CN115772671A - Self-sacrificial gas evolution anode and preparation method thereof - Google Patents

Self-sacrificial gas evolution anode and preparation method thereof Download PDF

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CN115772671A
CN115772671A CN202110984698.5A CN202110984698A CN115772671A CN 115772671 A CN115772671 A CN 115772671A CN 202110984698 A CN202110984698 A CN 202110984698A CN 115772671 A CN115772671 A CN 115772671A
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ruthenium
iridium
titanium
metal oxide
conductive substrate
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王小磊
李爽
郭伦莲
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Bluestar Beijing Chemical Machinery Co Ltd
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Bluestar Beijing Chemical Machinery Co Ltd
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Abstract

A self-sacrifice gas precipitation anode and a preparation method thereof, a conductive matrix is made of metal materials, and the outer surface of the conductive matrix is coated with a metal oxide anode active coating; the metal oxide anode active coating is composed of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin oxide and cerium oxide in lanthanide elements, and the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 16-30g/m 2 . The purpose is to provide a self-sacrifice gas evolution anode which can increase the active points on the surface of an electrode, accelerate the gas evolution and escape speed, reduce the gas evolution potential, change the consumption speed of other elements in an active coating, and prolong the service life of other noble metals in the coating by the sacrifice of cerium of the coating and a preparation method thereof.

Description

Self-sacrificial gas evolution anode and preparation method thereof
Technical Field
The invention relates to the field of electrolysis, in particular to a self-sacrificial gas precipitation anode and a preparation method thereof.
Background
In the fields of electricity and chemistry, a positive electrode means an electrode having a high electric potential, and a negative electrode means an electrode having a low electric potential, but for the anode and the cathode, an oxidation reaction always occurs at the anode, and a reduction reaction always occurs at the cathode.
The traditional sacrificial anode refers to the condition that the theoretical metal of an electrolytic cell is used as the anode, and the anode (metal) is gradually consumed along with the flowing current. Sacrificial anodes are generally only economically applied on structures and in low soil resistivity environments where the need to protect the current is small.
In recent years, as the application of electrolysis technology in the fields of water treatment, biocatalysis and the like is expanding, the technical requirements of improving the anode electrocatalytic performance and reducing the anode electrochemical corrosion become a focus. In the electrolysis technology in the fields of water treatment and biological catalysis, the chemical reaction on the surface of the electrode after the anode is electrified needs the electrode to have good catalytic performance, so that the reaction can be continuously carried out for a long time, and certain electrolysis efficiency is ensured, which can be realized by coating the electrode with a proper active coating. However, another significant problem faced after the catalytic reaction of the electrode in the water treatment and biocatalysis fields is the poisoning problem of the active coating, such as manganese poisoning and microorganism adhesion in seawater electrolysis, adhesion of noble metals, organic matters, microorganisms and the like in sewage treatment, and the poisoning failure of the active coating caused by the adhesion of the organic matters and microorganisms and the like in the biocatalysis process. The traditional solution is to clean or replace the electrodes by stopping electrolysis, which affects the operation of the electrolysis equipment on one hand, and on the other hand, the basic problem cannot be solved in cleaning and replacing and the cost is high.
Disclosure of Invention
The invention aims to provide a self-sacrificial gas evolution anode which can increase the active points on the surface of an electrode, accelerate the gas evolution and escape speed, reduce the gas evolution potential, change the consumption speed of other elements in an active coating and prolong the service life of other noble metals in the coating by the sacrifice of cerium of the coating and a preparation method thereof.
The self-sacrificial gas precipitation anode comprises a conductive substrate, wherein the conductive substrate is made of a metal material, and the outer surface of the conductive substrate is coated with a metal oxide anode active coating;
the metal oxide anode active coating is formed by oxides of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and oxides of cerium in lanthanide elements, and the coating amount of the metal oxide anode active coating oxides on the surface of the conductive substrate is 16-30g/m 2 ；
The metal oxide anode active coating comprises 74-98% of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in molar percentage and 2-26% of cerium in terms of metal components.
Preferably, the metal oxide anode active coating comprises 76 to 96 mole percent of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and 4 to 24 mole percent of cerium, calculated as metal components;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 18-28g/m 2 。
Preferably, the conductive substrate is made of titanium mesh, and the metal oxide anode active coating comprises 80 to 92 mole percent of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and 8 to 20 mole percent of cerium, calculated according to metal components;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 20-26g/m 2 。
Preferably, the metal oxide anode active coating is formed by ruthenium and titanium, or ruthenium and platinum, or iridium and tantalum, or iridium and vanadium, or iridium and platinum, or iridium and tin, or ruthenium and iridium and titanium, or ruthenium and iridium and tin, or ruthenium and titanium and tin, or ruthenium and iridium and palladium, or ruthenium and iridium and titanium and platinum, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and iron, or ruthenium and iridium and titanium and cobalt oxide and cerium oxide;
the metal oxide anode active coating comprises 82-88 mol% of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and 12-16 mol% of cerium, wherein the metal oxide anode active coating comprises metal components;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 24-25g/m 2 。
The preparation method of the anode capable of separating out the sacrificial gas comprises the following steps:
A. preparing a conductive matrix by using metal, cleaning the conductive matrix, removing dirt on the surface of the conductive matrix, and roughening the surface of the conductive matrix;
B. preparing soluble salts of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and soluble salts of cerium, dissolving the soluble salts of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin with dilute hydrochloric acid, and adding soluble salts of cerium to obtain a metal oxide anode activity coating liquid, wherein the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode activity coating liquid is 160-200 g/L and the content of cerium is 1-34 g/L according to metal components;
C. coating the metal oxide anode active coating liquid obtained in the step B on the conductive substrate treated in the step A, and heating the conductive substrate to 400-550 ℃ in an air atmosphere for 10-50 minutes, thereby forming a metal oxide anode active coating on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes; repeating the above steps for multiple times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 16-30g/m 2 And obtaining the self-sacrifice gas precipitation anode.
Preferably, in the step B, the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating liquid is 165g to 195g/L and the content of cerium is 3g to 30g/L in terms of metal components;
in the step C, the conductive substrate is heated to 430-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide anode active coating is formed on the surface of the conductive substrate; then the metal oxide anode obtained in the step B is coated with active coating againCoating the liquid on the conductive substrate, and heating the conductive substrate to 430-520 ℃ in air atmosphere for 15-45 minutes; repeating the above steps for multiple times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 18-28g/m 2 。
Preferably, the conductive substrate is made of titanium mesh, and in the step B, the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating liquid is 170 g-190 g/L and the content of cerium is 8 g-25 g/L according to metal components;
in the step C, the conductive substrate is heated to 450-500 ℃ in the air atmosphere for 20-40 minutes, so that a metal oxide anode active coating is formed on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 450-500 ℃ in air atmosphere for 20-40 minutes; repeating the above steps for multiple times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 20-26g/m 2 。
Preferably, in the step B, the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating liquid is 175-185 g/L and the content of cerium is 12-20 g/L according to the metal components;
in the step C, the conductive substrate is heated to 460 ℃ to 490 ℃ in the air atmosphere for 25 minutes to 35 minutes, so that a metal oxide anode active coating is formed on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 460-490 ℃ in air atmosphere for 25-35 minutes; repeating the above steps for many times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 24-25g/m 2 。
Preferably, the metal oxide anode active coating is composed of ruthenium and titanium, or ruthenium and platinum, or iridium and tantalum, or iridium and vanadium, or iridium and platinum, or iridium and tin, or ruthenium and iridium and titanium, or ruthenium and iridium and tin, or ruthenium and titanium and tin, or ruthenium and iridium and palladium, or ruthenium and iridium and titanium and platinum, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and iron, or ruthenium and iridium and titanium and cobalt oxide and cerium oxide.
The invention discloses a self-sacrifice gas precipitation anode, wherein a conductive matrix is made of a metal material, and the outer surface of the conductive matrix is coated with a metal oxide anode active coating; the metal oxide anode active coating is composed of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin oxide and cerium oxide in lanthanide elements, the surface of the metal oxide anode active coating is provided with two structures of protrusions and honeycombs, the structures enable the sacrificial electrode to be corroded more uniformly and finely when the sacrificial electrode is used for the sacrificial electrode, the electrode has larger surface area and capacitance and enhanced electrode activity when the self-sacrificial gas evolution anode is used for a traditional gas evolution electrode, small protrusions uniformly distributed on the surface of the metal oxide anode active coating enable gas to escape more quickly after gas evolution, the gas evolution potential is reduced, the active points on the surface of the electrode are increased, the gas evolution and escape speed is accelerated, and the consumption of elements such as ruthenium, iron, cobalt, tin and the like can be accelerated when the self-sacrificial gas evolution anode active coating is used for gas evolution, and the consumption of elements such as iridium, palladium, platinum, tantalum, titanium and vanadium can be reduced. Therefore, the self-sacrifice gas separation anode and the preparation method thereof have the characteristics that the active points on the surface of the electrode can be increased, the gas separation and escape speed is accelerated, the gas separation potential is reduced, the consumption speed of other elements in the active coating can be changed, and the service life of other noble metals in the coating is prolonged by the cerium sacrifice of the coating.
Further details and characteristics of the self-sacrificing gas evolving anode of the present invention and of the method for its preparation will become clear from a reading of the examples detailed hereinafter.
Detailed Description
The self-sacrifice gas separation anode comprises a conductive substrate, wherein the conductive substrate is made of a metal material, and the outer surface of the conductive substrate is coated with a metal oxide anode active coating;
the metal oxide anode active coating is formed by oxides of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and oxides of cerium in lanthanide elements, and the coating amount of the metal oxide anode active coating oxides on the surface of the conductive substrate is 16-30g/m 2 ；
The metal oxide anode active coating comprises 74-98% of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in molar percentage and 2-26% of cerium in terms of metal components.
As a further improvement of the invention, the metal oxide anode active coating comprises 76 to 96 mole percent of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and 4 to 24 mole percent of cerium, calculated according to metal components;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 18-28g/m 2 。
As a further improvement of the invention, the conductive substrate is made of titanium mesh, and the metal oxide anode active coating comprises 80-92 mol% of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and 8-20 mol% of cerium in terms of metal components;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 20-26g/m 2 。
As a further improvement of the invention, the metal oxide anode active coating is composed of ruthenium and titanium, or ruthenium and platinum, or iridium and tantalum, or iridium and vanadium, or iridium and platinum, or iridium and tin, or ruthenium and iridium and titanium, or ruthenium and iridium and tin, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and palladium, or ruthenium and iridium and titanium and platinum, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and iron, or ruthenium and iridium and titanium and cobalt oxide and cerium oxide;
the metal oxide anode active coating comprises 82-88 mol% of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and 12-16 mol% of cerium, wherein the metal oxide anode active coating comprises metal components;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 24-25g/m 2 (ii) a The surface of the metal oxide anode active coating has two structures of protrusion and honeycomb, and the two structures are uniformly distributed.
The self-sacrifice gas separation anode has bright appearance, and because the surface of the metal oxide anode active coating has two structures of protrusion and honeycomb and is uniformly distributed, the active points on the surface of the electrode can be increased, and the gas separation and escape speed is accelerated.
The cerium element can accelerate the consumption of ruthenium, iron, cobalt, tin and other elements and slow the consumption of iridium, palladium, platinum, tantalum, titanium and vanadium when the self-sacrifice gas separation anode is used for gas separation.
The preparation method of the anode capable of separating out the sacrificial gas comprises the following steps:
A. preparing a conductive matrix by using metal, cleaning the conductive matrix, removing dirt on the surface of the conductive matrix, and roughening the surface of the conductive matrix;
B. preparing soluble salts of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and soluble salts of cerium, dissolving the soluble salts of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin with dilute hydrochloric acid, and adding soluble salts of cerium to obtain a metal oxide anode activity coating liquid, wherein the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode activity coating liquid is 160-200 g/L and the content of cerium is 1-34 g/L according to metal components;
C. coating the metal oxide anode active coating liquid obtained in the step B on the conductive substrate treated in the step A, and heating the conductive substrate to 400-550 ℃ in an air atmosphere for 10-50 minutes, thereby forming a metal oxide anode active coating on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes; repeating the above steps for many times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 16-30g/m 2 And obtaining the self-sacrifice gas precipitation anode.
As a further improvement of the invention, in the step B, the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating liquid is 165-195 g/L and the content of cerium is 3-30 g/L in terms of metal components;
in the step C, the conductive substrate is heated to 430-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide anode active coating is formed on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 430-520 ℃ in air atmosphere for 15-45 minutes; repeating the above steps for many times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 18-28g/m 2 。
As a further improvement of the invention, the conductive substrate is made of a titanium mesh, and in the step B, the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating liquid is 170 g-190 g/L and the content of cerium is 8 g-25 g/L according to the metal components;
in the step C, the conductive matrix is heated to 450-500 ℃ in the air atmosphere for a heating timeFrom 20 minutes to 40 minutes, thereby forming a metal oxide anodic active coating on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 450-500 ℃ in air atmosphere for 20-40 minutes; repeating the above steps for several times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 20-26g/m 2 。
As a further improvement of the invention, in the step B, the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating liquid is 175-185 g/L and the content of cerium is 12-20 g/L in terms of metal components;
in the step C, the conductive substrate is heated to 460-490 ℃ in the air atmosphere for 25-35 minutes, so that the metal oxide anode active coating is formed on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 460-490 ℃ in air atmosphere for 25-35 minutes; repeating the above steps for many times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 24-25g/m 2 。
As a further improvement of the invention, the metal oxide anode active coating is formed by ruthenium and titanium, or ruthenium and platinum, or iridium and tantalum, or iridium and vanadium, or iridium and platinum, or iridium and tin, or ruthenium and iridium and titanium, or ruthenium and iridium and tin, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and palladium, or ruthenium and iridium and titanium and platinum, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and iron, or ruthenium and iridium and titanium and cobalt oxides and cerium oxides.
Example 1
The self-sacrifice gas separation anode and the preparation method thereof are as follows:
1. preparing a first metal oxide anode active coating liquid containing ruthenium, platinum and cerium, wherein the sum of the metal contents of ruthenium, platinum and cerium in the metal oxide anode active coating liquid is 180g/L, and the cerium content is 3g/L, and preparing a second metal oxide anode active coating liquid containing ruthenium, iridium, titanium, iron and cerium, wherein the sum of the metal contents of ruthenium, iridium, titanium, iron and cerium in the metal oxide anode active coating liquid is 180g/L, and the cerium content is 24g/L.
2. The conductive substrate is made of a titanium mesh, and the surface of the metal substrate of the titanium mesh is roughened and cleaned.
3. Preparing an active coating bottom layer coating, coating a first metal oxide anode active coating liquid on the titanium mesh obtained in the step (1), and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃ and the thermal oxidation time is 25 minutes; then coating a first metal oxide anode active coating liquid on the titanium mesh obtained in the step 1, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃ and the thermal oxidation time is 25 minutes; repeating the steps for 6 times in total;
4. coating the second metal oxide anode active coating liquid on the titanium mesh obtained in the step 4, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, and the thermal oxidation time is 25 minutes; then coating the second metal oxide anode active coating liquid on the titanium mesh, and then carrying out thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, and the thermal oxidation time is 25 minutes
5. And (5) performing thermal oxidation treatment on the titanium mesh coated with the composite coating obtained in the step (4), wherein the thermal oxidation temperature of the thermal oxidation treatment is 550 ℃, and the thermal oxidation time is 180 minutes, so as to obtain a self-sacrificial gas precipitation anode C1.
Example 2
The self-sacrifice gas separation anode and the preparation method thereof are as follows:
1. preparing an iridium tin cerium hydrochloric acid coating liquid with iridium, tin and cerium, wherein the total content of iridium, tin and cerium in the iridium tin cerium hydrochloric acid coating liquid is 170g/L, and the content of cerium is 24g/L, and preparing a ruthenium iridium titanium palladium cerium hydrochloric acid coating liquid with ruthenium, iridium, titanium, palladium and cerium, wherein the total content of ruthenium, iridium, titanium, palladium and cerium in the coating liquid is 170g/L, and the content of cerium is 3g/L.
2. And (3) roughening and cleaning the surface of the titanium mesh metal matrix.
3. Preparing an active coating bottom layer coating, coating the iridium tin cerium hydrochloric acid coating liquid on a titanium mesh, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 6; coating the ruthenium iridium titanium palladium cerium hydrochloric acid coating liquid on a titanium net coated with a bottom layer coating, and then carrying out thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 2 times.
4. And carrying out thermal oxidation treatment on the titanium mesh coated with the composite coating in the step 3 at the thermal oxidation temperature of 550 ℃ for 240 minutes to obtain a self-sacrificial gas precipitation anode C2.
Example 3
The self-sacrificial gas precipitation anode and the preparation method thereof are as follows:
1. preparing ruthenium-iridium-tin-cerium hydrochloric acid coating liquid with ruthenium, iridium, tin and cerium, wherein the total content of ruthenium, iridium, tin and cerium in the coating liquid is 175g/L, and the content of cerium is 3g/L, and preparing ruthenium-iridium-titanium-palladium-cerium hydrochloric acid coating liquid with ruthenium, iridium, titanium, palladium and cerium, wherein the total content of ruthenium, iridium, titanium, palladium and cerium in the coating liquid is 175g/L, and the content of cerium is 18g/L.
2. And (4) roughening and cleaning the surface of the titanium mesh metal matrix.
3. Preparing an active coating bottom layer coating, coating the ruthenium-iridium-tin-cerium hydrochloric acid coating liquid on a titanium mesh, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 6; coating the ruthenium iridium titanium palladium cerium hydrochloric acid coating liquid on a titanium net coated with a bottom layer coating, and then carrying out thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 2 times.
4. And (3) performing thermal oxidation treatment on the titanium mesh coated with the composite coating in the step (3), wherein the thermal oxidation temperature of the thermal oxidation treatment is 550 ℃, and the thermal oxidation time is 150 minutes, so as to obtain the self-sacrificial gas precipitation anode C3.
Example 4
The self-sacrifice gas separation anode and the preparation method thereof are as follows:
1. preparing a ruthenium-platinum-cerium hydrochloric acid coating solution containing ruthenium, platinum and cerium, wherein the total content of ruthenium, platinum and cerium in the coating solution is 175g/L, and the content of cerium in the coating solution is 8g/L, preparing a ruthenium-iridium-titanium-palladium-cerium hydrochloric acid coating solution containing ruthenium, iridium, titanium, palladium and cerium in the coating solution, wherein the total content of ruthenium, iridium, titanium, palladium and cerium in the coating solution is 175g/L, and the content of cerium in the coating solution is 18g/L.
2. And (4) roughening and cleaning the surface of the titanium mesh metal matrix.
3. Preparing an active coating bottom layer coating, coating the ruthenium platinum cerium hydrochloric acid coating liquid on a titanium mesh, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 6 times; coating ruthenium iridium titanium palladium cerium hydrochloric acid coating liquid on a titanium net coated with a bottom layer coating, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 2.
4. And (3) performing thermal oxidation treatment on the titanium mesh coated with the composite coating in the step (3), wherein the thermal oxidation temperature of the thermal oxidation treatment is 550 ℃, and the thermal oxidation time is 150 minutes, so as to obtain a self-sacrificial gas precipitation anode C4.
Example 5
The self-sacrifice gas separation anode and the preparation method thereof are as follows:
1. preparing ruthenium iridium titanium iron cerium hydrochloric acid coating liquid with ruthenium, iridium, titanium, iron and cerium, wherein the total content of ruthenium, iridium, titanium, iron and cerium in the coating liquid is 175g/L, and the content of cerium is 8g/L, and preparing ruthenium iridium titanium palladium cerium hydrochloric acid coating liquid with ruthenium, iridium, titanium, palladium and cerium, wherein the total content of ruthenium, iridium, titanium, palladium and cerium in the coating liquid is 175g/L, and the content of cerium is 18g/L.
2. And (4) roughening and cleaning the surface of the titanium mesh metal matrix.
3. Preparing an active coating bottom layer coating, coating the ruthenium iridium titanium iron cerium hydrochloric acid coating liquid on a titanium mesh, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 6; coating the ruthenium iridium titanium palladium cerium hydrochloric acid coating liquid on a titanium net coated with a bottom layer coating, and then carrying out thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 2 times.
4. And (3) carrying out thermal oxidation treatment on the titanium mesh coated with the composite coating in the step (3), wherein the thermal oxidation temperature of the thermal oxidation treatment is 550 ℃, and the thermal oxidation time is 150 minutes, so as to obtain a self-sacrificial gas precipitation anode C5.
Example 6
The self-sacrifice gas separation anode and the preparation method thereof are as follows:
1. preparing a ruthenium-iridium-titanium-palladium-cerium hydrochloric acid coating liquid with ruthenium, iridium, titanium, palladium and cerium, wherein the total content of ruthenium, iridium, titanium, palladium and cerium in the coating liquid is 175g/L, and the content of cerium is 8g/L, and preparing a ruthenium-iridium-titanium-iron-cerium hydrochloric acid coating liquid with ruthenium, iridium, titanium, iron and cerium, wherein the total content of ruthenium, iridium, titanium, iron and cerium in the coating liquid is 175g/L, and the content of cerium is 18g/L.
2. And (3) roughening and cleaning the surface of the titanium mesh metal matrix.
3. Preparing an active coating bottom layer coating, coating ruthenium iridium titanium palladium cerium hydrochloric acid coating liquid on a titanium net, and then performing thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 6; coating the ruthenium iridium titanium iron cerium hydrochloric acid coating liquid on a coated bottom layer coating titanium net, and then carrying out thermal oxidation treatment, wherein the thermal oxidation temperature of the thermal oxidation treatment is 515 ℃, the thermal oxidation time is 25 minutes, and the coating and thermal oxidation treatment times are 2 times.
4. And (3) performing thermal oxidation treatment on the titanium mesh coated with the composite coating in the step (3), wherein the thermal oxidation temperature of the thermal oxidation treatment is 550 ℃, and the thermal oxidation time is 150 minutes, so as to obtain a self-sacrificial gas precipitation anode C6.
The detection of the above-mentioned anode for sacrificial gas evolution C1-anode for sacrificial gas evolution C6 from anode for sacrificial gas evolution of the present invention is carried out by the following method:
32% at 90 ℃ of 8KA/m in NaOH aqueous solution 2 Continuously electrolyzing for 4h under current density, calculating the service life weight loss of the anode before and after electrolysis by using balance weighing, and calculating the residual percentage of the anode coating before and after electrolysis by using an X-ray fluorescence spectrometer; and 3.5mol/LNaCl sodium chloride at 90 ℃ of the electrochemical workstationThe chlorine evolution potential and capacitance of the electrode are detected in the aqueous solution. The results of the measurements are shown in the following table:
TABLE 1
Figure BDA0003230283360000081
The data listed in the table show that the addition of cerium element in the active coating of the self-sacrifice gas-evolution anode prepared by the preparation method changes the porous structure form of the gas-evolution electrode, reduces the gas-evolution potential, changes the consumption speed of other elements in the active coating, and obviously prolongs the service life of other noble metals in the coating by cerium sacrifice of the coating.
The invention has been carried out exploratory research aiming at the prior art, and found unexpectedly that the sensitivity of the sacrificial electrode and the protection capability of the working electrode can be improved by introducing a proper amount of elements which are easier to be corroded into the anode coating to change the potential of the sacrificial electrode for oxidation reaction, and simultaneously the original structure of the anode coating is changed by controlling the adding amount and proportion of the elements which are easier to be corroded, the surface of the metal oxide anode active coating has two structures of protrusion and honeycomb which are uniformly distributed, on one hand, the structure enables the self-sacrificial electrode to be corroded more uniformly and finely to prolong the service life of the sacrificial electrode when the self-sacrificial electrode is used for the sacrificial electrode, on the other hand, when the self-sacrificial gas evolution anode is used for the traditional gas evolution electrode, the honeycomb structure enables the electrode to have larger surface area and capacitance, the electrode activity is enhanced, and the small protrusions uniformly distributed on the crystal surface enable the gas to escape more rapidly after the gas is evolved, and the gas evolution potential is reduced.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention are intended to fall within the scope of the present invention defined by the claims.

Claims (9)

1. The self-sacrificial gas precipitation anode is characterized by comprising a conductive substrate, wherein the conductive substrate is made of a metal material, and the outer surface of the conductive substrate is coated with a metal oxide anode active coating;
the metal oxide anode active coating is formed by oxides of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and oxides of cerium in lanthanide elements, and the coating amount of the metal oxide anode active coating oxides on the surface of the conductive substrate is 16-30g/m 2 ；
The metal oxide anode active coating comprises 74-98% of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in molar percentage and 2-26% of cerium in terms of metal components.
2. The self-sacrificing gas evolving anode according to claim 1, characterized in that said metal oxide anodic active coating comprises, as metal components, from 76% to 96% by mole of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and from 4% to 24% by mole of cerium;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 18-28g/m 2 。
3. The self-sacrificing gas evolving anode according to claim 2, characterized in that said electrically conductive substrate is made of a titanium mesh and said metal oxide anodic active coating contains, in terms of metal components, from 80 to 92% by mole of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and from 8 to 20% by mole of cerium;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 20-26g/m 2 。
4. The self-sacrificial gas evolving anode according to claim 1 or 2 or 3, characterized in that said metal oxide anodic active coating is constituted by ruthenium and titanium, or ruthenium and platinum, or iridium and tantalum, or iridium and vanadium, or iridium and platinum, or iridium and tin, or ruthenium and iridium and titanium, or ruthenium and iridium and tin, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and palladium, or ruthenium and iridium and titanium and platinum, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and iron, or ruthenium and iridium and titanium and cobalt oxides together with cerium oxides;
the metal oxide anode active coating comprises 82-88% of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in molar percentage and 12-16% of cerium in terms of metal components;
the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 24-25g/m 2 。
5. The preparation method of the anode capable of self-releasing the sacrificial gas is characterized by comprising the following steps:
A. preparing a conductive matrix by using metal, cleaning the conductive matrix, removing dirt on the surface of the conductive matrix, and roughening the surface of the conductive matrix;
B. preparing soluble salts of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin and soluble salts of cerium, dissolving the soluble salts of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin with dilute hydrochloric acid, and adding soluble salts of cerium to obtain a metal oxide anode active coating liquid, wherein the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating liquid is 160-200 g/L and the content of cerium is 1-34 g/L in terms of metal components;
C. coating the metal oxide anode active coating liquid obtained in the step B on the conductive substrate treated in the step A, and heating the conductive substrate to 400 ℃ in the air atmosphereHeating at 10-50 min to 550 deg.c to form active metal oxide coating on the surface of the conducting substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes; repeating the above steps for many times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 16-30g/m 2 And obtaining the self-sacrifice gas precipitation anode.
6. The process for the preparation of a self-sacrificial gas evolving anode according to claim 5, characterized in that in step B the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anodic active coating liquid is between 165g and 195g/L and the content of cerium is between 3g and 30g/L, calculated as metal components;
in the step C, the conductive substrate is heated to 430-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide anode active coating is formed on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 430-520 ℃ in air atmosphere for 15-45 minutes; repeating the above steps for many times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 18-28g/m 2 。
7. The method according to claim 6, characterized in that the electrically conductive matrix is made of a titanium mesh, and in step B, the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anode active coating solution is 170g to 190g/L and the content of cerium is 8g to 25g/L, in terms of metal components;
in the step C, the conductive substrate is heated to 450-500 ℃ in the air atmosphere for 20-40 minutes, thereby forming on the surface of the conductive substrateA metal oxide anodic active coating; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 450-500 ℃ in air atmosphere for 20-40 minutes; repeating the above steps for several times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 20-26g/m 2 。
8. The self-sacrificial gas evolving anode according to claim 7, characterized in that in step B the content of ruthenium and/or iridium and/or titanium and/or palladium and/or platinum and/or cobalt and/or iron and/or tantalum and/or vanadium and/or tin in the metal oxide anodic active coating liquid is 175-185 g/L and the content of cerium is 12-20 g/L, calculated as metal components;
in the step C, the conductive substrate is heated to 460-490 ℃ in the air atmosphere for 25-35 minutes, so that the metal oxide anode active coating is formed on the surface of the conductive substrate; then coating the metal oxide anode active coating liquid obtained in the step B on a conductive substrate, and heating the conductive substrate to 460-490 ℃ in air atmosphere for 25-35 minutes; repeating the above steps for many times until the coating amount of the metal oxide anode active coating oxide on the surface of the conductive substrate is 24-25g/m 2 。
9. Self-sacrificial gas evolving anode according to any one of claims 5 to 8, characterized in that said metal oxide anodic active coating is constituted by ruthenium and titanium, or ruthenium and platinum, or iridium and tantalum, or iridium and vanadium, or iridium and platinum, or iridium and tin, or ruthenium and iridium and titanium, or ruthenium and iridium and tin, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and palladium, or ruthenium and iridium and titanium and platinum, or ruthenium and titanium and tin, or ruthenium and iridium and titanium and iron, or ruthenium and iridium and titanium and cobalt oxides together with cerium oxides.
CN202110984698.5A 2021-08-25 2021-08-25 Self-sacrificial gas evolution anode and preparation method thereof Pending CN115772671A (en)

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