A titanium-based platinum-nickel electrode material and its preparation method and application

Abstract

The present invention belongs to the field of electrode material technology, and provides a titanium-based platinum-nickel electrode material, a preparation method thereof, and an application thereof. The method comprises the following steps: sequentially performing a first anodization and a second anodization on a titanium sheet in an ammonium fluoride solution to obtain an oxidized titanium sheet; calcining the oxidized titanium sheet to obtain a titanium sheet containing a titanium dioxide layer; and electro-depositing the titanium sheet containing the titanium dioxide layer in a platinum-based electrolyte to obtain a titanium-based platinum-nickel electrode material. The titanium-based platinum-nickel electrode material prepared by the present invention effectively reduces the usage of Pt-based precious metals, and can maintain high activity and stability to generate hydrogen peroxide online under neutral conditions; its cathode current density efficiency reaches 76.40%, its anode current density efficiency reaches 70.23%, and its dual capacitance value is 1.33mF·cm ‑2 It is 4.2 times the dual capacitance value of titanium-based platinum-nickel electrode materials obtained without anodic oxidation, and has good prospects for industrial application.

Description

Technical Field

[0001] The present invention relates to the technical field of electrode materials, and in particular to a titanium-based platinum-nickel electrode material and a preparation method and application thereof. Background Art

[0002] As a green fuel and oxidant, hydrogen peroxide (H2O2) has received widespread attention in energy and environmental fields in recent years. Currently, the industrial synthesis method of H2O2 involves an energy-intensive anthraquinone redox process. Although this process can produce a large amount of high-concentration H2O2, it also requires complex large-scale equipment and produces a large amount of waste. In addition, in most cases, the concentration of H2O2 used is low, usually <9wt%. Compared with the anthraquinone redox process, it has significant 2 electrons (2e - ) pathway is considered a "green" pathway for online generation of H2O2. This process uses H2O, renewable electricity, and O2 from the air as inputs to produce H2O2 without any chemical waste output. However, during the reaction, O2 may be converted to hydrogen by the four-electron (4e - )ORR pathway (O2+4H + +4e - →2H2O) is reduced to H2O, or other side reactions occur, thereby reducing the production efficiency of H2O2. Therefore, designing an ideal catalyst for online synthesis of H2O2 is of great significance. Summary of the Invention

[0003] The purpose of the present invention is to overcome the problems existing in the prior art and provide a titanium-based platinum-nickel electrode material and a preparation method and application thereof.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing a titanium-based platinum-nickel electrode material, comprising the following steps:

[0006] (1) performing a first anodization and a second anodization on a titanium sheet in an ammonium fluoride solution in sequence to obtain an oxidized titanium sheet;

[0007] (2) calcining the oxidized titanium sheet to obtain a titanium sheet containing a titanium dioxide layer;

[0008] (3) Electrodepositing the titanium sheet containing the titanium dioxide layer in a platinum-based electrolyte to obtain the titanium-based platinum-nickel electrode material.

[0009] Preferably, the solvent of the ammonium fluoride solution in step (1) comprises ethylene glycol and water;

[0010] The mass volume ratio of the ammonium fluoride, ethylene glycol and water is 1-10 g: 100-1000 mL: 5-100 mL.

[0011] Preferably, in step (1), the voltage of the first anodization is 10 to 50 V, and the time is 10 to 100 min; the voltage of the second anodization is 10 to 50 V, and the time is 10 to 120 min.

[0012] Preferably, the calcination temperature in step (2) is 300-550° C. and the calcination time is 20-240 min.

[0013] Preferably, the platinum-based electrolyte in step (3) comprises a platinum salt, a quaternary ammonium salt and a hydrogen bond donor; the platinum salt is one or more of potassium chloroplatinate, potassium chloroplatinite, platinum acetylacetonate and chloroplatinic acid; the quaternary ammonium salt is one or more of choline chloride, tetramethylammonium chloride and benzyltriethylammonium chloride; and the hydrogen bond donor is ethylene glycol and / or glycerol.

[0014] Preferably, the molar volume ratio of the platinum salt to the hydrogen bond donor is 1-10 mmol:80-240 mL; and the molar ratio of the hydrogen bond donor to the quaternary ammonium salt is 1-10:1-5.

[0015] Preferably, the anode for the electrodeposition in step (3) is nickel foam, nickel cloth or nickel mesh;

[0016] The electrodeposition temperature is 70-90° C., the current is 0.005-0.1 A, and the time is 10-120 min.

[0017] During the electrodeposition process, the relationship between the concentration of the anode-dissolved nickel and the time is:

[0018] C=C0+2k p t 1 / 2 ;

[0019] C is the concentration of dissolved nickel ions, mol / L; C0 is the initial concentration of dissolved nickel ions, mol / L; t is the reaction time, s; k p is the reaction rate constant, mol·L -1 ·s -1 / 2 .

[0020] Preferably, during the electrodeposition in step (3), the relationship between the anodic dissolution current efficiency and the dissolution amount is: The relationship between cathode deposition current efficiency and deposition amount is:

[0021] η ais the anodic dissolution current efficiency, %; m1 is the amount of nickel dissolved in a certain time t, g; I is the current of the electrolytic cell, A; q1 is the electrochemical equivalent of nickel, 1.042g / (A·h); t is the electrolysis time, h; η c is the cathode deposition current efficiency, %; m2 is the amount of nickel deposited within a certain time t, g; m3 is the amount of platinum deposited within a certain time t, g; q2 is the electrochemical equivalent of platinum, 0.867 g / (A·h).

[0022] The present invention also provides a titanium-based platinum-nickel electrode material prepared by the preparation method.

[0023] The present invention also provides application of the titanium-based platinum-nickel electrode material in generating hydrogen peroxide.

[0024] The beneficial effects of the present invention are:

[0025] (1) The present invention uses titanium sheet as the base material and sequentially performs the first anodization and the second anodization in ammonium fluoride solution, which can expose more deposition sites for the subsequent electrodeposition process, increase the electrochemical specific surface area involved in the reaction, and thus help to improve the 2e - Selectivity of ORR.

[0026] (2) The present invention prepares titanium-based platinum-nickel electrode materials through a simple and scalable constant current electrodeposition process. In particular, nickel is gradually introduced through a sacrificial nickel anode. Compared with the commonly used inert anode, the introduction of the nickel anode can provide a nickel source, regulate the electrodeposition process, and thus significantly reduce the voltage (energy consumption) required by the system; and the anode itself participates in the dissolution, so that the decomposition of the solvent in the electrodeposition system and the contamination of the inert anode at high potential are expected to be significantly reduced.

[0027] (3) The present invention adopts a specific platinum-based electrolyte, which reduces the concentration of hydrogen atoms in the solution compared to the electroplating of metals in aqueous solution, effectively avoids the occurrence of hydrogen evolution reaction and hydrogen embrittlement, and avoids the decline in the aesthetics and mechanical properties of the coating.

[0028] (4) The titanium-based platinum-nickel electrode material prepared by the present invention not only effectively reduces the usage of Pt-based precious metals, but also can maintain high activity and stability to generate hydrogen peroxide online under neutral conditions, and has good industrial application prospects.

[0029] (5) The cathode current density efficiency of the titanium-based platinum-nickel electrode material prepared by the present invention reaches 76.40%, the anode current density efficiency reaches 70.23%, and the dual capacitance value is 1.33mF·cm -2 , which is 4.2 times the dual capacitance value of the titanium-based platinum-nickel electrode material obtained without anodic oxidation. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a SEM characterization image of the oxidized titanium sheet in Example 1;

[0031] Figure 2 This is a linear sweep voltammetry curve of the titanium-based platinum-nickel electrode material in Example 1;

[0032] Figure 3 The graph is a graph showing the relationship between the concentration and time of H2O2 produced by the titanium-based platinum-nickel electrode material under neutral conditions in Example 1;

[0033] Figure 4 Graph showing the relationship between the scan rate and current density of the titanium-based platinum-nickel electrode material in Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0034] The present invention provides a method for preparing a titanium-based platinum-nickel electrode material, comprising the following steps:

[0035] (1) performing a first anodization and a second anodization on a titanium sheet in an ammonium fluoride solution in sequence to obtain an oxidized titanium sheet;

[0036] (2) calcining the oxidized titanium sheet to obtain a titanium sheet containing a titanium dioxide layer;

[0037] (3) Electrodepositing the titanium sheet containing the titanium dioxide layer in a platinum-based electrolyte to obtain the titanium-based platinum-nickel electrode material.

[0038] In the present invention, the material of the titanium sheet in step (1) is preferably TA0, TA1, TA2, TC4 or TC16.

[0039] In the present invention, the titanium sheet in step (1) is preferably pretreated before use, and the pretreatment comprises the following steps: polishing the titanium sheet with metallographic sandpaper, placing it in acetone, hydrochloric acid, ethanol and water in sequence for ultrasonic treatment, and finally drying it to complete the pretreatment of the titanium sheet.

[0040] In the present invention, the polishing is a first polishing, a second polishing and a third polishing performed sequentially, and the mesh number of the metallographic sandpaper for the first polishing is preferably 100-320 mesh, more preferably 150-280 mesh, and more preferably 180-240 mesh; the mesh number of the metallographic sandpaper for the second polishing is preferably 800-2000 mesh, more preferably 1000-1500 mesh, and more preferably 1200-1400 mesh; the mesh number of the metallographic sandpaper for the third polishing is preferably 2500-7000 mesh, more preferably 3000-5000 mesh, and more preferably 3500-4000 mesh.

[0041] In the present invention, the frequency of ultrasonic treatment of the titanium sheet in acetone, hydrochloric acid, ethanol and deionized water is independently preferably 20 to 60 kHz, more preferably 30 to 50 kHz, more preferably 35 to 45 kHz; the time is independently preferably 30 to 210 min, more preferably 60 to 180 min, more preferably 80 to 120 min; the drying temperature is preferably 20 to 80°C, more preferably 30 to 60°C, more preferably 35 to 50°C; the time is preferably 5 to 60 min, more preferably 10 to 50 min, more preferably 20 to 40 min.

[0042] In the present invention, the solvent of the ammonium fluoride solution in step (1) comprises ethylene glycol and water; the mass volume ratio of the ammonium fluoride, ethylene glycol and water is preferably 1-10 g:100-1000 mL:5-100 mL, more preferably 2-9 g:200-900 mL:10-60 mL, and more preferably 3-8 g:300-800 mL:15-50 mL.

[0043] In the present invention, in step (1), the cathode of the first anodization is graphite, platinum sheet or titanium sheet; the graphite is a graphite rod or graphite sheet; the first anodization is carried out in an ammonium fluoride solution, and after the first anodization is completed, the obtained sample is placed in water for ultrasonic cleaning and then dried. After the drying is completed, the sample is placed in the same ammonium fluoride solution (the same as the first anodization) for a second anodization; the cathode of the second anodization is graphite, platinum sheet or titanium sheet; the graphite is a graphite rod or graphite sheet; after the second anodization is completed, the obtained sample is washed with water, then washed again with ethanol, and then dried for a second time.

[0044] In the present invention, the voltage of the first anodization is preferably 10 to 50 V, more preferably 20 to 40 V, and more preferably 25 to 35 V; the time is preferably 10 to 100 min, more preferably 20 to 90 min, and more preferably 30 to 80 min.

[0045] In the present invention, after the first anodization is completed, the frequency of the ultrasonic cleaning is preferably 20 to 60 kHz, more preferably 30 to 50 kHz, and more preferably 35 to 45 kHz; the time is preferably 10 to 90 min, more preferably 20 to 80 min, and more preferably 30 to 60 min; the drying temperature is preferably 20 to 80°C, more preferably 30 to 60°C, and more preferably 35 to 50°C; the time is preferably 5 to 60 min, more preferably 10 to 50 min, and more preferably 20 to 40 min.

[0046] In the present invention, the voltage of the second anodization is preferably 10 to 50 V, more preferably 20 to 40 V, and more preferably 25 to 35 V; the time is preferably 10 to 120 min, more preferably 20 to 100 min, and more preferably 30 to 90 min.

[0047] In the present invention, after the second anodization is completed, the secondary drying temperature is preferably 20-80°C, more preferably 30-60°C, more preferably 35-50°C; the time is preferably 5-60 min, more preferably 10-50 min, more preferably 20-40 min.

[0048] In the present invention, the calcination temperature in step (2) is preferably 300-550°C, more preferably 350-500°C, and more preferably 400-450°C; the calcination time is preferably 20-240 min, more preferably 50-210 min, and more preferably 80-180 min.

[0049] In the present invention, the platinum-based electrolyte in step (3) comprises a platinum salt, a quaternary ammonium salt and a hydrogen bond donor; the platinum salt is one or more of potassium chloroplatinate, potassium chloroplatinite, platinum acetylacetonate and chloroplatinic acid; the quaternary ammonium salt is one or more of choline chloride, tetramethylammonium chloride and benzyltriethylammonium chloride; and the hydrogen bond donor is ethylene glycol and / or glycerol.

[0050] In the present invention, the molar volume ratio of the platinum salt and the hydrogen bond donor is preferably 1-10 mmol:80-240 mL, more preferably 2-9 mmol:100-220 mL, and more preferably 3-8 mmol:150-170 mL; the molar ratio of the hydrogen bond donor and the quaternary ammonium salt is preferably 1-10:1-5, more preferably 2-9:2-4, and more preferably 3-8:2.5-3.5.

[0051] In the present invention, the anode for the electrodeposition in step (3) is nickel foam, nickel cloth or nickel mesh; the temperature of the electrodeposition is preferably 70-90°C, more preferably 75-85°C, and more preferably 77-83°C; the current is preferably 0.005-0.1A, more preferably 0.01-0.09A, and more preferably 0.03-0.07A; and the time is preferably 10-120min, more preferably 20-110min, and more preferably 50-80min.

[0052] In the present invention, during the electrodeposition process of step (3), the relationship between the concentration of the anode-dissolved metallic nickel and the time is:

[0053] C=C0+2k p t 1 / 2 ;

[0054] C is the concentration of dissolved nickel ions, mol / L; C0 is the initial concentration of dissolved nickel ions, mol / L; t is the reaction time, s; k p is the reaction rate constant, mol·L -1 ·s -1 / 2 .

[0055] In the present invention, during the electrodeposition process of step (3), the relationship between the anodic dissolution current efficiency and the dissolution amount is: The relationship between cathode deposition current efficiency and deposition amount is:

[0056] η a is the anodic dissolution current efficiency, %; m1 is the amount of nickel dissolved in a certain time t, g; I is the current of the electrolytic cell, A; q1 is the electrochemical equivalent of nickel, 1.042g / (A·h); t is the electrolysis time, h; η c is the cathode deposition current efficiency, %; m2 is the amount of nickel deposited within a certain time t, g; m3 is the amount of platinum deposited within a certain time t, g; q2 is the electrochemical equivalent of platinum, 0.867 g / (A·h).

[0057] In the present invention, after the electrodeposition in step (3) is completed, the obtained sample is sequentially washed with alcohol and washed with water to obtain the titanium-based platinum-nickel electrode material; the alcohol washing and water washing can be completed according to conventional technical means in the field, the purpose of the alcohol washing is to clean the introduced organic reagents, and the purpose of the water washing is to clean the inorganic ions on the surface of the electrode material.

[0058] The present invention also provides a titanium-based platinum-nickel electrode material prepared by the preparation method.

[0059] The present invention also provides application of the titanium-based platinum-nickel electrode material in generating hydrogen peroxide.

[0060] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0061] Example 1

[0062] The TA0 titanium sheet was polished with 200 mesh, 1200 mesh and 4000 mesh metallographic sandpaper in sequence, and then placed in acetone, hydrochloric acid, ethanol and water for ultrasonic treatment (the frequency of ultrasonic treatment was independently 40kHz and the time was independently 120min), and finally dried at 25°C for 60min to complete the pretreatment of the titanium sheet. 3g of ammonium fluoride, 940mL of ethylene glycol and 60mL of water were mixed to obtain an ammonium fluoride solution; the titanium sheet obtained by pretreatment was placed in the ammonium fluoride solution for the first anodic oxidation, the cathode was set to a platinum sheet, the voltage was 20V, and the time was 30min. The obtained sample was placed in water and ultrasonically cleaned at a frequency of 40kHz for 60min, and then dried at 25°C for 40min; after the drying was completed, it was placed in the same ammonium fluoride solution for the second anodic oxidation, the cathode was set to a platinum sheet, the voltage was 20V, and the time was 90min. After the end, the obtained sample was washed with water and then cleaned again with ethanol. The titanium sheet was washed and dried at 25°C for 30 minutes to obtain an oxidized titanium sheet; the oxidized titanium sheet was calcined at 450°C for 90 minutes to obtain a titanium sheet containing a titanium dioxide layer; 4 mmol of potassium chloroplatinite, 100 mL of ethylene glycol, and choline chloride (the molar ratio of ethylene glycol to choline chloride is 4:2) were mixed to obtain a platinum-based electrolyte; nickel foam was used as the anode and the prepared titanium sheet containing a titanium dioxide layer was used as the cathode, and electroplating was carried out at a temperature of 80°C and a current of 0.04A for 60 minutes. After the deposition, the obtained sample was washed with alcohol and washed with water in sequence to obtain the titanium-based platinum-nickel electrode material.

[0063] The oxidized titanium sheet prepared in this embodiment was subjected to SEM characterization to obtain the SEM characterization image of the oxidized titanium sheet in this embodiment, as shown in FIG. Figure 1 shown; from Figure 1 It can be seen from the figure that after anodization, each nanotube is tightly surrounded by 6 to 7 neighboring nanotubes, indicating that a relatively regular nanotube array structure is formed on the surface, which is conducive to promoting the mass transfer in the ORR reaction process and providing a channel for the timely desorption of H2O2 generated online, thus avoiding the further reduction of H2O2 caused by diffusion obstruction, thereby helping to improve 2e - Selectivity of ORR.

[0064] The electrochemical performance of the titanium-based platinum-nickel electrode material prepared in this embodiment was tested to obtain a linear sweep voltammetry curve of the titanium-based platinum-nickel electrode material in this embodiment, as shown in FIG. Figure 2 shown; from Figure 2 It can be seen that the onset potential of the titanium-based platinum-nickel electrode material is 0.673 V (vs. RHE), indicating that the electrode material has a high 2e - ORR activity.

[0065] The titanium-based platinum-nickel electrode material prepared in this embodiment is used to prepare H2O2, and a curve showing the relationship between the concentration and time of H2O2 produced by the titanium-based platinum-nickel electrode material in this embodiment under neutral conditions is obtained, as shown in FIG. Figure 3 shown; from Figure 3 It can be seen that the concentration of H2O2 increases with time. It is worth mentioning that the titanium-based platinum-nickel electrode material prepared in this example can produce 6.2 mg / L H2O2 in 20 minutes.

[0066] The titanium-based platinum-nickel electrode material prepared in this embodiment was subjected to a current density efficiency test, and the cathode current density efficiency of the titanium-based platinum-nickel electrode material in this embodiment was found to be 76.40%, and the anode current density efficiency was 70.23%.

[0067] Example 2

[0068] The TC4 titanium sheet was polished with 200 mesh, 1000 mesh and 5000 mesh metallographic sandpaper in sequence, and then placed in acetone, hydrochloric acid, ethanol and water for ultrasonic treatment (the frequency of ultrasonic treatment was independently 50kHz and the time was independently 80min), and finally dried at 60°C for 30min to complete the pretreatment of the titanium sheet. 6g of ammonium fluoride, 950mL of ethylene glycol and 50mL of water were mixed to obtain an ammonium fluoride solution; the titanium sheet obtained by pretreatment was placed in the ammonium fluoride solution for the first anodic oxidation, the cathode was set to a stone mill rod, the voltage was 50V, and the time was 60min. The obtained sample was placed in water and ultrasonically cleaned at a frequency of 50kHz for 30min, and then dried at 60°C for 30min; after drying, it was placed in the same ammonium fluoride solution for the second anodic oxidation, the cathode was set to a stone mill rod, the voltage was 50V, and the time was 90min. After the end, the obtained sample was washed with water and then cleaned again with ethanol. The titanium sheet was washed and dried at 60°C for 20 minutes to obtain an oxidized titanium sheet; the oxidized titanium sheet was calcined at 400°C for 120 minutes to obtain a titanium sheet containing a titanium dioxide layer; 3 mmol of platinum acetylacetonate, 100 mL of glycerol, and choline chloride (the molar ratio of ethylene glycol to choline chloride is 3:2) were mixed to obtain a platinum-based electrolyte; nickel foam was used as the anode and the prepared titanium sheet containing a titanium dioxide layer was used as the cathode, and electroplating was carried out at a temperature of 70°C and a current of 0.05A for 90 minutes. After the deposition, the obtained sample was washed with alcohol and washed with water in sequence to obtain the titanium-based platinum-nickel electrode material.

[0069] The titanium-based platinum-nickel electrode material prepared in this embodiment was subjected to a current density efficiency test, and the cathode current density efficiency of the titanium-based platinum-nickel electrode material in this embodiment was found to be 62.48%, and the anode current density efficiency was 64.10%.

[0070] Example 3

[0071] The TC16 titanium sheet was polished with 200 mesh, 1200 mesh and 3000 mesh metallographic sandpaper in sequence, and then placed in acetone, hydrochloric acid, ethanol and water for ultrasonic treatment (the frequency of ultrasonic treatment was independently 45kHz and the time was independently 100min), and finally dried at 55°C for 40min to complete the pretreatment of the titanium sheet. 6g of ammonium fluoride, 900mL of ethylene glycol and 100mL of water were mixed to obtain an ammonium fluoride solution; the titanium sheet obtained by pretreatment was placed in the ammonium fluoride solution for the first anodization, the cathode was set to a graphite sheet, the voltage was 30V, and the time was 50min. The obtained sample was placed in water and ultrasonically cleaned at a frequency of 45kHz for 40min, and then dried at 55°C for 30min; after drying, it was placed in the same ammonium fluoride solution for the second anodization, the cathode was set to a graphite sheet, the voltage was 30V, and the time was 60min. After the end, the obtained sample was washed with water and then cleaned again with ethanol. The titanium sheet was washed and dried at 55°C for 30 minutes to obtain an oxidized titanium sheet; the oxidized titanium sheet was calcined at 350°C for 150 minutes to obtain a titanium sheet containing a titanium dioxide layer; 7 mmol of potassium chloroplatinate, 150 mL of ethylene glycol, and tetramethylammonium chloride (the molar ratio of ethylene glycol to tetramethylammonium chloride is 4:3) were mixed to obtain a platinum-based electrolyte; a nickel mesh was used as an anode and the prepared titanium sheet containing a titanium dioxide layer was used as a cathode, and electroplating was carried out at a temperature of 85°C and a current of 0.07 A for 80 minutes. After the deposition was completed, the obtained sample was washed with alcohol and washed with water in sequence to obtain the titanium-based platinum-nickel electrode material.

[0072] The titanium-based platinum-nickel electrode material prepared in this embodiment was subjected to a current density efficiency test, and the cathode current density efficiency of the titanium-based platinum-nickel electrode material in this embodiment was found to be 73.18%, and the anode current density efficiency was 69.58%.

[0073] Comparative Example 1

[0074] TA1 titanium sheets were polished sequentially with 200-, 1200-, and 4000-grit metallographic sandpaper, then ultrasonically treated in acetone, hydrochloric acid, ethanol, and water (each at a frequency of 40 kHz and a duration of 120 minutes). Finally, the sheets were dried at 25°C for 40 minutes to complete the pretreatment. A platinum-based electrolyte was prepared by mixing 4 mmol of potassium chloroplatinite, 100 mL of ethylene glycol, and choline chloride (in a molar ratio of 4:2). Electrodeposition was performed at 80°C and 0.04 A for 60 minutes using nickel foam as the anode and the pretreated titanium sheet as the cathode. The sample was then washed with alcohol and then water to obtain a titanium-based platinum-nickel electrode material.

[0075] The titanium-based platinum-nickel electrode material prepared in this comparative example was subjected to a current density efficiency test, and the cathode current density efficiency of the titanium-based platinum-nickel electrode material in this embodiment was found to be 49.75%, and the anode current density efficiency was 53.02%.

[0076] The titanium-based platinum-nickel electrode material (labeled as TiO2@PtNi) prepared in Example 1 and the titanium-based platinum-nickel electrode material (labeled as Ti@PtNi) prepared in this comparative example were subjected to electrochemical performance tests, and the relationship curves between the scan rate and current density of the titanium-based platinum-nickel electrode material in Example 1 and this comparative example were obtained, as shown in FIG. Figure 4 shown; from Figure 4 As can be seen from the figure, the slope of the straight line is the capacitance value of the double layer, and the electrochemical specific surface area is proportional to the capacitance value of the double layer; the double capacitance value of the titanium-based platinum-nickel electrode material obtained after anodization is 1.33mF·cm -2 , which is 4.2 times the dual capacitance value of the titanium-based platinum-nickel electrode material obtained without anodic oxidation, indicating that the titanium-based platinum-nickel electrode material obtained after anodic oxidation has a larger electrochemical specific surface area, which not only improves the mass transfer between the catalyst and the electrolyte, but also provides additional active sites, which is beneficial to the 2e - The progress of ORR process.

[0077] From the above examples, it can be seen that the present invention provides a titanium-based platinum-nickel electrode material with a cathode current density efficiency of 76.40%, an anode current density efficiency of 70.23%, and a dual capacitance value of 1.33 mF·cm -2 , which is 4.2 times the dual capacitance value of a titanium-based platinum-nickel electrode material obtained without anodic oxidation. The titanium-based platinum-nickel electrode material provided by the present invention not only effectively reduces the use of Pt-based precious metals, but also maintains high activity and stability in the online generation of hydrogen peroxide under neutral conditions, showing great prospects for industrial application.

[0078] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a titanium-based platinum-nickel electrode material, characterized in that: It includes the following steps: (1) performing a first anodization and a second anodization on a titanium sheet in an ammonium fluoride solution in sequence to obtain an oxidized titanium sheet; (2) calcining the oxidized titanium sheet to obtain a titanium sheet containing a titanium dioxide layer; (3) electroplating the titanium sheet containing the titanium dioxide layer in a platinum-based electrolyte to obtain the titanium-based platinum-nickel electrode material; The platinum-based electrolyte in step (3) comprises a platinum salt, a quaternary ammonium salt and a hydrogen bond donor; The quaternary ammonium salt is one or more of choline chloride, tetramethylammonium chloride and benzyltriethylammonium chloride; the hydrogen bond donor is ethylene glycol and / or glycerol; The anode for the electrodeposition in step (3) is nickel foam, nickel cloth or nickel mesh; During the electrodeposition process, the relationship between the concentration of the anode-dissolved nickel and the time is: C=C0+2k p t 1 / 2 ; C is the concentration of dissolved nickel ions, mol / L; C0 is the initial concentration of dissolved nickel ions, mol / L; t is the reaction time, s; k p is the reaction rate constant, mol·L -1 ·s -1 / 2 .

2. The preparation method according to claim 1, wherein The solvent of the ammonium fluoride solution in step (1) comprises ethylene glycol and water; The mass volume ratio of the ammonium fluoride, ethylene glycol and water is 1-10 g: 100-1000 mL: 5-100 mL.

3. The preparation method according to claim 1 or 2, wherein In step (1), the voltage of the first anodization is 10 to 50 V, and the time is 10 to 100 min; the voltage of the second anodization is 10 to 50 V, and the time is 10 to 120 min.

4. The preparation method according to claim 3, wherein The calcination temperature in step (2) is 300-550° C. and the calcination time is 20-240 min.

5. The preparation method according to claim 4, wherein The platinum salt is one or more of potassium chloroplatinate, potassium chloroplatinite, platinum acetylacetonate and chloroplatinic acid.

6. The preparation method according to claim 5, wherein The molar volume ratio of the platinum salt to the hydrogen bond donor is 1-10 mmol:80-240 mL; the molar ratio of the hydrogen bond donor to the quaternary ammonium salt is 1-10:1-5.

7. The preparation method according to claim 6, wherein The temperature of the electrodeposition is 70-90° C., the current is 0.005-0.1 A, and the time is 10-120 min.

8. The preparation method according to claim 7, wherein During the electrodeposition step (3), the relationship between the anodic dissolution current efficiency and the dissolution amount is: The relationship between cathode deposition current efficiency and deposition amount is: ηa is the anodic dissolution current efficiency, %; m1 is the amount of nickel dissolved in a certain time t, g; I is the current of the electrolytic cell, A; q1 is the electrochemical equivalent of nickel, 1.042 g / (A·h); t is the electrolysis time, h; ηc is the cathode deposition current efficiency, %; m2 is the amount of nickel deposited in a certain time t, g; m3 is the amount of platinum deposited in a certain time t, g; q2 is the electrochemical equivalent of platinum, 0.867 g / (A·h).

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