CN108315761A - A kind of preparation method of water electrolysis hydrogen production three nickel of curing-nickel electrode material - Google Patents
A kind of preparation method of water electrolysis hydrogen production three nickel of curing-nickel electrode material Download PDFInfo
- Publication number
- CN108315761A CN108315761A CN201810342048.9A CN201810342048A CN108315761A CN 108315761 A CN108315761 A CN 108315761A CN 201810342048 A CN201810342048 A CN 201810342048A CN 108315761 A CN108315761 A CN 108315761A
- Authority
- CN
- China
- Prior art keywords
- nickel
- electrode material
- curing
- preparation
- thiocarbamide
- 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.)
- Withdrawn
Links
Classifications
-
- 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
-
- 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
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- 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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The present invention proposes a kind of preparation method of three nickel nickel electrode material of water electrolysis hydrogen production curing, using nickel foam as substrate, it is loaded into the alcohol vapour dissolved with thiocarbamide by argon gas, it is passed through ammonia simultaneously, cold plasma etching is carried out to nickel substrate, three nickel of curing/nickel combination electrode material is obtained after cooling.The present invention overcomes the complex method tedious process and binding performance of existing catalyst and electrode material are not excellent enough, the insufficient defect of catalytic activity, surface active is carried out by the oxide layer of plasma etching foam nickel surface, thiocarbamide is promoted to react to form three nickel of curing rapidly with nickel metal, catalyst and the electrode material interfacial structure of preparation are stablized.Further, the addition of alkaline gas makes surface topography become rough porous, improves the specific surface area of catalyst, and then promote combination electrode material catalytic activity.In addition, preparation process of the present invention is simple, there are the potentiality of large-scale production.
Description
Technical field
The present invention relates to water electrolysis hydrogen production technical fields, more particularly to a kind of water electrolysis hydrogen production three nickel of curing-nickel
The preparation method of electrode material.
Background technology
The development of human society be unable to do without the use of the energy, however content of the fossil fuel in the earth's crust is limited, Yi Jiqi
The problems such as air pollution and global warming of generation, cause the mankind that will face the serious energy and problem concerning life.Hydrogen Energy is a kind of
Environmental-friendly and reproducible novel energy, due to efficient, no pollution and is produced the features such as simple, development and application are conducive to
Solve the efficiency in current energy use and pollution problem.Water electrolysis hydrogen producing is to realize that industrialization is cheap to prepare H2Important hand
Section, can be made the product that purity is 99%~99.9%, and it is not only former to be used for hydrogen manufacturing as one of resource most abundant in nature for water
Material is sufficient, and environmentally safe, and water electrolysis hydrogen production would develop into the core technology of the following industries, has prodigious shadow
Ring power.
After device for preparing hydrogen adds additional power source, under voltage effect, the electronics of power cathode is with current transfer
To cathode material, the hydrogen ion in electrolyte obtains electronics in cathode and is reduced into hydrogen；According to charge balance law, electrolyte
In hydroxide ion be moved to anode material, lost in electrode surface and be electronically generated oxygen.Evolving hydrogen reaction（HER）It is anti-with analysis oxygen
It answers（OER）It is the significant process in electro-catalysis hydrogen manufacturing energy conversion, cathode material for hydrogen evolution and analysis oxygen anodes when improving cell reaction
The electro catalytic activity of material plays an important roll to improving electrolysis water hydrogen generation efficiency, reducing energy consumption and cost etc..
In order to avoid electrode material is overly dependent upon the precious metal alloys such as Pt, Ru with high costs or oxide, electrode material
Material generally using catalyst and the non-noble metal composite material of better catalytic activity, for catalyst surface structure design not
It is only capable of increasing the specific surface area of material, can largely expose more active points, moreover it is possible to be effectively increased and electrolyte
Contact, is conducive to the diffusion of proton.The complex method of catalyst and electrode material is mostly after preparing respectively using bonding at present
Agent is compound, tedious process and binding performance is not excellent enough.Meanwhile the catalyst with special construction such as large specific surface area exists
It is susceptible to microdeformation in electrode material recombination process, to influence its catalytic efficiency.Therefore, improve catalyst and electrode
The complex method of material, the catalytic performance of electrode material, which is improved, has highly important practical significance.
Chinese invention patent application number 201510730627.7 discloses a kind of New Co3Mo3C elctro-catalysts first prepare ratio
Surface area is 30-40m2·g-1Catalyst Co3Mo3C powder, then by catalyst Co3Mo3C is dispersed in isopropanol and perfluorinated
In the mixed solution of resin solution, ultrasound obtains dispersion liquid, and Co is immersed in after then cleaning nickel foam substrate3Mo3C electro-catalysis
In agent dispersing liquid, then by load C o3Mo3The matrix of C is dried in vacuo, and load C o is obtained3Mo3The catalysis of C elctro-catalysts is analysed
Hydrogen foam nickel electrode, preparation method is simple and easy to do, of low cost, however, the catalyst fines prepared with this solution have compared with
High-specific surface area, it is evenly dispersed more difficult in mixed solution, and elctro-catalyst and carrier metal after electrode material drying
Between be not formed effect bonding, in electrolysis water reaction process due to electro-catalysis object fall off shorten electrode life.
Chinese invention patent application number 201210508704.0 discloses a kind of preparation side of water electrolysis hydrogen production electrode material
Ni powder and Al powder are mixed and made into mixture, green compact then are made in mixture cold moudling, then by green compact in vacuum by method
Under the conditions of be heated to 350~500 DEG C, keep the temperature 60~90min, then heat to 700~950 DEG C, keep the temperature 30~120min, it is cold
But to room temperature to get the porous water electrolysis hydrogen production electrode materials of Ni-Al.The electrode material that the invention provides, even aperture distribution make
With lasting a long time, however Ni-Al is insufficient as the catalytic activity of electrode material, and electrolysis water hydrogen generation efficiency is relatively low.
To meet the needs of industrialized production, electrode material must can long-term stable work at higher current densities, and
With excellent catalytic hydrogen evolution performance, it is therefore proposed that the electrode material of a kind of high stability and high catalytic activity, urges raising
Changing liberation of hydrogen efficiency has important theory significance and practical value.
Invention content
It is not excellent enough for the complex method tedious process and binding performance of current catalyst and electrode material, catalysis
Active deficiency defect, the present invention proposes a kind of preparation method of three nickel of water electrolysis hydrogen production curing-nickel electrode material, to real
The preparation of the electrode material of existing high stability and high catalytic activity, preparation process is simple, has the potentiality of large-scale production.
To solve the above problems, the present invention uses following technical scheme：
A kind of preparation method of hydrogen manufacturing three nickel of curing-nickel electrode material, uses nickel foam for substrate, thiocarbamide as sulphur source,
Specifically include following steps：
（1）Thiocarbamide is mixed with ethyl alcohol, is placed on magnetic stirring apparatus, is continuously stirred under 30-80rpm speed conditions, allows thiocarbamide
It is completely dissolved and ethyl alcohol, obtains compound sulphur source solution；
（2）Nickel foam is immersed in reaction vessel, using the heating rate of 5-20 DEG C/min, 170-180 DEG C is warming up to, is passed through
Oxygen in reaction vessel is discharged argon gas 20 minutes, reheats the compound sulphur source solution, and the ethyl alcohol dissolved with thiocarbamide is made to steam
Hair forms steam, and control argon flow amount is 230-300sccm, and the alcohol vapour dissolved with thiocarbamide is loaded into reaction by argon gas
Container；
（3）It is passed through ammonia into reaction vessel, and processing, control etching are performed etching to the nickel foam using cold plasma
Temperature is 170-180 DEG C, and for etching after 10-15 hours, cooling obtains three nickel of curing-nickel combination electrode material.
Preferably, a concentration of 1.5-1.8g/100mL of the thiocarbamide.
Preferably, the nickel foam aperture is 350-400 μm, porosity 97-99%, surface density 410-480g/m3。
Preferably, before the nickel foam being immersed reaction vessel, nickel foam is dipped in acetone, deionized water, dilute hydrochloric acid successively
Middle ultrasonic cleaning, is finally rinsed with deionized water, and suck dry moisture is simultaneously dried in vacuo.
Preferably, the heating temperature of the compound sulphur source solution is 80-130 DEG C.
Preferably, the flow of the steam is 10-30sccm.
Preferably, the ammonia flow control is in 230-300sccm.
Preferably, the cold plasma uses microwave plasma, microwave power 2-13kW.
Preferably, it is 1r/7s-1r/20s that sample levels rotating speed is arranged in the etching process.
A kind of three nickel of hydrogen manufacturing curing-nickel electrode material is provided, is prepared by the above method, it is equal in foam nickel surface
Even cladding thickness is 30-100 nm, and three nickel of curing of aperture 2-20 nm is porous nano-sheet.
Complex method for catalyst and electrode material is mostly compound using adhesive after preparing respectively, tedious process
And binding performance is not excellent enough.Meanwhile the catalyst with special construction such as large specific surface area is that electrode material is compound
It is susceptible to microdeformation in the process, to influence its catalytic efficiency.The electrode material structure prepared in existing improvement plan is not
Stablize, catalytic activity is insufficient, and electrolysis water hydrogen generation efficiency is relatively low.In consideration of it, the present invention proposes a kind of water electrolysis hydrogen production curing
The preparation method of three nickel-nickel electrode material is loaded into the ethyl alcohol dissolved with thiocarbamide by argon gas and is steamed using nickel foam as substrate
Vapour, while being passed through ammonia and cold plasma etching is carried out to nickel substrate, obtain three nickel of curing/nickel combination electrode material after cooling
Material.Catalyst prepared by the present invention is directly prepared by electrode material, large specific surface area, and catalyst is tied with electrode material interface
Structure is stablized, and carries out surface active by the oxide layer of plasma etching foam nickel surface, promotes thiocarbamide and nickel metal anti-rapidly
Three nickel of curing should be formed.The addition of alkaline gas makes surface topography become rough porous simultaneously, improves the specific surface of catalyst
Product, and then promote catalytic activity.Further, preparation process of the present invention is simple, has the potentiality of large-scale production.
Three nickel of curing-nickel electrode material and nickel foam prepared by the present invention is existed as electrode material as electrode material
It is tested for the property using three electrode test systems on electrochemical workstation CHI660E, as shown in table 1.
Table 1：
| Performance indicator | The present invention | Nickel foam | The nickel foam of coated with nano catalyst |
| 10 mA cm of current density -2Overpotential mV | 90-122 | 642 | 224 |
| Tafel slope V/dec | 0.142-0.151 | 0.189 | 0.167 |
A kind of preparation method of water electrolysis hydrogen production three nickel of curing-nickel electrode material of the present invention is dashed forward compared with prior art
The characteristics of going out and excellent effect are：
1, the present invention uses nickel foam as electrode material, and thiocarbamide passes through plasma etching foam nickel surface as sulphur source
Oxide layer carries out surface active, promotes thiocarbamide to be reacted rapidly with nickel foam and forms two sulphur of catalyst on foamed nickel electrode material surface
Change three nickel, that is, the catalyst prepared is directly prepared by electrode material, and electrode material is firmly combined with catalyst interface, is overcome
Not excellent enough the defect of the binding performance of current catalyst and electrode material, improves electrode material and catalyst stable composition
Property.
2, the present invention is passed through ammonia and carries out cold plasma etching to nickel substrate, and the addition of alkaline gas makes catalyst surface
Pattern becomes rough porous, improves the specific surface area of catalyst, and then improves composite material catalytic activity.
3, catalyst of the present invention is directly prepared by electrode material, and large specific surface area, preparation process is simple, is had big
The potentiality of large-scale production.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）The thiocarbamide of a concentration of 1.5g/100mL is mixed with ethyl alcohol, is placed on magnetic stirring apparatus, under 80rpm speed conditions
It continuously stirs, thiocarbamide is allowed to be dissolved completely in ethyl alcohol, obtain compound sulphur source solution；
（2）It is 1 × 1cm by size2Aperture is 350 μm, porosity 97%, surface density 480g/m3Nickel foam be dipped in successively
Be cleaned by ultrasonic in acetone, deionized water, dilute hydrochloric acid, finally rinsed with deionized water, suck dry moisture and temperature be 60 DEG C, into
Row 24 h vacuum drying.Treated nickel foam is immersed in reaction vessel, using the heating rate of 5 DEG C/min, is warming up to
It 170 DEG C, is passed through argon gas 20 minutes, the oxygen in reaction vessel is discharged, reheat the compound sulphur source solution, heating temperature is
80 DEG C, make the ethanol evaporation dissolved with thiocarbamide, form steam, control argon flow amount is 250sccm, and the flow of steam is
Alcohol vapour dissolved with thiocarbamide is loaded into reaction vessel by 10sccm by argon gas；
（3）Ammonia is passed through into reaction vessel, using microwave plasma, control microwave power is 10kW, to the nickel foam
Processing is performed etching, it is 1r/7s that setting sample stage, which horizontally rotates speed, and the foam nickel surface on sample stage is made uniformly to etch, and is controlled
Etching temperature processed is 170 DEG C, and etching is cooling to obtain in foam nickel surface uniform fold thickness being 40 nm, aperture 13 after 10 hours
Three nickel of curing of nm is three nickel of curing-nickel combination electrode material of porous nano-sheet.
The electrode material prepared in the embodiment of the present invention is tested：Three are used on electrochemical workstation CHI660E
Electrode test system, test use three-electrode system, i.e. working electrode, reference electrode and to electrode.Electrolysis water Hydrogen Evolution Performance is surveyed
The electrolyte of examination is 0.5M H2SO4.In order to ensure the H in electrolyte2Content is in saturation state, is needed during test
The H of high-purity is constantly passed through into electrolyte2.Calomel electrode is reference electrode, is to electrode, 25 DEG C of water-bath controls with carbon-point
Temperature, electrode scanning range are -0.3-1.0V, and 5mV/s sweep speeds test and obtain Tafel slope 0.149V/dec, liberation of hydrogen mistake
When current potential 90mV, current density is 10 mAcm-2.In 10 mAcm of current density-2Lower continued electrolysis is after 20 hours, liberation of hydrogen
Overpotential maintains 93mV or so without apparent decaying.
Embodiment 2
（1）The thiocarbamide of a concentration of 1.8g/100mL is mixed with ethyl alcohol, is placed on magnetic stirring apparatus, under 60rpm speed conditions
It continuously stirs, thiocarbamide is allowed to be dissolved completely in ethyl alcohol, obtain compound sulphur source solution；
（2）It is 1 × 1cm by size2Aperture is 400 μm, porosity 99%, surface density 410g/m3Nickel foam be dipped in successively
Be cleaned by ultrasonic in acetone, deionized water, dilute hydrochloric acid, finally rinsed with deionized water, suck dry moisture and temperature be 80 DEG C, carry out
12h is dried in vacuo.Treated nickel foam is immersed in reaction vessel, using the heating rate of 12 DEG C/min, is warming up to 172
DEG C, it is passed through argon gas 20 minutes, the oxygen in reaction vessel is discharged, reheat the compound sulphur source solution, heating temperature 130
DEG C, making the ethanol evaporation dissolved with thiocarbamide, forms steam, control argon flow amount is 230sccm, and the flow of steam is 30sccm,
The alcohol vapour dissolved with thiocarbamide is loaded into reaction vessel by argon gas；
（3）Ammonia is passed through into reaction vessel, using microwave plasma, control microwave power is 2kW, to the nickel foam into
Row etching processing, it is 1r/20s that setting sample stage, which horizontally rotates speed, and the foam nickel surface on sample stage is made uniformly to etch, and is etched
After 12 hours, cooling to obtain in foam nickel surface uniform fold thickness being 50 nm, three nickel of curing of 10 nm of aperture is porous
Three nickel of curing of nanometer sheet-nickel combination electrode material.
The electrode material prepared in the embodiment of the present invention is tested：Three are used on electrochemical workstation CHI660E
Electrode test system, test use three-electrode system, i.e. working electrode, reference electrode and to electrode.Electrolysis water Hydrogen Evolution Performance is surveyed
The electrolyte of examination is 0.5M H2SO4.In order to ensure the H in electrolyte2Content is in saturation state, is needed during test
The H of high-purity is constantly passed through into electrolyte2.Calomel electrode is reference electrode, is to electrode, 25 DEG C of water-bath controls with carbon-point
Temperature, electrode scanning range are -0.3-1.0V, and 5mV/s sweep speeds test and obtain Tafel slope 0.144V/dec, liberation of hydrogen mistake
When current potential 92mV, current density is 10 mAcm-2.In 10 mAcm of current density-2Lower continued electrolysis is after 20 hours, liberation of hydrogen
Overpotential maintains 93mV or so without apparent decaying.
Embodiment 3
（1）The thiocarbamide of a concentration of 1.7g/100mL is mixed with ethyl alcohol, is placed on magnetic stirring apparatus, under 40rpm speed conditions
It continuously stirs, thiocarbamide is allowed to be dissolved completely in ethyl alcohol, obtain compound sulphur source solution；
（2）It is 1 × 1cm by size2Aperture is 370 μm, porosity 97%, surface density 410g/m3Nickel foam be dipped in successively
Be cleaned by ultrasonic in acetone, deionized water, dilute hydrochloric acid, finally rinsed with deionized water, suck dry moisture and temperature be 68 DEG C, into
Row 19 h vacuum drying.Treated nickel foam is immersed in reaction vessel, using the heating rate of 8 DEG C/min, is warming up to
It 178 DEG C, is passed through argon gas 20 minutes, the oxygen in reaction vessel is discharged, reheat the compound sulphur source solution, heating temperature is
102 DEG C, make the ethanol evaporation dissolved with thiocarbamide, form steam, control argon flow amount is 280sccm, and the flow of steam is
Alcohol vapour dissolved with thiocarbamide is loaded into reaction vessel by 24sccm by argon gas；
（3）Ammonia is passed through into reaction vessel, using microwave plasma, control microwave power is 6kW, to the nickel foam into
Row etching processing, it is 1r/10s that setting sample stage, which horizontally rotates speed, and the foam nickel surface on sample stage is made uniformly to etch, and is etched
After 15 hours, cooling to obtain in foam nickel surface uniform fold thickness being 100 nm, three nickel of curing of aperture 2nm is porous receive
Three nickel of curing-nickel combination electrode material of rice piece.
The electrode material prepared in the embodiment of the present invention is tested：Three are used on electrochemical workstation CHI660E
Electrode test system, test use three-electrode system, i.e. working electrode, reference electrode and to electrode.Electrolysis water Hydrogen Evolution Performance is surveyed
The electrolyte of examination is 0.5M H2SO4.In order to ensure the H in electrolyte2Content is in saturation state, is needed during test
The H of high-purity is constantly passed through into electrolyte2.Calomel electrode is reference electrode, is to electrode, 25 DEG C of water-bath controls with carbon-point
Temperature, electrode scanning range are -0.3-1.0V, and 5mV/s sweep speeds test and obtain Tafel slope 0.147V/dec, liberation of hydrogen mistake
When current potential 96mV, current density is 10 mAcm-2.In 10 mAcm of current density-2Lower continued electrolysis is after 20 hours, liberation of hydrogen
Overpotential maintains 93mV or so without apparent decaying.
Embodiment 4
（1）The thiocarbamide of a concentration of 1.7 g/100mL is mixed with ethyl alcohol, is placed on magnetic stirring apparatus, under 70rpm speed conditions
It continuously stirs, thiocarbamide is allowed to be dissolved completely in ethyl alcohol, obtain compound sulphur source solution；
（2）It is 1 × 1cm by size2Aperture is 390 μm, porosity 98%, surface density 460g/m3Nickel foam be dipped in successively
Be cleaned by ultrasonic in acetone, deionized water, dilute hydrochloric acid, finally rinsed with deionized water, suck dry moisture and temperature be 77 DEG C, carry out
24 h are dried in vacuo.Treated nickel foam is immersed in reaction vessel, using the heating rate of 20 DEG C/min, is warming up to
It 180 DEG C, is passed through argon gas 20 minutes, the oxygen in reaction vessel is discharged, reheat the compound sulphur source solution, heating temperature is
120 DEG C, make the ethanol evaporation dissolved with thiocarbamide, form steam, control argon flow amount is 300sccm, and the flow of steam is
Alcohol vapour dissolved with thiocarbamide is loaded into reaction vessel by 27sccm by argon gas；
（3）Ammonia is passed through into reaction vessel, using microwave plasma, control microwave power is 11kW, to the nickel foam
Processing is performed etching, it is 1r/18s that setting sample stage, which horizontally rotates speed, and the foam nickel surface on sample stage is made uniformly to etch, and is carved
After erosion 13 hours, cooling to obtain in foam nickel surface uniform fold thickness being 70 nm, three nickel of curing of 8 nm of aperture is porous
Three nickel of curing of nanometer sheet-nickel combination electrode material.
The electrode material prepared in the embodiment of the present invention is tested：Three are used on electrochemical workstation CHI660E
Electrode test system, test use three-electrode system, i.e. working electrode, reference electrode and to electrode.Electrolysis water Hydrogen Evolution Performance is surveyed
The electrolyte of examination is 0.5M H2SO4.In order to ensure the H in electrolyte2Content is in saturation state, is needed during test
The H of high-purity is constantly passed through into electrolyte2.Calomel electrode is reference electrode, is to electrode, 25 DEG C of water-bath controls with carbon-point
Temperature, electrode scanning range are -0.3-1.0V, and 5mV/s sweep speeds test and obtain Tafel slope 0.142V/dec, liberation of hydrogen mistake
When current potential 107mV, current density is 10 mAcm-2.In 10 mAcm of current density-2Lower continued electrolysis is after 20 hours, liberation of hydrogen
Overpotential maintains 100mV or so without apparent decaying.
Embodiment 5
（1）The thiocarbamide of a concentration of 1.8g/100mL is mixed with ethyl alcohol, is placed on magnetic stirring apparatus, under 30rpm speed conditions
It continuously stirs, thiocarbamide is allowed to be dissolved completely in ethyl alcohol, obtain compound sulphur source solution；
（2）It is 1 × 1cm by size2Aperture is 390 μm, porosity 98%, surface density 410g/m3Nickel foam be dipped in successively
Be cleaned by ultrasonic in acetone, deionized water, dilute hydrochloric acid, finally rinsed with deionized water, suck dry moisture and temperature be 75 DEG C, into
Row 18 h vacuum drying.Treated nickel foam is immersed in reaction vessel, using the heating rate of 15 DEG C/min, is warming up to
It 175 DEG C, is passed through argon gas 20 minutes, the oxygen in reaction vessel is discharged, reheat the compound sulphur source solution, heating temperature is
110 DEG C, make the ethanol evaporation dissolved with thiocarbamide, form steam, control argon flow amount is 230sccm, and the flow of steam is
Alcohol vapour dissolved with thiocarbamide is loaded into reaction vessel by 28sccm by argon gas；
（3）Ammonia is passed through into reaction vessel, using microwave plasma, control microwave power is 4kW, to the nickel foam into
Row etching processing, it is 1r/20s that setting sample stage, which horizontally rotates speed, and the foam nickel surface on sample stage is made uniformly to etch, and is etched
After 11 hours, cooling to obtain in foam nickel surface uniform fold thickness being 80 nm, three nickel of curing of 20 nm of aperture is porous
Three nickel of curing of nanometer sheet-nickel combination electrode material.
The electrode material prepared in the embodiment of the present invention is tested：Three are used on electrochemical workstation CHI660E
Electrode test system, test use three-electrode system, i.e. working electrode, reference electrode and to electrode.Electrolysis water Hydrogen Evolution Performance is surveyed
The electrolyte of examination is 0.5M H2SO4.In order to ensure the H in electrolyte2Content is in saturation state, is needed during test
The H of high-purity is constantly passed through into electrolyte2.Calomel electrode is reference electrode, is to electrode, 25 DEG C of water-bath controls with carbon-point
Temperature, electrode scanning range are -0.3-1.0V, and 5mV/s sweep speeds test and obtain Tafel slope 0.151V/dec, liberation of hydrogen mistake
When current potential 122mV, current density is 10 mAcm-2.In 10 mAcm of current density-2Lower continued electrolysis is after 20 hours, liberation of hydrogen
Overpotential maintains 106mV or so without apparent decaying.
Comparative example 1
Aperture identical with size in embodiment 1 is 350 μm, porosity 97%, surface density 480g/m3Nickel foam conduct
Electrode material.
The electrode material prepared in comparative example 1 is tested, test condition is identical as embodiment 1-5, and experiment obtains tower
When Fei Er slope 0.189V/dec, overpotential of hydrogen evolution 642mV, current density is 10 mAcm-2.In 10 mA of current density
cm-2Lower continued electrolysis is after 20 hours, overpotential of hydrogen evolution decaying 19%.
Comparative example 2
Compound concentration is each 200ml of nickel nitrate solution of 0.1M vulcanized sodium and 0.1M, is stirred evenly under normal temperature condition, with glass
For substrate, substrate is submerged initially in 5min in sodium sulfide solution, is cleaned with deionized water after taking-up and removes undesired impurities, be then immersed in
5min in nickel nitrate solution finally takes out and is dried, in deionized water by surface sulfide nickel nano material stripping dispersion, will
It is coated in the foam nickel surface of size in the same manner as in Example 1, by dry obtained electrode material.
The electrode material prepared in comparative example 2 is tested, test condition is identical as embodiment 1-5, and experiment obtains tower
When Fei Er slope 0.167V/dec, overpotential of hydrogen evolution 224mV, current density is 10 mAcm-2.In 10 mA of current density
cm-2Lower continued electrolysis is after 20 hours, overpotential of hydrogen evolution decaying 6%.
It can be obtained by above-mentioned comparison, electrode material catalytic activity and catalytic life prepared by the present invention is significantly larger than steeped
The vulcanization Ni substrate of foam nickel substrate and surface coating nanometer nickel sulfide material.
Claims (10)
1. a kind of hydrogen manufacturing preparation method of three nickel of curing-nickel electrode material, which is characterized in that use nickel foam for substrate,
Thiocarbamide specifically includes following steps as sulphur source：
（1）Thiocarbamide is mixed with ethyl alcohol, is placed on magnetic stirring apparatus, is continuously stirred under 30-80rpm speed conditions, allows thiocarbamide
It is dissolved completely in ethyl alcohol, obtains compound sulphur source solution；
（2）Nickel foam is immersed in reaction vessel, using the heating rate of 5-20 DEG C/min, 170-180 DEG C is warming up to, is passed through
Oxygen in reaction vessel is discharged argon gas 20 minutes, reheats the compound sulphur source solution, and the ethyl alcohol dissolved with thiocarbamide is made to steam
Hair forms steam, and control argon flow amount is 230-300sccm, and the alcohol vapour dissolved with thiocarbamide is loaded into reaction by argon gas
Container；
（3）It is passed through ammonia into reaction vessel, and processing, control etching are performed etching to the nickel foam using cold plasma
Temperature is 170-180 DEG C, and for etching after 10-15 hours, cooling obtains three nickel of curing-nickel combination electrode material.
2. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
A concentration of 1.5-1.8g/100mL of the thiocarbamide.
3. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
The nickel foam aperture is 350-400 μm, porosity 97-99%, surface density 410-480g/m3。
4. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
Before the nickel foam is immersed reaction vessel, nickel foam, which is dipped in successively in acetone, deionized water, dilute hydrochloric acid, to be cleaned by ultrasonic, finally
It is rinsed with deionized water, suck dry moisture is simultaneously dried in vacuo.
5. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
The heating temperature of the compound sulphur source solution is 80-130 DEG C.
6. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
The flow of the steam is 10-30sccm.
7. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
The ammonia flow control is in 230-300sccm.
8. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
The cold plasma uses microwave plasma, microwave power 2-13kW.
9. the preparation method of a kind of hydrogen manufacturing three nickel of curing-nickel electrode material according to claim 1, which is characterized in that
It is 1r/7s-1r/20s that sample levels rotating speed is arranged in the etching process.
10. a kind of hydrogen manufacturing three nickel of curing-nickel electrode material, which is characterized in that prepared by the method described in claim 1-9
It forms, is 30-100 nm in foam nickel surface uniform fold thickness, three nickel of curing of aperture 2-20 nm is porous nano-sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810342048.9A CN108315761A (en) | 2018-04-17 | 2018-04-17 | A kind of preparation method of water electrolysis hydrogen production three nickel of curing-nickel electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810342048.9A CN108315761A (en) | 2018-04-17 | 2018-04-17 | A kind of preparation method of water electrolysis hydrogen production three nickel of curing-nickel electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108315761A true CN108315761A (en) | 2018-07-24 |
Family
ID=62897746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810342048.9A Withdrawn CN108315761A (en) | 2018-04-17 | 2018-04-17 | A kind of preparation method of water electrolysis hydrogen production three nickel of curing-nickel electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108315761A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020624A (en) * | 2019-11-29 | 2020-04-17 | 哈尔滨工业大学 | Preparation method of high-frequency vibration corrosion self-supporting electrocatalyst |
| CN111282582A (en) * | 2020-03-19 | 2020-06-16 | 苏州楚捷新材料科技有限公司 | Preparation method of foam nickel-based catalyst for hydrogen production by water electrolysis |
| CN112117469A (en) * | 2020-09-10 | 2020-12-22 | 广州大学 | Foamed nickel electrocatalyst and preparation method thereof |
| CN113186558A (en) * | 2021-03-15 | 2021-07-30 | 浙江大学 | Sponge nickel/octa-sulfide nine-nickel composite material and preparation method and application thereof |
| CN113403640A (en) * | 2021-06-16 | 2021-09-17 | 曾祥燕 | Transition group metal compound hydrogen evolution film and radio frequency back sputtering modification preparation method |
-
2018
- 2018-04-17 CN CN201810342048.9A patent/CN108315761A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111020624A (en) * | 2019-11-29 | 2020-04-17 | 哈尔滨工业大学 | Preparation method of high-frequency vibration corrosion self-supporting electrocatalyst |
| CN111282582A (en) * | 2020-03-19 | 2020-06-16 | 苏州楚捷新材料科技有限公司 | Preparation method of foam nickel-based catalyst for hydrogen production by water electrolysis |
| CN112117469A (en) * | 2020-09-10 | 2020-12-22 | 广州大学 | Foamed nickel electrocatalyst and preparation method thereof |
| CN112117469B (en) * | 2020-09-10 | 2022-02-15 | 广州大学 | Foamed nickel electrocatalyst and preparation method thereof |
| CN113186558A (en) * | 2021-03-15 | 2021-07-30 | 浙江大学 | Sponge nickel/octa-sulfide nine-nickel composite material and preparation method and application thereof |
| CN113403640A (en) * | 2021-06-16 | 2021-09-17 | 曾祥燕 | Transition group metal compound hydrogen evolution film and radio frequency back sputtering modification preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110148759B (en) | Preparation method of high-current-density-oriented proton exchange membrane fuel cell gas diffusion layer | |
| CN108315761A (en) | A kind of preparation method of water electrolysis hydrogen production three nickel of curing-nickel electrode material | |
| CN109449466B (en) | Preparation method of membrane electrode and preparation method of anode catalyst layer of membrane electrode | |
| CN109713321A (en) | A kind of adjustable membrane electrode of pore structure and preparation method thereof | |
| CN104846397B (en) | One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed | |
| CN109560310B (en) | Fuel cell ultra-low platinum loading self-humidifying membrane electrode and preparation method thereof | |
| CN112786937B (en) | Fuel cell membrane electrode and preparation method thereof | |
| CN111261878B (en) | Catalyst slurry containing aqueous gel, catalyst layer and fuel cell electrode produced therefrom | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN108832140A (en) | A kind of atomic layer deposition method prepares low platinum load copper nano-wire composite catalyst and its oxygen reduction reaction application | |
| CN114318361B (en) | Preparation method of vanadium oxide modified Raney nickel alloy electrode, electrode and application | |
| CN115064710A (en) | Membrane electrode CCM and preparation method thereof, membrane electrode assembly MEA and fuel cell | |
| CN114759199A (en) | Method for preparing Fe/N co-doped carbon nanotube under assistance of ZIF-8 derived carboxylate and application of method | |
| CN108232212B (en) | Hollow carbon nanosphere-loaded nano Ag particle fuel cell oxygen reduction catalyst and preparation method and application thereof | |
| CN116641081A (en) | Nickel-iron hydroxide gas diffusion electrode and preparation method and application thereof | |
| CN115472852A (en) | Preparation method and application of fuel cell oxygen evolution catalyst | |
| CN109037703A (en) | The preparation method and its application in zinc and air cell that a kind of surface has the bifunctional electrocatalyst of the fine nanometer package assembly of fold | |
| CN108842162A (en) | For electrochemical reduction CO2SnO2Nanometer sheet gas-diffusion electrode and method | |
| CN115050972A (en) | Polyhedral carbon shell layer loaded transition metal-based hydrogen oxidation catalyst carrier and preparation method and application thereof | |
| CN114899430A (en) | High-durability and anti-reversal-pole fuel cell CCM and preparation method thereof | |
| CN107482232A (en) | A kind of fuel cell oxygen reduction electrocatalyst phosphorus, the preparation method of nitrogen co-doped carbon material | |
| CN109585857A (en) | A kind of preparation method of fuel cell nitrogen-doped carbon carried platinum-based catalyst | |
| TWI459622B (en) | Preparation of Thin Film Fuel Cell Electrode Using Nano Carbide Carrier Catalyst by Low Voltage Electrophoresis | |
| CN110165241A (en) | Corrosion-resistant microporous layers of a kind of fuel cell based on graphitized carbon and preparation method thereof | |
| CN115763843B (en) | Preparation method of Fe/N-C composite catalyst |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180724 |
|
| WW01 | Invention patent application withdrawn after publication |