CN114481190A - Preparation method of electrode for hydrogen production, electrode for hydrogen production and electrolysis device - Google Patents

Preparation method of electrode for hydrogen production, electrode for hydrogen production and electrolysis device Download PDF

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CN114481190A
CN114481190A CN202210121443.0A CN202210121443A CN114481190A CN 114481190 A CN114481190 A CN 114481190A CN 202210121443 A CN202210121443 A CN 202210121443A CN 114481190 A CN114481190 A CN 114481190A
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active coating
substrate
heat treatment
organic salt
electrode
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高珊
李爽
付正
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Bluestar Beijing Chemical Machinery Co Ltd
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Bluestar Beijing Chemical Machinery Co Ltd
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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
    • 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
    • C25B11/04—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
    • C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The application discloses a preparation method of an electrode for hydrogen production, the electrode for hydrogen production and an electrolysis device, wherein the preparation method comprises the following steps: obtaining soluble organic salt; dissolving the soluble organic salt in an organic solution with a set concentration range, and uniformly mixing to obtain an active coating masking liquid; carrying out roughening treatment on the surface of a nickel or nickel alloy substrate; carrying out heat treatment on the roughened substrate in an oxygen-containing atmosphere to oxidize the surface of the substrate to obtain a metal substrate with the surface containing nickel oxide; coating the active coating masking liquid on the surface of a substrate subjected to surface oxidation treatment, carrying out heat treatment on the substrate coated with the active coating masking liquid in an oxygen-containing atmosphere, and rapidly cooling to room temperature to generate an active coating; repeating the coating of the active coating liquid to generate a plurality of active coatings, and carrying out final heat treatment. The electrode has the advantages of low oxygen evolution overpotential, long service life and more accurate content ratio of main components.

Description

Preparation method of electrode for hydrogen production, electrode for hydrogen production and electrolysis device
Technical Field
The application relates to a hydrogen production technology by using electrolyte, in particular to a preparation method of an electrode for hydrogen production, the electrode for hydrogen production and an electrolysis device.
Background
Currently, with the continuous attention on environmental protection and energy conservation and the proposal of carbon peak reaching and carbon neutralization development targets in China, relevant enterprises will further accelerate the carbon reduction process. At present, the hydrogen production mode is mainlyDerived from the reforming of fossil fuels, in such a way that the production process necessarily emits large quantities of CO2. In the hydrogen production process for producing hydrogen by electrolyzing water, the hydrogen comes from water, and no CO is generated in the production process2And (5) discharging. The water electrolysis equipment, namely the electrolysis bath, is very suitable for the centralized production of hydrogen due to the modular characteristic, and the hydrogen production by water electrolysis is particularly suitable for being combined with renewable energy sources such as photovoltaic energy, wind energy and the like. With the cost reduction of renewable energy sources, particularly solar energy and wind energy, the hydrogen production by electrolyzing water by using the renewable energy sources is more and more concerned internationally.
At present, a metal oxide active coating nickel-based anode is adopted as an oxygen evolution anode in the water electrolysis hydrogen production device, but the electrochemical performance of the nickel-based anode is influenced in the electrolysis use process, so that the service life of the nickel-based anode is short, the oxygen evolution effect is poor, and the electrolysis efficiency of the electrolysis device is greatly reduced.
Disclosure of Invention
In view of the above problems, the present invention provides a method for producing an electrode for hydrogen production, and an electrolysis apparatus, in which the electrode has a low oxygen evolution overpotential, a long service life at a high current density, and a precise main content ratio.
In a first aspect, the present application provides a method for preparing an electrode for hydrogen production, comprising:
obtaining soluble organic salt; wherein the soluble organic salt is a metal organic salt;
dissolving the soluble organic salt in an organic solution with a set concentration range, and uniformly mixing to obtain an active coating masking liquid; wherein the total weight concentration of all metal elements in the active coating dope is kept within a set range;
carrying out roughening treatment on the surface of a nickel or nickel alloy substrate;
carrying out heat treatment on the roughened substrate in an oxygen-containing atmosphere to oxidize the surface of the substrate to obtain a metal substrate with the surface containing nickel oxide; wherein the heat treatment temperature is kept at 320-550 ℃, and the heat treatment time is kept at 18-60 minutes;
coating the active coating masking liquid on the surface of a substrate subjected to surface oxidation treatment, carrying out heat treatment on the substrate coated with the active coating masking liquid in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is raised to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, and after the heat treatment is finished, cooling the substrate to room temperature within the time period of not more than 40 seconds, so that a first active coating is generated on the outer surface of the substrate coated with the active coating masking liquid;
continuously coating an active coating liquid on a first active coating of a substrate, carrying out heat treatment on the first active coating coated with the active coating liquid on the substrate in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is increased to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, and after the heat treatment is finished, the substrate is cooled to room temperature within a time period of not more than 40 seconds, so that a second active coating is generated on the outer surface of the first active coating of the substrate coated with the active coating liquid; repeatedly coating the active coating liquid on the active coating of the substrate and carrying out corresponding heat treatment until the coating amount of the active coating on the surface of the substrate is more than or equal to 50g/m2；
The coating amount of the active coating on the surface of the substrate is more than or equal to 50g/m2In the case of (3), the substrate is further subjected to heat treatment in an oxygen-containing atmosphere for 45 to 105 minutes, and the active coating layer of the heat-treated substrate is used as an electrode for hydrogen production.
In some embodiments, the metal element in the metal organic salt comprises at least one of:
ruthenium Ru, iridium Ir, rhodium Rh, palladium Pd, platinum Pt, lanthanum La, iron Fe, cobalt Co, nickel Ni, copper Cu, manganese Mn, aluminum Al, barium Ba, strontium Sr.
In some embodiments, the metal organic salt comprises a first type of organic salt; the first type of organic salt comprises at least one of soluble organic salts of La, Co, Ni.
In some embodiments, the metal organic salt further comprises a second type of organic salt; the second type of organic salt includes at least one of soluble organic salts of Ru, Ir.
In some embodiments, the organic solution comprises an acetic acid solution.
In some embodiments, the total weight concentration of all metal elements in the organic solution is from 175g/L to 230 g/L; wherein, the mole percentage of the metal element in the first organic salt is 74-100%, and the mole percentage of the metal element in the second organic salt is 0-26%.
In some embodiments, the concentration of acetic acid in the acetic acid solution is 4% to 28% by volume.
In some embodiments, the concentration of acetic acid in the acetic acid solution is 5% to 11% by volume.
In some embodiments, the repeated coating of the active coating liquid on the active coating of the substrate and the corresponding heat treatment are repeated 8 to 10 times;
the single-layer coating amount of the active coating coated on the active coating of the substrate is 5.0g/m2-6.3g/m2。
In a second aspect, the present application provides an electrode for hydrogen production, which is produced by the aforementioned production method for an electrode for hydrogen production.
In a third aspect, the present application provides an electrolysis apparatus for hydrogen production, wherein the aforementioned electrode for hydrogen production is used as an anode in the electrolysis apparatus.
According to the electrode for hydrogen production, the soluble organic salt and the corresponding organic solution are used for preparing the active coating liquid, and in the process of active coating, the organic solution has relatively less corrosion on the nickel or nickel alloy substrate, so that nickel and the like in the substrate cannot penetrate into the active coating, and the proportion of each component element in the active coating is more accurate. In the embodiment of the application, after the active coating masking liquid is coated on the substrate to form the electrode coating, the electrode coating is subjected to high-temperature oxidation heat treatment under the set condition, so that the electrode for hydrogen production prepared in the embodiment of the application has the advantages of low oxygen evolution overpotential, long service life under high current density and more accurate content ratio of main components in the electrode, the electrochemical performance of the electrode for hydrogen production is improved, the service life of the electrode is prolonged, the hydrogen production efficiency of the electrolysis device is improved, and the cost is saved because the electrode of the electrolysis device is not required to be frequently replaced.
The above description is only an overview of the technical solutions of the present application, and the present application may be implemented in accordance with the content of the description so as to make the technical means of the present application more clearly understood, and the detailed description of the present application will be given below in order to make the above and other objects, features, and advantages of the present application more clearly understood.
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Various additional advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Moreover, like reference numerals are used to refer to like elements throughout. In the drawings:
fig. 1 shows a schematic process flow diagram of a method for manufacturing an electrode for hydrogen production according to an embodiment of the present application.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are merely used to more clearly illustrate the technical solutions of the present application, and therefore are only examples, and the protection scope of the present application is not limited thereby.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having," and any variations thereof, in the description and claims of this application are intended to cover non-exclusive inclusions.
In the description of the embodiments of the present application, the technical terms "first", "second", and the like are used only for distinguishing different objects, and are not to be construed as indicating or implying relative importance or implicitly indicating the number, specific order, or primary-secondary relationship of the technical features indicated. In the description of the embodiments of the present application, "a plurality" means two or more unless specifically defined otherwise.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment, the drawings, and the like can be included in at least one embodiment of the present application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
In the description of the embodiments of the present application, the term "and/or" is only one kind of association relationship describing the association object, and means that three relationships may exist, for example, a and/or B, and may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
In the description of the embodiments of the present application, the term "plurality" refers to two or more (including two), and similarly, "plural sets" refers to two or more (including two), and "plural pieces" refers to two or more (including two).
In the description of the embodiments of the present application, the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", and the like, indicate the directions or positional relationships indicated in the drawings, and are only for convenience of description of the embodiments of the present application and for simplicity of description, but do not indicate or imply that the referred device or element must have a specific direction, be constructed and operated in a specific direction, and thus, should not be construed as limiting the embodiments of the present application.
In the description of the embodiments of the present application, unless otherwise explicitly stated or limited, the terms "mounted," "connected," "fixed," and the like are used in a broad sense, and for example, may be fixedly connected, detachably connected, or integrated; mechanical connection or electrical connection is also possible; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the embodiments of the present application can be understood by those of ordinary skill in the art according to specific situations.
The essence of the technical solution of the embodiments of the present application is further clarified below by specific examples.
Fig. 1 is a schematic process flow diagram illustrating a method for manufacturing an electrode for hydrogen generation according to an embodiment of the present application, and as shown in fig. 1, the process flow diagram of the method for manufacturing an electrode for hydrogen generation according to the embodiment of the present application at least includes:
a process 101: obtaining soluble organic salt; wherein the soluble organic salt is a metal organic salt.
The soluble organic salt may be obtained by directly preparing the soluble organic salt, for example, purchasing the soluble organic salt, or preparing the soluble organic salt by a substitution reaction, an acid-base neutralization reaction, or the like. The metal element in the metal organic salt in the embodiment of the present application includes at least one of:
ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), platinum (Pt), lanthanum (La), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), aluminum (Al), barium (Ba), strontium (Sr).
In the embodiments of the present application, the metal organic salt includes a first type organic salt; the first type of organic salt comprises at least one of soluble organic salts of La, Co, Ni. The first organic salt is mainly soluble organic salt of transition metal elements such as La, Co, Ni and the like.
The metal organic salt also comprises a second type of organic salt; the second type of organic salt includes at least one of soluble organic salts of Ru, Ir. The metal element in the second type of organic salt is generally referred to as a noble metal.
It will be appreciated by those skilled in the art that the metallic elements associated with the soluble organic salts selected for use in the examples herein have been determined by a number of experiments and tests.
The process 102 is as follows: and dissolving the soluble organic salt in an organic solution with a set concentration range, and uniformly mixing to obtain the active coating masking liquid. Wherein the total weight concentration of all metal elements in the active coating dope is maintained within a set range. The volume ratio of the concentration of acetic acid in the acetic acid solution is 4-28%. Preferably, the volume ratio of the acetic acid concentration in the acetic acid solution is 5% to 11%. Specifically, the volume ratio of the acetic acid concentration in the acetic acid solution is 9.5%, 9.1%, 8.0%, 8.1%, 8.6%, 8.9%, 7.6%, 7%, 6.5%, 6.2%, 5.8%, 5.2%, and the like.
In the examples of the present application, the organic solution is preferably a solution having less than 6 carbons, and is not limited to acetic acid. In the case where the acetic acid solution is replaced with another organic solution, the specific volume concentration of the organic solution may be adjusted.
In the embodiment of the application, after the soluble organic salt is added into the organic solution, the concentration of all metal elements in the active coating liquid is 175g/L-230 g/L. Preferably, the concentration of all metal elements in the active coating liquid is 185g/L-200g/L, wherein the mole percentage of the noble metal elements is 0-26%, and the mole percentage of the transition metal elements is 74-100% according to the metal components.
The process 103 is as follows: the surface of a substrate of nickel or a nickel alloy is subjected to roughening treatment.
In the embodiment of the present application, the roughening treatment mainly includes sanding, pickling, and the like on the surface of the nickel or nickel alloy substrate. The sanding process includes impact sanding using diamonds, sand, slag, etc. The surface of the substrate of nickel or nickel alloy is roughened to a number of roughness points per micrometer of 125 to 250. The acid used in the acid washing treatment may include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, chromic acid, hydrofluoric acid, or a mixed acid of the above acids, and the like.
It should be understood by those skilled in the art that the roughening treatment of the surface of the substrate made of nickel or nickel alloy may be performed in parallel with the above-mentioned active coating liquid, i.e., the flow process in the embodiment of the present application is not limited to the timing, and the roughening treatment of the surface of the substrate made of nickel or nickel alloy may be performed first, followed by the preparation of the active coating liquid, and the like.
The process 104 is as follows: carrying out heat treatment on the roughened substrate in an oxygen-containing atmosphere to oxidize the surface of the substrate to obtain a metal substrate with the surface containing nickel oxide; wherein the heat treatment temperature is kept at 320-550 ℃, and the heat treatment time is kept at 18-60 minutes.
In the present embodiment, the heat treatment temperature may be preferably maintained at 350 ℃, 370 ℃, 380 ℃, 410 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃ or the like. The heat treatment time period is maintained at 20 minutes, 25 minutes, 30 minutes, 35 minutes, 38 minutes, 40 minutes, 45 minutes, 49 minutes, 51 minutes, 55 minutes, 57 minutes, or the like.
The process 105 is as follows: coating the active coating masking liquid on the surface of a substrate subjected to surface oxidation treatment, carrying out heat treatment on the substrate coated with the active coating masking liquid in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is raised to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, and after the heat treatment is finished, the substrate is cooled to room temperature within a time period of not more than 40 seconds, so that a first active coating is generated on the outer surface of the substrate coated with the active coating masking liquid.
As an implementation example, the temperature is raised to 380 ℃ within 2 minutes, and the temperature is kept for 5 minutes; or raising the temperature to 390 ℃ within 1 minute, and keeping the temperature for 8 minutes; or heating to 360 ℃ within 3 minutes, and keeping the temperature for 12 minutes; alternatively, the temperature may be raised to 370 ℃ within 4 minutes, and the temperature may be maintained for 14 minutes. It will be understood by those skilled in the art that the shorter the time period for heating to 350-400 ℃, the higher the stability of the components of the active coating of the hydrogen production electrode of the embodiment of the present application, and the less nickel and the like in the matrix are able to penetrate into the active coating of the electrode, so that the stability and the service life of the electrode of the embodiment of the present application are longer.
In the present embodiment, the heat treatment condition is preferably to raise the temperature to 360 ℃, 380 ℃, 390 ℃ or the like within 5 minutes. The holding time is 6 minutes, 8 minutes, 10 minutes, 12 minutes, 15 minutes, etc.
After the heat treatment is completed, the substrate is cooled to room temperature within a time period of not more than 40 seconds, and specifically, the substrate after the heat treatment can be placed in a cooling chamber of inert gas, such as a cooling chamber of dry ice, solid nitrogen, solid helium, solid neon and the like, so that the substrate after the heat treatment is rapidly cooled to room temperature. In general, the shorter the cooling time to room temperature, the better, and the specific cooling time period is not limited in the examples of the present application.
The process 106 is as follows: continuously coating an active coating liquid on a first active coating of a substrate, carrying out heat treatment on the first active coating coated with the active coating liquid on the substrate in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is increased to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, and after the heat treatment is finished, the substrate is cooled to room temperature within a time period of not more than 40 seconds, so that a second active coating is generated on the outer surface of the first active coating of the substrate coated with the active coating liquid; repeatedly coating the active coating liquid on the active coating of the substrate and carrying out corresponding heat treatment until the coating amount of the active coating on the surface of the substrate is more than or equal to 50g/m2。
In the present embodiment, the heat treatment condition is preferably to raise the temperature to 360 ℃, 380 ℃, 390 ℃ or the like within 5 minutes. The incubation time is 6 minutes, 8 minutes, 10 minutes, 12 minutes, 13 minutes, 15 minutes, etc.
After the heat treatment is completed, the substrate is cooled to room temperature within a time period of not more than 40 seconds, and specifically, the substrate after the heat treatment can be placed in a cooling chamber of inert gas, such as a cooling chamber of dry ice, solid nitrogen, solid helium, solid neon and the like, so that the substrate after the heat treatment is rapidly cooled to room temperature. Generally, the shorter the cooling time to room temperature, the better, and the specific cooling time period is not limited in the examples of the present application.
In the embodiment of the application, the repetition times of repeatedly coating the active coating liquid on the active coating of the substrate and carrying out corresponding heat treatment are 8 to 10 times; the single-layer coating amount of the active coating coated on the active coating of the substrate is 5.0g/m2-6.3g/m2。
The process 107: the coating amount of the active coating on the surface of the substrate is more than or equal to 50g/m2In the case of (3), the substrate is further subjected to heat treatment in an oxygen-containing atmosphere for 45 to 105 minutes, and the active coating layer of the heat-treated substrate is used as an electrode for hydrogen production.
In the embodiment of the present application, the time period for further heat treatment of the substrate in the oxygen-containing atmosphere is preferably 50 minutes, 55 minutes, 60 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 100 minutes, or the like.
In the examples of the present application, the hydrogen production electrode produced by the above method is used as an anode in an electrolyte electrode device, that is, as an anode for oxygen evolution in a hydrogen production/electrolysis device.
The technical solutions of the embodiments of the present application are further described below by specific examples.
The anode for producing hydrogen from alkaline water is prepared by the following steps:
A. preparing soluble organic salt of metal element, wherein the metal element can be one or more of Ru, Ir, Rh, Pd, Pt, La, Fe, Co, Ni, Cu, Mn, Al, Ba and Sr.
B. Dissolving soluble organic salt of metal elements in 4-28% (VOL) of organic solution with less than 6 carbon atoms, keeping the concentration of all metal elements in the solution at 175-230 g/L, and mixing uniformly to obtain the active coating liquid.
C. The metal matrix of nickel or nickel alloy is sanded and pickled to roughen the surface.
D. And D, carrying out heat treatment on the metal matrix obtained in the step C in an oxygen-containing atmosphere at the temperature of 320-550 ℃ for 18-60 minutes to oxidize the surface of the metal matrix to obtain the metal matrix containing nickel oxide.
E. And D, coating the active coating solution obtained in the step B on the surface of the metal substrate treated in the step D, then carrying out heat treatment on the metal substrate coated with the coating solution in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is increased to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, and after the heat treatment is finished, the metal substrate is rapidly cooled to room temperature, and an active coating is generated on the outer surface of the metal substrate.
F. Continuously coating a layer of active coating liquid on the metal substrate obtained in the step E to the newly generated active coating, then carrying out heat treatment on the metal substrate coated with the coating liquid in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is increased to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, after the heat treatment is finished, the metal substrate is rapidly cooled to the room temperature, and a new active coating is generated on the outer surface of the previously generated active coatingThe active coating is circulated until the coating amount of the active coating on the surface of the metal substrate is more than or equal to 50g/m2(ii) a The last heat treatment time is 50-100 minutes, and the anode for producing hydrogen by using alkaline water is obtained.
As a preferable example of the embodiment of the present application, in step a, the metal element includes a noble metal element and a transition metal element, wherein the soluble organic salt of the noble metal element may be a soluble organic salt of Ru or Ir; the soluble organic salt of the transition metal element may be a soluble organic salt of La, Co, Ni, or the like. In the step B, 5-11% (VOL) acetic acid solution is selected as the organic solution, the concentration of all metals in the solution is 180g/L-200g/L, and the molar percentage of the noble metal elements is 0% -26% and the molar percentage of the transition metal elements is 74% -100% according to the metal components.
For the electrode preparation method of the electrolytic device, the roll coating method is generally adopted in the industry, but the active coating liquid of the roll coating method adopts inorganic salt and inorganic solution, and the active coating liquid needs to be used repeatedly, in the preparation process, the active coating liquid corrodes the substrate relatively seriously, related metal elements in the substrate can permeate into the active coating liquid, and the related metal elements in the substrate can permeate into the active coating of the electrode along with the coating, so that the preparation method can influence the accuracy of the main content proportion of the active coating. For example, nitric acid or hydrochloric acid, which is a representative inorganic solution in the roll coating method, is generally selected and has strong corrosiveness to nickel and nickel alloy in the substrate, and the nickel element in the active coating of the substrate is increased, so that the main content proportioning error of the active coating of the manufactured electrode is large, and the electrochemical performance of the electrode is seriously influenced.
In the embodiment of the application, the organic acid solution is used for replacing the inorganic salt solution and the inorganic acid solution, and the inorganic acid has much weaker corrosion to the substrate and hardly corrodes the substrate, so that the content of nickel or nickel alloy elements in the active coating liquid is almost zero in the process of coating the active coating liquid on the substrate.
The embodiment of the application screens the organic salt metal elements and the organic solution, so that the prepared anode electrode for hydrogen production from alkaline water has three advantages: (1) the metal element proportion of the active coating is more accurate; (2) low oxygen evolution overpotential; (3) longer service life at high current density.
Example 1
Taking ruthenium acetate, nickel acetate and cobalt acetate, adding 10% (VOL) acetic acid solution, stirring until the ruthenium acetate, the nickel acetate and the cobalt acetate are completely dissolved, and enabling the atomic percentage content of the ruthenium acetate, the nickel acetate and the cobalt acetate to be Ru: 31%, Ni: 23%, Co: 46 percent, and the concentration of all metals reaches 200g/L to obtain the active coating liquid. And uniformly brushing the active coating liquid on a metal substrate made of the pretreated nickel expanded metal. Baking at 400 deg.C for 15 min after each coating, cooling the substrate to room temperature, and repeatedly coating the active coating with active coating solution to coat the active coating on the substrate to a coating amount of 50g/m or more2And finally, carrying out heat treatment again for 60 minutes to obtain the anode for hydrogen production by alkaline water.
The anode for producing hydrogen by using the alkaline water is prepared at 80 ℃, 30 percent KOH and 10KA/m2Under the condition, the initial oxygen evolution overpotential is 210mV, after 2000 hours of electrolysis, the coating residual quantity is 87%, and the oxygen evolution overpotential is 222 mV. Ni in the applied liquid of the active coating was measured at 0.02 ppm.
Example 2
Adding 25% (VOL) acetic acid solution into ruthenium acetate, nickel acetate and cobalt acetate, and stirring until the ruthenium acetate, the nickel acetate and the cobalt acetate are completely dissolved, so that the contents of atomic percentages of the ruthenium acetate, the nickel acetate and the cobalt acetate are Ru: 31%, Ni: 23%, Co: 46 percent, and the concentration of all metals reaches 200g/L to obtain the active coating liquid. And uniformly brushing the active coating liquid on a metal substrate made of the pretreated nickel expanded metal. Baking at 390 ℃ after each coating for 14 minutes, rapidly cooling the substrate to room temperature after heat treatment, and repeatedly coating the active coating liquid on the obtained active coating to ensure that the coating amount of the active coating on the substrate is more than or equal to 50g/m2Further heat treatment, heat treatmentThe treatment time is 55 minutes, and the anode for preparing hydrogen from alkaline water is obtained.
The anode for producing hydrogen by using the alkaline water is prepared at 80 ℃, 30 percent KOH and 10KA/m2Under the condition, the initial oxygen evolution overpotential is 226mV, after 2000 hours of electrolysis, the coating residual quantity is 85 percent, and the oxygen evolution overpotential is 235 mV. Ni in the used active coating liquid was measured to be 0.03 ppm.
Comparative example 1
Taking ruthenium nitrate, nickel nitrate and cobalt nitrate, adding 10% (VOL) nitric acid solution, and stirring until the mixture is completely dissolved, so that the atomic percentage content of the mixture is Ru: 31%, Ni: 23%, Co: 46 percent, and the concentration of all metals reaches 200g/L to obtain the active coating liquid. And uniformly brushing the active coating liquid on a metal substrate made of the pretreated nickel expanded metal. After each coating, baking at 400 ℃ for 15 minutes to ensure that the coating amount is more than or equal to 50g/m2And carrying out heat treatment for 60 minutes again to obtain the anode for hydrogen production by alkaline water.
The anode for producing hydrogen by using the alkaline water is prepared at 80 ℃, 30 percent KOH and 10KA/m2Under the condition, the initial oxygen evolution overpotential is measured to be 225mV, and after 2000 hours of electrolysis, the coating residual quantity is 83 percent, and the oxygen evolution overpotential is 232 mV. Ni in the used active coating liquid was measured at 5 ppm.
Therefore, after the anode for alkaline water hydrogen production prepared by the nitric acid solution is used for a period of time, the Ni content in the active coating masking liquid is very high, and the quality of the anode is poorer than that of the anode for alkaline water hydrogen production prepared by acetate and the corresponding solution.
Comparative example 2
Taking ruthenium chloride, nickel chloride and cobalt chloride, adding 10% (VOL) chloric acid solution, stirring until the ruthenium chloride, the nickel chloride and the cobalt chloride are completely dissolved, and enabling the atomic percentage content of the ruthenium chloride, the nickel chloride and the cobalt chloride to be Ru: 31%, Ni: 23%, Co: 46 percent, and the concentration of all metals reaches 200g/L to obtain the active coating liquid. And uniformly brushing the active coating liquid on a metal substrate made of the pretreated nickel expanded metal. After each coating, baking at 400 ℃ for 15 minutes to ensure that the coating amount is more than or equal to 50g/m2And the last heat treatment time is 60 minutes, so that the anode for preparing hydrogen from alkaline water is obtained.
The anode for hydrogen production by alkaline water is tested to have initial oxygen evolution overpotential of 238mV under the conditions of 80 ℃, 30% KOH and 10KA/m2, and after 2000 hours of electrolysis, the coating residual quantity is 79% and the oxygen evolution overpotential is 249 mV. Ni in the used active coating liquid was measured at 8 ppm.
Therefore, after the anode for producing hydrogen from alkaline water prepared by using the chloric acid solution is used for a period of time, the Ni content in the coating liquid of the active coating is very high, and the quality of the anode is poorer than that of the anode for producing hydrogen from alkaline water prepared by using acetate and the corresponding solution.
It should be emphasized that, since the soluble organic salt and the organic solution are used in the embodiments of the present application, after the active coating layer is formed on the substrate, the corresponding preparation conditions need to be selected again for the subsequent heat treatment and related treatments. According to the preparation method disclosed by the application, the prepared electrode is high in physical stability and good in electrochemical performance.
Therefore, the alkaline water hydrogen production anode has the characteristics of low oxygen evolution overpotential, long service life under high current density and accurate main content ratio.
The examples of the present application also describe an electrode for hydrogen production, which is produced by the method for producing an electrode for hydrogen production of the foregoing examples.
The embodiment of the application also describes an electrolysis device for hydrogen production, which comprises an electrolysis chamber, wherein an electrolysis electrode is arranged in the electrolysis chamber, and the anode of the electrolysis electrode adopts the electrode for hydrogen production prepared by the preparation method of the electrode for hydrogen production in the embodiment.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present disclosure, and the present disclosure should be construed as being covered by the claims and the specification. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. The present application is not intended to be limited to the particular embodiments disclosed herein but is to cover all embodiments that may fall within the scope of the appended claims.

Claims (11)

1. A method for producing an electrode for hydrogen production, comprising:
obtaining soluble organic salt; wherein the soluble organic salt is a metal organic salt;
dissolving the soluble organic salt in an organic solution with a set concentration range, and uniformly mixing to obtain an active coating masking liquid; wherein the total weight concentration of all metal elements in the active coating masking liquid is kept within a set range;
carrying out roughening treatment on the surface of a nickel or nickel alloy substrate;
carrying out heat treatment on the roughened substrate in an oxygen-containing atmosphere to oxidize the surface of the substrate to obtain a metal substrate with the surface containing nickel oxide; wherein the heat treatment temperature is kept at 320-550 ℃, and the heat treatment time is kept at 18-60 minutes;
coating the active coating masking liquid on the surface of a substrate subjected to surface oxidation treatment, carrying out heat treatment on the substrate coated with the active coating masking liquid in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is raised to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, and after the heat treatment is finished, cooling the substrate to room temperature within the time period of not more than 40 seconds, so that a first active coating is generated on the outer surface of the substrate coated with the active coating masking liquid;
continuously coating an active coating liquid on a first active coating of a substrate, carrying out heat treatment on the first active coating coated with the active coating liquid in an oxygen-containing atmosphere, wherein the heat treatment condition is that the temperature is increased to 350-400 ℃ within 5 minutes, the temperature is kept for 5-16 minutes, cooling the substrate to room temperature within 40 seconds after the heat treatment is finished, and generating a second active coating on the outer surface of the first active coating of the substrate coated with the active coating liquidCoating; repeatedly coating the active coating liquid on the active coating of the substrate and carrying out corresponding heat treatment until the coating amount of the active coating on the surface of the substrate is more than or equal to 50g/m2；
The coating amount of the active coating on the surface of the substrate is more than or equal to 50g/m2In the case of (3), the substrate is further subjected to heat treatment in an oxygen-containing atmosphere for 45 to 105 minutes, and the active coating layer of the heat-treated substrate is used as an electrode for hydrogen production.
2. The method according to claim 1, wherein the metal element in the metal organic salt includes at least one of:
ruthenium Ru, iridium Ir, rhodium Rh, palladium Pd, platinum Pt, lanthanum La, iron Fe, cobalt Co, nickel Ni, copper Cu, manganese Mn, aluminum Al, barium Ba, strontium Sr.
3. The method of claim 2, wherein the metal organic salt comprises a first type of organic salt; the first type of organic salt comprises at least one of soluble organic salts of La, Co, Ni.
4. The method of claim 3, wherein the metal organic salt further comprises a second type of organic salt; the second type of organic salt includes at least one of soluble organic salts of Ru, Ir.
5. The method of claim 4, wherein the organic solution comprises an acetic acid solution.
6. The method according to claim 5, wherein the total weight concentration of all metal elements in the organic solution is 175g/L to 230 g/L; wherein, the mole percentage of the metal element in the first organic salt is 74-100%, and the mole percentage of the metal element in the second organic salt is 0-26%.
7. The method according to claim 5, wherein the concentration of acetic acid in the acetic acid solution is 4 to 28% by volume.
8. The method according to claim 5, wherein the concentration of acetic acid in the acetic acid solution is 5 to 11% by volume.
9. The preparation method according to any one of claims 1 to 8, wherein the number of repetitions of applying the active coating dope on the active coating of the substrate and performing the corresponding heat treatment is 8 to 10;
the single-layer coating amount of the active coating coated on the active coating of the substrate is 5.0g/m2-6.3g/m2。
10. An electrode for hydrogen production, characterized in that the electrode is produced by the method for producing an electrode for hydrogen production according to any one of claims 1 to 9.
11. An electrolysis apparatus for producing hydrogen, wherein the hydrogen production electrode according to claim 10 is used as an anode in the electrolysis apparatus.
CN202210121443.0A 2022-02-09 2022-02-09 Preparation method of electrode for hydrogen production, electrode for hydrogen production and electrolysis device Pending CN114481190A (en)

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