CN113690455B - Long-life anode electrode material and preparation method thereof - Google Patents

Long-life anode electrode material and preparation method thereof Download PDF

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CN113690455B
CN113690455B CN202110936831.XA CN202110936831A CN113690455B CN 113690455 B CN113690455 B CN 113690455B CN 202110936831 A CN202110936831 A CN 202110936831A CN 113690455 B CN113690455 B CN 113690455B
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李想
刘长影
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Hangzhou Xingtai Environmental Protection Technology Co ltd
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Abstract

The invention provides a long-life anode electrode material and a preparation method thereof, and relates to the fields of new materials, new energy and environmental protection, in particular to the technical fields of electrooxidation degradation pollutants, electrically-driven membrane pollution-resistant electrodes, water electrolysis hydrogen production and hydrogen fuel cell electrodes in the environmental protection industry. The main technical scheme adopted is as follows: an anode electrode material comprises a metal substrate, a transition layer and a noble metal functional coating. Wherein the transition layer is deposited on the substrate; the noble metal functional coating is deposited on the transition layer; the transition layer is made of corrosion-resistant and high-potential-resistant metal oxide; the noble metal functional coating is one or more metals of ruthenium, iridium, platinum, gold and silver, and a certain amount of non-noble metal(s) of tin, antimony, lead, manganese, nickel, silicon, cobalt and zinc is also doped in the noble metal coating. The invention mainly improves the binding force between the electrode coating and the metal substrate, reduces the content of noble metal, improves the electrode efficiency and prolongs the electrode service life.

Description

Long-life anode electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of new materials, energy sources and environmental protection, relates to a long-life anode electrode material and a preparation method thereof, and particularly relates to a preparation method of a coating of a metal bipolar plate and a diffusion layer in the fields of an electrooxidation coating electrode, an electric driving membrane, a fuel cell and hydrogen production by water electrolysis in the environmental protection field.
Background
The industries of printing and dyeing, pharmacy, petroleum refining, coal chemical industry and the like relate to a large amount of organic refractory wastewater, and the industrial problem is solved due to the high content of macromolecular organic matters, complex components and difficult biochemical degradation. The electro-oxidation technology is a potential advanced oxidation technology, has the advantages of simple equipment, no differential oxidation, no pollutant emission, low energy consumption and the like, and becomes an environment-friendly technology with great market demand. The electrode is used as the core of electrochemical technology, which affects the service life and cost of the electrode, and the existing electro-oxidation electrodes include lead dioxide electrode, BDD electrode, ruthenium oxide iridium electrode, platinum electrode, etc. The problems of short service life, high cost, poor treatment effect and the like of the electrode in the current market generally exist.
Particularly in the water electrolysis hydrogen production and hydrogen fuel cell industry, the bipolar plate material cost accounts for 25-35% of the whole equipment cost, and more materials are graphite plates, titanium metal plates and the like, so that the price is high, and the machining performance is poor. Therefore, researchers turn the research direction to the stainless steel material with large market usage amount, low price, good machining, toughness and strength. However, the fuel cell and the water electrolysis hydrogen production equipment have harsh operating conditions and high stainless steel contact resistance, so that the problem of serious corrosion can occur in operation. The current method for modifying the stainless steel material comprises the processes of heat treatment, gold and silver plating on the surface, carbon film, polyaniline, nitriding and the like, but the processes are complex and difficult to produce in batches, and the requirements of contact resistance and corrosion potential cannot be well met.
In order to improve the resource utilization of waste water and waste salt, in zero discharge of waste water, concentrated brine (salt content is more than 5%) generated in a waste water process is commonly used in an electrode solution of an electrically-driven membrane to play a role in electric conduction, but the salt-containing waste water generated in the waste water generally contains a certain amount of organic pollution factors.
Disclosure of Invention
In view of the above, the invention provides a long-life anode electrode material and a preparation method thereof, and mainly aims to improve the binding force between a substrate and a coating, and the coating is not easy to fall off by adopting a multi-layer structure design. By doping a certain amount of additive components into the noble metal solution, the stability of the noble metal catalyst is improved, the loading capacity of the noble metal is reduced, and the cost of the electrode is reduced.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
a long life anode electrode material, said anode electrode material comprising:
the metal substrate is a titanium or titanium alloy flat plate, porous titanium, a titanium net or a titanium felt;
a transition layer supported on the metal substrate; the transition layer is made of conductive and electrochemical corrosion resistant metal oxide, and the metal comprises one or more of tin, antimony, tantalum, niobium, manganese, cobalt, iron and nickel;
the noble metal functional coating is loaded on the transition layer; the noble metal is one or more of ruthenium, iridium, platinum, gold and silver.
Further, the loading amount of the transition layer is 0.5mg/cm 2 -50mg/cm 2 Preferably, the loading is 0.5mg/cm 2 -2mg/cm 2 The loading amount of the noble metal functional coating is 0.1mg/cm 2 -20mg/cm 2 Preferably, the loading is 0.5mg/cm 2 -3mg/cm 2 。
Furthermore, the transition layer and the precious metal functional coating are deposited by one of a dip-coating method, a spin-coating method, screen printing, ultrasonic spraying and brushing, and the ultrasonic spraying method, the screen printing and the brushing are preferably selected; the deposition of the transition layer and the noble metal functional coating is prepared by adopting a multi-time loading method, wherein the number of the loading layers is 2-30, preferably 5-15.
The invention also provides a preparation method of the long-life anode electrode material, which comprises the following steps:
(1) Matrix pretreatment: carrying out oil removal cleaning and acid etching on the surface of a metal matrix to adjust the metal components and the proportion of the metal components on the surface of the matrix, improving the roughness of the surface of a coating, and carrying out heat treatment on the matrix in a reducing atmosphere;
(2) Depositing a transition layer: depositing conductive and electrochemical corrosion resistant metal oxide on the surface of the metal matrix;
(3) Noble metal functional coating: and a noble metal functional coating is loaded on the transition layer.
Further, the matrix pretreatment step comprises:
firstly, the method comprises the following steps: preparing 5-20% solution by using one or more of oxalic acid, hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid, heating, putting the substrate into the solution for degreasing, cleaning and etching treatment, and performing ultrasonic cleaning and drying on the substrate after the substrate is finished; preferably, the acid etching solution is oxalic acid or hydrochloric acid; the mass fraction of the solution is 5-15%, the heating temperature is 40-90 ℃, and the oil removing etching time is 30-120 min.
Secondly, the method comprises the following steps: putting the matrix into an atmosphere furnace, introducing reducing gas, heating the matrix to 200-600 ℃, carrying out heat treatment for 1h, and then naturally cooling, wherein the reducing gas is a mixed gas of hydrogen and argon and nitrogen, or a mixed gas of carbon monoxide and argon and nitrogen, and the volume fraction of the hydrogen and the carbon monoxide is 3% -7%.
Further, the deposition step of the transition layer comprises: dissolving one or more metal salts of tin, antimony, tantalum, niobium, manganese, cobalt, iron and nickel in one or more organic solvents of methanol, ethanol, isopropanol, ethylene glycol, propanol, acetone, formic acid, acetic acid and oxalic acid to prepare a solution with a certain concentration; coating the coating liquid containing the metal on the surface of a substrate uniformly, putting the substrate into a high-temperature furnace at 200-600 ℃ for 10-50min, taking out, repeating the steps for a plurality of times, preserving the heat in the high-temperature furnace for 1h for the last time, and cooling to room temperature. The molar concentration of the metal salt of tin, antimony, tantalum, niobium, manganese, cobalt, nickel and iron is 5mM-500mM. The drying is performed to improve the binding force, and the dried coating is subjected to subsequent high-temperature roasting treatment to finally form the metal oxide in order to load firmly again.
Further, the step of depositing the noble metal functional coating comprises: preparing chloroiridic acid, chloroplatinic acid and ruthenium trichloride noble metal acid or salt into a solution with a certain concentration in one or more organic solvents of methanol, ethanol, isopropanol, ethylene glycol, propanol, acetone, formic acid, acetic acid and oxalic acid; uniformly coating the coating liquid containing the noble metal on the surface of the substrate, putting the substrate into a high-temperature furnace at 200-600 ℃ for 10-50min, taking out, repeating the steps for a plurality of times, preserving the heat in the high-temperature furnace for 1h for the last time, and cooling to room temperature, wherein the molar concentration of the noble metal acid or salt of ruthenium, iridium and platinum is 5mM-300mM.
Furthermore, part of one or more metal ions or semiconductor components of tin, antimony, lead, manganese, nickel, silicon, cobalt and zinc are added into the noble metal solution, and the mass content is 5-20%.
And further, after the loading of the noble metal coating is finished, transferring the coating electrode into a reducing atmosphere furnace, introducing hydrogen and argon mixed gas (the volume fraction of hydrogen is 5%), preserving heat for 1h at the temperature of 200-600 ℃, and cooling to room temperature.
Furthermore, the preparation method of the anode electrode material is used for preparing an electro-oxidation electrode, an electrically-driven membrane pollution-resistant electrode, a bipolar plate of a hydrogen fuel cell and a diffusion layer for hydrogen production by electrolyzing water.
Compared with the prior art, the long-life electrode and the preparation method thereof have the following beneficial effects:
the coating prepared by the traditional sol-gel heat treatment adopts the last heat treatment forming process, and cracks can be formed on the coating after the heat treatment, and extend from the surface to the position of a matrix. The existence of cracks causes strong oxidation particles such as proton hydrogen, hydroxyl free radical and the like generated in the electro-oxidation process to permeate into a matrix through the cracks, so that the problems of oxidation of the surface of the matrix, resistance increase, reduction of the binding force with a coating and the like are caused, and finally, the oxidation potential is increased and the coating is stripped. The invention adopts the transition layer, the noble metal coating and the reduction atmosphere for 3 times of sintering heat treatment process, so that the cracks formed each time are shielded, and the generation of through cracks is inhibited. Meanwhile, the precious metal coating deposition and the subsequent process can repair the cracks generated last time, and the strong oxidant is inhibited from permeating into the interior through the cracks.
Furthermore, metal ions such as tin, antimony, manganese, cobalt, zinc and the like are doped into the noble metal colloidal solution, so that the conductivity of the noble metal coating is improved, and the oxidation potential of the electrode is reduced. The doping of the ions forms a rod-shaped surface structure in the heat treatment process, so that the surface area is increased, the binding force of the coating is improved, the formation of snowflake crystals on the surface of the coating by noble metal particles is inhibited, and the service life of the electrode of the noble metal coating is prolonged. Meanwhile, due to the doping of cheap ions (the highest can reach 40%), the noble metal loading of the coating is greatly reduced, and the coating cost is reduced. Especially, the substrate with the porous titanium structure is adopted, so that the specific surface area is very large, the apparent current density of the electrode is reduced, and the service life of the electrode can be prolonged.
Drawings
FIG. 1 micro-topography of a porous titanium substrate long-life electrode;
FIG. 2 shows the morphology of a long-life electrode of a porous titanium substrate.
Detailed description of the invention
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the present invention will be further described with reference to the following embodiments, but the scope of the present invention is not limited thereto.
In one aspect, embodiments of the present invention provide a long-life anode electrode material, including: a metal substrate; the transition layer is loaded on the metal substrate; the noble metal functional coating is deposited on the transition layer; the transition layer is made of conductive and electrochemical corrosion-resistant metal oxide, and the selected metal component comprises at least one of tin, antimony, tantalum, niobium, manganese, cobalt, iron, nickel and the like; the loading amount of the transition layer is 0.5mg/cm 2 -50mg/cm 2 (ii) a Preferably, the loading is 0.5mg/cm 2 -2mg/cm 2 (ii) a Wherein the noble metal component is one or more of ruthenium, iridium, platinum, gold and silver, and the loading capacity of the noble metal functional coating is 0.1mg/cm 2 -20mg/cm 2 (ii) a Preferably, the loading is 0.5mg/cm 2 -3mg/cm 2 。
The substrate is a titanium or titanium alloy flat plate, porous titanium, a titanium mesh or a titanium felt;
the transition layer and the noble metal functional coating are coated by an ultrasonic spraying method, a silk screen printing method and a spraying method;
on the other hand, the embodiment of the invention also provides a preparation method of the long-life anode electrode material, wherein the preparation method comprises the following steps:
(1) Pretreatment of
Firstly, the method comprises the following steps: preparing 5% -20% solution by oxalic acid, hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid, heating, putting the substrate into the solution for degreasing, cleaning and etching treatment, and performing ultrasonic cleaning and drying on the substrate after the degreasing, cleaning and etching treatment is finished; the step mainly removes oil and etching, treats pitted surface, removes surface oxides and pollutants, and improves the binding force of the coating.
Secondly, the method comprises the following steps: putting the matrix into an atmosphere furnace, introducing reducing gas, heating the matrix to 200-600 ℃, carrying out heat treatment for 1h, and then naturally cooling.
(2) The deposition step of the transition layer comprises the following steps:
dissolving metal salts of tin, antimony, tantalum, niobium, manganese, cobalt, nickel, iron and the like in organic solutions of methanol, ethanol, isopropanol, glycol, propanol, acetone, formic acid, acetic acid, oxalic acid and the like to prepare a solution with a certain concentration; coating the coating liquid containing the metal on the surface of a substrate uniformly, treating for 10-50min at 200-600 ℃ in a high-temperature furnace, taking out, and repeating the steps for a plurality of times. And preserving the heat for 1h in a high-temperature furnace for the last time, and cooling to room temperature.
Preferably, the molar concentration of the metal salt of tin, antimony, tantalum, niobium, manganese, cobalt, nickel and iron is 5-500 mM;
(3) The loading step of the noble metal functional coating comprises the following steps:
dissolving noble metal acid or salt such as chloro-iridic acid, chloroplatinic acid, ruthenium trichloride and the like in one or more organic solvents such as methanol, ethanol, isopropanol, glycol, propanol, acetone, formic acid, acetic acid, oxalic acid and the like to prepare solution with certain concentration; coating the noble metal-containing coating liquid on the surface of the substrate uniformly, putting the substrate into a high-temperature furnace at 200-600 ℃ for 10-50min, taking out, and repeating the steps for a plurality of times. And preserving the heat for 1h in a high-temperature furnace for the last time, and cooling to room temperature. Preferably, the noble metal solvent further contains a part of metal ions or semiconductor components such as tin, antimony, lead, manganese, nickel, silicon, cobalt, zinc, and the like.
The specific preparation examples are as follows:
example 1
Preparing a hydrochloric acid solution with the mass fraction of 15%, putting the hydrochloric acid solution into a water bath kettle, heating the hydrochloric acid solution to 80 ℃, weighing the cut porous titanium, etching the cut porous titanium for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing hydrogen and argon mixed gas (the volume fraction of the hydrogen is 5%), heating to 600 ℃, carrying out thermal reduction for 1h, and then naturally cooling to room temperature.
Transition layer: weighing stannic chloride to prepare 200mM ethylene glycol, oxalic acid and acetone solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), and stirring for more than 24 h. And (3) flatly placing the etched titanium sheet, dipping the titanium sheet into a tin salt solution by using a wool brush to brush the tin salt solution on the surface of the titanium plate, transferring the loaded titanium sheet into a muffle furnace after the solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating to increase weight to 1mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by a program, carrying out heat treatment for 1h, and then naturally cooling.
Noble metal functional layer: weighing chloroiridic acid solution to prepare 100mM ethylene glycol, oxalic acid and acetone solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), and stirring for more than 24 h. Dipping a wool brush with a chloroiridic acid solution, brushing the chloroiridic acid solution on the surface of the transition layer, transferring the loaded titanium sheet into a muffle furnace after a solvent is volatilized, controlling the temperature at 400 ℃, heating for 10min, taking out and cooling to finish the 1 st layer, and continuously brushing the 2 nd layer for 6 layers in sequence. Weighing with an analytical balance, and calculating the weight gain to 2mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into a reducing atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
Example 2
Preparing an oxalic acid solution with the mass fraction of 15%, putting the oxalic acid solution into a water bath kettle, heating the oxalic acid solution to 80 ℃, weighing the cut porous titanium, and etching the porous titanium for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing hydrogen and nitrogen mixed gas (the volume fraction of the hydrogen is 7%), heating to 600 ℃, carrying out thermal reduction for 1h, and then naturally cooling to room temperature.
Transition layer: manganese dichloride is weighed to prepare 200mM ethylene glycol, oxalic acid and acetone solution (volume fraction, ethylene glycol 80%, propanol 15% and acetic acid 5%), and the mixture is stirred for more than 24 hours. And (3) flatly placing the etched titanium sheet, dipping a tin salt solution by using a wool brush to brush the tin salt solution on the surface of the titanium plate, transferring the loaded titanium sheet to a muffle furnace after the solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating to increase weight to 1mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace to be heated to 550 ℃ in a programmed manner, carrying out heat treatment for 1h, and then naturally cooling.
Noble metal functional layer: weighing a chloroiridic acid solution to prepare a 100mM ethylene glycol, oxalic acid and acetone solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), adding 20mM cobalt nitrate, and stirring for more than 24 hours. Dipping a wool brush into a chloroiridic acid solution, coating the chloroiridic acid solution on the surface of the transition layer, transferring the chloroiridic acid solution to a muffle furnace after a solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously coating the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating the weight gain to 2mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by a program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into a reducing atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
Example 3
Preparing a nitric acid solution with the mass fraction of 15%, putting the nitric acid solution into a water bath, heating the nitric acid solution to 80 ℃, weighing the cut porous titanium, etching the cut porous titanium for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing carbon monoxide and argon mixed gas (the volume fraction of the carbon monoxide is 3%), heating to 600 ℃, carrying out thermal reduction for 1h, and then naturally cooling to room temperature.
Transition layer: weighing cobalt dichloride to prepare 200mM ethylene glycol, acetone and oxalic acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), and stirring for more than 24 h. And (3) flatly placing the etched titanium sheet, dipping the titanium sheet into a tin salt solution by using a wool brush to brush the tin salt solution on the surface of the titanium plate, transferring the loaded titanium sheet into a muffle furnace after the solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating to increase weight to 1mg/cm 2 And finishing brushing. And finally, transferring the titanium sheets to a muffle furnace to be heated to 550 ℃ in a programmed manner after the steps are sequentially finished, and naturally cooling the titanium sheets after 1h of heat treatment.
Noble metal functional layer: weighing chloroplatinic acid solution to prepare 100mM ethylene glycol, acetone and oxalic acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), adding tin tetrachloride 20mM, and stirring for more than 24 h. And (3) dipping a wool brush into a chloroiridic acid solution, brushing the chloroiridic acid solution on the surface of the titanium plate, transferring the titanium plate to a muffle furnace after a solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating the weight gain to 2mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by a program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into a reducing atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
Example 4
Preparing a hydrochloric acid solution with the mass fraction of 15%, putting the hydrochloric acid solution into a water bath kettle, heating the hydrochloric acid solution to 80 ℃, weighing the cut porous titanium, etching the cut porous titanium for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing hydrogen and argon mixed gas (the volume fraction of the hydrogen is 5%), heating to 600 ℃, carrying out thermal reduction for 1h, and then naturally cooling to room temperature.
Transition layer: weighing stannic chloride to prepare 200mM ethylene glycol, acetone and oxalic acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), and stirring for more than 24 h. Will etchAnd (3) flatting the finished titanium sheet, dipping the titanium sheet with a wool brush to obtain a tin salt solution, brushing the tin salt solution on the surface of the titanium plate, transferring the loaded titanium sheet into a muffle furnace after the solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling, finishing the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance to calculate the weight gain of 1mg/cm 2 And finishing brushing without high-temperature treatment for 1h.
Noble metal functional layer: weighing a chloroiridic acid solution to prepare a 100mM ethylene glycol, acetone and nitric acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), adding 20mM cobalt nitrate, and stirring for more than 24 hours. Dipping a wool brush into a chloroiridic acid solution, coating the chloroiridic acid solution on the surface of the transition layer, transferring the chloroiridic acid solution to a muffle furnace after a solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously coating the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating the weight gain to 2mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by a program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into a reducing atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
Example 5
Preparing a hydrochloric acid solution with the mass fraction of 15%, putting the hydrochloric acid solution into a water bath kettle, heating the hydrochloric acid solution to 80 ℃, weighing the cut porous titanium, etching the cut porous titanium for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing hydrogen and argon mixed gas (the volume fraction of the hydrogen is 5%), heating to 600 ℃, carrying out thermal reduction for 1h, and then naturally cooling to room temperature.
Transition layer: weighing stannic chloride to prepare 200mM ethylene glycol, acetone and oxalic acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), and stirring for more than 24 h. And (3) flatly placing the etched titanium sheet, dipping the titanium sheet into a tin salt solution by using a wool brush to brush the tin salt solution on the surface of the titanium plate, transferring the loaded titanium sheet into a muffle furnace after the solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating to increase weight to 1mg/cm 2 Finishing brushing without high temperature treatment1h。
Noble metal functional layer: weighing chloroiridic acid solution to prepare 100mM ethylene glycol, acetone and oxalic acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), adding 20mM lead nitrate, and stirring for more than 24 h. Dipping a wool brush into a chloroiridic acid solution, brushing the chloroiridic acid solution on the surface of the transition layer, transferring the chloroiridic acid solution to a muffle furnace after a solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating the weight gain to 2mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into a reducing atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
Example 6
Preparing a hydrochloric acid solution with the mass fraction of 15%, putting the hydrochloric acid solution into a water bath kettle, heating the hydrochloric acid solution to 80 ℃, weighing the cut porous titanium, etching the cut porous titanium for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing hydrogen and argon mixed gas (the volume fraction of the hydrogen is 5%), heating to 600 ℃, carrying out thermal reduction for 1h, and then naturally cooling to room temperature.
Noble metal functional layer: weighing the chloroiridic acid solution to prepare 100mM ethylene glycol solution (volume fraction, 80% of ethylene glycol, 15% of acetone and 5% of oxalic acid), and stirring for more than 24 h. Dipping a wool brush with a chloroiridic acid solution, brushing the chloroiridic acid solution on the surface of a titanium plate, transferring the loaded titanium plate into a muffle furnace after a solvent is volatilized, controlling the temperature at 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance, and calculating the weight gain to 2mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into a reducing atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
Example 7
Preparing a hydrochloric acid solution with the mass fraction of 15%, putting the hydrochloric acid solution into a water bath kettle, heating the hydrochloric acid solution to 80 ℃, weighing the cut porous titanium, etching the cut porous titanium for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing hydrogen and argon mixed gas (the volume fraction of the hydrogen is 5%), programming to 600 ℃, carrying out thermal reduction for 1 hour, and naturally cooling to room temperature.
Transition layer: weighing stannic chloride to prepare 200mM ethylene glycol, acetone and oxalic acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), and stirring for more than 24 h. And (3) flatly placing the etched titanium sheet, dipping a tin salt solution by using a wool brush to brush the tin salt solution on the surface of the titanium plate, transferring the loaded titanium sheet to a muffle furnace after the solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 12 layers in sequence. Weighing with an analytical balance, and calculating the weight gain to 2mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by a program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into an atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
Example 8
Preparing a hydrochloric acid solution with the mass fraction of 15%, putting the hydrochloric acid solution into a water bath, heating the hydrochloric acid solution to 80 ℃, weighing the cut porous titanium, and then etching for 120min. Taking out, ultrasonically cleaning and drying. Transferring the porous titanium into an atmosphere furnace, introducing hydrogen and argon mixed gas (the volume fraction of the hydrogen is 5%), heating to 600 ℃, carrying out thermal reduction for 1h, and then naturally cooling to room temperature.
Transition layer: tin tetrachloride is weighed to prepare 200mM ethylene glycol, acetone and oxalic acid solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), and the mixture is stirred for more than 24 hours. And (3) flatly placing the etched titanium sheet, dipping the titanium sheet into a tin salt solution by using a wool brush to brush the tin salt solution on the surface of the titanium plate, transferring the loaded titanium sheet into a muffle furnace after the solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously brushing the layer 2 for 6 layers in sequence. Weighing with an analytical balance to calculate the weight gain of 1mg/cm 2 And finishing brushing. Transferring the mixture into a muffle furnace, raising the temperature to 550 ℃, carrying out heat treatment for 1h, and then naturally cooling.
Noble metal functional layer: weighing chloroiridic acidThe solution is prepared into 100mM ethylene glycol, oxalic acid and acetone solution (volume fraction, ethylene glycol 80%, acetone 15% and oxalic acid 5%), cobalt nitrate 20mM is added, and the mixture is stirred for more than 24 hours. Dipping a wool brush into a chloroiridic acid solution, coating the chloroiridic acid solution on the surface of the transition layer, transferring the chloroiridic acid solution to a muffle furnace after a solvent is volatilized, controlling the temperature to be 400 ℃, heating for 10min, taking out and cooling to finish the layer 1, and continuously coating the layer 2 for totally coating 9 layers in sequence. Weighing with an analytical balance, and calculating to increase weight to 3mg/cm 2 And finishing brushing. And transferring the loaded titanium sheet to a muffle furnace, raising the temperature to 550 ℃ by a program, carrying out heat treatment for 1h, and then naturally cooling. And finally, transferring the coated electrode into an atmosphere furnace, preserving the heat for 1h at 550 ℃, and cooling to room temperature.
The anode electrode materials prepared in the respective examples were subjected to performance tests as shown in the following table:
composition (mM) Resistance (m omega) Life (h) Remarks for note
Example 1 Sn200，Ir100 7.5 83000 Heat treatment for 1h, heat treatment for 1h + reduction heat treatment for 1h
Example 2 Mn200，Ir100+Co20 6.8 105500 Heat treatment for 1h, heat treatment for 1h + reduction heat treatment for 1h
Example 3 Co200，Pt100+Sn20 6.9 110000 Heat treatment for 1h, heat treatment for 1h + reduction heat treatment for 1h
Example 4 Sn200，Ir100+Co20 6.8 56000 Heat treatment 1h + reduction Heat treatment 1h, in comparison with example 2
Example 5 Sn200，Ir100+Pb20 7.0 78000 Heat treatment 1h + reduction Heat treatment 1h, in comparison with example 2
Example 6 Ir100 6.7 47500 Only oxide layer of noble metal
Example 7 Sn200 6.4 35000 Only the transition oxide layer
Example 8 Sn200，Ir100+Co20 7.0 134000 Example 2 Loading 2mg/cm 2 Example 8 Loading 3mg/cm 2
The service life test method comprises the following steps: working electrode with effective area of 1cm 2 The platinum sheet electrode is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, 0.5M sulfuric acid is used as electrolyte, a constant current electrolysis mode is adopted, the current is set to be 0.25A, and when the electrolysis voltage reaches 5V, the electrode is determined to be invalid. Time T through accelerated experiment 1 And the life of the electrode is estimated. The calculation formula is as follows: (I) 2 /I 1 ） 2 ×T 1 ，I 2 To accelerate the test current, I 1 For practical use of the current, T 1 The test life is accelerated.
The examples 1,2 and 3 show that the electrode has a structure of a transition layer and a precious metal functional layer, adopts the electrode treated at high temperature twice, has long service life and meets the use requirement; examples 4,5 compare with examples 1,2,3, and demonstrate that although examples 4,5 have a structure of a transition layer and a noble metal functional layer, the electrode life is significantly reduced after only one final high temperature heat treatment; examples 6,7 compare with examples 1,2,3, which show that electrodes with only a transition layer or only a noble metal functional layer have a significantly reduced lifetime; example 8 compared with example 2 shows that the loading of the noble metal functional layer is an important factor for improving the lifetime of the anode electrode material.
The anode electrode material is used for a working electrode which is polluted and degraded in the environmental field, has more complex working environment and higher requirement on the tolerance of the electrode, and can also be used for a conductive electrode with a conductive function, such as an electrically-driven membrane pollution-resistant conductive electrode, and a bipolar plate, a diffusion layer and an end plate of a hydrogen fuel cell, which mainly have the function of electronic conductivity and are used for hydrogen production by electrolyzing water.

Claims (9)

1. A long life anode electrode material for an electrooxidation electrode or an electrodriven membrane fouling resistant electrode, the anode electrode material comprising:
the metal substrate is one of a titanium or titanium alloy flat plate, porous titanium and a titanium felt;
a transition layer supported on the metal substrate; the transition layer is a metal oxide which is conductive and resistant to electrochemical corrosion, the metal in the metal oxide comprises one or more of tin, antimony, tantalum, niobium, manganese, cobalt, iron and nickel, and the loading capacity of the transition layer is 0.5mg/cm 2 -2mg/cm 2 ；
A noble metal functional coating supported on the transition layer; the noble metal is one or more of ruthenium, iridium, platinum, gold and silver, the noble metal functional coating is also doped with one or more non-noble metal ions or semiconductor components of a certain amount of tin, antimony, lead, manganese, nickel, silicon, cobalt and zinc, and the loading amount of the noble metal functional coating is 0.5mg/cm 2 -3mg/cm 2 。
2. The long-life anode electrode material for the electro-oxidation electrode or the electrically-driven film pollution-resistant electrode as claimed in claim 1, wherein the transition layer and the precious metal functional coating are deposited by one of a dip-coating method, a spin-coating method, screen printing, ultrasonic spraying and brush coating; the deposition of the transition layer and the noble metal functional coating is prepared by a multiple loading method, and the number of the loading layers is 5-15.
3. A method for preparing a long-life anode electrode material for an electrooxidation electrode or an electrically-driven membrane fouling-resistant electrode according to claim 1, comprising the steps of:
(1) Matrix pretreatment: carrying out degreasing cleaning and acid etching treatment on the surface of a metal matrix to improve the roughness of the surface of the matrix, putting the matrix subjected to degreasing cleaning and acid etching treatment into a reducing atmosphere for heat treatment, and adjusting the metal components and the proportion of the metal components on the surface of the matrix;
(2) Depositing a transition layer: depositing conductive and electrochemical corrosion resistant metal oxide on the surface of the metal matrix;
(3) Noble metal functional coating: a noble metal functional coating is loaded on the transition layer, and a certain amount of one or more metal ions or semiconductor components of tin, antimony, lead, manganese, nickel, silicon, cobalt and zinc are doped in the noble metal functional coating;
(4) And after the loading of the noble metal functional coating is finished, transferring the electrode into a reducing atmosphere furnace for heat treatment.
4. The method for preparing a long-life anode electrode material for an electrooxidation electrode or an electrically-driven membrane contamination-resistant electrode according to claim 3, wherein the substrate pretreatment step comprises:
firstly: preparing a solution with the mass fraction of 5% -20% by using one or more of oxalic acid, hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid, heating, putting the substrate into the solution for degreasing cleaning and acid etching treatment, and after the degreasing cleaning and acid etching treatment are finished, ultrasonically cleaning and drying the substrate; the heating temperature is 80-90 ℃, and the oil removing etching time is 30-120 min;
secondly, the method comprises the following steps: putting the matrix into an atmosphere furnace, introducing reducing gas, heating the matrix to 200-600 ℃, carrying out heat treatment for 1h, and then naturally cooling, wherein the reducing gas is a mixed gas of hydrogen and argon or hydrogen and nitrogen, or a mixed gas of carbon monoxide and argon or carbon monoxide and nitrogen, and the volume fraction of hydrogen and carbon monoxide is 3% -7%.
5. The method for preparing long-life anode electrode material for an electro-oxidation electrode or an electrically-driven membrane fouling-resistant electrode as claimed in claim 3, wherein the step of depositing the transition layer comprises:
dissolving one or more metal salts of tin, antimony, tantalum, niobium, manganese, cobalt, iron and nickel in one or more organic solvents of methanol, ethanol, isopropanol, glycol, propanol, acetone, formic acid, acetic acid and oxalic acid to prepare a solution with a certain concentration; and uniformly coating the solution on the surface of a substrate, putting the substrate into a high-temperature furnace, preserving heat for 10-50min at 200-600 ℃, taking out, repeating the steps for a plurality of times, preserving heat for 1h in the high-temperature furnace for the last time, and cooling to room temperature, wherein the molar concentration of the metal salts of tin, antimony, tantalum, niobium, manganese, cobalt, nickel and iron is 5-500 mM.
6. The method for preparing long-life anode electrode material for an electro-oxidation electrode or an electrically-driven membrane fouling-resistant electrode as claimed in claim 3, wherein the step of depositing the noble metal functional coating comprises:
preparing a solution with a certain concentration from chloroiridic acid, chloroplatinic acid and ruthenium trichloride noble metal acid or salt in one or more organic solvents of methanol, ethanol, isopropanol, ethylene glycol, propanol, acetone, formic acid, acetic acid and oxalic acid; and uniformly coating the solution on the surface of a substrate, putting the substrate into a high-temperature furnace, preserving heat for 10-50min at 200-600 ℃, taking out, repeating the steps for a plurality of times, preserving heat for 1h in the high-temperature furnace for the last time, and cooling to room temperature, wherein the molar concentration of the noble metal acid or salt of ruthenium, iridium and platinum is 5mM-300mM.
7. The method for preparing the long-life anode electrode material for the electro-oxidation electrode or the electrically-driven film pollution-resistant electrode as claimed in claim 6, wherein the noble metal solution is further added with one or more metal ions or semiconductor components of tin, antimony, lead, manganese, nickel, silicon, cobalt and zinc, and the mass content is 5-20%.
8. The method for preparing the long-life anode electrode material for the electro-oxidation electrode or the electrically-driven membrane pollution-resistant electrode as claimed in claim 3, wherein after the loading of the noble metal functional coating is completed, the electrode is transferred to a reducing atmosphere furnace, one or more of hydrogen, nitrogen and argon are introduced, the temperature is kept at 200-600 ℃ for 1h, and the temperature is cooled to room temperature.
9. The method for preparing the long-life anode electrode material for the electric oxidation electrode or the electric-driven membrane pollution-resistant electrode according to any one of claims 3 to 8, wherein the method for preparing the anode electrode material is used for preparing the electric oxidation electrode, the electric-driven membrane pollution-resistant electrode or a bipolar plate or a diffusion layer of an electrolytic water hydrogen production and hydrogen fuel cell.
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