A multi-metal layered titanium anode material and a preparation process and application thereof

Abstract

The application belongs to the technical field of electrochemical materials and application, and provides a multi-metal layered titanium anode material, which is mainly applied to the processes of water electrolysis hydrogen production, wastewater treatment and electrochemical energy storage, and belongs to the direction of new energy and environmental governance.The multi-metal layered titanium anode material comprises, from bottom to top, a titanium substrate, a bonding layer, a catalytic layer and a protective layer; the material of the catalytic layer is a composite of ruthenium dioxide and iridium dioxide, wherein the molar ratio of ruthenium dioxide to iridium dioxide is 1:2-3, and the thickness of the catalytic layer is 3-4 mu m.The multi-metal layered titanium anode material prepared by the application exhibits high stability and high efficiency in the fields of water electrolysis hydrogen production, wastewater treatment and electrochemical energy storage, can prolong the service life and improve the energy utilization rate, meets the needs of energy saving and emission reduction, green low carbon, resource recycling and strategic emerging industry development, and has significant economic benefits and social value.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemical materials and application technology, in particular to a multi-metal layered titanium anode material and its preparation process and application, which is mainly applied to water electrolysis hydrogen production, wastewater treatment and electrochemical energy storage processes, and belongs to the direction of new energy and environmental governance. BACKGROUND

[0002] The large-scale consumption of traditional fossil energy not only leads to the continuous increase of greenhouse gas emissions such as carbon dioxide, but also causes serious environmental pollution problems. In order to cope with this challenge, electrochemical technology has gradually become an important way to promote clean energy utilization and achieve environmental governance. Especially in the fields of water electrolysis hydrogen production, industrial wastewater treatment and electrochemical energy storage, efficient, stable and economical electrode materials play a decisive role in the performance of the whole system. The electrode is not only the key interface of energy and material conversion, but also its catalytic performance, stability and service life directly determine the energy consumption level, operation cost and sustainability of application. Therefore, the development of high-performance electrode materials has become one of the core problems in this field.

[0003] In recent years, titanium-based electrodes have attracted widespread attention in electrochemical applications due to their good mechanical strength and corrosion resistance. However, simply relying on titanium materials themselves cannot meet the needs of complex reaction environments, and is prone to activity decline due to surface passivation. Therefore, researchers generally choose to load functional coatings on the titanium substrate to achieve activity enhancement and life extension.

[0004] The existing research mainly focuses on three directions. First, some studies attempt to improve the adhesion performance of the electrode substrate and the coating. This type of research often improves the adhesion and overall structural stability of the coating by performing surface pretreatment on the substrate surface or adding a transition layer between the substrate and the active layer. This method improves the durability of the electrode in harsh environments to some extent, but due to the limited selection of material types and combinations, and the lack of systematic control of parameters such as thickness and uniformity, the coating may still peel off or crack during long-term operation. Second, in terms of improving the catalytic activity of the electrode, research generally focuses on selecting high-activity materials or using material composites to balance activity and stability. Some studies use a combination of two materials to achieve better catalytic performance and durability in electrode reactions. However, most existing technologies remain at the conceptual composite stage, lacking detailed design of proportions, composition matching, and structure regulation. This rough composite approach leads to large variations in electrode performance, making it difficult to ensure stability and repeatability between different batches. Meanwhile, the extensive use of valuable materials also results in high costs, limiting their application in large-scale industrialization. Third, to address the problem of electrode deactivation and corrosion during long-term operation, some studies propose introducing protective measures on the electrode surface. The usual approach is to add a protective coating to delay the performance degradation of the electrode under strong oxidation or high current density conditions. This method can achieve certain results in the short term, but its durability is still insufficient in continuous operation and complex wastewater environments. Single or limited protective measures cannot completely prevent the destruction of the electrode surface structure, leading to reduced electrode lifespan and increased operating costs.

[0005] From an application perspective, electrolytic water hydrogen production is currently the main technical path for large-scale green hydrogen production. However, this process places extremely high demands on electrode materials. Electrodes not only need to have high catalytic activity and low hydrogen or oxygen overpotential, but also must maintain stability during long-term operation. Existing electrode materials can meet certain performance indicators, but in large-scale industrial applications, they often suffer from efficiency decline, high energy consumption, and insufficient lifespan.

[0006] In the field of wastewater treatment, electrochemical oxidation technology is widely recognized as an efficient and environmentally friendly treatment method. Through electrode surface reactions, organic pollutants and toxic and harmful substances can be effectively removed, achieving deep treatment and harmless discharge. However, the complexity of pollutants in wastewater and the wide variety of components pose higher challenges to the stability and corrosion resistance of electrode materials. Existing electrode materials often experience surface activity decline, coating peeling, or electrode lifespan shortening when treating high-concentration organic wastewater or wastewater containing chlorine, fluorine, and other special components. In particular, under continuous operation and high-load conditions, the performance of traditional binary electrode systems decays rapidly, making it difficult to meet the long-term needs of industrial wastewater treatment.

[0007] In the field of electrochemical energy storage, including supercapacitors and metal-air batteries, the requirements for electrode materials are more stringent. Electrodes not only need to have high specific capacity and high rate performance, but also must remain stable during thousands or even tens of thousands of charge-discharge cycles. However, the cycle life of existing electrode materials is generally limited, and there are still deficiencies in terms of rate performance, energy density, etc. This has largely limited the large-scale application of electrochemical energy storage technology, making it difficult to effectively match renewable energy generation, thereby affecting the stability and flexibility of the overall energy system.

[0008] In addition to the limitations of the materials themselves, the existing electrode preparation process also has obvious shortcomings. Most of the disclosed technologies are only described as "high-temperature calcination" or "deposition treatment", lacking systematic research on key parameters. For example, factors such as calcination temperature, holding time, heating rate, and atmosphere have a significant impact on coating structure and performance, but existing technologies rarely precisely define these process conditions. This imperfect process control leads to large fluctuations in electrode performance between different batches, making it difficult to achieve stable mass production. Similarly, the preparation conditions of the precursor solution, such as the type, concentration, solvent system, and pH value of the metal salt, often lack uniform standards, further affecting the coating quality and electrode repeatability.

[0009] Current disclosed electrode technologies still mainly focus on limited material systems and relatively simple structural designs, lacking systematic solutions for complex application environments. This results in existing electrodes being difficult to balance high activity, long life, and low cost comprehensive requirements, and there are still obvious bottlenecks in the promotion of green energy and environmental governance.

[0010] In summary, although existing technologies have made certain achievements in electrode design, there are still obvious shortcomings in structural diversity, performance stability, process controllability, and application adaptability. These shortcomings not only restrict the large-scale promotion of water electrolysis hydrogen production, but also limit the application prospects of electrochemical wastewater treatment and energy storage technology. Under the dual drive of new energy and environmental governance, the research and development of high-performance electrode materials is still an important direction that needs to be broken through. How to ensure high catalytic activity and durability while achieving process optimization and cost control has become a key problem that needs to be solved in the current development of electrochemical technology. SUMMARY

[0011] The present application aims at the problems of insufficient electrolytic stability, low wastewater treatment efficiency and limited energy storage life of existing electrode materials, and provides a multi-metal layered titanium anode material, a preparation process and application thereof. Through the synergistic design of the adhesive layer, the catalytic layer and the protective layer, the material realizes efficient and stable operation of the electrode in different electrochemical environments. The present application can significantly improve the bonding force and corrosion resistance of the electrode, and improve the electrocatalytic activity and service life, so as to balance high efficiency and high stability, and break through the limitation of the prior art that performance and durability cannot be met at the same time.

[0012] Compared with the existing single system or binary system electrode, the multi-component layered structure constructed by the present application not only exhibits better long-term stability and higher catalytic efficiency, but also realizes lower use amount of noble metal in the preparation process through process optimization, reduces the overall cost, and has good economic feasibility and large-scale potential.

[0013] The material of the present application can be widely used in the fields of clean energy water electrolysis hydrogen production, industrial wastewater treatment and electrochemical energy storage devices, and has outstanding advantages in reducing energy consumption, improving efficiency and prolonging life.

[0014] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0015] The present application provides a multi-metal layered titanium anode material, which comprises a titanium substrate, an adhesive layer, a catalytic layer and a protective layer from bottom to top.

[0016] The material of the catalytic layer is a composite of ruthenium dioxide and iridium dioxide, wherein the molar ratio of ruthenium dioxide to iridium dioxide is 1:2-3, and the thickness of the catalytic layer is 3-4 mu m.

[0017] As a preferred, the material of the adhesive layer is a composite of titanium dioxide, tantalum pentoxide and tin dioxide, wherein the molar ratio of titanium dioxide, tantalum pentoxide and tin dioxide is 1:1-2:2-3, and the thickness of the adhesive layer is 0.5-1 mu m.

[0018] As a preferred, the material of the titanium substrate is industrial pure titanium, and the thickness of the titanium substrate is 80-100 mu m.

[0019] As a preferred, the material of the protective layer is a composite of platinum dioxide, palladium oxide and manganese dioxide,

[0020] Wherein, the molar ratio of platinum dioxide, palladium oxide and manganese dioxide is 1-2:2-3:1, and the thickness of the protective layer is 1-1.5 mu m.

[0021] The present application also provides a preparation process of the multi-metal layered titanium anode material, comprising the following steps:

[0022] 1) sandblasting and pickling treatment of the titanium substrate to obtain an activated titanium substrate;

[0023] 2) after spraying the bonding layer precursor solution on the surface of the activated titanium substrate, baking at 450~500℃ for 1~2h to obtain a bottom layer containing a bonding layer;

[0024] 3) after spraying the catalytic layer precursor solution on the surface of the bottom layer, baking at 500~600℃ for 2~3h to obtain an electrode containing a catalytic layer;

[0025] 4) after depositing the protective layer precursor solution on the surface of the electrode, baking at 400~450℃ for 0.5~1h to obtain a multi-metal layered titanium anode material.

[0026] Preferably, the pressure of the sandblasting in step 1) is 0.3~0.5MPa, and the sandblasting time is 5~8min;

[0027] The pickling uses hydrochloric acid with a mass fraction of 0.1~0.2%, the pickling temperature is 60~80℃, and the pickling time is 20~30min.

[0028] Preferably, the precursor solutions of the bonding layer, the catalytic layer and the protective layer are all chloride or nitrate solutions of the corresponding metals;

[0029] The total concentration of metal elements in the precursor solution is 1~2mol / L, the solvent is water and / or alcohol, and the pH is 4~6.

[0030] Preferably, the pressure of the spraying in steps 2) and 3) is 0.2~0.3MPa, and the spraying distance is 15~20cm;

[0031] In step 4), the deposition uses electrochemical deposition, the deposition current density is 10~15mA / cm 2 , the deposition temperature is 30~40℃, and the deposition time is 15~20min.

[0032] Preferably, the heating rate of the baking in steps 2)~4) is 10~15℃ / min, and the baking is carried out in an air atmosphere.

[0033] The application also provides the use of the multi-metal layered titanium anode material in water electrolysis for hydrogen production, wastewater treatment or electrochemical energy storage devices.

[0034] The beneficial effects of the application include the following points:

[0035] 1) The application constructs a multi-layer composite structure of bonding layer, catalytic layer and protective layer on the surface of the titanium substrate in sequence, significantly improves the bonding force and overall stability of the electrode, avoids coating cracking or peeling, and prolongs the service life of the electrode.

[0036] 2) The application adopts a multi-component catalytic layer design with an optimized ratio, enabling the electrode to have high electrocatalytic activity and chemical stability, and exhibiting excellent long-term stability and repeatability in various application scenarios such as water electrolysis, wastewater treatment, and electrochemical energy storage.

[0037] 3) The application sets a multi-component protective layer, effectively resisting corrosion and deactivation under high current density and complex medium environment, significantly improving the durability and continuous operation performance of the electrode compared to the traditional single protective layer design.

[0038] 4) The application optimizes key processes such as sandblasting, spraying, baking, and electrodeposition, achieving uniformity and repeatability of material structure, while reducing the use of precious metals and production costs, making it feasible for industrialization.

[0039] 5) The electrode of the application exhibits excellent performance in clean energy hydrogen production, wastewater treatment, and energy storage devices. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 Voltage-time curve of the electrode prepared for Example 1, Comparative Example 4 and Comparative Example 5 in water electrolysis experiment;

[0041] Figure 2 COD removal rate-time curve of the electrode prepared for Example 2, Comparative Example 2 and Comparative Example 6 in wastewater treatment experiment;

[0042] Figure 3 Specific capacitance retention rate-cycle number curve of the electrode prepared for Example 3, Example 4, Comparative Example 1, Comparative Example 3, Comparative Example 7 and Comparative Example 8 in electrochemical energy storage process. DETAILED DESCRIPTION

[0043] The application provides a multi-metal layered titanium anode material, which comprises a titanium substrate, a bonding layer, a catalytic layer and a protective layer from bottom to top.

[0044] The material of the catalytic layer is a composite of ruthenium dioxide and iridium dioxide, wherein the molar ratio of ruthenium dioxide to iridium dioxide is 1:2-3, and the thickness of the catalytic layer is 3-4 μm.

[0045] In the application, the molar ratio of ruthenium dioxide to iridium dioxide is 1:2-3, preferably 1:2.4-2.6, and further preferably 1:2.5.

[0046] In the present application, the material of the adhesive layer is preferably a composite of titanium dioxide, tantalum pentoxide and tin dioxide, wherein the molar ratio of titanium dioxide, tantalum pentoxide and tin dioxide is preferably 1:1~2:2~3, further preferably 1:1.4~1.6:2.4~2.6, and more preferably 1:1.5:2.5; the thickness of the adhesive layer is preferably 0.5~1 μm, further preferably 0.6~0.8 μm, and more preferably 0.7 μm.

[0047] In the present application, the material of the titanium substrate is preferably industrial pure titanium, and the thickness of the titanium substrate is preferably 80~100 μm, further preferably 85~95 μm, and more preferably 90 μm.

[0048] In the present application, the material of the protective layer is preferably a composite of platinum dioxide, palladium oxide and manganese dioxide, wherein the molar ratio of platinum dioxide, palladium oxide and manganese dioxide is preferably 1~2:2~3:1, further preferably 1.4~1.6:2.4~2.6:1, and further preferably 1.5:2.5:1; the thickness of the protective layer is preferably 1~1.5 μm, further preferably 1.2~1.4 μm, and more preferably 1.3 μm.

[0049] The present application also provides a preparation process of the multi-metal layered titanium anode material, comprising the following steps:

[0050] 1) sandblasting and pickling treatment of the titanium substrate to obtain an activated titanium substrate;

[0051] 2) after spraying the adhesive layer precursor solution on the surface of the activated titanium substrate, calcining at 450~500℃ for 1~2h to obtain a bottom layer containing an adhesive layer;

[0052] 3) after spraying the catalytic layer precursor solution on the surface of the bottom layer, calcining at 500~600℃ for 2~3h to obtain an electrode containing a catalytic layer;

[0053] 4) after depositing the protective layer precursor solution on the surface of the electrode, calcining at 400~450℃ for 0.5~1h to obtain a multi-metal layered titanium anode material.

[0054] In the present application, the pressure of the sandblasting in step 1) is preferably 0.3~0.5MPa, further preferably 0.35~0.45MPa, and more preferably 0.4MPa; the time of the sandblasting is preferably 5~8min, further preferably 6~7min, and more preferably 6.5min; the sandblasting preferably uses white corundum grits, and the particle size of the grits is preferably 150~180μm, further preferably 160~170μm, and more preferably 165μm.

[0055] In the present application, the acid pickling in step 1) is preferably carried out using hydrochloric acid with a mass fraction of 0.1-0.2%, further preferably hydrochloric acid with a mass fraction of 0.15%; the temperature of acid pickling is preferably 60-80°C, further preferably 65-75°C, and more preferably 70°C; and the time of acid pickling is preferably 20-30 min, further preferably 24-26 min, and more preferably 25 min.

[0056] In the present application, after the acid pickling in step 1) is completed, the titanium substrate is preferably rinsed with deionized water for 2-4 times, further preferably 3 times, and more preferably dried at 100-120°C for 15-20 min, further preferably dried at 105-115°C for 16-18 min, and more preferably dried at 110°C for 17 min.

[0057] In the present application, the precursor solutions of the bonding layer, the catalytic layer and the protective layer are all preferably chloride or nitrate solutions of the corresponding metal;

[0058] The total concentration of metal elements in the precursor solution is preferably 1-2 mol / L, and further preferably 1.5 mol / L; the solvent is preferably water and / or an alcohol, and the alcohol is preferably methanol, ethanol or isopropanol; and the pH is preferably 4-6, and further preferably 5.

[0059] In the present application, the spraying pressure in steps 2) and 3) is preferably 0.2-0.3 MPa, further preferably 0.24-0.26 MPa, and more preferably 0.25 MPa; the spraying distance is preferably 15-20 cm, further preferably 16-18 cm, and more preferably 17 cm; the spraying angle is preferably 80-90°, further preferably 85°; the speed of the spray gun movement is preferably 5-10 cm / s, further preferably 6-8 cm / s, and more preferably 7 cm / s; the flow rate of the sprayed liquid is preferably 2-3 mL / min, further preferably 2.5 mL / min; and the spraying times are preferably 2-4 times, further preferably 3 times, and each spraying is followed by a calcination process.

[0060] In the present application, the calcination temperature in step 2) is 450-500°C, preferably 460-480°C, and further preferably 470°C; and the calcination time is 1-2 h, preferably 1.4-1.6 h, and further preferably 1.5 h.

[0061] In the present application, the calcination temperature in step 3) is 500-600°C, preferably 540-560°C,

[0062] and further preferably 550°C; and the calcination time is 2-3 h, preferably 2.4-2.6 h, and further preferably 2.5 h.

[0063] In this invention, the deposition in step 4) is preferably performed using electrochemical deposition; the deposition current density is preferably 10~15 mA / cm². 2 Further preferred is 12~14 mA / cm 2 More preferably 13 mA / cm 2 The deposition temperature is preferably 30~40℃, more preferably 34~36℃, and even more preferably 35℃; the deposition time is preferably 15~20min, more preferably 16~18min, and even more preferably 17min.

[0064] In this invention, the roasting temperature in step 4) is 400~450℃, preferably 420~440℃, more preferably 430℃, and the roasting time is 0.5~1h, preferably 0.6~0.8h, more preferably 0.7h.

[0065] In this invention, the heating rate of the calcination in steps 2) to 4) is preferably 10 to 15 °C / min, more preferably 12 to 14 °C / min, and even more preferably 13 °C / min; the calcination is preferably carried out in an air atmosphere.

[0066] The present invention also provides the application of the aforementioned multi-metal multilayer titanium anode material in water electrolysis for hydrogen production, wastewater treatment, or electrochemical energy storage devices.

[0067] The technical solutions provided by the present invention will be 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.

[0068] In this invention, since the molar number of metal ions remains constant during the calcination process, the molar ratio of each metal element in the precursor solution corresponds to the molar ratio of each component in the final oxide. For example, when the molar ratio of ruthenium to iridium in the catalyst precursor solution is 1:2, the molar ratio of ruthenium dioxide to iridium dioxide in the catalyst layer formed after calcination is also 1:2.

[0069] In this invention, all alcohol solvents are anhydrous alcohols, all water is deionized water, and the grade of industrial pure titanium sheet is TA1. Example 1

[0070] A 90 μm thick industrial pure titanium sheet was used as the titanium substrate and subjected to sandblasting and acid pickling treatments. The sandblasting was performed using white corundum abrasive with a particle size of 165 μm, at a pressure of 0.4 MPa and a time of 6 min. The sandblasted titanium sheet was then placed in 0.15% hydrochloric acid and acid-washed at 70 °C for 25 min. After acid washing, it was rinsed three times with deionized water and dried at 110 °C for 17 min to obtain the activated titanium substrate.

[0071] Titanium tetrachloride, tantalum pentachloride and stannous nitrate were dissolved in a water-ethanol mixed solvent (volume ratio of water to ethanol was 2:1), the pH of the solution was adjusted to 5, the total concentration of metal elements in the solution was controlled to be 1.5 mol / L, and the molar ratio of Ti, Ta and Sn was 1:1.5:2.5, to obtain a binder layer precursor solution; the binder layer precursor solution was sprayed on the surface of the activated titanium substrate to form a coating, the spraying pressure was 0.25 MPa, the spraying distance was 17 cm, the spraying angle was 85°, the flow rate of the spraying liquid was 2.5 mL / min, and the substrate surface was walked 2 times at a speed of 7 cm / s according to the movement of the spraying gun until the wet film was evenly covered, after each spraying, the temperature was increased to 470°C at a rate of 10°C / min in an air atmosphere, and the coating was calcined at 470°C for 1.5 h, the spraying-calcining cycle was repeated for 3 times, to obtain a bottom layer containing a binder layer, the thickness of the binder layer was 0.7 μm, and the binder layer was composed of titanium dioxide, tantalum pentoxide and tin dioxide.

[0072] Ruthenium trichloride and iridium nitrate were dissolved in a water-isopropanol mixed solvent (volume ratio of water to isopropanol was 2:1), the pH of the solution was adjusted to 5, the total concentration of metal elements in the solution was controlled to be 1.5 mol / L, and the molar ratio of Ru and Ir was 1:2, to obtain a catalytic layer precursor solution; the catalytic layer precursor solution was sprayed on the surface of the bottom layer to form a coating, the spraying parameters were the same as those of the binder layer, after each spraying, the temperature was increased to 550°C at a rate of 10°C / min in an air atmosphere, and the coating was calcined at 550°C for 2.5 h, the spraying-calcining cycle was repeated for 3 times, to obtain an electrode containing a catalytic layer, the thickness of the catalytic layer was 3.5 μm, and the catalytic layer was composed of ruthenium dioxide and iridium dioxide.

[0073] Hexahydrate chloroplatinic acid, palladium nitrate dihydrate and manganese nitrate tetrahydrate were dissolved in ethanol, the pH of the solution was adjusted to 5, the total concentration of metal elements in the solution was controlled to be 1.5 mol / L, and the molar ratio of Pt, Pd and Mn was 1.5:2.5:1, to obtain a protective layer precursor solution; the protective layer was deposited on the surface of the electrode by electrochemical deposition, the deposition current density was 13 mA / cm², the temperature was 35°C, and the time was 17 min, after the deposition was completed, the temperature was increased to 430°C at a rate of 13°C / min in an air atmosphere, and the coating was calcined at 430°C for 0.7 h, to obtain a multi-metal layered titanium anode material with a protective layer thickness of 1.3 μm, and the protective layer was composed of platinum dioxide, palladium oxide and manganese dioxide. Example 2

[0074] An industrial pure titanium sheet with a thickness of 80 μm was taken as the titanium substrate, and sand blasting and acid pickling were performed in sequence. The sand used for sand blasting was white corundum sand with a particle size of 150 μm, the pressure for sand blasting was 0.3 MPa, the time for sand blasting was 8 min, then the titanium sheet after sand blasting was placed in hydrochloric acid with a mass fraction of 0.1% at 80 ℃ for acid pickling for 20 min, after acid pickling, the titanium sheet was washed with deionized water for 2 times, and then dried at 100 ℃ for 20 min, to obtain an activated titanium substrate.

[0075] Titanium tetrachloride, tantalum pentachloride and stannous nitrate were dissolved in a water-methanol mixed solvent (volume ratio of water to ethanol was 1:1), the pH of the solution was adjusted to 4, the total concentration of metal elements in the solution was controlled to be 2 mol / L, and the molar ratio of Ti, Ta and Sn was 1:1:2, to obtain a binder layer precursor solution; the binder layer precursor solution was sprayed on the surface of the activated titanium substrate to form a coating, the spraying pressure was 0.2 MPa, the spraying distance was 15 cm, the spraying angle was 80°, the flow rate of the spraying liquid was 2 mL / min, and the substrate surface was walked 3 times at a speed of 5 cm / s according to the moving speed of the spraying gun until the wet film was evenly covered, after each spraying, the temperature was raised to 450 ℃ at a rate of 12 ℃ / min in an air atmosphere, and then the sample was calcined at 450 ℃ for 2 h, the spraying-calcining cycle was repeated 4 times, to obtain a bottom layer containing a binder layer, the thickness of the binder layer was 0.5 μm, and the binder layer was composed of titanium dioxide, tantalum pentoxide and tin dioxide.

[0076] Ruthenium trichloride and iridium nitrate were dissolved in a water-isopropanol mixed solvent (volume ratio of water to isopropanol was 1:1), the pH of the solution was adjusted to 4, the total concentration of metal elements in the solution was controlled to be 2 mol / L, and the molar ratio of Ru and Ir was 1:3, to obtain a catalytic layer precursor solution; the catalytic layer precursor solution was sprayed on the surface of the bottom layer to form a coating, and the spraying parameters were the same as those of the binder layer, after each spraying, the temperature was raised to 500 ℃ at a rate of 15 ℃ / min in an air atmosphere, and then the sample was calcined at 500 ℃ for 3 h, the spraying-calcining cycle was repeated 4 times, to obtain an electrode containing a catalytic layer, the thickness of the catalytic layer was 3 μm, and the catalytic layer was composed of ruthenium dioxide and iridium dioxide.

[0077] Chloroplatinic acid hexahydrate, palladium nitrate dihydrate and manganese nitrate tetrahydrate were dissolved in ethanol, the pH of the solution was adjusted to 4, the total concentration of metal elements in the solution was controlled to be 2 mol / L, and the molar ratio of Pt, Pd and Mn was 1:2:1, to obtain a protective layer precursor solution; the protective layer was deposited on the surface of the electrode by electrochemical deposition, the deposition current density was 10 mA / cm², the temperature was 30 ℃, and the time was 20 min, after deposition, the temperature was raised to 400 ℃ at a rate of 15 ℃ / min in an air atmosphere, and then the sample was calcined at 400 ℃ for 1 h, to obtain a multi-metal layered titanium anode material with a protective layer thickness of 1 μm, and the protective layer was composed of platinum dioxide, palladium oxide and manganese dioxide. Example 3

[0078] An industrial pure titanium sheet with a thickness of 100 μm was used as the titanium substrate, and sand blasting and acid pickling were performed in sequence. The sand used for sand blasting was white corundum sand with a particle size of 180 μm, the pressure for sand blasting was 0.5 MPa, and the time for sand blasting was 5 min. Subsequently, the titanium sheet after sand blasting was placed in hydrochloric acid with a mass fraction of 0.2%, and acid pickling was performed at 60°C for 30 min. After acid pickling, the titanium sheet was washed with deionized water for 4 times, and dried at 120°C for 15 min to obtain an activated titanium substrate.

[0079]

[0080] Titanium tetrachloride, tantalum pentachloride and stannous nitrate were dissolved in a water-ethanol mixed solvent (the volume ratio of water to ethanol was 3:1), the pH of the solution was adjusted to 6, the total concentration of metal elements in the solution was controlled to be 1 mol / L, and the molar ratio of Ti, Ta and Sn was 1:2:2, to obtain a binder layer precursor solution. The binder layer precursor solution was sprayed on the surface of the activated titanium substrate to form a coating layer, the spraying pressure was 0.3 MPa, the spraying distance was 20 cm, the spraying angle was 90°, the flow rate of the spraying liquid was 3 mL / min, and the substrate surface was walked 2 times at a speed of 10 cm / s according to the moving speed of the spraying gun until the wet film was evenly covered. After each spraying, the temperature was increased to 500°C at a rate of 12°C / min in an air atmosphere, and the coating was calcined at 500°C for 1 h. The spraying-calcining cycle was repeated twice to obtain a bottom layer containing a binder layer, and the thickness of the binder layer was 1 μm. The binder layer was composed of titanium dioxide, tantalum pentoxide and tin dioxide.

[0081] Ruthenium trichloride and iridium nitrate were dissolved in a water-isopropanol mixed solvent (the volume ratio of water to isopropanol was 3:1), the pH of the solution was adjusted to 6, the total concentration of metal elements in the solution was controlled to be 1 mol / L, and the molar ratio of Ru and Ir was 1:3 to obtain a catalytic layer precursor solution. The catalytic layer precursor solution was sprayed on the surface of the bottom layer to form a coating layer, and the spraying parameters were the same as those of the binder layer. After each spraying, the temperature was increased to 600°C at a rate of 10°C / min in an air atmosphere, and the coating was calcined at 600°C for 2 h. The spraying-calcining cycle was repeated twice to obtain an electrode containing a catalytic layer, and the thickness of the catalytic layer was 4 μm. The catalytic layer was composed of ruthenium dioxide and iridium dioxide.

[0082] ​Hexachloroplatinic acid hexahydrate, palladium nitrate dihydrate and manganese nitrate tetrahydrate were dissolved in ethanol, the pH of the solution was adjusted to 6, the total concentration of metal elements in the solution was controlled to be 1 mol / L, and the molar ratio of Pt, Pd and Mn was 2:2:1, to obtain a protective layer precursor solution; the protective layer was deposited on the surface of the electrode by electrochemical deposition, the deposition current density was 15 mA / cm2, the temperature was 40°C, and the deposition time was 15 min; after deposition, the temperature was raised to 450°C at a rate of 14°C / min in an air atmosphere, and the sample was calcined at 450°C for 0.5 h, to obtain a multi-metal layered titanium anode material with a protective layer thickness of 1.5 μm, and the protective layer was composed of platinum dioxide, palladium oxide and manganese dioxide. Example 4

[0083] An industrial pure titanium sheet with a thickness of 85 μm was used as a titanium substrate, and sand blasting and pickling were sequentially performed. The sand used for sand blasting was white corundum sand with a particle size of 170 μm, the sand blasting pressure was 0.45 MPa, and the sand blasting time was 7 min; then the titanium sheet after sand blasting was placed in hydrochloric acid with a mass fraction of 0.18%, and pickling was performed at 65°C for 25 min; after pickling, the titanium sheet was washed with deionized water for 4 times, and dried at 115°C for 16 min, to obtain an activated titanium substrate.

[0084] Titanium tetrachloride, tantalum pentachloride and stannous nitrate were dissolved in a water-ethanol mixed solvent (the volume ratio of water to ethanol was 2:1), the pH of the solution was adjusted to 5, the total concentration of metal elements in the solution was controlled to be 2 mol / L, and the molar ratio of Ti, Ta and Sn was 1:1:3, to obtain a binder layer precursor solution; the binder layer precursor solution was sprayed on the surface of the activated titanium substrate to form a coating, the spraying pressure was 0.3 MPa, the spraying distance was 16 cm, the spraying angle was 85°, the flow rate of the spraying liquid was 2.5 mL / min, and the substrate surface was walked 2 times at a speed of 8 cm / s according to the movement of the spraying gun until the wet film was evenly covered; after each spraying, the temperature was raised to 480°C at a rate of 10°C / min in an air atmosphere, and the sample was calcined at 480°C for 1.8 h; the spraying-calcining cycle was repeated 3 times, to obtain a bottom layer containing a binder layer, the thickness of the binder layer was 0.85 μm, and the binder layer was composed of titanium dioxide, tantalum pentoxide and tin dioxide.

[0085] The ruthenium trichloride and iridium nitrate are dissolved in a water-isopropyl alcohol mixed solvent (volume ratio of water to isopropyl alcohol is 2:1), the pH of the solution is adjusted to 5, the total concentration of metal elements in the solution is controlled to be 1.4 mol / L, and the molar ratio of Ru to Ir is 1:2.5, to obtain a catalyst layer precursor solution; the catalyst layer precursor solution is sprayed on the surface of the bottom layer to form a coating, and the spraying parameters are the same as those of the bonding layer, after each spraying, the temperature is raised to 560°C at a rate of 10°C / min in an air atmosphere, and the coating is calcined at 560°C for 2.4 h, the spraying-calcining cycle is repeated for 3 times, to obtain an electrode containing a catalyst layer, the thickness of the catalyst layer is 4 μm, and the catalyst layer is composed of ruthenium dioxide and iridium dioxide.

[0086] The hexahydrate chloroplatinic acid, the palladium nitrate dihydrate and the manganese nitrate tetrahydrate are dissolved in ethanol, the pH of the solution is adjusted to 5, the total concentration of metal elements in the solution is controlled to be 2 mol / L, and the molar ratio of Pt, Pd and Mn is 1:3:1, to obtain a protective layer precursor solution; the protective layer is deposited on the surface of the electrode by electrochemical deposition, the deposition current density is 14 mA / cm², the temperature is 40°C, and the deposition time is 16 min, after the deposition is completed, the temperature is raised to 450°C at a rate of 15°C / min in an air atmosphere, and the coating is calcined at 450°C for 0.8 h, to obtain a multi-metal layered titanium anode material with a protective layer thickness of 1.4 μm, and the protective layer is composed of platinum dioxide, palladium oxide and manganese dioxide. Comparative Example 1

[0087] The same as Example 1, except that no protective layer is provided outside the catalyst layer, that is, after the preparation of the bonding layer and the catalyst layer is completed, no deposition and calcination of the protective layer precursor solution is performed, and the electrode is directly obtained. Comparative Example 2

[0088] The same as Example 2, except that the bonding layer is not sprayed on the surface of the activated titanium substrate, the catalyst layer precursor solution is directly sprayed on the surface of the titanium substrate and calcined, and then the protective layer is deposited, to obtain the electrode. Comparative Example 3

[0089] The same as Example 3, except that the material of the bonding layer is only a composite of titanium dioxide and tantalum pentoxide, the molar ratio of Ti to Ta is 1:1, and the remaining process conditions remain unchanged, to obtain the electrode. Comparative Example 4

[0090] The same as Example 4, except that the material of the protective layer is only single platinum dioxide, and the remaining process conditions remain unchanged, to obtain the electrode. Comparative Example 5

[0091] The same as Example 1, except that the molar ratio of Ru to Ir in the catalyst layer precursor solution is set to 1:1, and the rest of the process conditions remain unchanged, to obtain the electrode. Comparative Example 6

[0092] The same as Example 2, except that the binder layer is only calcined at 300℃ for 3h after spraying, and the rest of the process conditions remain unchanged, to obtain the electrode. Comparative Example 7

[0093] The same as Example 3, except that the catalyst layer is calcined at 700℃ for 0.5h after spraying, and the rest of the process conditions remain unchanged, to obtain the electrode. Comparative Example 8

[0094] The same as Example 1, except that the current density for electrochemical deposition of the protective layer is modified to 5mA / cm², the temperature is modified to 25℃, and the time is modified to 30min, and the rest of the process conditions remain unchanged, to obtain the electrode.

[0095] Application Example 1

[0096] The electrodes prepared in Example 1, Comparative Example 4 and Comparative Example 5 are respectively used for water electrolysis experiments. The experimental conditions are: the electrolyte is a 1mol / L potassium hydroxide solution, the temperature is 30℃, the current density is 200mA / cm², and the continuous operation time is 100h. During the test process, the working voltage of the electrolytic cell is recorded in real time with time, and the voltage-time curve is drawn as shown in Figure 1 .

[0097] It can be seen from Figure 1 that the voltage of the electrode in Example 1 only rises from 1.65 V to 1.68 V within 100h, and the voltage rise is 0.03 V; the voltage rise of the electrode in Comparative Example 4 is 0.09 V; the voltage rise of the electrode in Comparative Example 5 is 0.12 V, which indicates that the electrode in Example 1 exhibits the best stability and durability under long-time electrolysis conditions, and the three-layer design and the optimized Ru:Ir ratio significantly improve the service life and efficiency of the electrode.

[0098] Application Example 2

[0099] The electrodes prepared in Example 2, Comparative Example 2 and Comparative Example 6 are respectively used for wastewater treatment experiments. The experimental conditions are: the initial COD (chemical oxygen demand) in the simulated wastewater is 500mg / L, the pH is 7.0, the current density is 50mA / cm², the electrolyte volume is 500mL, and the continuous electrolysis operation time is 8h at room temperature (25℃). During the test process, the COD concentration in the solution is determined by sampling at regular intervals, and the COD removal rate-time curve is drawn as shown in Figure 2 .

[0100] Depend on Figure 2 It can be seen that the COD removal rate of the electrode in Example 2 reached 92% within 8 hours, the COD removal rate of the electrode in Comparative Example 2 was 75%, and the COD removal rate of the electrode in Comparative Example 6 was only 68%. This shows that the electrode in Example 2 exhibits higher organic pollutant removal efficiency and stronger stability in the wastewater treatment process, and verifies the advantages of the three-layer structure of binder-catalyst-protective layer in complex wastewater environment.

[0101] Application Example 3

[0102] The electrodes prepared in Examples 3 and 4, as well as Comparative Examples 1, 3, 7, and 8, were assembled into symmetrical electrochemical energy storage devices. The experimental conditions were: 1 mol / L sulfuric acid solution as the electrolyte, 10 A / g as the current density, and cyclic charge-discharge testing within a voltage window of 0–1.0 V, for a total of 5000 cycles. During the test, the retention rate of the device's specific capacitance with the number of cycles was recorded in real time, and a specific capacitance retention rate-cycle count curve was plotted, as shown below. Figure 3 As shown.

[0103] Depend on Figure 3 It can be seen that: the specific capacitance retention rate of the electrode in Example 3 was 91% after 5000 cycles, while that in Example 4 was 93%; the specific capacitance retention rates in Comparative Example 1 were 68%, in Comparative Example 3 were 74%, in Comparative Example 7 were 62%, and in Comparative Example 8 were 70%. This indicates that the electrodes in the examples have significantly better cycle stability and energy retention capabilities than those in the comparative examples in electrochemical energy storage applications; the three-layer stacked structure, the optimized ratio of materials in each layer, and the reasonable deposition / calcination process are the key factors in achieving high stability.

[0104] The comparative results of the examples and comparative examples in three typical applications—water electrolysis, wastewater treatment, and electrochemical energy storage—show that the multi-metal multilayer titanium anode material of this invention has significant advantages in long-term operational stability, pollutant removal efficiency, and cycle life retention. Through the rational design and optimized proportions of the binder layer, catalytic layer, and protective layer, this material overcomes the bottleneck of existing technologies that struggle to balance activity and stability, achieving a significant improvement in overall performance and providing an efficient and reliable solution for various electrochemical application scenarios.

[0105] The material of this invention can not only effectively reduce energy consumption and improve hydrogen production efficiency in clean energy hydrogen production, and significantly improve the removal effect of organic pollutants in wastewater treatment, but also maintain excellent cycle stability and energy retention capacity in electrochemical energy storage devices, and has broad industrial application potential.

[0106] The above merely describes the preferred embodiments of the present application, and it should be pointed out that, for those skilled in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as falling within the protection scope of the present application.

Claims

1. A multi-metal stacked titanium anode material, characterized in that, The multi-metal multilayer titanium anode material comprises, from bottom to top, a titanium substrate, a bonding layer, a catalyst layer, and a protective layer; The catalyst layer is made of a composite of ruthenium dioxide and iridium dioxide, wherein ruthenium dioxide and... The molar ratio of iridium dioxide is 1:2~3, and the thickness of the catalyst layer is 3~4μm; The adhesive layer is a composite of titanium dioxide, tantalum pentoxide, and tin dioxide, wherein the molar ratio of titanium dioxide, tantalum pentoxide, and tin dioxide is 1:1~2:2~3, and the thickness of the adhesive layer is 0.5~1μm. The protective layer is a composite of platinum dioxide, palladium oxide, and manganese dioxide, wherein the molar ratio of platinum dioxide, palladium oxide, and manganese dioxide is 1~2:2~3:1, and the thickness of the protective layer is 1~1.5μm.

2. The multi-metal multilayer titanium anode material according to claim 1, characterized in that, The titanium substrate is made of industrially pure titanium, and its thickness is 80~100μm.

3. The preparation process of the multi-metal multilayer titanium anode material according to claim 1 or 2, characterized in that, Includes the following steps: 1) The titanium substrate is subjected to sandblasting and acid pickling to obtain an activated titanium substrate; 2) After spraying the binder precursor solution onto the surface of the activated titanium substrate, calcine it at 450~500℃ for 1~2h to obtain the bottom layer containing the binder layer. 3) After spraying the catalyst precursor solution onto the bottom surface, calcine it at 500~600℃ for 2~3h to obtain an electrode containing a catalyst layer; 4) A protective layer is deposited on the electrode surface using electrochemical deposition in the protective layer precursor solution, with a deposition current density of 10~15 mA / cm². 2 The deposition temperature is 30~40℃, the deposition time is 15~20min, and the material is calcined at 400~450℃ for 0.5~1h to obtain a multi-metal multilayer titanium anode material.

4. The preparation process according to claim 3, characterized in that, Step 1) The sandblasting pressure is 0.3~0.5MPa, and the sandblasting time is 5~8min; The pickling process uses hydrochloric acid with a mass fraction of 0.1-0.2%, the pickling temperature is 60-80℃, and the pickling time is 20-30 minutes.

5. The preparation process according to claim 4, characterized in that, The precursor solutions for the bonding layer, catalyst layer, and protective layer are all chloride or nitrate solutions of the corresponding metals. The total concentration of metal elements in the precursor solution is 1-2 mol / L, the solvent is water and / or alcohol, and the pH is 4-6.

6. The preparation process according to claim 5, characterized in that, Steps 2) and 3) The spraying pressure is 0.2~0.3MPa, and the spraying distance is 15~20cm.

7. The preparation process according to claim 6, characterized in that, The heating rate for calcination in steps 2) to 4) is 10-15°C / min, and the calcination is carried out in an air atmosphere.

8. The application of the multi-metal stacked titanium anode material according to claim 1 or 2 in water electrolysis for hydrogen production, wastewater treatment, or electrochemical energy storage devices.

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