CN115725997A - High current density electrolytic active cathode and preparation method thereof - Google Patents
High current density electrolytic active cathode and preparation method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 29
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Abstract
A high current density electrolytic active cathode and a preparation method thereof comprise a conductive substrate, wherein the outer surface of the conductive substrate is coated with a metal oxide cathode bottom active coating, the outer surface of the metal oxide cathode bottom active coating is coated with a metal oxide cathode outer active coating, the metal oxide cathode bottom active coating is formed by oxides of a transition element VIII group and oxides of lanthanide elements, and the metal oxide cathode outer active coating is formed by oxides of the transition element VIII group. The purpose is to provide a method which can be at 8KA/m 2 The cathode of the ion membrane electrolytic cell is operated under high current density, has low oxygen evolution overpotential under the high current density electrolysis condition, long service life, lower energy consumption and stable operation, and meets the use requirements of long-term high current density start and stable operation of chlor-alkali production users, and the likeThe high current density electrolytic active cathode and the preparation method thereof help users to reduce cost and improve economic benefits.
Description
Technical Field
The invention relates to the field of electrolysis, in particular to a high-current-density electrolytic active cathode and a preparation method thereof.
Background
The chlor-alkali industry is an industrial production industry which takes chlorine and caustic soda as main products, and the products of the chlor-alkali industry are widely applied in the economic development of China and play an important role in promoting the social and economic development. In recent years, with the rapid development of the chlor-alkali industry and the continuous expansion of the market of chlor-alkali products, the technology of the ion membrane electrolytic cell and the matched electrodes thereof of chlor-alkali electrolysis equipment is continuously innovated, and especially with the improvement of the technical management level of chlor-alkali users, the normal operation of the ion membrane electrolytic cell under the condition of high current density is promoted to be possible. Meanwhile, users also put higher requirements on the ton alkali power consumption and the electrode service life of the ion membrane electrolytic cell. Researches out an ion-exchange membrane electrolytic cell electrode suitable for high-current density operation, and focuses on meeting the requirements of users on reducing the energy consumption of chlor-alkali production and ensuring the stable operation of equipment under the condition of long-term high current density.
The current density of the traditional electrolytic active cathode is usually 2KA/m 2 -4KA/m 2 This requires the development of a high current density operation, i.e. at 4KA/m 2 The electrolytic active cathode operated under the current density needs an electrode which can be used for generating hydrogen under high current density and has low hydrogen evolution overpotential and long service life, and the prior high current density electrolytic active cathode generally does not have the performance, and the prior latest electrolytic active cathode technology is 6KA/m 2 The hydrogen evolution overpotential is about 75mV when the reactor operates under the current density.
The cathode suitable for high current density electrolysis is developed through experimental research, the electrode has a good service life under the high current density electrolysis condition, the energy consumption is reduced, and the cost is reduced, so that the economic benefit is obviously improved.
Disclosure of Invention
The invention aims to provide a catalyst which can be 8KA/m 2 The cathode of the ion membrane electrolytic cell is operated under high current density, has low hydrogen evolution overpotential under the high current density electrolysis condition, long service life, lower energy consumption and stable operation, meets the use requirements of a chlor-alkali production user on long-term high current density start and stable operation, and simultaneously helps the user to reduce the equipment input cost and improve the hydrogen evolution overpotentialAn economically efficient high current density electrolytic active cathode and a method for making the same.
The high-current-density electrolytic active cathode comprises a conductive substrate, wherein the conductive substrate is made of a metal material, the outer surface of the conductive substrate is coated with a metal oxide cathode bottom active coating, the outer surface of the metal oxide cathode bottom active coating is coated with a metal oxide cathode outer active coating, the metal oxide cathode bottom active coating is formed by oxides of a transition element group VIII and oxides of lanthanide, and the metal oxide cathode outer active coating is formed by oxides of the transition element group VIII;
the ratio of the number of atoms of the VIII group of the transition elements in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the lanthanide series elements is 2.3-10.1, and the content of the oxides of the VIII group of the transition elements in the active coating of the bottom layer of the metal oxide cathode is 6-16g/m 2 ；
The ratio of the number of atoms of the VIII group of the transition elements in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the VIII group of the transition elements in the active coating of the outer layer of the metal oxide cathode is 5.9-23.4.
Preferably, the transition element group VIII in the active coating of the bottom layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum, and the lanthanide element is cerium and/or praseodymium;
the transition element VIII group in the active coating of the outer layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum.
The surface area of the active cathode conductive base material nickel wire metal base material is 12-16cm 2 /g。
Preferably, the atomic number ratio of ruthenium, rhodium, palladium and/or platinum to cerium and/or praseodymium in the metal oxide cathode bottom active coating is 4.0-8.1, and the oxide content of ruthenium, rhodium, palladium and/or platinum in the metal oxide cathode bottom active coating is 8-14g/m 2 ；
The atomic number ratio of the ruthenium, rhodium, palladium and/or platinum in the active coating at the bottom layer of the metal oxide cathode to the ruthenium, rhodium, palladium and/or platinum in the active coating at the outer layer of the metal oxide cathode is 8.8-17.6.
The surface area of the active cathode conductive base material nickel wire metal base material is 13-15cm 2 /g。
The preparation method of the high current density electrolytic active cathode comprises the following steps:
A. cleaning a conductive substrate made of a metal material, removing surface dirt of the conductive substrate, making the surface of the conductive substrate rough, and thermally oxidizing for 15-45 minutes at 400-500 ℃;
B. preparing soluble salts of transition elements in the VIII group and soluble salts of lanthanide elements;
C. dissolving soluble salts of VIII family transition elements by using dilute hydrochloric acid, and adding soluble salts of lanthanide elements to obtain cathode bottom layer active coating liquid, wherein the content of the metal elements in the cathode bottom layer active coating liquid is 125 g-175 g/L according to metal components, and the ratio of the number of VIII family transition elements atoms to the number of lanthanide elements atoms is 2.3-10.1;
dissolving soluble salt of a VIII group of transition elements by using dilute nitric acid to obtain cathode outer layer active coating liquid, wherein the content of metal elements in the cathode outer layer active coating liquid is 55-85 g/L according to metal components;
the ratio of the number of atoms of the VIII family of transition elements in the cathode bottom layer active coating liquid to the number of atoms of the VIII family of transition elements in the cathode outer layer active coating liquid is 5.9-23.4;
D. c, coating the cathode bottom layer active coating liquid obtained in the step C on the conductive substrate treated in the step A, and heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes, thereby forming a metal oxide cathode active coating on the surface of the conductive substrate; and C, coating the cathode bottom layer active coating liquid obtained in the step C on a conductive substrate again, heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes, and repeating the steps for a plurality of times until the content of the transition element VIII group oxide in the metal oxide cathode bottom layer active coating is 6-16g/m 2 ；
E. D, coating the cathode outer layer active coating liquid obtained in the step C on the conductive substrate treated in the step D, and heating the conductive substrate to 400-550 ℃ in an air atmosphere for 10-50 minutes, thereby forming a metal oxide cathode active coating on the surface of the conductive substrate; and C, coating the cathode outer layer active coating liquid obtained in the step C on a conductive substrate again, heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes, and repeating the heating for multiple times until the ratio of the number of the transition element group VIII atoms in the metal oxide cathode outer layer active coating to the number of the transition element group VIII atoms in the metal oxide cathode bottom layer active coating meets the requirement, so that the high-current-density active gas is obtained and is separated out of the cathode.
Preferably, in the step C, the content of the metal element in the cathode bottom layer active coating liquid is 130g/L to 170g/L in terms of metal component, wherein the ratio of the number of atoms in the group VIII of the transition element to the number of atoms in the lanthanide element is 4.0 to 8.1;
the content of metal elements in the cathode outer layer active coating liquid is 60 g/L-80 g/L according to metal components;
the transition element VIII group in the active coating of the bottom layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum, and the lanthanide is cerium and/or praseodymium;
the VIII family of transition elements in the active coating of the outer layer of the oxide cathode is ruthenium, rhodium, palladium and/or platinum;
in the step C, the conductive substrate is heated to 420-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide cathode active coating is formed on the surface of the conductive substrate; then coating the cathode bottom layer active coating liquid obtained in the step C on a conductive substrate again, heating the conductive substrate to 420-520 ℃ in air atmosphere for 15-45 minutes, and repeating the steps for 6-12 times until the content of the transition element VIII group oxide in the metal oxide cathode bottom layer active coating is 8-14g/m 2 ；
In the step C, the conductive substrate is heated to 420-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide cathode active coating is formed on the surface of the conductive substrate; and C, coating the cathode outer layer active coating liquid obtained in the step C on a conductive substrate again, heating the conductive substrate to 420-520 ℃ in an air atmosphere for 15-45 minutes, and repeating the steps for a plurality of times until the ratio of the number of the transition element VIII group atoms in the metal oxide cathode outer layer active coating to the number of the transition element VIII group atoms in the metal oxide cathode bottom layer active coating meets the requirement, so that the high-current-density active gas is obtained and is separated out of the cathode.
The invention relates to a high current density electrolytic active cathode and a preparation method thereof, which adopts the special process steps of the invention, and comprises two different solution systems for preparing an active cathode bottom coating and an outer coating, wherein the bottom coating adopts hydrochloric acid solution, the outer coating adopts nitric acid solution, the ratio of the number of atoms of a transition element group VIII in the active coating of the metal oxide cathode bottom layer to the number of atoms of lanthanide is 2.3-10.1, and the oxide content of the transition element group VIII in the active coating of the metal oxide cathode bottom layer is 6-16g/m 2 The ratio of the number of atoms of the VIII group of the transition element in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the VIII group of the transition element in the active coating of the outer layer of the metal oxide cathode is 5.9-23.4; the active cathode hydrogen evolution active points of the high current density electrolysis active cathode are increased, the electrode service life is long during high current density electrolysis, the electrolysis energy consumption is low, and meanwhile, the electrode manufacturing process is excellent and the cost performance is improved. Therefore, the high current density electrolytic active cathode and the preparation method thereof have the advantages that the current density electrolytic active cathode can be 8KA/m 2 The cathode of the ion membrane electrolytic cell is operated under high current density, has low oxygen evolution overpotential under the high current density electrolysis condition, long service life, lower energy consumption and stable operation, so as to meet the use requirements of a chlor-alkali production user on long-term high current density start and stable operation, and simultaneously help the user to reduce the equipment investment cost and improve the economic benefit.
Further details and features of the high current density electrolytically-active cathode of the present invention and the process for its preparation will be apparent from a reading of the examples detailed below.
Detailed Description
The high-current-density electrolytic active cathode comprises a conductive substrate, wherein the conductive substrate is made of a metal material, the outer surface of the conductive substrate is coated with a metal oxide cathode bottom active coating, the outer surface of the metal oxide cathode bottom active coating is coated with a metal oxide cathode outer active coating, the metal oxide cathode bottom active coating is formed by oxides of a transition element group VIII and oxides of lanthanide, and the metal oxide cathode outer active coating is formed by oxides of the transition element group VIII;
the ratio of the atomic number of the VIII group of the transition elements in the active coating of the bottom layer of the metal oxide cathode to the atomic number of the lanthanide elements is 2.3-10.1, and the oxide content of the VIII group of the transition elements in the active coating of the bottom layer of the metal oxide cathode is 6-16g/m 2 ；
The ratio of the number of atoms of the VIII group of the transition element in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the VIII group of the transition element in the active coating of the outer layer of the metal oxide cathode is 5.9-23.4.
The surface area of the active cathode conductive substrate nickel wire metal substrate is 12-16cm2/g.
As a further improvement of the invention, in the active coating of the bottom layer of the metal oxide cathode, the transition element group VIII is ruthenium, rhodium, palladium and/or platinum, and the lanthanide element is cerium and/or praseodymium;
the transition element VIII group in the active coating of the outer layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum.
The ratio of the number of atoms of the VIII group of the transition element in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the lanthanide element is 2.3-10.1, and the content of the oxide of the VIII group of the transition element in the active coating of the bottom layer of the metal oxide cathode is 6-16g/m < 2 >;
the ratio of the number of atoms of the VIII group of the transition element in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the VIII group of the transition element in the active coating of the outer layer of the metal oxide cathode is 5.9-23.4.
Preferably, the transition element group VIII in the active coating of the metal oxide cathode bottom layer is ruthenium, rhodium, palladium and/or platinum, and the lanthanide element is cerium and/or praseodymium;
the transition element VIII group in the active coating of the outer layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum.
Preferably, the atomic number ratio of the ruthenium, rhodium, palladium and/or platinum to the cerium and/or praseodymium in the active coating of the bottom layer of the metal oxide cathode is 4.0-8.1, and the oxide content of the ruthenium, rhodium, palladium and/or platinum in the active coating of the bottom layer of the metal oxide cathode is 8-14g/m 2 ；
The atomic number ratio of the ruthenium, rhodium, palladium and/or platinum in the active coating at the bottom layer of the metal oxide cathode to the ruthenium, rhodium, palladium and/or platinum in the active coating at the outer layer of the metal oxide cathode is 8.8-17.6.
The surface area of the active cathode conductive substrate nickel wire metal substrate is 13-15cm 2 /g。
The preparation method of the high current density electrolytic active cathode comprises the following steps:
A. cleaning a conductive substrate made of a metal material, removing surface dirt of the conductive substrate, making the surface of the conductive substrate rough, and thermally oxidizing for 15-45 minutes at 400-500 ℃;
B. preparing soluble salts of transition elements in the VIII group and soluble salts of lanthanide elements;
C. dissolving soluble salts of VIII family transition elements by using dilute hydrochloric acid, and adding soluble salts of lanthanide elements to obtain cathode bottom layer active coating liquid, wherein the content of the metal elements in the cathode bottom layer active coating liquid is 125 g-175 g/L according to metal components, and the ratio of the number of VIII family transition elements atoms to the number of lanthanide elements atoms is 2.3-10.1;
dissolving soluble salt of a transition element group VIII by using dilute nitric acid to obtain cathode outer layer active coating liquid, wherein the content of metal elements in the cathode outer layer active coating liquid is 55-85 g/L according to metal components;
the ratio of the number of atoms of the VIII family of the transition element in the cathode bottom layer active coating liquid to the number of atoms of the VIII family of the transition element in the cathode outer layer active coating liquid is 5.9-23.4;
D. c, coating the cathode bottom layer active coating liquid obtained in the step C 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, so that a metal oxide cathode active coating is formed on the surface of the conductive substrate; then coating the cathode bottom layer active coating liquid obtained in the step C on a conductive substrate, heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes, repeating the heating for multiple times until the content of the transition element VIII group oxide in the metal oxide cathode bottom layer active coating is 6-16g/m 2 ；
E. C, coating the cathode outer layer active coating liquid obtained in the step C on the conductive substrate treated in the step D, and heating the conductive substrate to 400-550 ℃ in an air atmosphere for 10-50 minutes, so that a metal oxide cathode active coating is formed on the surface of the conductive substrate; and C, coating the cathode outer layer active coating liquid obtained in the step C on a conductive substrate again, heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes, and repeating the heating for multiple times until the ratio of the number of the transition element group VIII atoms in the metal oxide cathode outer layer active coating to the number of the transition element group VIII atoms in the metal oxide cathode bottom layer active coating meets the requirement, so that the high-current-density active gas is obtained and is separated out of the cathode.
As a further improvement of the invention, in the step C, the content of the metal elements in the cathode bottom layer active coating liquid is 130 g-170 g/L calculated by the metal components, wherein the ratio of the number of atoms of the VIII group of the transition elements to the number of atoms of the lanthanide elements is 4.1-8.0;
the content of metal elements in the cathode outer layer active coating liquid is 60 g-80 g/L according to metal components;
the ratio of the number of atoms of the VIII family of the transition element in the cathode bottom layer active coating liquid to the number of atoms of the VIII family of the transition element in the cathode outer layer active coating liquid is 8.8-17.6;
the transition element VIII group in the active coating of the bottom layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum, and the lanthanide is cerium and/or praseodymium;
the VIII family of transition elements in the active coating of the outer layer of the oxide cathode is ruthenium, rhodium, palladium and/or platinum;
in the step C, the conductive substrate is heated to 420-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide cathode active coating is formed on the surface of the conductive substrate; then coating the cathode bottom active coating liquid obtained in the step C on a conductive substrate, heating the conductive substrate to 420-520 ℃ in air atmosphere for 15-45 minutes, repeating the heating for 6-12 times until the content of the transition element VIII group oxide in the active coating of the metal oxide cathode bottom is 8-14g/m 2 ；
In the step C, the conductive substrate is heated to 420-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide cathode active coating is formed on the surface of the conductive substrate; and C, coating the cathode outer layer active coating liquid obtained in the step C on a conductive substrate again, heating the conductive substrate to 420-520 ℃ in an air atmosphere for 15-45 minutes, and repeating the heating for 1-4 times until the ratio of the number of the transition element group VIII atoms in the metal oxide cathode outer layer active coating to the number of the transition element group VIII atoms in the metal oxide cathode bottom layer active coating meets the requirement, so that the high-current-density active gas is obtained and is separated out of the cathode. .
The mass percentages of the elements in the active coating layer in terms of metal components can be detected by an X-ray fluorescence tester.
The cathode for high current density electrolysis adopts the special process steps of the invention, and comprises the steps of preparing a bottom coating and an outer coating of an active cathode by adopting two different solution systems, wherein the coating liquid of the bottom coating adopts a hydrochloric acid solution, and the coating liquid of the outer coating adopts a nitric acid solution; due to the adoption of the specific technical characteristics, the cathode for high current density electrolysis can stably run for a long time under the electrolysis condition with higher current density, has lower hydrogen evolution overpotential, and meets the use requirements of energy conservation, consumption reduction, quality improvement and efficiency improvement of chlor-alkali users.
Example 1
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. soluble salts of ruthenium, cerium and platinum are dissolved by hydrochloric acid, cathode bottom layer active coating liquid with the total noble metal content of 150g/L is prepared according to the atomic weight ratio of ruthenium, cerium and platinum of 70: 20: 10 and is used for preparing a bottom layer coating, and cathode outer layer active coating liquid with the metal content of 55g/L is prepared by nitric acid solution of platinum and is used for preparing an outer layer coating.
2. Selecting
Weaving a nickel wire mesh as a conductive matrix to ensure that the surface area of the conductive matrix reaches 17cm 2 (ii) in terms of/g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 500 deg.C for 40 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step 1 on the metal nickel wire mesh obtained in the step 2, drying at 80 ℃ for 3 minutes, and then thermally oxidizing at 565 ℃ for 30 minutes; the above process was repeated 12 times to complete the formation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel wire mesh coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 15 minutes at 500 ℃; the above process was repeated 4 times to complete the outer coating.
5. And (3) thermally oxidizing the metal nickel screen coated with the outer coating obtained in the step (4) at 585 ℃ for 100 minutes to obtain the electrode A1, wherein the number ratio of metal atoms in the bottom coating to the number ratio of metal atoms in the outer coating is 17.
Example 2
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. dissolving soluble salts of ruthenium and cerium by using hydrochloric acid, preparing a cathode bottom layer active coating liquid with the total noble metal content of 135g/L according to the atomic weight ratio of ruthenium to 70: cerium to be used for preparing a bottom layer coating, and preparing a cathode outer layer active coating liquid with the metal content of 85g/L from a nitric acid solution of platinum to be used for preparing an outer layer coating.
2. Selecting
Weaving a nickel wire mesh as a conductive matrix to ensure that the surface area of the conductive matrix reaches 13cm 2 (iv) g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 400 c for 15 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step 1 on the metal nickel wire mesh obtained in the step 2, then drying for 15 minutes at 160 ℃, and then thermally oxidizing for 45 minutes at 500 ℃; and repeating the process for 8 times to finish the preparation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel wire mesh coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 40 minutes at 500 ℃; and repeating the process for 2 times to finish the preparation of the outer coating.
5. And (3) thermally oxidizing the metal nickel screen coated with the outer coating obtained in the step (4) at 550 ℃ for 100 minutes to obtain the electrode A2, wherein the number ratio of metal atoms in the bottom coating to the metal atoms in the outer coating is 8.
Example 3
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. soluble salts of ruthenium, cerium and platinum are dissolved by hydrochloric acid, cathode bottom layer active coating liquid with the total noble metal content of 140g/L is prepared according to the atomic weight ratio of ruthenium, cerium and platinum, the cathode bottom layer active coating liquid is used for preparing a bottom layer coating, and a cathode outer layer active coating liquid with the metal content of 70g/L is prepared by a nitric acid solution of platinum and is used for preparing an outer layer coating.
2. Selecting
The nickel silk screen is woven to be used as a conductive matrix, so that the surface area of the conductive matrix reaches 15cm 2 (ii) in terms of/g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step (1) on the metal nickel screen obtained in the step (2), then drying at 160 ℃ for 10 minutes, and then thermally oxidizing at 530 ℃ for 25 minutes; and repeating the process for 10 times to finish the preparation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel screen coated with the bottom layer coating obtained in the step (3), and then carrying out thermal oxidation at 530 ℃ for 25 minutes; and repeating the process for 3 times to finish the manufacture of the outer coating.
5. And (3) carrying out thermal oxidation on the metal nickel screen coated with the outer coating obtained in the step (4) at 530 ℃ for 80 minutes to obtain an electrode A3 with the metal atom number ratio of 10 in the bottom coating to the metal atom number ratio in the outer coating.
Example 4
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. soluble salts of ruthenium, cerium and platinum are dissolved by hydrochloric acid, cathode bottom layer active coating liquid with the total noble metal content of 140g/L is prepared according to the atomic weight ratio of ruthenium, cerium and platinum, namely, 85: 10: 5, and is used for preparing a bottom layer coating, and cathode outer layer active coating liquid with the metal content of 75g/L is prepared by nitric acid solution of platinum and is used for preparing an outer layer coating.
2. Selecting
The nickel silk screen is woven to be used as a conductive substrate, so that the surface area of the conductive substrate reaches 14cm 2 (iv) g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step 1 on the metal nickel wire mesh obtained in the step 2, then drying at 100 ℃ for 10 minutes, and then thermally oxidizing at 510 ℃ for 30 minutes; and repeating the process for 9 times to finish the preparation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel screen coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 20 minutes at 510 ℃; and repeating the process for 3 times to finish the manufacture of the outer coating.
5. And (3) thermally oxidizing the metal nickel screen coated with the outer coating obtained in the step (4) at 510 ℃ for 80 minutes to obtain the electrode A4 with the metal atom number ratio of 9 in the bottom coating to the metal atom number ratio in the outer coating.
Example 5
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. soluble salts of ruthenium, cerium and platinum are dissolved by hydrochloric acid, cathode bottom layer active coating liquid with the total noble metal content of 140g/L is prepared according to the atomic weight ratio of ruthenium, cerium and platinum 5, the cathode bottom layer active coating liquid is used for preparing a bottom layer coating, and a cathode outer layer active coating liquid with the metal content of 75g/L is prepared by a nitric acid solution of platinum, and is used for preparing an outer layer coating.
2. Selecting
The nickel silk screen is woven to be used as a conductive substrate, so that the surface area of the conductive substrate reaches 14cm 2 (iv) g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step (1) on the metal nickel screen obtained in the step (2), drying at 130 ℃ for 10 minutes, and then thermally oxidizing at 530 ℃ for 30 minutes; the above process was repeated 12 times to complete the formation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel screen coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 15 minutes at 510 ℃; and repeating the process for 2 times to finish the manufacture of the outer coating.
5. And (3) carrying out thermal oxidation on the metal nickel screen coated with the outer coating obtained in the step (4) at 530 ℃ for 80 minutes to obtain an electrode A5 with the metal atom number ratio of 16 in the bottom coating to the metal atom number ratio in the outer coating.
Example 6
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. soluble salts of ruthenium, cerium and platinum are dissolved by hydrochloric acid, cathode bottom layer active coating liquid with the total noble metal content of 140g/L is prepared according to the atomic weight ratio of ruthenium, cerium and platinum 5, the cathode bottom layer active coating liquid is used for preparing a bottom layer coating, and a cathode outer layer active coating liquid with the metal content of 75g/L is prepared by a nitric acid solution of platinum, and is used for preparing an outer layer coating.
2. Selecting
The nickel silk screen is woven to be used as a conductive substrate, so that the surface area of the conductive substrate reaches 14cm 2 (ii) in terms of/g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step 1 on the metal nickel wire mesh obtained in the step 2, then drying at 130 ℃ for 10 minutes, and then thermally oxidizing at 530 ℃ for 30 minutes; and repeating the process for 10 times to finish the preparation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step 1 on the metal nickel wire mesh coated with the bottom layer coating obtained in the step 3, and then thermally oxidizing for 15 minutes at 510 ℃; and repeating the process for 3 times to finish the manufacture of the outer coating.
5. And (3) carrying out thermal oxidation on the metal nickel screen coated with the outer coating obtained in the step (4) at 530 ℃ for 80 minutes to obtain the electrode A6, wherein the number ratio of metal atoms in the bottom coating to the metal atoms in the outer coating is 10.
Comparative example 1
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. dissolving soluble salts of ruthenium, cerium and platinum by hydrochloric acid, preparing a cathode bottom layer active coating liquid with the total noble metal content of 140g/L according to the atomic weight ratio of ruthenium, cerium and platinum to 5, and preparing a cathode outer layer active coating liquid with the metal content of 75g/L by using a platinum nitric acid solution for preparing an outer layer.
2. Selecting
Nickel wire mesh is woven as conductive baseThe surface area of the conductive substrate was set to 11.5cm2/g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step 1 on the metal nickel wire mesh obtained in the step 2, then drying at 130 ℃ for 10 minutes, and then thermally oxidizing at 530 ℃ for 30 minutes; and repeating the process for 10 times to finish the preparation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel screen coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 15 minutes at 510 ℃; and repeating the process for 3 times to finish the manufacture of the outer coating.
5. And (3) thermally oxidizing the metal nickel screen coated with the outer coating obtained in the step (4) at 530 ℃ for 80 minutes to obtain an electrode C1 with the metal atom number ratio of 10 in the bottom coating to the metal atom number ratio in the outer coating.
Comparative example 2
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. soluble salts of ruthenium, cerium and platinum are dissolved by hydrochloric acid, cathode bottom layer active coating liquid with the total noble metal content of 140g/L is prepared according to the atomic weight ratio of ruthenium, cerium and platinum 5, the cathode bottom layer active coating liquid is used for preparing a bottom layer coating, and a cathode outer layer active coating liquid with the metal content of 75g/L is prepared by a nitric acid solution of platinum, and is used for preparing an outer layer coating.
2. Selecting
The nickel wire mesh is woven to be used as a conductive substrate, so that the surface area of the conductive substrate reaches 16.5cm2/g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step 1 on the metal nickel wire mesh obtained in the step 2, then drying at 130 ℃ for 10 minutes, and then thermally oxidizing at 530 ℃ for 30 minutes; and repeating the process for 10 times to finish the preparation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel screen coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 15 minutes at 510 ℃; and repeating the process for 3 times to finish the manufacture of the outer coating.
5. And (3) carrying out thermal oxidation on the metal nickel screen coated with the outer coating obtained in the step (4) at 530 ℃ for 80 minutes to obtain an electrode C2 with the metal atom number ratio of 10 in the bottom coating to the metal atom number ratio in the outer coating.
Comparative example 3
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. soluble salts of ruthenium, cerium and platinum are dissolved by hydrochloric acid, cathode bottom layer active coating liquid with the total noble metal content of 140g/L is prepared according to the atomic weight ratio of ruthenium, cerium and platinum, namely, 80: 15: 5, and is used for preparing a bottom layer coating, and cathode outer layer active coating liquid with the metal content of 75g/L is prepared by hydrochloric acid solution of platinum and is used for preparing an outer layer coating.
2. Selecting
The nickel wire mesh is woven to be used as a conductive substrate, so that the surface area of the conductive substrate reaches 14cm < 2 >/g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step 1 on the metal nickel wire mesh obtained in the step 2, then drying at 130 ℃ for 10 minutes, and then thermally oxidizing at 530 ℃ for 30 minutes; the above process was repeated 10 times to complete the formation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel screen coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 15 minutes at 510 ℃; and repeating the process for 3 times to finish the manufacture of the outer coating.
5. And (3) thermally oxidizing the metal nickel screen coated with the outer coating obtained in the step (4) at 530 ℃ for 80 minutes to obtain an electrode C3 with the metal atom number ratio of 10 in the bottom coating to the metal atom number ratio in the outer coating.
Comparative example 4
The preparation method of the high current density electrolytic active cathode comprises the following steps:
1. dissolving soluble salts of ruthenium, cerium and platinum by nitric acid, preparing cathode bottom layer active coating liquid with the total noble metal content of 140g/L according to the atomic weight ratio of ruthenium, cerium and platinum 5 for preparing a bottom layer coating, and preparing cathode outer layer active coating liquid with the metal content of 75g/L by using a platinum nitric acid solution for preparing an outer layer coating.
2. Selecting
The nickel wire mesh is woven to be used as a conductive substrate, so that the surface area of the conductive substrate reaches 14cm < 2 >/g. The metallic nickel substrate was cleaned and surface roughened and thermally oxidized at 450 c for 30 minutes.
3. Coating the cathode bottom layer active coating liquid obtained in the step (1) on the metal nickel screen obtained in the step (2), drying at 130 ℃ for 10 minutes, and then thermally oxidizing at 530 ℃ for 30 minutes; and repeating the process for 10 times to finish the preparation of the bottom coating.
4. Coating the cathode outer layer active coating liquid obtained in the step (1) on the metal nickel screen coated with the bottom layer coating obtained in the step (3), and then thermally oxidizing for 15 minutes at 510 ℃; and repeating the process for 3 times to finish the manufacture of the outer coating.
5. And (3) carrying out thermal oxidation on the metal nickel screen coated with the outer coating obtained in the step (4) at 530 ℃ for 80 minutes to obtain an electrode C4 with the metal atom number ratio of 10 in the bottom coating to the metal atom number ratio in the outer coating.
Example 7
All the high current density electrolytic active cathodes of the invention are tested by the following methods: 8KA/m in aqueous NaOH solution at 90 ℃ 32% 2 Continuously electrolyzing for 14 days under current density, calculating the weight loss of the cathode life before and after electrolysis by using balance weighing, measuring and calculating the residual percentage of the cathode coating before and after electrolysis by using an X-ray fluorescence spectrometer, and detecting 6KA/m after continuous electrolysis of the cathode by using specific detection equipment 2 Hydrogen evolution overpotential. The results of the measurements are shown in the following table:
table 1.
| Serial number | Electrode number | Loss of Life weight mg | Coating residue% | 8KA/m 2 Hydrogen evolution overpotential mV |
| 1 | A1 | 2.4 | 96.2 | 80 |
| 2 | A2 | 3.3 | 93.1 | 67 |
| 3 | A3 | 1.0 | 97.0 | 74 |
| 4 | A4 | 0.9 | 95.3 | 71 |
| 5 | A5 | 0.3 | 97.6 | 69 |
| 6 | A6 | 0.3 | 99.8 | 70 |
| 7 | C1 | 6.8 | 94.1 | 99 |
| 8 | C2 | 5.3 | 94.7 | 108 |
| 9 | C3 | 8.3 | 89.7 | 102 |
| 10 | C4 | 7.2 | 91.2 | 97 |
The data listed in table 1 show that the high current density electrolytic active cathode of the present invention optimizes the components and the ratio of the bottom active coating to enhance the binding force with the base material required by the present invention, so that the lifetime loss is very small and the coating residue is increased after electrolysis; meanwhile, the active coating is coated on the surface area of a preferable substrate according to the actual operation condition and the comprehensive operation effect of the electrode, so that the specific surface area is maximized, and the active coating of the electrode is miniaturized, so that the electrode is more favorable for contact with electrolyte and rapid escape of gas from the surface of the electrode under the condition of small total difference of active ingredients, and the electrode is ensured to be lower in hydrogen evolution overpotential and lower in energy consumption under high current density; in addition, the invention adopts a mode of adding a bottom active coating and an outer active coating into a double coating, on one hand, the consumption of noble metal can be reduced, the electrode cost is reduced, on the other hand, the invention unexpectedly discovers that although the bottom active coating is prepared by adopting a hydrochloric acid solution, the outer active coating is prepared by adopting a nitric acid solution, the integral performance of the electrode optimized by screening the components of the electrode active coating is rather superior to the performance of the electrode prepared by adopting the hydrochloric acid solution or the nitric acid solution for both the bottom and the outer layers, the electrode life is reduced, the coating residue and the hydrogen evolution overpotential are obviously improved, which is different from the traditional cognition, because the active coating prepared by adopting the hydrochloric acid solution for the bottom coating is better combined with the base material, the nitric acid solution adopted for the outer layer ensures that the dissolution of the coating is reduced, the appearance of the active component is diversified, the binding force between the outer layer and the inner layer is enhanced, and the binding force between the electrode coatings is further improved by adopting the nitric acid solution for the outer layer, so that the electrode coating has more hydrogen evolution active components, the service life and the catalytic activity of the electrode under the high current density electrolysis condition are ensured, and the economic benefit of the high current density electrolysis can be obviously reduced, and the economic benefit of the electrode can be improved by using the high current density electrolysis cathode. Therefore, the high-current-density electrolytic active cathode can be an ion membrane electrolytic cell cathode which has longer service life, lower energy consumption and stable operation under the current density electrolysis condition, so as to meet the use requirements of a chlor-alkali production user on long-term high-current-density start and stable operation, and simultaneously help the user to reduce the equipment investment cost and improve the economic benefit.
The above-mentioned 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 of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A high current density electrolytically activated cathode characterized by: the conductive substrate is made of metal materials, the outer surface of the conductive substrate is coated with a metal oxide cathode bottom active coating, the outer surface of the metal oxide cathode bottom active coating is coated with a metal oxide cathode outer active coating, the metal oxide cathode bottom active coating is formed by oxides of a transition element group VIII and oxides of lanthanide, and the metal oxide cathode outer active coating is formed by oxides of a transition element group VIII;
the ratio of the number of atoms of the VIII group of the transition elements in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the lanthanide series elements is 2.3-10.1, and the content of the oxides of the VIII group of the transition elements in the active coating of the bottom layer of the metal oxide cathode is 6-16g/m 2 ；
The ratio of the number of atoms of the VIII group of the transition element in the active coating of the bottom layer of the metal oxide cathode to the number of atoms of the VIII group of the transition element in the active coating of the outer layer of the metal oxide cathode is 5.9-23.4.
2. An active cathode conductive substrate as claimed in claim 1, preferably a nickel gauze, and having a metal substrate surface area of 12-16cm 2 /g。
3. A high current density electrolytically active cathode as claimed in claim 1, 2 wherein: the transition element VIII group in the active coating of the bottom layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum, and the lanthanide is cerium and/or praseodymium;
the transition element VIII group in the active coating of the outer layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum.
4. A high current density electrolytically active cathode as claimed in claim 1, 2 or 3, wherein: the atomic number of ruthenium, rhodium, palladium and/or platinum in the bottom active coating of the metal oxide cathodeThe atomic number ratio of the metal oxide cathode to the cerium and/or the praseodymium is 2.9-9.5, and the oxide content of ruthenium, rhodium, palladium and/or platinum in the active coating of the bottom layer of the metal oxide cathode is 6.7-15.3g/m 2 ；
The atomic number ratio of the ruthenium, rhodium, palladium and/or platinum in the active coating at the bottom layer of the metal oxide cathode to the ruthenium, rhodium, palladium and/or platinum in the active coating at the outer layer of the metal oxide cathode is 6.9-21.4.
5. The high current density electrolytically active cathode of claim 4, wherein: the ratio of the number of atoms of ruthenium, rhodium, palladium and/or platinum to the number of atoms of cerium and/or praseodymium in the active coating of the metal oxide cathode bottom layer is 3.5-8.9, and the content of the oxide of ruthenium, rhodium, palladium and/or platinum in the active coating of the metal oxide cathode bottom layer is 7.4-14.7g/m 2 ；
The atomic number ratio of the ruthenium, rhodium, palladium and/or platinum in the active coating at the bottom layer of the metal oxide cathode to the ruthenium, rhodium, palladium and/or platinum in the active coating at the outer layer of the metal oxide cathode is 7.8-19.5.
6. The high current density electrolytically active cathode of claim 5, wherein: the ratio of the atomic number of ruthenium, rhodium, palladium and/or platinum to the atomic number of cerium and/or praseodymium in the active coating of the metal oxide cathode bottom layer is 4.0-8.1, and the content of ruthenium, rhodium, palladium and/or platinum oxide in the active coating of the metal oxide cathode bottom layer is 8-14g/m 2 ；
The atomic number ratio of the ruthenium, rhodium, palladium and/or platinum in the active coating at the bottom layer of the metal oxide cathode to the ruthenium, rhodium, palladium and/or platinum in the active coating at the outer layer of the metal oxide cathode is 8.8-17.6.
7. The preparation method of the high current density electrolytic active cathode is characterized in that: which comprises the following steps:
A. cleaning a conductive substrate made of a metal material, removing surface dirt of the conductive substrate, making the surface of the conductive substrate rough, and thermally oxidizing for 15-45 minutes at 400-500 ℃;
B. preparing soluble salts of transition elements in the VIII group and soluble salts of lanthanide elements;
C. dissolving soluble salts of VIII family transition elements by using dilute hydrochloric acid, and adding soluble salts of lanthanide elements to obtain cathode bottom layer active coating liquid, wherein the content of the metal elements in the cathode bottom layer active coating liquid is 125 g-175 g/L according to metal components, and the ratio of the number of VIII family transition elements atoms to the number of lanthanide elements atoms is 2.3-10.1;
dissolving soluble salt of a transition element group VIII by using dilute nitric acid to obtain cathode outer layer active coating liquid, wherein the content of metal elements in the cathode outer layer active coating liquid is 55-85 g/L according to metal components;
D. c, coating the cathode bottom layer active coating liquid obtained in the step C 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, so that a metal oxide cathode active coating is formed on the surface of the conductive substrate; then coating the cathode bottom layer active coating liquid obtained in the step C on a conductive substrate, heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes, repeating the heating for multiple times until the content of the transition element VIII group oxide in the metal oxide cathode bottom layer active coating is 6-16g/m 2 ；
E. C, coating the cathode outer layer active coating liquid obtained in the step C on the conductive substrate treated in the step D, and heating the conductive substrate to 400-550 ℃ in an air atmosphere for 10-50 minutes, so that a metal oxide cathode active coating is formed on the surface of the conductive substrate; and C, coating the cathode outer layer active coating liquid obtained in the step C on a conductive substrate again, heating the conductive substrate to 400-550 ℃ in air atmosphere for 10-50 minutes, and repeating the heating for multiple times until the ratio of the number of the transition element group VIII atoms in the metal oxide cathode outer layer active coating to the number of the transition element group VIII atoms in the metal oxide cathode bottom layer active coating meets the requirement, so that the high-current-density active gas is obtained and is separated out of the cathode.
8. The method of high current density electrolytically activated cathodes of claim 7, wherein: in the step C, the content of metal elements in the cathode bottom layer active coating liquid is 130 g/L-170 g/L according to metal components, wherein the ratio of the number of atoms of the VIII group of the transition elements to the number of atoms of the lanthanide elements is 2.9-9.5;
the content of metal elements in the cathode outer layer active coating liquid is 60 g/L-80 g/L according to metal components;
the transition element VIII group in the active coating of the bottom layer of the metal oxide cathode is ruthenium, rhodium, palladium and/or platinum, and the lanthanide is cerium and/or praseodymium;
the VIII family of transition elements in the active coating of the outer layer of the oxide cathode is ruthenium, rhodium, palladium and/or platinum;
in the step C, the conductive substrate is heated to 420-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide cathode active coating is formed on the surface of the conductive substrate; then coating the cathode bottom active coating liquid obtained in the step C on a conductive substrate, heating the conductive substrate to 420-520 ℃ in air atmosphere for 15-45 minutes, repeating the heating for 6-12 times until the content of the transition element VIII group oxide in the active coating of the metal oxide cathode bottom is 6.7-15.3g/m 2 ；
In the step C, the conductive substrate is heated to 420-520 ℃ in the air atmosphere for 15-45 minutes, so that the metal oxide cathode active coating is formed on the surface of the conductive substrate; and C, coating the cathode outer layer active coating liquid obtained in the step C on a conductive substrate, heating the conductive substrate to 420-520 ℃ in an air atmosphere for 15-45 minutes, repeating the heating for 1-4 times until the ratio of the number of the transition element group VIII atoms in the active coating on the outer layer of the metal oxide cathode to the number of the transition element group VIII atoms in the active coating on the bottom layer of the metal oxide cathode meets the requirement, and obtaining the high-current-density active gas separated cathode.
9. The method of high current density electrolytically activated cathode of claim 8, wherein: in the step C, the ratio of the number of atoms of the VIII group of transition elements in the cathode bottom layer active coating liquid to the number of atoms of lanthanide elements is 3.5-8.9 according to metal components.
10. The method of high current density electrolytically activated cathode of claim 9, wherein: in the step C, the ratio of the number of atoms of the VIII family of transition elements to the number of atoms of lanthanide elements in the cathode bottom layer active coating liquid is 4.0-8.1 according to the metal components.
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