CN113668005A - Porous nickel electrode and preparation method thereof - Google Patents
Porous nickel electrode and preparation method thereof Download PDFInfo
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- CN113668005A CN113668005A CN202111048850.5A CN202111048850A CN113668005A CN 113668005 A CN113668005 A CN 113668005A CN 202111048850 A CN202111048850 A CN 202111048850A CN 113668005 A CN113668005 A CN 113668005A
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- 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
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- 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
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- 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
- C25B11/061—Metal or alloy
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- 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
- C25B11/089—Alloys
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- 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
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Abstract
The invention discloses a porous nickel electrode and a preparation method thereof, the porous nickel electrode comprises a substrate, wherein the substrate is nickel-based nano amorphous alloy, the surface of the substrate is covered with an electrode layer, the electrode layer comprises nano porous nickel, the electrode is flaky and the surface of the electrode is net-shaped, the electrode substrate is purified by using a metal electromigration load technology, the electrode substrate is pretreated, the surface of the electrode substrate is cleaned, the preparation of the nano porous nickel is firstly completed, the smelting of the nickel alloy is completed, the prepared nickel alloy is selectively corroded by an alloying removal process, the nano porous nickel alloy is obtained by corrosion, the alloy is pressed into a thin strip according to the size requirement and cut into sections; the real surface area of the nano porous nickel is far larger than the apparent area, so that the contact area of the electrolyte and the electrode material can be effectively increased, the real current density on the surface of the electrode can be effectively reduced in the industrial electrolysis process with higher current density, and the hydrogen evolution overpotential of the electrode in the electrolysis reaction process is greatly reduced.
Description
Technical Field
The invention relates to the technical field of electrodes, in particular to a porous nickel electrode and a preparation method thereof.
Background
At present, a new energy technical revolution is rising in the world, the international energy pattern is also changing deeply, renewable energy is gradually becoming a main source of newly added electric power, the structure and the operation mode of a power grid are changed significantly, the medium is used as a clean low-carbon energy utilization medium, large-scale consumption of fluctuating renewable energy can be realized, hydrogen has the dual property of energy and matter communication, the medium is an important link for extending electric energy to various industry fields to replace fossil fuel, and no atmospheric pollutants and greenhouse gases are discharged in the use process, so the development of the hydrogen energy industry is an important way for the challenges, and has important strategic significance for constructing a low-carbon clean energy system, responding to environmental challenges, promoting energy revolution, ensuring energy safety and the like;
the hydrogen production by water electrolysis is regarded as the mainstream technology applied to the renewable energy consumption and production of green hydrogen in the future, and is mainly divided into 3 types: the hydrogen production by alkaline electrolysis of water, the hydrogen production by proton exchange membrane electrolysis of water and the hydrogen production by solid oxide electrolyte electrolysis of water are relatively mature, the hydrogen production devices run commercially at home and abroad, the SOE technology is still in the research and development demonstration stage, and the PEM water electrolysis hydrogen production device has higher cost which is about 3 times that of the alkaline water electrolysis device generally;
at present, the main problems of hydrogen production by water electrolysis are high energy consumption and low efficiency, and 80% -90% of cost is electricity charge in water electrolysis production, so that the key point of how to reduce the energy consumption of water electrolysis is the problem, and therefore, a porous nickel electrode and a preparation method thereof are provided.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the porous nickel electrode and the preparation method thereof, the real surface area of the nano porous nickel is far larger than the apparent area, and the contact area between the electrolyte and the electrode material can be effectively increased, so that the real current density of the electrode surface can be effectively reduced in the industrial electrolysis process with higher current density, and the hydrogen evolution overpotential of the electrode in the electrolysis reaction process is greatly reduced.
In order to solve the technical problems, the invention provides the following technical scheme: the porous nickel electrode comprises a substrate, wherein the substrate is nickel-based nano amorphous alloy, an electrode layer is covered on the surface of the substrate and comprises nano porous nickel, and the electrode is flaky and has a net-shaped surface.
Preferably, the substrate comprises nickel foam and the outer surface of the electrode is corrugated.
A preparation method of a porous nickel electrode comprises the following steps:
s1, selecting nickel-based nano amorphous alloy as an electrode substrate;
s2, purifying the electrode substrate by using a metal electromigration load technology;
s3, pretreating the electrode substrate, and finishing surface cleaning;
s4, preparing nano porous nickel, namely firstly, smelting a nickel alloy;
s5, selectively corroding parts of the prepared nickel alloy through a de-alloying process;
s6, corroding to obtain the nano-porous nickel alloy;
and S7, pressing the alloy into thin strips according to the size requirement and cutting the thin strips into sections.
Preferably, the surface treatment in the step S3 includes polishing, removing an oxide film, and cleaning.
Preferably, the nickel alloy in the step S4 is a NiFeMn alloy, wherein the content of Ni atoms is 10% to 30%, the content of Mn atoms is 50% to 75%, and the balance is Fe atoms.
Preferably, in the step S5, a chemical dealloying method or an electrochemical dealloying method is selected.
Preferably, the pore size distribution in the step S6 is between 5 and 80nm, and the specific surface area is between 10 and 100m 2/g.
Compared with the prior art, the invention can achieve the following beneficial effects:
the nickel-based nano amorphous alloy can enable chemical bonds formed by the hydrogen evolution electrode and active H in a solution to have proper adsorption bond strength, so that in the electrochemical process of hydrogen evolution reaction, the adsorption or desorption capacity of the active H is improved, the polarization resistance in the electrochemical reaction process of hydrogen evolution can be effectively reduced, the hydrogen evolution electrocatalytic activity of the electrode is improved, the contact area between the electrode and electrolyte is increased by the nano porous nickel, the real current density of a polar plate is improved, the real surface area of the nano porous nickel is far larger than the apparent area, the contact area between the electrolyte and an electrode material can be effectively increased, the real current density of the electrode surface can be effectively reduced in the industrial electrolysis process with high current density, and the hydrogen evolution overpotential of the electrode in the electrolysis reaction process is greatly reduced.
Detailed Description
The present invention will be further described with reference to specific embodiments for the purpose of facilitating an understanding of technical means, characteristics of creation, objectives and functions realized by the present invention, but the following embodiments are only preferred embodiments of the present invention, and are not intended to be exhaustive. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention. The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
A porous nickel electrode comprises a substrate, wherein the substrate is nickel-based nano amorphous alloy, an electrode layer is covered on the surface of the substrate and comprises nano porous nickel, and the electrode is flaky and has a net-shaped surface.
The invention discloses a matrix comprising foamed nickel, wherein the outer surface of an electrode is corrugated;
a preparation method of a porous nickel electrode comprises the following steps:
s1, selecting nickel-based nano amorphous alloy as an electrode substrate;
s2, purifying the electrode substrate by using a metal electromigration load technology;
s3, pretreating the electrode substrate, and finishing surface cleaning, wherein the surface treatment comprises polishing, removing an oxidation film and cleaning;
s4, preparing nano porous nickel, namely firstly, smelting a nickel alloy;
s5, selectively corroding parts of the prepared nickel alloy through a de-alloying process;
s6, corroding to obtain the nano-porous nickel alloy;
and S7, pressing the alloy into thin strips according to the size requirement and cutting the thin strips into sections.
Example 2
A preparation method of a porous nickel electrode comprises the following steps:
s1, selecting nickel-based nano amorphous alloy as an electrode substrate;
s2, purifying the electrode substrate by using a metal electromigration load technology;
s3, pretreating the electrode substrate, and finishing surface cleaning, wherein the surface treatment comprises polishing, removing an oxidation film and cleaning;
s4, preparing nano porous nickel, namely firstly smelting a nickel alloy, wherein the nickel alloy is NiFeMn alloy, the Ni atom content is 10%, the Mn atom content is 75%, and the balance is Fe atoms;
s5, selectively corroding the nickel alloy part through a de-alloying process, selecting a chemical de-alloying method, and corroding with 0.005-0.05mol/L hydrochloric acid or 0.2-8mol/L weak acidic ammonium sulfate solution for 2-8 hours;
s6, corroding to obtain the nano-porous nickel alloy;
and S7, pressing the alloy into thin strips according to the size requirement and cutting the thin strips into sections.
Example 3
A preparation method of a porous nickel electrode comprises the following steps:
s1, selecting nickel-based nano amorphous alloy as an electrode substrate;
s2, purifying the electrode substrate by using a metal electromigration load technology;
s3, pretreating the electrode substrate, and finishing surface cleaning, wherein the surface treatment comprises polishing, removing an oxidation film and cleaning;
s4, preparing nano porous nickel, namely smelting a nickel alloy, wherein the nickel alloy is NiFeMn alloy, the Ni atom content is 30%, the Mn atom content is 50%, and the balance is Fe atoms;
s5, selectively corroding the nickel alloy part through a de-alloying process, selecting an ammonium sulfate solution of 1-5 mol/L by using an electrochemical de-alloying method according to the relation between potential and PH, selecting a de-alloying potential of-0.2V-1.2V, and controlling the de-alloying time to be 2-8 h;
s6, corroding to obtain the nano-porous nickel alloy;
and S7, pressing the alloy into thin strips according to the size requirement and cutting the thin strips into sections.
Example 4
A preparation method of a porous nickel electrode comprises the following steps:
s1, selecting foamed nickel as an electrode substrate;
s2, pretreating the electrode substrate, and finishing surface cleaning, wherein the surface treatment comprises polishing, removing an oxidation film and cleaning;
s3, preparing nano porous nickel, namely smelting a nickel alloy, wherein the nickel alloy is a Ni-Ti-Zr-Al alloy, and removing surface oxide skin of a Ni-Ti-Zr-Al alloy ingot;
s4, selectively corroding a part of the prepared nickel alloy through a de-alloying process, placing the nickel alloy in hydrofluoric acid corrosive liquid at room temperature for free de-alloying treatment for 1-5 hours, and then washing with deionized water;
s5, corroding to obtain the nano-porous nickel alloy;
and S6, pressing the alloy into thin strips according to the size requirement and cutting the thin strips into sections.
The invention provides a porous nickel electrode and a preparation method thereof, the nickel-based nano amorphous alloy can ensure that a chemical bond formed by a hydrogen evolution electrode and active H in a solution has proper adsorption bond strength, therefore, in the electrochemical process of hydrogen evolution reaction, the method is beneficial to improving the adsorption or desorption capacity of active H, further effectively reducing the polarization resistance in the hydrogen evolution electrochemical reaction process, thereby improving the hydrogen evolution electrocatalytic activity of the electrode, increasing the contact area between the electrode and the electrolyte and improving the real current density of the polar plate, wherein the real surface area of the nano porous nickel is far larger than the apparent area, effectively increasing the contact area between the electrolyte and the electrode material, therefore, in the industrial electrolysis process with higher current density, the real current density on the surface of the electrode can be effectively reduced, and the hydrogen evolution overpotential of the electrode in the electrolysis reaction process is greatly reduced.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The porous nickel electrode is characterized by comprising a substrate, wherein the substrate is nickel-based nano amorphous alloy, an electrode layer covers the surface of the substrate and comprises nano porous nickel, and the electrode is flaky and has a net-shaped surface.
2. A porous nickel electrode according to claim 1, wherein: the substrate comprises foamed nickel, and the outer surface of the electrode is corrugated.
3. A preparation method of a porous nickel electrode is characterized by comprising the following steps:
s1, selecting nickel-based nano amorphous alloy as an electrode substrate;
s2, purifying the electrode substrate by using a metal electromigration load technology;
s3, pretreating the electrode substrate, and finishing surface cleaning;
s4, preparing nano porous nickel, namely firstly, smelting a nickel alloy;
s5, selectively corroding parts of the prepared nickel alloy through a de-alloying process;
s6, corroding to obtain the nano-porous nickel alloy;
and S7, pressing the alloy into thin strips according to the size requirement and cutting the thin strips into sections.
4. The method for preparing a porous nickel electrode according to claim 3, wherein: the surface treatment in the step S3 includes polishing, removing an oxide film, and cleaning.
5. The method for preparing a porous nickel electrode according to claim 3, wherein: the nickel alloy in the step S4 is NiFeMn alloy, wherein the content of Ni atoms is 10-30%, the content of Mn atoms is 50-75%, and the balance is Fe atoms.
6. The method for preparing a porous nickel electrode according to claim 3, wherein: in the step S5, a chemical dealloying method or an electrochemical dealloying method is selected.
7. The method for preparing a porous nickel electrode according to claim 3, wherein: the pore diameter distribution in the step S6 is between 5 and 80nm, and the specific surface area is 10 to 100m 2/g.
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| CN202111048850.5A CN113668005A (en) | 2021-09-08 | 2021-09-08 | Porous nickel electrode and preparation method thereof |
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| CN202111048850.5A CN113668005A (en) | 2021-09-08 | 2021-09-08 | Porous nickel electrode and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117568835A (en) * | 2023-11-20 | 2024-02-20 | 株洲国创轨道科技有限公司 | Preparation method of high-performance porous self-supporting electrolyzed water hydrogen evolution electrode and rapid printing device |
Citations (4)
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| CN106967997A (en) * | 2017-02-24 | 2017-07-21 | 天津工业大学 | A kind of efficient self-supporting catalysis electrode and its preparation method and application |
| CN107863253A (en) * | 2017-10-16 | 2018-03-30 | 天津工业大学 | A kind of nanoporous nickel-iron-manganese alloys/oxides combination electrode and preparation method thereof |
| CN107868959A (en) * | 2016-09-23 | 2018-04-03 | 中国科学院金属研究所 | A kind of lithographic method for increasing foam nickel electrode electrochemical surface area |
| 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 |
-
2021
- 2021-09-08 CN CN202111048850.5A patent/CN113668005A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868959A (en) * | 2016-09-23 | 2018-04-03 | 中国科学院金属研究所 | A kind of lithographic method for increasing foam nickel electrode electrochemical surface area |
| CN106967997A (en) * | 2017-02-24 | 2017-07-21 | 天津工业大学 | A kind of efficient self-supporting catalysis electrode and its preparation method and application |
| CN107863253A (en) * | 2017-10-16 | 2018-03-30 | 天津工业大学 | A kind of nanoporous nickel-iron-manganese alloys/oxides combination electrode and preparation method thereof |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117568835A (en) * | 2023-11-20 | 2024-02-20 | 株洲国创轨道科技有限公司 | Preparation method of high-performance porous self-supporting electrolyzed water hydrogen evolution electrode and rapid printing device |
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