution by water electrolysis | |
| CN112501645B (en) | Nickel hydroxide/nickel screen composite hydrogen and oxygen evolution electrode, preparation method and application thereof | |
| JP2008138282A (en) | Anode for alkaline electrolysis | |
| CN108054022A (en) | A kind of non-crystaline amorphous metal combination electrode of surface layer porous structure nickel cobalt oxide and preparation method thereof | |
| CN113149141A (en) | Graphite-phase carbon nitride modified lead dioxide electrode and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220817 Address after: No. 231, Lishan Road, Zhucheng City, Weifang City, Shandong Province, 262200 Patentee after: Shandong Aohydrogen Power Technology Co., Ltd. Address before: 226019 Jiangsu city of Nantong province sik Road No. 9 Patentee before: NANTONG University |