CN110205636B - Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode - Google Patents
Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode Download PDFInfo
- Publication number
- CN110205636B CN110205636B CN201910324963.XA CN201910324963A CN110205636B CN 110205636 B CN110205636 B CN 110205636B CN 201910324963 A CN201910324963 A CN 201910324963A CN 110205636 B CN110205636 B CN 110205636B
- Authority
- CN
- China
- Prior art keywords
- nickel
- electrode
- catalytic electrode
- self
- supporting
- 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.)
- Active
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 56
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004020 conductor Substances 0.000 claims abstract description 9
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 2
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229910003271 Ni-Fe Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- -1 using as cathode Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BPNRRQFZIBQRMK-UHFFFAOYSA-N [O-2].[Ta+5].[Ir+3].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ta+5].[Ir+3].[O-2].[O-2].[O-2] BPNRRQFZIBQRMK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
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
- 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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- 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
Abstract
The invention discloses a preparation method of a self-supporting three-dimensional porous structure bifunctional catalytic electrode, belonging to the technical field of hydrogen and oxygen preparation by electrolyzing water. The preparation of the bifunctional catalytic electrode takes a nickel net as a cathode and an inert conductor as an anode, and the electrodeposition is carried out in aqueous solution of nickel chloride and ammonium chloride under the conditions of normal temperature and normal pressure to prepare three-dimensional hierarchical porous nickel; then taking the obtained nickel net as a cathode of electrodeposition, using an inert conductor as an anode, immersing the nickel net into an aqueous solution containing nickel nitrate, ferrous sulfate and ethylene glycol, and performing electrodeposition treatment under the conditions of normal temperature and normal pressure to obtain a nickel iron/nickel catalytic electrode with a porous hierarchical structure; the invention realizes the electrode which has large effective active area, bubble precipitation channel and excellent conductivity and shows excellent electrochemical hydrogen and oxygen evolution performance under alkaline condition by two-step electrodeposition. The preparation process is simple, quick, pollution-free and easy to amplify, and is convenient for industrial production and manufacturing.
Description
Technical Field
The invention belongs to the technical field of hydrogen and oxygen preparation by electrolyzing water. In particular to a preparation method of a self-supporting three-dimensional porous structure bifunctional catalytic electrode,
background
With the rapid increase of energy demand and exhaustion of fossil fuels, there is a strong demand for the development of a green and clean energy source to replace the fossil fuels. The hydrogen is considered as an energy carrier in the future due to the advantages of high combustion heat value, wide source, no pollution of reaction products and the like. However, most of hydrogen is derived from the reforming process of natural gas or coal and petroleum at present, and is accompanied with the emission of a large amount of environmental pollutants such as carbon dioxide, sulfur dioxide and the like. Therefore, the development of a zero-carbon-emission hydrogen production technology by water electrolysis is one of the most potential hydrogen production technologies in the future. At present, the hydrogen production process by water electrolysis has high energy consumption and high cost, seriously hinders the development of large-scale water electrolysis industry, develops a hydrogen evolution catalyst and an oxygen evolution catalyst with high catalytic activity, and is an effective method for reducing the energy consumption in the water electrolysis process. Platinum group noble metals are considered to be the best performing hydrogen evolution catalysts, while iridium dioxide or ruthenium dioxide are the best oxygen evolution catalysts. Because the content of the metal elements in the earth crust is small, the market price is high, and the metal elements cannot be popularized and applied in the field of commercial electrolyzed water. Therefore, the research and development of the water electrolysis catalyst with low price, simple preparation process and high activity are very important. In addition, when preparing hydrogen evolution and oxygen evolution catalytic electrodes, if the anode and the cathode are made of different materials, the number of manufacturing equipment is increased, and the manufacturing cost is increased. Therefore, the self-supporting bifunctional catalytic electrode which is simple in research, development and preparation process, low in price and high in catalytic activity has important value.
At present, most of the electrocatalysts used in industry are powdery catalysts, and active materials need to be fixed on a current collector by using a binder and the like, and the processes have obvious defects. On one hand, the catalytic active sites are easily covered by the binder, reducing the catalytic activity; on the other hand, the use of the binder inevitably increases the preparation cost, and the preparation process is complicated. In order to solve the problem, the invention provides a preparation method of a self-supporting three-dimensional porous structure bifunctional catalytic electrode. The electrocatalyst and the current collector are combined into a whole, so that the preparation cost of the electrode can be reduced, and the stability of the catalytic electrode can be obviously improved. Meanwhile, the prepared electrode can be used as an anode hydrogen evolution electrode and a cathode oxygen evolution electrode, and the preparation cost of the electrode special for water electrolysis is greatly reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a self-supporting three-dimensional porous structure bifunctional catalytic electrode, which is characterized in that the method is used for preparing a nickel iron/nickel catalytic electrode with a porous hierarchical structure;
the preparation method of the self-supporting three-dimensional porous structure bifunctional catalytic electrode comprises the following steps:
the method comprises the following steps: taking a nickel net as a cathode and an inert conductor as an anode, and carrying out normal temperature and normal pressure treatment in an aqueous solution of nickel chloride and ammonium chloride at a current density of 1-5A/cm2Carrying out electrodeposition treatment under the condition;
step two: washing the cathode metallic nickel screen obtained in the first step with deionized water, wherein the metallic nickel screen is used as a cathode for the second step of electrodeposition, an inert conductor is used as an anode, and the metallic nickel screen is immersed in an aqueous solution containing nickel nitrate, ferrous sulfate and ethylene glycol at normal temperature and normal pressure and with the current density of 2-50mA/cm2Carrying out electrodeposition treatment under the condition to obtain a nickel iron/nickel catalytic electrode with a porous hierarchical structure, namely a self-supporting three-dimensional porous structure dual-function catalytic electrode;
and step three, after the two-step electrodeposition treatment in the given sequence, taking out the nickel mesh of the ferronickel/nickel electrode with the porous hierarchical structure, cleaning the surface with deionized water, and drying to obtain the finished product of the self-supporting three-dimensional porous structure bifunctional catalytic electrode.
The volume ratio of water to glycol in the water liquid used in the second step is 1: 0-1: 4.
The molar ratio of nickel nitrate to ferrous sulfate in the aqueous liquid in the second step is 1: 5-5: 1
The inert conductor is platinum or titanium ruthenium plating.
The metal nickel net in the first step can be replaced by foamed nickel, nickel wires, foamed copper, copper nets, carbon cloth and graphene films.
The prepared porous hierarchical structure ferronickel/nickel electrode is used for electrolyzing potassium hydroxide aqueous solution to produce hydrogen and oxygen, and the ferronickel/nickel electrode is used as a hydrogen evolution electrode and an oxygen evolution electrode.
The concentration of the electrolytic potassium hydroxide aqueous solution is 1-6 molar concentration.
Compared with the prior art, the preparation method has the advantages that the preparation process is simple, the technical method is easy to amplify, the raw materials are low in price, and the prepared electrode has high catalytic activity and excellent stability, can be used as an anode oxygen evolution electrode and a cathode hydrogen evolution electrode. The electrode is used for large-scale water electrolysis hydrogen production, and the energy consumption and the hydrogen production cost of the water electrolysis hydrogen production are effectively reduced. Therefore, the following advantages are provided:
1. the synthesis process is simple and quick, and the catalyst is only realized by two-step short-time electrodeposition;
2. the self-supporting three-dimensional porous structure bifunctional catalytic electrode is used as an anode and a cathode for electrolyzing water with the current density of 10mA/cm2The overpotential is only 33 millivolts, which is superior to that of noble metal platinum gold and commercial iridium tantalum oxide as cathode andperformance of the cell at the anode.
3. The bifunctional catalytic electrode can still keep lower overpotential and long-term use stability even under high current density, and the technical performance is superior to that of a noble metal catalyst.
Drawings
FIG. 1 is a scanning electron micrograph of a catalytic electrode, wherein a and b are scanning electron micrographs of porous-level nickel on a nickel mesh at different magnifications; c. d is the scanning electron microscope image of the nickel iron/nickel catalytic electrode with different magnification.
FIG. 2 is the oxygen evolution characteristics of a self-supporting three-dimensional porous structured nickel iron/nickel catalytic electrode;
FIG. 3 is a graph showing the effect of current density on the catalytic activity of the Ni-Fe/Ni catalytic electrode for oxygen evolution in step one;
FIG. 4 is a graph of the effect of aqueous solution composition on the catalytic activity of the ferronickel/nickel catalytic electrode for oxygen evolution in step two;
figure 5 is a graph of the hydrogen evolution performance of a nickel iron/nickel catalytic electrode.
Figure 6-1. linear voltammetric sweep curves of nickel iron/nickel catalytic electrodes as anode and cathode of electrolyzed water.
FIG. 6-2. Nickel iron/Nickel catalytic electrode for Water Electrolysis Process technical Performance
Detailed Description
The invention provides a preparation method of a self-supporting three-dimensional porous structure bifunctional catalytic electrode, and the prepared nickel iron/nickel catalytic electrode has a porous hierarchical structure.
The preparation method of the self-supporting three-dimensional porous structure bifunctional catalytic electrode comprises the following steps:
the method comprises the following steps: taking a nickel net as a cathode and an inert conductor (platinum or titanium ruthenium-plated) as an anode, and in an aqueous solution of nickel chloride and ammonium chloride, the current density is 1-5A/cm at normal temperature and normal pressure2Carrying out electrodeposition treatment under the condition;
step two: washing the cathode metallic nickel mesh obtained in the first step with deionized water, wherein the metallic nickel mesh is used as a cathode for the second step of electrodeposition, an inert conductor is used as an anode, and the cathode metallic nickel mesh is immersed in the electrolytic solution containing nickel nitrate and ferrous sulfate(molar ratio of 1: 5-5: 1) in an aqueous solution of ethylene glycol at normal temperature and normal pressure, and at a current density of 2-50mA/cm2Carrying out electrodeposition treatment under the condition to obtain a ferronickel/nickel electrode with a porous hierarchical structure, namely a self-supporting three-dimensional porous structure dual-function catalytic electrode;
and step three, after the two-step electrodeposition treatment in the given sequence, taking out the nickel mesh of the ferronickel/nickel electrode with the porous hierarchical structure, cleaning the surface with deionized water, and drying to obtain the finished product of the self-supporting three-dimensional porous structure bifunctional catalytic electrode. The present invention will be further described with reference to the following embodiments.
Example 1
The method comprises the following steps: cleaning nickel screen with dilute hydrochloric acid, ethanol, and ultrapure water, using as cathode, platinum sheet as anode, and configuring 0.1M Ni (Cl)2And 2M NH4Putting a Cl solution serving as an electrolyte into a beaker, connecting a positive electrode and a negative electrode of a direct current power supply with a platinum sheet and a nickel screen respectively, and installing the Cl solution into the beaker to enable the solution to immerse the electrodes; setting the current density to be 3A/cm at room temperature2And the electrodeposition treatment was carried out for 90 seconds.
Step two: immersing the porous nickel subjected to electrodeposition in the first step as a cathode in 1.5M Fe (NO)3)2And 1.5M Ni (NO)3)2(volume ratio 1: 1) in the electrolyte solution, connecting the positive pole of a direct current power supply with a platinum sheet, connecting the negative pole of the direct current power supply with a nickel net, and setting the current density to be 5mA/cm at room temperature2And performing electrodeposition treatment for 450 seconds to obtain the self-supporting three-dimensional porous-level nickel iron/nickel electrode.
In fig. 1, a and b are Scanning Electron Microscope (SEM) images of porous nickel obtained by electrodeposition in step one of example 1, and it can be seen that a hierarchical porous structure is formed on the nickel mesh fiber. In fig. 1, c and d are SEM images of ni-fe/ni after electrodeposition in step two of example 1, and it can be seen that the layered ni-fe hydroxide grows uniformly on the hierarchical porous ni.
Testing the prepared oxygen evolution electrode serving as a working electrode, a platinum sheet serving as a counter electrode and mercury oxide serving as a reference electrode in a 1M KOH solutionFollowing an electrochemical linear voltammetric scan, as shown in FIG. 2, it can be seen that the nickel iron/nickel exhibits excellent oxygen evolution activity at a current density of 10mA/cm2The overpotential required is only 190 mV.
Example 2
Cleaning nickel screen with dilute hydrochloric acid, ethanol, and ultrapure water, using as cathode, platinum sheet as anode, 0.1MNi (Cl)2And 2M NH4Cl solution is used as electrolyte, and the current density is respectively set to be 1A/cm under the condition of room temperature2、3A/cm2、5A/cm2And electrodeposition is carried out for 90 seconds. Porous nickel after electrodeposition as cathode, 1.5MFe (NO)3)2And 1.5M Ni (NO)3)2(volume ratio 1: 1) as electrolyte, at room temperature, at a current density of 5mA/cm2And electrodepositing for 450 seconds to obtain the self-supporting three-dimensional porous-level nickel iron/nickel electrode. The method comprises a second step of electrodepositing with a current density of 2-50mA/cm2Can also be implemented within the scope
FIG. 3 is the effect of current density in step one of example 2, and it can be seen that when the electrodeposition in step two is ensured to be the same, the electrodeposition current density in step one is increased, and the catalytic activity as an oxygen evolution catalytic electrode is also remarkably increased, but when the current density in step one is more than 3mA/cm2Then, the catalytic activity is similar.
Example 3
Cleaning nickel screen with dilute hydrochloric acid, ethanol, and ultrapure water, using as cathode, platinum sheet as anode, 0.1MNi (Cl)2And 2M NH4Cl solution is used as electrolyte, and the current density is 3A/cm at room temperature2And electrodeposition is carried out for 90 seconds. Using the electrodeposited porous nickel as a cathode, and 1.5M Fe (NO)3)2And 1.5M Ni (NO)3)2(volume ratio 1: 1) as electrolyte, the ratio of water dissolved in water to glycol is 1: 0. 1: 1. 1:4 at room temperature, the current density was kept at 5mA/cm2And performing electrodeposition treatment for 450 seconds to obtain the self-supporting three-dimensional porous-level nickel iron/nickel electrode. The method comprises a second step of electrodepositing with a current density of 2-50mA/cm2Within the range ofApplying (a) to
FIG. 4 is a graph showing the effect of different electrolyte ratios on catalytic electrode activity in example 3, and it can be seen that the catalytic activity increases to a small extent as the proportion of ethylene glycol increases.
Example 4
Cleaning nickel screen with dilute hydrochloric acid, ethanol, and ultrapure water, using as cathode, platinum sheet as anode, 0.1MNi (Cl)2And 2M NH4Cl solution is used as electrolyte, and the current density is 3A/cm at room temperature2And electrodeposition is carried out for 90 seconds. Using the electrodeposited porous nickel as a cathode, 1.5M Fe (NO)3)2And 1.5M Ni (NO)3)2(volume ratio 1: 1) as electrolyte, at room temperature, at a current density of 5mA/cm2And electrodepositing for 200 seconds to obtain the self-supporting three-dimensional porous-level nickel iron/nickel electrode.
FIG. 5 shows that the Ni-Fe/Ni electrode of example 3 is used as a hydrogen evolution electrode, and the Ni-Fe bimetal is grown in situ on the porous nickel layer, so that the hydrogen evolution activity of the Ni-Fe can be remarkably improved, and the current density of the Ni-Fe/Ni electrode is 10mA/cm2The overpotential required is only 132mV.
Example 5
Electrochemical linear voltammetric scans in a 1M KOH solution using the electrode prepared in example 2 as the anode and the electrode prepared in example 4 as the cathode (FIG. 6-1) showed excellent electrochemical performance at a current density of 10mA/cm2At the same time, the required electrolysis voltage is only 1.56V, and the bifunctional catalyst shows excellent stability at 500mA/cm2The electrolytic voltage does not change obviously when the constant current electrolytic water runs for 200 hours (figure 6-2).
Claims (2)
1. A preparation method of a self-supporting three-dimensional porous structure bifunctional catalytic electrode is characterized in that the method is used for preparing a nickel iron/nickel catalytic electrode with a porous hierarchical structure;
the preparation method of the self-supporting three-dimensional porous structure bifunctional catalytic electrode comprises the following steps:
the method comprises the following steps: taking a nickel net as a cathode and an inert conductor as an anode, and carrying out normal temperature and normal pressure treatment in an aqueous solution of nickel chloride and ammonium chloride at a current density of 1-5A/cm2Carrying out electrodeposition treatment under the condition;
step two: washing the cathode metal nickel mesh obtained in the first step with deionized water, wherein the metal nickel mesh is used as a cathode for the second step of electrodeposition, an inert conductor platinum or titanium ruthenium plating is used as an anode, and the metal nickel mesh is immersed in an aqueous solution containing nickel nitrate, ferrous sulfate and ethylene glycol at normal temperature and normal pressure with the current density of 2-50mA/cm2Carrying out electrodeposition treatment under the condition to obtain a nickel iron/nickel catalytic electrode with a porous hierarchical structure, namely a self-supporting three-dimensional porous structure dual-function catalytic electrode;
step three, after the two-step electrodeposition treatment in the given sequence, taking out the nickel mesh of the ferronickel/nickel electrode with the porous hierarchical structure, cleaning the surface with deionized water, and drying to obtain the finished product of the self-supporting three-dimensional porous structure bifunctional catalytic electrode; the volume ratio of water to glycol in the water liquid used in the second step is 1: 0-1: 4; and the mol ratio of the nickel nitrate to the ferrous sulfate in the step two immersed in the aqueous solution containing the nickel nitrate, the ferrous sulfate and the ethylene glycol is 1: 5-5: 1.
2. the method for preparing the self-supporting three-dimensional porous structure bifunctional catalytic electrode as claimed in claim 1, wherein the prepared porous hierarchical structure ferronickel/nickel electrode is used for electrolyzing potassium hydroxide aqueous solution to produce hydrogen and oxygen, and the ferronickel/nickel electrode is used as both hydrogen evolution electrode and oxygen evolution electrode;
the concentration of the electrolytic potassium hydroxide aqueous solution is 1-6 molar concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910324963.XA CN110205636B (en) | 2019-04-22 | 2019-04-22 | Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910324963.XA CN110205636B (en) | 2019-04-22 | 2019-04-22 | Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110205636A CN110205636A (en) | 2019-09-06 |
| CN110205636B true CN110205636B (en) | 2020-09-22 |
Family
ID=67786126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910324963.XA Active CN110205636B (en) | 2019-04-22 | 2019-04-22 | Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110205636B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112044458B (en) * | 2020-08-21 | 2021-07-20 | 广东工业大学 | Multi-level metal phosphide and preparation method and application thereof |
| CN112695340B (en) * | 2021-01-03 | 2022-01-04 | 山东海氢能源科技有限公司 | Preparation method of S-La-Ni/foamed nickel cathode material |
| CN112921351B (en) * | 2021-01-22 | 2022-06-10 | 清华大学 | Preparation method and application of self-supporting catalytic electrode |
| CN113913846A (en) * | 2021-11-09 | 2022-01-11 | 西南石油大学 | Water electrolysis hydrogen production oxygen generation reaction device |
| CN114000176B (en) * | 2021-12-02 | 2023-01-24 | 合肥工业大学 | Preparation method of difunctional electrolyzed water catalyst coating |
| CN114927705B (en) * | 2022-05-16 | 2023-10-27 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of self-supporting bubble-free suspension electrode for oxygen precipitation reaction |
| CN114990627B (en) * | 2022-07-13 | 2023-12-01 | 长沙理工大学 | NiFe LDHs-NiFe alloy gradient transition catalytic material and application thereof |
| CN115369418A (en) * | 2022-08-04 | 2022-11-22 | 同济大学 | Electrode with integrated composite structure of matrix and catalyst layer and preparation method thereof |
| CN116575045B (en) * | 2023-07-14 | 2023-09-26 | 西湖大学 | MEA water splitting device applied to water splitting catalysis and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2015303818B2 (en) * | 2014-08-11 | 2020-08-13 | Newsouth Innovations Pty Limited | Catalytic assembly |
| CN107385489B (en) * | 2016-05-15 | 2019-05-17 | 北京化工大学 | A kind of three-dimensional manometer flower-shape Ni-Fe complex hydroxide analysis oxygen anodes for carbonate electrolyte |
| JP2018043193A (en) * | 2016-09-14 | 2018-03-22 | 株式会社東芝 | Light-transmitting oxygen evolution catalyst and production method of the same, and chemical reactor using the same |
| CN108193227A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Oxygen electrode and its preparation and application are analysed in the electro-catalysis of nickel-ferric spinel base |
-
2019
- 2019-04-22 CN CN201910324963.XA patent/CN110205636B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110205636A (en) | 2019-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110205636B (en) | Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode | |
| CN106917105B (en) | A kind of preparation method of water decomposition self-supporting transient metal sulfide foam electrode | |
| CN109659143B (en) | Nickel hydroxide/trinickel disulfide/foamed nickel compound and preparation method and application thereof | |
| CN111905744B (en) | Nickel-iron hydroxide composite material, catalyst, preparation method and application | |
| CN112626540B (en) | Multi-stage structure electrode for water electrolysis and preparation method thereof | |
| CN112264047B (en) | Noble metal monoatomic catalyst for electrolyzing water to generate oxygen and preparation method and application thereof | |
| CN108554426B (en) | Difunctional cobalt diselenide material and preparation and application thereof | |
| Xu et al. | One-step electrosynthesis of NiFe-NF electrodes for highly efficient overall water splitting | |
| CN110711597B (en) | Co-Mo-P-O electrocatalyst and preparation method and application thereof | |
| CN105148920A (en) | Self-supporting transition metal-metal alloy catalyst as well as preparation method and application of self-supporting transition metal-metal alloy catalyst | |
| CN113136597B (en) | Copper-tin composite material and preparation method and application thereof | |
| CN110404540B (en) | Preparation method of hollow-out iron-selenium derivative catalyst, product and application thereof | |
| CN115142073A (en) | Preparation and application of FeCoNiCuMn nano high-entropy alloy electrocatalyst | |
| Ganci et al. | Electrodeposited nickel–zinc alloy nanostructured electrodes for alkaline electrolyzer | |
| CN111569884B (en) | Ni-Fe catalyst and preparation method and application thereof | |
| CN113005476A (en) | Preparation method and application of nickel hydroxide/nickel electrode | |
| CN110230072B (en) | Preparation method and application of N-NiZnCu LDH/rGO nanosheet array material on foamed nickel | |
| CN112501645B (en) | Nickel hydroxide/nickel screen composite hydrogen and oxygen evolution electrode, preparation method and application thereof | |
| CN112921351B (en) | Preparation method and application of self-supporting catalytic electrode | |
| CN105047884A (en) | Three-dimensional oxygen-evolution electrode anode material, and preparation method and application thereof | |
| CN114150329A (en) | Efficient nickel-based self-assembly oxygen evolution electrode | |
| CN113293407A (en) | Iron-rich nanobelt oxygen evolution electrocatalyst and preparation method thereof | |
| CN116103693B (en) | Hydrogen evolution electrode, preparation method thereof and application thereof in hydrogen production by water electrolysis | |
| CN113604837B (en) | Hydrogen production catalytic material and preparation method and application thereof | |
| CN114807967B (en) | Preparation method of Ir-modified Ni/NiO porous nanorod array full-water-splitting 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221104 Address after: No. 10, Tianjingshan Road, Wuhu Hi tech Industrial Development Zone, Yijiang District, Wuhu City, Anhui Province 241000 Patentee after: Anhui Qinghe Energy Technology Co.,Ltd. Address before: 100084 Tsinghua University, Beijing, Haidian District Patentee before: TSINGHUA University |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No. 10, Tianjingshan Road, Wuhu Hi tech Industrial Development Zone, Yijiang District, Wuhu City, Anhui Province 241000 Patentee after: Anhui Qinghydrogen Energy Technology Co.,Ltd. Address before: No. 10, Tianjingshan Road, Wuhu Hi tech Industrial Development Zone, Yijiang District, Wuhu City, Anhui Province 241000 Patentee before: Anhui Qinghe Energy Technology Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |