CN113816469A - Preparation method of gradient functional alloy coating electrode for electrodeposition and prepared electrode - Google Patents
Preparation method of gradient functional alloy coating electrode for electrodeposition and prepared electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of an electrodeposition gradient functional alloy coating electrode, which relates to the technical field of electrodes and comprises the following steps: (1) pretreating a titanium-based material; (2) preparing gradient electrodeposition liquid; (3) sequentially carrying out electrodeposition treatment on the titanium-based material pretreated in the step (1) in the gradient deposition liquid in the step (2), wherein the water bath temperature is 40-50 ℃, and the pulse electrodeposition current density of each gradient is 0.1-0.5A/dm2The deposition time is 0.05-0.1h, the duty ratio is 40-80%, and the frequency is 0-1.0 kHz; (4) and cleaning the deposited titanium substrate with water, drying and sintering to obtain the alloy coating electrode. The invention also provides an alloy coating electrode prepared by the method. The invention has the beneficial effects that: the preparation method is simple, and the prepared electrode has the characteristics of good stability, high degradation efficiency and good activity.
Description
Technical Field
The invention relates to the technical field of electrodes, in particular to a preparation method of an electrodeposition gradient functional alloy coating electrode and the prepared electrode.
Background
With the rapid development of science and technology in China, the electrode industry plays a great role in the economic development process, and research, popularization and application of the electrode promote the great progress of new energy, hydrogen energy, electrochemical industry and the like. The electrode industry data show that the failure of the electrode has a strong correlation with the crack on the coating, and the generation of the crack is caused by the thermal stress generated by different expansion coefficients of the substrate and the coating in the sintering process, so that the bonding force of the substrate and the coating is reduced or the coating is peeled off, and how to prevent and reduce the crack generation is an important direction of the coating alloy electrode. By elaborately synthesizing the electrocatalytic material, the production appearance can be greatly changed, and even a technical revolution is initiated; the preparation and production of a highly efficient electrode is therefore of great importance in the field of electrochemical catalysis.
The core element of electrocatalytic oxidation is an electrocatalytic electrode material, so that a catalytic electrode material with good performance becomes a main reason for restricting the development of the technology. Chinese patent publication No. CN109292918A reports "a method for preparing a DSA electrode", which uses a noble metal loading method, and physical methods such as spin coating or dipping to coat and sinter and form the electrode; the electrode has the advantages of high manufacturing cost, poor bonding force of electrode base materials, long and complex manufacturing process flow, and volatile organic solvent, which can seriously pollute the environment and the working environment of workers. Chinese patent application with publication number CN111762819A reports "a gradient content positive electrode material and a preparation method thereof", which adopts a gradient synthesis process method controlled by the total molar amount of Fe, Co, Al and Ni; although the method avoids the use of organic solvent, the method is easy to oxidize and has unstable structure in the synthesis process, and simultaneously carries out gradient deposition and thickness control according to the change of the flow of each element, and the control procedure of the method is complex and is not beneficial to industrial production; in addition, the electrode structure has poor thermal stability and short service life, and can be produced only in laboratory level at present.
Disclosure of Invention
The invention aims to solve the technical problems that the electrode in the prior art is poor in stability, short in service life, complex in preparation method and easy to pollute the environment and the working environment of workers, and provides a preparation method for an electrodeposition gradient functional alloy coating electrode.
The invention solves the technical problems through the following technical means:
a preparation method for electrodepositing a gradient functional alloy coating electrode comprises the following steps:
(1) pretreatment of the titanium-based material: polishing and washing the titanium-based material, deoiling, etching by using acid liquor, cleaning, airing and drying to form a conductive base material;
(2) preparing a gradient electrodeposition solution: the gradient electrodeposition solution mainly comprises the following raw materials in concentration:
the RuCl3With TaCl5The concentration ratio of the Sn element to the Sb element to the Ta element to the Pt element is 1:1, heating and stirring the raw materials in a water bath, standing and aging for 12-24h, wherein the Sn element, the Sb element, the Ru element and the Pt element are respectively prepared according to 10 concentration gradients, the concentration of the Sn element is gradually reduced to 0.05mol/l, the concentration of the Sb element is gradually reduced to 0.005mol/l, and the concentrations of the Ru element, the Ta element and the Pt element are gradually increased to 0.05 mol/l;
(3) sequentially carrying out electrodeposition treatment on the titanium-based material pretreated in the step (1) in the gradient deposition liquid in the step (2), wherein the water bath temperature is 40-50 ℃, and the pulse electrodeposition current density of each gradient is 0.1-0.5A/dm2The deposition time is 0.05-0.1h, the duty ratio is 40-80%, and the frequency is 0-1.0 kHz;
(4) and cleaning the deposited titanium substrate with water, drying and sintering to obtain the alloy coating electrode.
Has the advantages that: the alloy coating electrode manufactured by the invention comprises a stress structure tightly combined with a base material, a conductive and compact mosaic structure and a rare earth doped high-activity gradient functional catalytic coating nano material, and can effectively eliminate structural stress; the service life is long; in 1mol/l sulfuric acid solution, 1A/cm2And a pole pitch of 1cm, and a long life under a deterioration testReaches 60h and has good stability.
The alloy coating electrode manufactured by the invention has the characteristics of high degradation efficiency and good activity, can quickly reduce organic pollutants in wastewater, improves the biodegradability of the wastewater, and has low energy consumption.
The preparation method is simple and has strong operability, and no volatile substance is generated by adopting water as a solvent; the defects that the traditional brushing method has long process flow, VOCs pollution is generated by using an organic solvent in the production process, the working environment of workers is poor and the like are overcome.
Preferably, the rare earth element comprises La, Co, Ce or Nd.
Preferably, in the step (1), the titanium-based material is respectively polished by 100-mesh, 500-mesh and 1000-mesh sandpaper to form a certain rough surface.
Preferably, the ground titanium-based material is boiled in an alkaline solution to remove oil.
Preferably, the alkali solution is an aqueous NaOH solution or an aqueous KOH solution.
Preferably, the mass concentration of the alkali solution is 40%, and the cooking time is 1-2 h.
Preferably, the acid solution in step (1) comprises one or more of oxalic acid, hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the deoiled titanium-based material is placed in acid liquor for cooking for 1-2 hours.
Preferably, the drying temperature in the step (4) is 80-100 ℃.
Preferably, the sintering temperature in the step (4) is 500-600 ℃, and the sintering time is 1-2 h.
An alloy coating electrode prepared by the preparation method.
The invention has the advantages that: the alloy coating electrode manufactured by the invention comprises a stress structure tightly combined with a base material, a conductive and compact mosaic structure and a rare earth doped high-activity gradient functional catalytic coating nano material, can effectively eliminate structural stress and has the characteristic of long service life; in 1mol/l sulfuric acid solution, 1A/cm2The length of the material reaches 60 hours under a reinforced degradation test with the electrode spacing of 1cm, and the material has good stabilityAnd (5) performing qualitative determination.
The alloy coating electrode manufactured by the invention has the characteristics of high degradation efficiency and good activity, can quickly reduce organic pollutants in wastewater, improves the biodegradability of the wastewater, and has low energy consumption.
The preparation method is simple and has strong operability, and no volatile substance is generated by adopting water as a solvent; the defects that the traditional brushing method has long process flow, VOCs pollution is generated by using an organic solvent in the production process, the working environment of workers is poor and the like are overcome.
The invention can effectively reduce the cell voltage and further reduce the energy consumption by adopting the technology of fusing the nano conductive particles by electrodeposition.
Drawings
FIG. 1 is a flow chart of a process for electrodepositing a gradient functional alloy coated electrode in an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a three-dimensional oblique section for electrodeposition of a gradient functional alloy coating electrode in an embodiment of the present invention;
FIG. 3 is a schematic representation of an electrode for electrodeposition of a gradient functional alloy coating in example 1 of the present invention;
FIG. 4 is an SEM image of an electrode for electrodeposition of a gradient functional alloy coating in example 1 of the present invention;
FIG. 5 is an SEM image of an electrode for electrodeposition of a gradient functional alloy coating in comparative example 1 of the present invention;
FIG. 6 is a graph comparing the enhanced lifetime of an electrode for electrodeposition of a gradient functional alloy coating with a commercial Ru-Ir-Ta ternary electrode in accordance with example 1 of the present invention;
FIG. 7 is a graph of the electrooxidation efficiency and specific energy consumption for the electrodeposition of a gradient functional alloy coating electrode in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The preparation method for the electrodeposition gradient functional alloy coating electrode has the preparation flow shown in figure 1 and comprises the following steps:
(1) pretreatment of the titanium-based material: respectively polishing a titanium plate by using 100-mesh, 500-mesh and 1000-mesh sand paper to form a certain roughness on the surface of the titanium plate, washing the titanium plate by using deionized water, then carrying out ultrasonic treatment for 30min, and airing the titanium plate for later use;
performing alkali washing and cooking on the treated base material for 1 hour by using a 40% NaOH solution to remove oil, performing washing and air drying, performing cooking and etching for 1 hour by using 10% oxalic acid, performing washing and air drying, and performing high-temperature drying at 550 ℃ in a nitrogen tube furnace to form a conductive base material for later use;
(2) preparing a gradient electrodeposition solution:
Sn-Sb and Ru-Ta-Pt are configured according to 10 gradients, the Sn-Sb element is gradually reduced, and the Ru-Ta-Pt element is gradually increased to the maximum value, wherein the Sn, Sb, Ru, Ta and Pt elements are respectively prepared according to 10 equal-difference concentration gradients, the concentration of the Sn element is gradually reduced from 0.5mol/l to 0.05mol/l, the concentration of the Sb element is gradually reduced from 0.05mol/l to 0.005mol/l, the concentrations of the Ru, Ta and Pt elements are gradually increased from 0.01mol/l to 0.05mol/l, and a deposition solution is dissolved, ultrasonically heated and stirred in a water bath for 30min and aged for 12h for later use;
if the first electrodeposition solution is: 0.5mol/l SnCl4、0.05mol/l SbCl30.01mol/l rare earth element La (NO)3)3、0.02mol/l RuCl3With TaCl5Mixture, 0.01mol/l chloroplatinic acid, 0.1mol/l citric acid, 20ml/l HCl, 5ml/l PTFE emulsion (60%), 0.5g/l nano TiN, 0.2g/l TiO2The nano particles and the solvent are water. Wherein RuCl3In a concentration of 0.01mol/l, TaCl5The concentration of (2) is 0.01 mol/l.
The tenth electrodeposition solution was: 0.05mol/l SnCl4、0.005mol/l SbCl30.01mol/l rare earth element La (NO)3)3、0.1mol/l RuCl3With TaCl5Mixture, 0.05mol/l chloroplatinic acid, 0.1mol/l citric acid, 20ml/l HCl, 5ml/l PTFE emulsion (60%), 0.5g/l nano TiN, 0.2g/l TiO2The nano particles and the solvent are water. Wherein RuCl3Has a concentration of 0.025mol/l, TaCl5The concentration of (B) is 0.025 mol/l.
(3) Carrying out electrodeposition treatment on the titanium-based material prepared in the step (1) in gradient deposition liquid, wherein in the electrodeposition process, a cathode is the titanium material to be deposited, an anode is a Pt sheet with the same volume, a reference electrode is an Ag/AgCl electrode, a salt bridge is a saturated potassium chloride solution, the water bath stirring temperature is 40 ℃, and the deposition current density is 1.0A/dm2The deposition time is 0.05h, the applied waveform is direct current square wave, the duty ratio is 50 percent, and the frequency is 60 Hz; washing with deionized water, and drying in an oven at 80 deg.C;
(4) repeating the gradient electrodeposition in sequence; and sintering the obtained product in a furnace at 550 ℃ for 2.0h, and annealing the obtained product, wherein the structure of the pulse electrodeposition gradient functional alloy coating electrode is shown in figure 2, the areas of the coatings of all layers are the same, and the material of the alloy coating electrode is shown in figure 3.
Example 2
The preparation method for the electrodeposition gradient functional alloy coating electrode has the preparation flow shown in figure 1 and comprises the following steps:
(1) pretreatment of the titanium-based material: respectively polishing a titanium plate by using 100-mesh, 500-mesh and 1000-mesh sand paper to form a certain roughness on the surface of the titanium plate, washing the titanium plate by using deionized water, then carrying out ultrasonic treatment for 30min, and airing the titanium plate for later use;
carrying out alkali washing and cooking on the treated base material by using a 40% NaOH solution for 2h to remove oil, carrying out washing and air drying, then carrying out cooking and etching by using 10% oxalic acid for 2h, washing and air drying for later use, and drying at a high temperature of 600 ℃ in a nitrogen tube furnace to form a conductive base material for later use;
(2) preparing a gradient electrodeposition solution:
the method comprises the following steps of configuring Sn-Sb and Ru-Ta-Pt according to 10 gradients, gradually reducing Sn-Sb elements and gradually increasing Ru-Ta-Pt elements to maximum values, wherein the Sn, Sb, Ru, Ta and Pt elements are respectively prepared according to 10 equal differential concentration gradients, the concentration of the Sn element is gradually reduced from 0.25mol/l to 0.05mol/l, the concentration of the Sb element is gradually reduced from 0.025mol/l to 0.005mol/l, the concentrations of the Ru, Ta and Pt elements are gradually increased from 0.01mol/l to 0.05mol/l, dissolving, carrying out ultrasonic treatment and water bath heating stirring on a deposition solution for 30min, and aging for 12h for later use; wherein RuCl3With TaCl5The concentration ratio of (A) to (B) is 1: 1;
(3) carrying out electrodeposition treatment on the titanium-based material prepared in the step (1) in gradient deposition liquid, wherein a cathode is the titanium material to be deposited, an anode is a Pt sheet with the same volume, a reference electrode is an Ag/AgCl electrode, a salt bridge is a saturated potassium chloride solution, the water bath stirring temperature is 40 ℃, and the deposition current density is 1.0A/dm2Depositing for 1h, wherein the applied waveform is a direct current square wave, the duty ratio is 50%, and the frequency is 60 Hz; washing with deionized water, and drying in a 90 ℃ oven;
(4) repeating the gradient electrodeposition in sequence; and sintering in a furnace at 550 ℃ for 2.0h, and annealing.
Example 3
The preparation method for the electrodeposition gradient functional alloy coating electrode has the preparation flow shown in figure 1 and comprises the following steps:
(1) pretreatment of the titanium-based material: respectively polishing a titanium plate by using 100-mesh, 500-mesh and 1000-mesh sand paper to form a certain roughness on the surface of the titanium plate, washing the titanium plate by using deionized water, then carrying out ultrasonic treatment for 30min, and airing the titanium plate for later use;
carrying out alkali washing and cooking on the treated base material by using a 40% NaOH solution for 2h to remove oil, carrying out washing and air drying, then carrying out cooking and etching by using 10% oxalic acid for 2h, washing and air drying for later use, and drying at high temperature of 650 ℃ in a nitrogen tube furnace to form a conductive base material for later use;
(2) preparing a gradient electrodeposition solution:
the method comprises the following steps of configuring Sn-Sb and Ru-Ta-Pt according to 10 gradients, gradually reducing Sn-Sb elements and gradually increasing Ru-Ta-Pt elements to maximum values, wherein the Sn, Sb, Ru, Ta and Pt elements are respectively prepared according to 10 equal-difference concentration gradients, the concentration of the Sn element is gradually reduced from 0.5mol/l to 0.05mol/l, the concentration of the Sb element is gradually reduced from 0.05mol/l to 0.005mol/l, the concentrations of the Ru, Ta and Pt elements are gradually increased from 0.025mol/l to 0.05mol/l, dissolving, carrying out ultrasonic treatment and water bath heating stirring on a deposition solution for 60min, and aging for 12 hours for later use; wherein RuCl3With TaCl5The concentration ratio of (A) to (B) is 1: 1;
(3) carrying out electrodeposition treatment on the titanium-based material prepared in the step (1) in gradient deposition liquid, wherein a cathode is the titanium material to be deposited, an anode is a Pt sheet with the same volume, a reference electrode is an Ag/AgCl electrode, a salt bridge is a saturated potassium chloride solution, the water bath stirring temperature is 40 ℃, and the deposition current density is 1.0A/dm2The deposition time is 0.05h, the applied waveform is direct current square wave, the duty ratio is 50 percent, and the frequency is 60 Hz; washing with deionized water, and drying in an oven at 100 ℃;
(4) repeating the gradient electrodeposition in sequence; and sintering in a furnace at 550 ℃ for 2.0h, and annealing.
Comparative example 1
The method is characterized in that a gradient electrodeposition form is not adopted, a one-time electrodeposition forming mode is directly adopted for manufacturing, other conditions are the same, and the method comprises the following specific steps:
(1) pretreatment of the titanium-based material: respectively polishing a titanium plate by using 100-mesh, 500-mesh and 1000-mesh sand paper to form a certain roughness on the surface of the titanium plate, washing the titanium plate by using deionized water, then carrying out ultrasonic treatment for 30min, and airing the titanium plate for later use;
performing alkali washing and cooking on the treated base material for 1 hour by using a 40% NaOH solution to remove oil, performing washing and air drying, performing cooking and etching for 1 hour by using 10% oxalic acid, performing washing and air drying, and performing high-temperature drying at 550 ℃ in a nitrogen tube furnace to form a conductive base material for later use;
(2) preparing an electrodeposition solution:
wherein RuCl3With TaCl5The concentration of (b) is 0.025mol/l respectively;
(3) carrying out electrodeposition treatment on the titanium-based material prepared in the step (1) in a deposition solution, wherein a cathode is the titanium material to be deposited, an anode is a Pt sheet with the same volume, a reference electrode is an Ag/AgCl electrode, a salt bridge is a saturated potassium chloride solution, the water bath stirring temperature is 40 ℃, and the deposition current density is 1.0A/dm2The deposition time is 0.05h, the direct current square wave, the duty ratio is 50 percent, and the frequency is 60 Hz; washing with deionized water, and drying in an oven at 80 deg.C;
(4) and sintering in a furnace at 550 ℃ for 2.0h, and annealing.
Comparative example 2
A commercially available Ru-Ir-Ta catalytic electrode material was purchased from Suzhou platinum sharp electrode industries, Inc.
Experimental data and analysis:
strengthening experiment: immersing the obtained electrode materialAdding into 1mol/L sulfuric acid solution, the inter-polar distance is 15mm, and the current density is 10000A/m2And carrying out an oxidation experiment to verify the use duration.
Catalytic performance experiments: catalytic degradation of 2g/l toluene in NH solution4The Cl saturated solution was subjected to electrooxidation for 60min, and the electrocatalytic efficiency was evaluated by the concentration before and after degradation (toluene concentration before treatment-toluene concentration after treatment)/toluene concentration before treatment.
The detection method is gas chromatography, the sample amount is 1 mul, the concentration after reaction is converted according to a standard curve corresponding to the characteristic peak area, and then the calculation is carried out according to an efficiency formula.
FIG. 4 is an SEM image of the coated electrode prepared in example 1 of the present invention, and it can be seen that the electrodeposited gradient functional electrode prepared in the present invention has uniform surface cracks and few through cracks and structural cracks; SEM images of example 2 and example 3 coated electrodes are similar to figure 3.
FIG. 5 is an SEM image of a coated electrode prepared in comparative example 1 of the present invention, and it can be seen that the depth of the crack structure on the surface of the electrocatalytic electrode material by non-gradient direct pulse electrodeposition is deep, and a small amount of through cracks are visible; the deeper the structural crack depth is, the larger the catalytic performance and stress structure of the electrode material is, and the great destructiveness is realized during the use.
The results of the strengthening test are shown in fig. 6, and the results show that the coated electrode prepared in example 1 of the present invention has a good life for the strengthening test. The prepared gradient functional alloy coating electrode has lower cell voltage than a commercial electrode, and the strengthening experiment results of the coating electrodes of the example 2 and the example 3 are similar to the strengthening experiment results of the example 1.
The catalytic performance experiment is shown in FIG. 7, and the degradation effect analysis shows that the electrooxidation efficiency of the catalytic degradation has better efficiency and energy consumption level under different current densities, and is superior to that of the commercially purchased Ru-Ir-Ta catalytic electrode material.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method for an electrodeposition gradient functional alloy coating electrode is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment of the titanium-based material: polishing and washing the titanium-based material, deoiling, etching by using acid liquor, cleaning, airing and drying to form a conductive base material;
(2) preparing a gradient electrodeposition solution: the gradient electrodeposition solution mainly comprises the following raw materials in concentration:
the RuCl3With TaCl5The concentration ratio of the Sn element to the Sb element is 1:1, heating and stirring the raw materials in a water bath, standing and aging for 12-24h, wherein the Sn element, the Sb element, the Ru element, the Ta element and the Pt element are respectively prepared according to 10 equal difference concentration gradients, the concentration of the Sn element is gradually reduced to 0.05mol/l, the concentration of the Sb element is gradually reduced to 0.005mol/l, and the concentrations of the Ru element, the Ta element and the Pt element are gradually increased to 0.05 mol/l;
(3) sequentially carrying out electrodeposition treatment on the titanium-based material pretreated in the step (1) in the gradient deposition liquid in the step (2), wherein the water bath temperature is 40-50 ℃, and the pulse electrodeposition current density of each gradient is 0.1-0.5A/dm2The deposition time is 0.05-0.1h, the duty ratio is 40-80%, and the frequency is 0-1.0 kHz;
(4) and cleaning the deposited titanium substrate with water, drying and sintering to obtain the alloy coating electrode.
2. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 1, characterized in that: the rare earth element comprises La, Co, Ce or Nd.
3. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 1, characterized in that: and (2) respectively polishing the titanium-based material by using 100-mesh, 500-mesh and 1000-mesh sand paper in the step (1).
4. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 1, characterized in that: and (3) steaming and deoiling the polished titanium-based material in an alkaline solution.
5. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 1, characterized in that: the alkali solution is NaOH aqueous solution or KOH aqueous solution.
6. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 5, characterized in that: the mass concentration of the alkali solution is 40%, and the cooking time is 1-2 h.
7. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 1, characterized in that: the acid solution in the step (1) comprises one or more of oxalic acid, hydrochloric acid, sulfuric acid and nitric acid.
8. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 1, characterized in that: and (3) putting the deoiled titanium-based material into an acid liquor for cooking for 1-2 hours.
9. The method for preparing an electrode for electrodeposition of a gradient functional alloy coating according to claim 1, characterized in that: the sintering temperature in the step (4) is 500-600 ℃, and the sintering time is 1-2 h.
10. An alloy coated electrode made by the method of any one of claims 1 to 9.
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