CN115216803A - Method for preparing multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition - Google Patents

Abstract

The invention discloses a method for preparing a multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition. The method for preparing the multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition comprises the following steps: pre-treating a coating of the electrodeposition substrate; dissolving the nano salt surface layer film, and exposing the electrodeposition attachment points to obtain an electrodeposition substrate; carrying out electrodeposition on the electrodeposition substrate; repeating the operation for 4-5 times; and (5) post-treatment. The invention has low development power consumption and strong stability, promotes the reduction of the cost of hydrogen production by water electrolysis, and realizes large-scale development.

Description

A method for preparing multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition

technical field

The invention relates to the technical field of hydrogen energy, in particular to a method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition.

Background technique

The underground storage of hydrogen has been continuously explored and researched by various countries. In the early stage, artificial gas was mixed with methane in the proportion of 50-60% and injected into the underground storage. In the later stage, pure hydrogen (95% hydrogen plus 3% to 4%) was also carried out. % of carbon dioxide) underground storage, among which, France, Germany, the United Kingdom, the United States and other European and American countries have more research and practice in hydrogen underground storage, and my country has relatively little research in this area. At present, in order to cope with the energy crisis, all countries are actively implementing the strategy of energy strategic reserve. The underground salt cavern reserve is the most important part of the energy strategic reserve work. Due to the advantages of economy and other advantages, it is now internationally recognized as the best underground storage place for strategic energy such as natural gas and oil. In recent years, the construction of underground salt cavern hydrogen storage systems has developed rapidly in my country, which has very important guidance for the future storage and application of hydrogen in my country. significance.

Due to the huge amount of hydrogen used for hydrogen storage in salt caverns, a low-cost hydrogen production method that can produce hydrogen in large quantities is required. Hydrolysis is used to produce hydrogen in the prior art, and the hydrogen evolution electrode plays a very important role in the hydrogen production system. Existing hydrogen evolution electrodes have high content of precious metals and high cost, and electrodes with low power consumption and strong stability need to be developed.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition.

The technical solution adopted by the present invention to solve the technical problem is: a method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition, which specifically includes the following steps:

S1. Coating pretreatment of electrodeposited substrate: the substrate is subjected to alkali degreasing and acid deoxidization pretreatment to obtain a pretreated substrate;

S2, dissolve the nano-salt surface film, expose the electrodeposition attachment points, and obtain the electrodeposition substrate: put the pretreated substrate prepared in S1 in a hot alcohol cleaning solution for 1 to 2 minutes, and then take it out. The heating temperature is 40°C to 45°C, Preparation of electrodeposited substrate;

S3. Electrodeposition of the electrodeposition substrate: The electrodeposition substrate obtained from S2 is used as the cathode, the platinum sheet is used as the anode, the anode and the cathode are both placed in the electrodeposition solution, and electrodeposition is carried out under stirring conditions of 80 °C. The stirring speed is 60 ~100r/min; electrodeposition conditions are: electrodeposition area is 1cm ² , control constant voltage 1.35V, electrodeposition time is 30min;

S4. Repeat operations S1 to S3 for 4 to 5 times to obtain semi-finished electrodes;

S5, post-processing, place the electrode semi-finished product prepared in S4 in the hot alcohol cleaning solution of S2, control the temperature to 60°C, and place it under sealed conditions for 18-24 hours; then take it out and wash it with water, and dry it to obtain a multi-layer framework for hydrogen evolution. Electrode finished product.

Further, the step S1 specifically includes the following steps:

S11, the coupling agent is dissolved in the alcohol-water mixture, acetic acid is added, and the pH value of the solution is controlled to be 4.5 to 5.5 to prepare the coupling agent mixture;

S12, dissolving the nano-salt in the nafion solution to prepare a nano-salt mixture;

S13, the substrate is first soaked in the coupling agent mixture, then taken out to dry, and then soaked in the nano-salt mixture and then dried to obtain a pretreated substrate.

Further, in the alcohol-water mixture of S11, the volume ratio of alcohol and water is (90-95): (5-10); the mass of the coupling agent is 0.5-1% of the mass of the coupling agent mixture; the coupling The agent is silane coupling agent, titanate coupling agent or propylene glycol methyl ether; alcohol is ethanol or ethylene glycol.

Further, the mass ratio of the nano-salt and the nafion solution in the S12 is 1:5 to 1:3; the nano-salt is a nano-salt with D90=100nm, and the nafion solution is an ethanol solution containing nafion 117, wherein the mass percentage of nafion 117 is 5%.

Further, in described S2, every hundred weight part of hot alcohol cleaning solution comprises the raw material of following weight part:

Wherein, the surfactant A is sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, sodium fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, One or more of fatty alcohol polyoxyethylene ether phosphate esters.

Further, the electrodeposition solution in described S3 includes the raw material of following mass parts:

Wherein, the surfactant B is sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, sodium fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, One or more of fatty alcohol polyoxyethylene ether phosphate esters.

The beneficial effects of the present invention are: the present invention is simple in structure, reasonable in design, easy to operate, and has the following advantages:

(1) Construct a high-specific-area electrode structure, greatly increase the contact area between the electrolyte and the electrode, upgrade the traditional surface treatment process to a three-dimensional treatment process, and achieve a breakthrough in the multi-layer electrode preparation method;

(2) Optimizing the composition of the electrode, improving the activity and stability of the electrode by alloying, the invention has low power consumption and strong stability, which promotes the reduction of the cost of hydrogen production by electrolysis of water and realizes large-scale development.

Description of drawings

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Fig. 1 is the scanning electron microscope image of nano-salt under the nafion film wrapping;

Fig. 2 is the scanning electron microscope image of the surface of the multilayer electrodeposition structure;

Fig. 3 is the scanning electron microscope image of the surface of common electrodeposited structure;

Figure 4 is an oxygen evolution polarization curve.

Detailed ways

The present invention will now be described in further detail with reference to the accompanying drawings and preferred embodiments.

A method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition specifically comprises the following steps:

S1. Coating pretreatment of electrodeposited substrate: the substrate is subjected to alkali degreasing and acid deoxidization pretreatment to obtain a pretreated substrate;

S2, dissolve the nano-salt surface film, expose the electrodeposition attachment points, and obtain the electrodeposition substrate: put the pretreated substrate prepared in S1 in a hot alcohol cleaning solution for 1 to 2 minutes, and then take it out. The heating temperature is 40°C to 45°C, Electrodeposition substrates were obtained; each one hundred parts by weight of the hot alcohol cleaning solution included the raw materials of the following parts by weight:

Wherein, the surfactant A is sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, sodium fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate , one or more of fatty alcohol polyoxyethylene ether phosphate ester;

S3. Electrodeposition of the electrodeposition substrate: The electrodeposition substrate obtained from S2 is used as the cathode, the platinum sheet is used as the anode, the anode and the cathode are both placed in the electrodeposition solution, and electrodeposition is carried out under stirring conditions of 80 °C. The stirring speed is 60 ~100r/min; the electrodeposition conditions are: the electrodeposition area is 1cm ² , the control constant voltage is 1.35V, and the electrodeposition time is 30min; wherein, the electrodeposition solution includes the following raw materials by mass:

Wherein, the surfactant B is sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, sodium fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate, One or more of fatty alcohol polyoxyethylene ether phosphates; ascorbic acid mainly prevents oxidation of nickel sulfate hexahydrate, ferrous sulfate heptahydrate and cobalt sulfate heptahydrate,

S4. Repeat operations S1 to S3 for 4 to 5 times to obtain semi-finished electrodes;

S5, post-processing, place the electrode semi-finished product prepared in S4 in the hot alcohol cleaning solution of S2, control the temperature to 60°C, and place it under sealed conditions for 18-24 hours; then take it out and wash it with water, and dry it to obtain a multi-layer framework for hydrogen evolution. Electrode finished product.

Step S1 specifically includes the following steps:

S11, the coupling agent is dissolved in the alcohol-water mixture, acetic acid is added, the pH value of the solution is controlled to be 4.5, and the coupling agent mixture is prepared;

S12, dissolving the nano-salt in the nafion solution to prepare a nano-salt mixture;

S13, the substrate is first soaked in the coupling agent mixture, then taken out to dry, and then soaked in the nano-salt mixture and then dried to obtain a pretreated substrate.

In the alcohol-water mixture of S11, the volume ratio of alcohol and water is (90-95): (5-10); the mass of the coupling agent is 0.5-1% of the mass of the coupling agent mixture; the coupling agent is silane coupling agent, titanate coupling agent or propylene glycol methyl ether; alcohol is ethanol or ethylene glycol; the mass ratio of nano-salt and nafion solution in S12 is 1:5～1:3; nano-salt is nano-salt with D90=100nm, The nafion solution is an ethanol solution containing nafion 117, wherein the mass percentage of nafion 117 is 5%.

Example 1

A method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition specifically comprises the following steps:

S1. Coating pretreatment of electrodeposited substrate: the substrate is subjected to alkali degreasing and acid deoxidization pretreatment to obtain a pretreated substrate;

S2. Dissolve the nano-salt surface film, expose the electrodeposition attachment points, and obtain an electrodeposition substrate: The pretreated substrate prepared in S1 is placed in a hot alcohol cleaning solution for 1 min, and then taken out, and the heating temperature is 40 °C to obtain an electrodeposition substrate. ; Every one hundred parts by weight of hot alcohol cleaning solution includes the raw materials of the following parts by weight:

S3. Electrodeposition of the electrodeposition substrate: the electrodeposition substrate obtained from S2 is used as the cathode, the platinum sheet is used as the anode, the anode and the cathode are both placed in the electrodeposition solution, and electrodeposition is carried out under stirring conditions of 80 °C, and the stirring speed is 60r /min; the electrodeposition conditions are: the electrodeposition area is 1cm ² , the control constant voltage is 1.35V, and the electrodeposition time is 30min; wherein, the electrodeposition solution includes the following raw materials by mass:

S4. Repeat operations S1 to S3 for 5 times to obtain semi-finished electrodes;

S5, post-processing, put the electrode semi-finished product prepared in S4 in the hot alcohol cleaning solution of S2, control the temperature to 60 °C, and place it under sealed conditions for 22 hours; then take it out and wash it with water, and dry it to make a multi-layer skeleton hydrogen evolution electrode finished product .

Step S1 specifically includes the following steps:

S11, the coupling agent is dissolved in the alcohol-water mixture, acetic acid is added, and the pH value of the solution is controlled to be 4.5 to 5.5 to prepare the coupling agent mixture;

S12, dissolving the nano-salt in the nafion solution to prepare a nano-salt mixture;

S13, the substrate is first soaked in the coupling agent mixture, then taken out to dry, and then soaked in the nano-salt mixture and then dried to obtain a pretreated substrate.

In the alcohol-water mixture of S11, the volume ratio of alcohol and water is 90:10; the mass of the coupling agent is 0.5% of the mass of the coupling agent mixture; the coupling agent is a silane coupling agent; the alcohol is ethanol; the nano-salt in S12 The mass ratio of nafion solution and nafion solution is 1:5; the nano-salt is nano-salt with D90=100nm, and the nafion solution is an ethanol solution containing nafion 117, wherein the mass percentage of nafion 117 is 5%.

Example 2

A method for preparing multi-layer skeleton hydrogen-evolution electrode by multi-layer electrodeposition is different from embodiment 1 in that:

In S2, the pretreated substrate prepared in S1 is placed in a hot alcohol cleaning solution for 1.5 minutes and taken out, and the heating temperature is 40°C to prepare an electrodeposited substrate; in addition, each hundred weight parts of the hot alcohol cleaning solution includes the following weight parts The raw material:

In S3, electrodeposition is carried out under a stirring condition of 80 °C, and the stirring speed is 70 r/min; in addition, the electrodeposition solution includes the following raw materials in parts by mass:

In S4, the operations S1 to S3 are repeated 4 times to obtain an electrode semi-finished product.

It was placed under sealed conditions in S5 for 19h.

In the alcohol-water mixture of S11, the volume ratio of alcohol and water is 92:8; the mass of the coupling agent is 0.8% of the mass of the coupling agent mixture; the coupling agent is a titanate coupling agent; the alcohol is ethylene glycol; The mass ratio of nano-salt and nafion solution in S12 was 1:3.

Example 3

A method for preparing multi-layer skeleton hydrogen-evolution electrode by multi-layer electrodeposition is different from embodiment 1 in that:

In S2, the pretreated substrate prepared in S1 is placed in a hot alcohol cleaning solution for cleaning for 2 minutes and taken out, and the heating temperature is 45 ° C to prepare an electrodeposited substrate; in addition, each hundred weight parts of the hot alcohol cleaning solution includes the following weight parts raw material:

In S3, electrodeposition is carried out under a stirring condition of 80 °C, and the stirring speed is 100 r/min; in addition, the electrodeposition solution includes the following raw materials in parts by mass:

In S4, operations S1 to S3 are repeated 5 times to obtain semi-finished electrodes.

S5 under sealed conditions for 24h.

In the alcohol-water mixture of S11, the volume ratio of alcohol and water is 95:5; the mass of the coupling agent is 0.7% of the mass of the coupling agent mixture; the coupling agent is propylene glycol methyl ether; the alcohol is ethylene glycol; The mass ratio of salt and nafion solution is 1:4.

Example 4

A method for preparing multi-layer skeleton hydrogen-evolution electrode by multi-layer electrodeposition is different from embodiment 1 in that:

In S2, the pretreated substrate prepared in S1 is placed in a hot alcohol cleaning solution for cleaning for 1 min and taken out, and the heating temperature is 43° C. to prepare an electrodeposited substrate; in addition, each hundred weight parts of the hot alcohol cleaning solution includes the following weight parts raw material:

In S3, electrodeposition is carried out under a stirring condition of 80 °C, and the stirring speed is 90 r/min; in addition, the electrodeposition solution includes the following raw materials in parts by mass:

In S4, the operations S1 to S3 are repeated 4 times to obtain an electrode semi-finished product.

It was placed under sealed conditions in S5 for 18h.

In the alcohol-water mixture in S11, the volume ratio of alcohol and water is 94:6; the mass of the coupling agent is 0.6% of the mass of the coupling agent mixture; the coupling agent is a silane coupling agent; the alcohol is ethanol; the nano-salt in S12 The mass ratio of nafion solution is 1:3.

Example 5

A method for preparing multi-layer skeleton hydrogen-evolution electrode by multi-layer electrodeposition is different from embodiment 1 in that:

In S2, the pretreated substrate prepared in S1 was placed in a hot alcohol cleaning solution for 1.5 minutes and taken out, and the heating temperature was 44°C to prepare an electrodeposited substrate; in addition, each hundred weight parts of the hot alcohol cleaning solution included the following weight parts The raw material:

In S3, electrodeposition is carried out under a stirring condition of 80 °C, and the stirring speed is 80 r/min; in addition, the electrodeposition solution includes the following raw materials in parts by mass:

In S4, the operations S1 to S3 are repeated 4 times to obtain an electrode semi-finished product.

S5 under sealed conditions for 20h.

In the alcohol-water mixture in S11, the volume ratio of alcohol and water is 93:7; the mass of the coupling agent is 1% of the mass of the coupling agent mixture; the coupling agent is propylene glycol methyl ether; the alcohol is ethanol; the nano-salt and The mass ratio of nafion solution is 1:5.

Comparative Example 1

A method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition specifically comprises the following steps:

S1. Coating pretreatment of electrodeposited substrate: the substrate is subjected to alkali degreasing and acid deoxidization pretreatment to obtain a pretreated substrate;

S2. Dissolve the nano-salt surface film, expose the electrodeposition attachment points, and obtain an electrodeposition substrate: The pretreated substrate prepared in S1 is placed in a hot alcohol cleaning solution for 1 min, and then taken out, and the heating temperature is 40 °C to obtain an electrodeposition substrate. ; Every one hundred parts by weight of hot alcohol cleaning solution includes the raw materials of the following parts by weight:

S3. Electrodeposition of the electrodeposition substrate: the electrodeposition substrate obtained from S2 is used as the cathode, the platinum sheet is used as the anode, the anode and the cathode are both placed in the electrodeposition solution, and electrodeposition is carried out under stirring conditions of 80 °C, and the stirring speed is 60r /min; the electrodeposition conditions are: the electrodeposition area is 1cm ² , the control constant voltage is 1.35V, and the electrodeposition time is 30min; wherein, the electrodeposition solution includes the following raw materials by mass:

S4. Repeat operations S1 to S3 for 5 times to obtain semi-finished electrodes;

S5, post-processing, put the electrode semi-finished product prepared in S4 in the hot alcohol cleaning solution of S2, control the temperature to 60 °C, and place it under sealed conditions for 22 hours; then take it out and wash it with water, and dry it to make a multi-layer skeleton hydrogen evolution electrode finished product .

Step S1 specifically includes the following steps:

S11. Add acetic acid to the alcohol water, and control the pH value of the solution to be 4.5 to 5.5 to prepare an acetic alcohol mixture;

S12, dissolving the nano-salt in the nafion solution to prepare a nano-salt mixture;

S13, the substrate is first soaked in an acetic alcohol mixed solution, then taken out to dry, and then soaked in a nano-salt mixed solution and then dried to obtain a pretreated substrate.

The alcohol in S11 is ethanol; the mass ratio of nano-salt and nafion solution in S12 is 1:5; the nano-salt is a nano-salt with D90=100 nm, and the nafion solution is an ethanol solution containing nafion 117, wherein the mass percentage of nafion 117 is 5%.

Comparative Example 2

A method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition specifically comprises the following steps:

S1. Coating pretreatment of electrodeposited substrate: the substrate is subjected to alkali degreasing and acid deoxidization pretreatment to obtain a pretreated substrate;

S2. Electrodeposition of the electrodeposition substrate: The electrodeposition substrate prepared in S1 is used as the cathode, the platinum sheet is used as the anode, the anode and the cathode are both placed in the electrodeposition solution, and the electrodeposition is carried out under the stirring condition of 80 °C, and the stirring speed is 60r /min; the electrodeposition conditions are: the electrodeposition area is 1cm ² , the control constant voltage is 1.35V, and the electrodeposition time is 30min; wherein, the electrodeposition solution includes the following raw materials by mass:

Wherein, the surfactant B is aliphatic alcohol polyoxyethylene ether sodium sulfate;

S3. Repeat operations S1 to S2 for 5 times to obtain semi-finished electrodes;

S4, post-processing, put the electrode semi-finished product prepared in S3 in a hot alcohol cleaning solution, control the temperature to 60°C, and place it under sealed conditions for 22 hours; then take it out, wash it with water, and dry it to make a multi-layer skeleton hydrogen evolution electrode product; One hundred parts by weight of the hot alcohol cleaning solution includes the following raw materials by weight:

Step S1 specifically includes the following steps:

S11, the coupling agent is dissolved in the alcohol-water mixture, acetic acid is added, and the pH value of the solution is controlled to be 4.5 to 5.5 to prepare the coupling agent mixture;

S12, dissolving the nano-salt in the nafion solution to prepare a nano-salt mixture;

S13, the substrate is first soaked in the coupling agent mixture, then taken out to dry, and then soaked in the nano-salt mixture and then dried to obtain a pretreated substrate.

In the alcohol-water mixture of S11, the volume ratio of alcohol and water is 90:10; the mass of the coupling agent is 0.5% of the mass of the coupling agent mixture; the coupling agent is a silane coupling agent; the alcohol is ethanol; the nano-salt in S12 The mass ratio of nafion solution and nafion solution is 1:5; the nano-salt is nano-salt with D90=100nm, and the nafion solution is an ethanol solution containing nafion 117, wherein the mass percentage of nafion 117 is 5%.

Comparative Example 3

A method for preparing a framework hydrogen evolution electrode by electrodeposition, specifically comprising the following steps:

S1. Coating pretreatment of electrodeposited substrate: the substrate is subjected to alkali degreasing and acid deoxidization pretreatment to obtain a pretreated substrate;

S2. Dissolve the nano-salt surface film, expose the electrodeposition attachment points, and obtain an electrodeposition substrate: The pretreated substrate prepared in S1 is placed in a hot alcohol cleaning solution for 1 min, and then taken out, and the heating temperature is 40 °C to obtain an electrodeposition substrate. ; Every one hundred parts by weight of hot alcohol cleaning solution includes the raw materials of the following parts by weight:

S3. Electrodeposition of the electrodeposition substrate: the electrodeposition substrate obtained from S2 is used as the cathode, the platinum sheet is used as the anode, the anode and the cathode are both placed in the electrodeposition solution, and electrodeposition is carried out under stirring conditions of 80 °C, and the stirring speed is 60r /min; the electrodeposition conditions are: the electrodeposition area is 1cm ² , the control constant voltage is 1.35V, and the electrodeposition time is 30min; wherein, the electrodeposition solution includes the following raw materials by mass:

S4, post-processing, put the electrode semi-finished product prepared by S3 in the hot alcohol cleaning solution of S2, control the temperature to 60 °C, and place it under sealing conditions for 22 hours; .

Step S1 specifically includes the following steps:

S11, the coupling agent is dissolved in the alcohol-water mixture, acetic acid is added, and the pH value of the solution is controlled to be 4.5 to 5.5 to prepare the coupling agent mixture;

S12, dissolving the nano-salt in the nafion solution to prepare a nano-salt mixture;

S13, the substrate is first soaked in the coupling agent mixture, then taken out to dry, and then soaked in the nano-salt mixture and then dried to obtain a pretreated substrate.

In the alcohol-water mixture of S11, the volume ratio of alcohol and water is 90:10; the mass of the coupling agent is 0.5% of the mass of the coupling agent mixture; the coupling agent is a silane coupling agent; the alcohol is ethanol; the nano-salt in S12 The mass ratio of nafion solution and nafion solution is 1:5; the nano-salt is nano-salt with D90=100nm, and the nafion solution is an ethanol solution containing nafion 117, wherein the mass percentage of nafion 117 is 5%.

Comparative Example 4

A method for preparing a multi-layer framework hydrogen evolution electrode by multi-layer electrodeposition specifically comprises the following steps:

S1. Coating pretreatment of electrodeposited substrate: the substrate is subjected to alkali degreasing and acid deoxidization pretreatment to obtain a pretreated substrate;

S2. Dissolve the nano-salt surface film, expose the electrodeposition attachment points, and obtain an electrodeposition substrate: The pretreated substrate prepared in S1 is placed in a hot alcohol cleaning solution for 1 min, and then taken out, and the heating temperature is 40 °C to obtain an electrodeposition substrate. ; Every one hundred parts by weight of hot alcohol cleaning solution includes the raw materials of the following parts by weight:

S3. Electrodeposition of the electrodeposition substrate: the electrodeposition substrate obtained from S2 is used as the cathode, the platinum sheet is used as the anode, the anode and the cathode are both placed in the electrodeposition solution, and electrodeposition is carried out under stirring conditions of 80 °C, and the stirring speed is 60r /min; the electrodeposition conditions are: the electrodeposition area is 1cm ² , the control constant voltage is 1.35V, and the electrodeposition time is 30min; wherein, the electrodeposition solution includes the following raw materials by mass:

S4, repeating operations S1 to S3 for 5 times to obtain a finished electrode product.

Step S1 specifically includes the following steps:

S11, the coupling agent is dissolved in the alcohol-water mixture, acetic acid is added, and the pH value of the solution is controlled to be 4.5 to 5.5 to prepare the coupling agent mixture;

S12, dissolving the nano-salt in the nafion solution to prepare a nano-salt mixture;

S13, the substrate is first soaked in the coupling agent mixture, then taken out to dry, and then soaked in the nano-salt mixture and then dried to obtain a pretreated substrate.

In the alcohol-water mixture of S11, the volume ratio of alcohol and water is 90:10; the mass of the coupling agent is 0.5% of the mass of the coupling agent mixture; the coupling agent is a silane coupling agent; the alcohol is ethanol; the nano-salt in S12 The mass ratio of nafion solution and nafion solution is 1:5; the nano-salt is nano-salt with D90=100nm, and the nafion solution is an ethanol solution containing nafion 117, wherein the mass percentage of nafion 117 is 5%.

To sum up, the oxygen evolution polarization curves of Example 5, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are shown in Figure 4, which shows that the oxygen evolution performance of Example 5 is significantly better than that of Comparative Example 1 Oxygen evolution performance of ~3.

In addition, Fig. 2 is the scanning electron microscope diagram of the surface of the multilayer electrodeposition structure, and Fig. 3 is the scanning electron microscope diagram of the surface of the ordinary electrodeposition structure. It can be seen from Fig. 2 and Fig. 3 that the multilayer electrodeposition structure The multi-layer electrodeposited structure is more dense and the structure is more stable.

What is described in the above specification is only the specific embodiment of the present invention, and various examples do not limit the essential content of the present invention. Those of ordinary skill in the art can modify or modify the specific embodiment described above after reading the specification. variations without departing from the spirit and scope of the invention.

Claims (6)

1. A method for preparing a multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition is characterized by comprising the following steps: the method specifically comprises the following steps:

s1, pre-treating a coating of an electrodeposition substrate: carrying out alkali oil removal and acid oxide layer removal pretreatment on the substrate to obtain a pretreated substrate;

s2, dissolving the nano salt surface layer film, and exposing an electrodeposition attachment point to obtain an electrodeposition substrate: placing the pretreated substrate prepared in the step S1 in hot alcohol cleaning solution, cleaning for 1-2 min, and taking out, wherein the heating temperature is 40-45 ℃ to prepare an electrodeposition substrate;

s3, performing electrodeposition on the electrodeposition substrate: taking the electrodeposition substrate prepared in the step (2) as a cathode, taking a platinum sheet as an anode, placing the anode and the cathode in an electrodeposition solution, and carrying out electrodeposition under the condition of stirring at 80 ℃, wherein the stirring speed is 60-100 r/min; the electrodeposition conditions were: the electrodeposition area is 1cm ² Controlling the constant voltage to be 1.35V, and controlling the electrodeposition time to be 30min;

s4, repeating the operation of S1-S3 for 4-5 times to obtain a semi-finished product of the electrode;

s5, post-processing: placing the semi-finished product of the electrode prepared in the step S4 in hot alcohol cleaning solution of the step S2, controlling the temperature to be 60 ℃, and placing for 18-24 hours under a sealing condition; then taking out and washing with clean water, and drying to obtain the finished product of the multilayer skeleton hydrogen evolution electrode.

2. The method for preparing the multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition as claimed in claim 1, wherein: the step S1 specifically includes the steps of:

s11, dissolving a coupling agent in the alcohol-water mixed solution, adding acetic acid, and controlling the pH value of the solution to be 4.5-5.5 to prepare a coupling agent mixed solution;

s12, dissolving the nano salt in nafion solution to prepare nano salt mixed solution;

s13, firstly, placing the substrate in the coupling agent mixed solution for soaking, then taking out and airing, then placing the substrate in the nano salt mixed solution for soaking and airing, and obtaining the pretreated substrate.

3. The method for preparing the multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition as claimed in claim 2, wherein: in the alcohol-water mixed solution of S11, the volume ratio of alcohol to water is (90-95): (5-10); the mass of the coupling agent is 0.5-1% of that of the coupling agent mixed solution; the coupling agent is silane coupling agent, titanate coupling agent or propylene glycol methyl ether; the alcohol is ethanol or ethylene glycol.

4. The method for preparing the multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition as claimed in claim 2, wherein: the mass ratio of the nano salt to the nafion solution in the S12 is 1:5-1:3; the nano salt is D90=100nm, the nafion solution is an ethanol solution containing nafion117, and the mass percent of nafion117 is 5%.

5. The method for preparing the multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition as claimed in claim 1, wherein: in the S2, each hundred parts by weight of the hot alcohol cleaning solution comprises the following raw materials in parts by weight:

wherein the surfactant A is one or more of sodium dodecyl benzene sulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate, secondary alkyl sodium sulfonate, sodium fatty acid methyl ester sulfonate, fatty acid methyl ester ethoxylate sulfonate and fatty alcohol-polyoxyethylene ether phosphate.

6. The method for preparing the multilayer skeleton hydrogen evolution electrode by multilayer electrodeposition as claimed in claim 1, wherein: the electrodeposition solution in S3 comprises the following raw materials in parts by mass:

the surfactant B is one or more of sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate, secondary alkyl sodium sulfonate, fatty acid methyl ester ethoxylate sulfonate and fatty alcohol-polyoxyethylene ether phosphate.

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