Acid platinum plating solution for preparing platinum plating layer on surface of titanium plate, electroplating method and platinum-plated titanium plate

Abstract

The invention relates to an acidic platinum plating solution for preparing a platinum plating layer on the surface of a titanium plate, an electroplating method and a platinum-plated titanium plate, the acidic platinum plating solution is prepared by mixing and dissolving a platinum source, sulfamic acid, sulfuric acid and benzotriazole in deionized water, and the pH value is 0.5-3.0. After the titanium plate is subjected to oil removal cleaning and acid treatment, the titanium plate is subjected to platinum electroplating in an acid electroplating solution by using a direct-current power supply deposition method, cleaning, drying and high-temperature treatment are performed after electroplating, and the platinum-plated titanium plate is obtained. Compared with the prior art, the acidic electroplating liquid is stable in pH and has excellent uniform plating performance and deep plating capacity, and during electroplating, acid treatment (demolding and surface activation treatment) is conducted on a titanium plate in two steps, so that the surface binding force of a platinum plating layer and the titanium plate is improved, and the electroplating efficiency is improved. The platinum plating layer which is uniform, compact, bright and flat in surface and low in porosity can be plated through simple and convenient operation, and the platinum plating layer has excellent acid corrosion resistance, conductivity performance and adhesive force.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electroplating platinum, in particular to an acidic platinum plating solution for preparing a platinum plating layer on the surface of a titanium plate, an electroplating method and a platinum-plated titanium plate. BACKGROUND

[0002] Platinum-plated titanium technology combines the high strength and toughness of titanium, small specific gravity and corrosion resistance, and the excellent electrochemical activity and catalytic function of platinum, opening up a new perspective for material applications. As a highly efficient fuel cell electrode material, platinum-plated titanium can significantly improve energy conversion efficiency and inject strong impetus into the development of green energy; the platinum plating layer effectively enhances the biocompatibility of titanium alloys, providing patients with safer and more reliable medical options; at the same time, the platinum plating layer also provides a layer of strong protection for chemical equipment, greatly extending the service life of the equipment and significantly reducing maintenance costs. Platinum-plated titanium technology has a wide range of applications and is not limited to specific industries, but also plays an important role in catalyst, sensor manufacturing and parts production under harsh conditions, becoming an indispensable key material technology in today's industrial and technological development.

[0003] The pH value of an alkaline platinum electroplating solution is usually maintained between 10-14. Compared with an acidic platinum plating solution with a pH value of 0.5-3.0, the deposition rate of an alkaline platinum plating solution is slower, which directly affects production efficiency and makes it difficult to meet the needs of industrial production. In addition, platinum complexes in alkaline solutions have high stability requirements. If the pH value is not properly controlled, precipitation and decomposition phenomena can easily occur, thereby affecting the quality of the plating layer. Moreover, alkaline electroplating systems are extremely sensitive to impurities, and trace contamination can cause plating defects, increasing the complexity of the process. Patent CN105386095A discloses an alkaline P-salt platinum electroplating solution and an electroplating method thereof, which contains 20-30 g / L P-salt, 90-110 g / L ammonium nitrate, 8-12 g / L potassium nitrite or sodium nitrite and 2-6 mg / L calcium chloride calculated as calcium. The plating layer obtained by electroplating under alkaline conditions using this plating solution has low porosity, high brightness and good plating layer quality. However, due to the high amount of platinum used, this method is limited in large-scale applications. In addition, the patent uses current pulse technology for electroplating, which has high requirements and is difficult to operate. If not handled properly, burrs can occur and the uniformity and quality of the plating layer can be affected. Moreover, alkaline electroplating solutions also involve waste liquid treatment and pollution control problems.

[0004] In contrast, the platinum deposition rate of acidic platinum plating solution (pH 0.5-3.0) is faster, which can greatly improve the efficiency of electroplating and meet the needs of high-efficiency industrial production. At the same time, the preparation of acidic solution is simple, the process control is easy to achieve and the stability is high; while the alkaline solution is sensitive to pH, easy to precipitate or decompose and needs to be adjusted multiple times. In addition, the acidic plating solution has strong adaptability to the substrate and low pretreatment requirements, while the alkaline system is sensitive to impurities, which can easily lead to defects in the plated layer. Therefore, the acidic platinum plating solution is superior to the alkaline solution in efficiency, stability and applicability.

[0005] Chinese patent CN115787011A discloses an electroplating solution and method for preparing a platinum coating on the surface of a titanium current collector for electrolytic water hydrogen production. The content of each component in the electroplating solution is: 6g / L-13g / L of dinitrosodiaminoplatinum calculated as platinum, 2g / L-10g / L of sulfamic acid, 15g / L-35g / L of citric acid, 20g / L-45g / L of disodium hydrogen phosphate, 10g / L-40g / L of sodium dodecyl sulfate, and the pH of the plating solution is 4.5-5.5. The electroplating solution in the above patent has strong throwing power and deep plating capacity, and the platinum coating is dense. However, the electroplating time required by the patent to prepare a platinum coating on the surface of a titanium plate is relatively long, which is more than 1 hour, and the thickness of the platinum coating is relatively thick, and the consumption of precious metals is still high, resulting in high cost. SUMMARY

[0006] The purpose of the present application is to provide an acidic platinum plating solution for preparing a platinum coating on the surface of a titanium plate, an electroplating method and a platinum-plated titanium plate. The acidic platinum plating solution has excellent stability, throwing power and deep plating capacity, and the pH does not need to be continuously adjusted. The prepared platinum coating is uniform, dense and thin, and the operation is simple, the electroplating time is short, and the cost of precious metal consumption is low.

[0007] The purpose of the present application can be achieved by the following technical solutions:

[0008] In one aspect, the present application provides an acidic platinum plating solution for preparing a platinum coating on the surface of a titanium plate. The acidic platinum plating solution is an aqueous solution comprising the following components: 1-50g / L of platinum source calculated as platinum, 30-90g / L of sulfamic acid, 2-20ml / L of sulfuric acid, 0.1-5.0g / L of OP-10, and 0.1-5.0g / L of benzotriazole. The pH of the acidic platinum plating solution is 0.5-3.0.

[0009] Preferably, the platinum source is selected from one or more of dinitrosodiaminoplatinum, potassium tetranitroplatinate, chloroplatinic acid, dinitrosylplatinic acid sulfate or platinum nitrate.

[0010] Further preferably, the platinum source is chloroplatinic acid.

[0011] Further preferably, the acidic plating solution for platinum comprises the following components: chloroplatinic acid 15 g / L, sulfamic acid 40 g / L, sulfuric acid 3.5 ml / L, OP-10 0.3 g / L, and benzotriazole 1.0 g / L, calculated based on platinum.

[0012] Preferably, the acidic plating solution for platinum is prepared by adding a platinum source, sulfamic acid, sulfuric acid, OP-10, and benzotriazole into deionized water in a certain ratio and heating to dissolve.

[0013] Further preferably, the heating temperature is 90-95°C.

[0014] Further preferably, the sulfamic acid serves as a buffer and complexing agent, the sulfuric acid serves as a conductive agent, the benzotriazole serves as a brightener and corrosion inhibitor, and the OP-10 serves as a wetting agent and dispersant.

[0015] In the present application, the acidic plating solution for platinum has a small pH value variation range due to the presence of a large amount of acidic substances in the plating solution, and has high stability without the need for continuous pH adjustment. This acidic plating solution for platinum is suitable for large-scale commercial production.

[0016] In the present application, the acidic plating solution for platinum uses sulfuric acid as a conductive agent. During the electroplating process, a small amount of sulfuric acid as a strong electrolyte additive mainly plays the roles of improving the conductivity of the electroplating solution, improving the quality of the platinum coating, controlling the deposition rate, preventing passivation, adjusting the acidity, and reducing undesirable side reactions. It promotes the uniform reduction of platinum ions by increasing the conductivity of the electroplating solution and stabilizing current conduction, improves the density and adhesion of the coating, thereby optimizing the electroplating process and ensuring the uniformity and quality of the coating.

[0017] In the present application, the acidic plating solution for platinum uses sulfamic acid as a buffer and complexing agent, which can stabilize platinum ions and prevent premature reduction or precipitation of platinum ions, thereby ensuring the stability of the electroplating solution. It forms a complex by combining with platinum ions, thereby improving the solubility of platinum and controlling the uniform deposition of platinum during the electroplating process.

[0018] In the present application, the acidic plating solution for platinum uses OP-10 (dodecyl phenol polyoxyethylene ether) as a wetting agent and dispersant, which improves the wettability and stability of the electroplating solution. During the electroplating process, it can reduce the surface tension of the liquid, improve the coverage of the electroplating solution on the substrate surface, reduce the formation of bubbles, and promote the uniform deposition of metal ions.

[0019] The use of benzotriazole as a brightener in the acidic platinum plating solution of the present invention primarily inhibits grain growth and promotes nucleation through adsorption, achieving grain refinement, thereby reducing microroughness, enhancing specular reflection, and obtaining a bright coating. Furthermore, benzotriazole can act as a corrosion inhibitor, effectively preventing corrosion and ensuring bonding strength. Its ability to inhibit cathodic hydrogen evolution helps improve current efficiency, reduce coating defects (pinholes and pitting), and improve coating density.

[0020] The various additives (sulfamic acid, sulfuric acid, OP-10, and benzotriazole) in the acidic platinum plating solution of the present invention can assist the use of the acidic platinum electroplating solution, thereby improving the shortcomings of the electroplating solution, such as uneven coating, low-quality coating, unstable sedimentation rate, and low adhesion. By regulating the electroplating solution and current density, these additives can improve the uniformity, density, and glossiness of the coating, strengthen adhesion, improve process stability and efficiency, and reduce side reactions and harmful substances, thereby improving the controllability of the platinum plating process. The synergistic combined effect of multiple agents promotes the overall quality and production efficiency of acidic platinum electroplating.

[0021] In a second aspect, the present invention provides an electroplating method for preparing a platinum coating on a titanium plate surface using the acidic platinum plating solution, comprising the following steps:

[0022] S1: Degreasing and degreasing the titanium plate;

[0023] S2: Acid treatment is performed on the titanium plate after degreasing and deoiling: demolding treatment and surface activation treatment are performed in sequence:

[0024] S3: placing the acid-treated titanium plate in an acidic platinum plating solution and electroplating platinum using a direct current electrodeposition method;

[0025] S4: The electroplated titanium plate is sequentially cleaned, dried, and subjected to high-temperature heat treatment to obtain a platinum-plated titanium plate.

[0026] Preferably, in step S1, the degreasing treatment refers to cleaning the titanium plate with anhydrous ethanol, then degreasing the titanium plate with a metal degreasing and degreasing agent, and then cleaning and drying the titanium plate with an acetone aqueous solution and deionized water in sequence after degreasing.

[0027] Further preferably, in step S1, the use of anhydrous ethanol for cleaning refers to ultrasonic cleaning for 15-25 minutes, the concentration of the metal degreasing and degreasing agent is 2-5wt.%, the degreasing treatment refers to degreasing and degreasing the titanium plate at 50-70°C for 10-20 minutes, and the use of acetone aqueous solution for cleaning refers to ultrasonic cleaning with 15-25 ml / L acetone aqueous solution for 3-8 minutes.

[0028] Preferably, in step S2, the demolding treatment refers to placing the titanium plate in a mixed acid A solution for demolding treatment at room temperature for 4-8 minutes.

[0029] Further preferably, in step S2, the normal temperature is 20-30℃, and the time for the demolding treatment is 6 min.

[0030] Further preferably, in step S2, the mixed acid A solution comprises hydrofluoric acid, nitric acid, polyethylene glycol and deionized water.

[0031] Further preferably, in step S2, the volume ratio of the hydrofluoric acid, the nitric acid, the polyethylene glycol and the deionized water is 5-20 mL: 10-50 mL: 1-10 mL: 90-110 mL.

[0032] Further preferably, in step S2, the volume ratio of the hydrofluoric acid, the nitric acid, the polyethylene glycol and the deionized water is 5-20 mL: 10-50 mL: 1-10 mL: 100 mL.

[0033] Further preferably, in step S2, the volume ratio of the hydrofluoric acid, the nitric acid, the polyethylene glycol and the deionized water is 5 mL: 15 mL: 5 mL: 100 mL.

[0034] In the present application, the mixed acid A solution composed of hydrofluoric acid, nitric acid and polyethylene glycol is used to demold the surface of the titanium plate, wherein the polyethylene glycol can slow down the corrosion rate and improve the uniformity of the demolding, so as to remove the oxides on the surface of the titanium plate and improve the surface flaws caused by physical factors in the early processing of the sample.

[0035] Preferably, in step S2, the surface activation treatment refers to placing the titanium plate after the demolding treatment in a mixed acid B solution and treating it at 40-60℃ for 20-40 min to obtain roughness.

[0036] Further preferably, in step S2, the surface activation treatment refers to treating it at 40℃ for 30 min.

[0037] Further preferably, in step S2, the mixed acid B solution comprises hydrochloric acid, phosphoric acid and deionized water.

[0038] Further preferably, in step S2, the volume ratio of the hydrochloric acid, the phosphoric acid and the deionized water is 5-30 mL: 5-30 mL: 80-110 mL.

[0039] Further preferably, in step S2, the volume ratio of the hydrochloric acid, the phosphoric acid and the deionized water is 5-30 mL: 5-30 mL: 100 mL.

[0040] Further preferably, in step S2, the volume ratio of the hydrochloric acid, the phosphoric acid and the deionized water is 10 mL: 10 mL: 100 mL.

[0041] In the present application, the titanium plate surface is activated by using a mixed acid B solution composed of hydrochloric acid and phosphoric acid, the titanium plate surface is chemically etched, the titanium surface layer material is dissolved to form a micro-etching structure, so as to increase the surface area and roughness, and further improve the adhesion of the titanium plate and the plating layer.

[0042] Preferably, in step S3, a pure platinum mesh is used as the anode, and the titanium plate after acid treatment is used as the cathode.

[0043] Further preferably, in step S3, the titanium plate is a pure metal titanium plate with a titanium content of 99%.

[0044] Preferably, in step S3, the area ratio of the anode to the cathode is 1:2-6, and further preferably 1:4.

[0045] Preferably, in step S3, the temperature of the acidic platinum plating solution is 40-70℃, the current density during platinum electroplating is 1.0-5.0 A / dm 2 , and the electroplating time is 1-8 min.

[0046] Further preferably, in step S3, the temperature of the acidic platinum plating solution is 50℃, the current density during platinum electroplating is 2.0 A / dm 2 , and the electroplating time is 4 min.

[0047] Preferably, in step S4, the cleaning refers to rinsing with normal temperature deionized water for 10-20 s, and further preferably for 10 s.

[0048] Preferably, in step S4, the drying temperature is 60-120℃, and the time is 10-30 min.

[0049] Further preferably, in step S4, the drying temperature is 100℃, and the time is 20 min.

[0050] Further preferably, in step S4, the drying temperature is 60℃, and the time is 30 min.

[0051] Preferably, in step S4, the high-temperature heat treatment refers to maintaining the temperature at 400-600℃ under vacuum conditions for 60-120 min.

[0052] Further preferably, in step S4, the high-temperature heat treatment temperature is 500℃, and the heat treatment time is preferably 90 min.

[0053] In the present application, high-temperature heat treatment can further reduce the porosity and internal stress of the platinum plating layer.

[0054] Preferably, the electroplating method for preparing a platinum plating layer on the surface of a titanium plate by using an acidic platinum plating solution comprises the following steps:

[0055] (1) ultrasonic cleaning the titanium plate in anhydrous ethanol solution for 20 minutes, then using 3wt.% metal degreasing agent to remove oil and grease from the titanium plate for 15 minutes at 60°C; then using 20ml / L acetone solution to ultrasonic clean for 5 minutes, and then using deionized water to clean and dry for standby.

[0056] (2) using a mixed solution of hydrofluoric acid, nitric acid, polyethylene glycol and deionized water to remove the oxide film of the titanium plate, and then using a mixed acid solution of hydrochloric acid, phosphoric acid and pure water to acid etch the titanium plate, chemically etching the surface of the titanium plate, forming a micro-etching structure by dissolving the surface layer material of titanium, thereby increasing the surface area and roughness, and improving the adhesion of the titanium plate to other materials and its interaction with the environment.

[0057] (3) using the acid-treated titanium plate in step (2) as the cathode and a pure platinum mesh as the anode, depositing platinum on the surface of the titanium plate by direct current electrodeposition.

[0058] (4) cleaning the platinum-coated titanium plate with deionized water at room temperature, and then drying it in an oven.

[0059] (5) placing the dried titanium plate in a vacuum furnace for high-temperature heat treatment to further enhance the adhesion of the plating layer.

[0060] In a third aspect, the present application provides a platinum-coated titanium plate prepared by using the acidic platinum plating solution to prepare a platinum plating layer on the surface of the titanium plate.

[0061] Preferably, the platinum-coated titanium plate comprises a titanium plate and a platinum plating layer thereon, and the thickness of the platinum plating layer is 0.20-0.30μm.

[0062] Preferably, the platinum plating layer is obtained by closely arranging platinum particles on the titanium plate, and the particle size of the platinum particles is 150nm-250nm.

[0063] Further preferably, the platinum-coated titanium plate is used for electrolytic water hydrogen production.

[0064] The alkaline platinum plating solution has some disadvantages, such as low deposition rate, poor plating layer quality, difficulty in controlling plating layer uniformity, and low adhesion. The alkaline plating solution is prone to produce colloidal or turbid liquid and is accompanied by a pungent odor, resulting in high production difficulty and high production cost. The pH value of the alkaline plating solution is high, and the equipment needs higher corrosion resistance, increasing the maintenance cost. The alkaline platinum plating solution has certain disadvantages in efficiency, plating layer quality and process control compared with the acidic platinum plating solution.

[0065] The acidic platinum plating solution of the present application has multiple advantages compared to neutral and alkaline electroplating solutions, mainly reflected in higher deposition rate and higher plating layer quality, capable of forming uniform, dense and smooth platinum layer with stronger adhesion, reducing the risk of plating layer peeling. In addition, the process control of acidic electroplating solution is relatively simple and stable, suitable for large-scale production, the applicability of acidic electroplating platinum solution is strong, especially the application effect on metal substrate is better, the waste liquid treatment is convenient, and it is suitable for various industrial needs.

[0066] The acidic platinum plating solution of the present application uses sulfamic acid as a buffer and complexing agent, sulfuric acid as a conductive agent, OP-10 as a wetting agent and dispersing agent, and benzotriazole as a brightener and corrosion inhibitor, to prepare an acidic platinum plating solution with a pH value of 0.5-3.0, so that the plating solution has good electrodeposition capacity. The two acid additives (sulfuric acid and sulfamic acid) in the acidic platinum plating solution can significantly improve the adhesion of the plating layer and improve various deficiencies in the electroplating process, such as uneven plating layer, low quality, unstable deposition rate and low adhesion, etc. By adjusting the composition of the electroplating solution and the current density, these additives can effectively promote the uniformity, density and gloss of the plating layer, improve the adhesion of the plating layer, and enhance the stability and efficiency of the process. At the same time, the additives can also reduce the occurrence of side reactions, thereby improving the controllability and production quality of the platinum plating process. The synergistic effect of multiple additives can significantly improve the overall performance of the acidic platinum plating process by optimizing various parameters in the electroplating process, ensuring the consistency and stability of the plating layer quality, and further enhancing production efficiency.

[0067] The present application can control the thickness of platinum plating layer on the surface of titanium plate to 0.20-0.30 μm by using pH-stable acidic electroplating solution and two-step pretreatment of titanium plate. The titanium substrate surface platinum particle size is significantly reduced, and the particle arrangement is more compact, optimizing the degree of platinum layer particle refinement, improving the conductivity and corrosion resistance of titanium plate. In the electroplating process, the uniform thin plating layer with a thickness of 0.20-0.30 μm, the platinum particle diameter is small and closely arranged, ensuring good catalytic performance and high reaction activity. The fine and compact arrangement of platinum particles enhances the electrode stability, reduces the consumption of noble metals and production cost, significantly improves the catalytic effect, service life and overall production benefit.

[0068] The acidic platinum plating solution of the present application uses sulfuric acid and sulfamic acid as acids in the solution to maintain the stability of pH, without the need for continuous pH adjustment, thereby ensuring uniform deposition of platinum layer and excellent plating layer quality during electrodeposition. Among them, sulfuric acid (through its HSO4 - / SO4 2- buffer pair) and sulfamic acid (through its H2NSO3H / H2NSO3 -The conjugate acid-base pairs in solution form a mixed buffer system. Their pKa values are similar (about 1.99 and 1.0), both target the low pH range (0-3), and their effective buffer ranges significantly overlap (about 1-2). Through the respective ionization equilibrium of the conjugate acid-base pairs, they can synergistically consume a small amount of added acid (H + ) or base (OH - ), thereby stabilizing the pH value of the solution, especially in the pH region where they are jointly effective (such as around pH ~ 1.5).

[0069] The stable pH value can effectively avoid the instability of the plating layer quality caused by pH fluctuations, improving the controllability and efficiency of the deposition process. Acidic platinum plating solution shows good effect in reducing platinum metal waste, facilitates platinum source recovery, and has certain advantages in environmental protection. The use of harmful chemicals in the composition of the plating solution is less, and the harmful substance content of the waste liquid can be effectively controlled, reducing the pollution to the environment. Therefore, the acidic platinum plating solution shows excellent performance in stability, efficiency and environmental protection, and has the potential to be widely used in the fields of electronics, energy, catalysis, etc.

[0070] The core advantage of the present application compared to the prior art is: through the innovative plating solution system (containing OP-10 wetting agent / dispersant and benzotriazole brightener / corrosion inhibitor multifunctional synergistic additive combination, mild acidic environment with pH 0.5-3.0, and flexibility of 5 kinds of platinum sources), fine three-step pretreatment process (oil removal → demolding treatment → surface activation treatment significantly improves the interfacial bonding force) and high current density short-time electroplating (1.0-5.0 A / dm 2 , 1-8 min), controllable preparation of ultra-thin (0.20-0.30 μm) nanoporous platinum coating (particle size 150-250 nm, low porosity) can be realized, thereby reducing the consumption cost of noble metals. The structure endows the coating with high specific electrochemical active area, combined with the platinum-titanium interface diffusion strengthened by vacuum heat treatment at 400-600°C, which significantly reduces the platinum usage (cost optimization) while having excellent bonding strength, electrical conductivity and corrosion resistance, especially suitable for high-demand scenarios such as electrolytic water hydrogen production.

[0071] Compared with the prior art, the present application has the following beneficial effects:

[0072] (1)The application prepares an acidic platinum plating solution with pH value between 0.5 and 3.0 by dissolving a platinum source, sulfamic acid, sulfuric acid, OP-10 and benzotriazole in water, the acidic platinum plating solution has excellent stability, uniform plating performance and deep plating capacity, the platinum plating layer prepared by the acidic platinum plating solution and the electroplating method has the advantages of uniformity, compactness, thin thickness, high surface bonding force between the platinum plating layer and the titanium plate, not easy to fall off, excellent conductivity and corrosion resistance, simple operation, short electroplating time and low consumption cost of noble metal.

[0073] (2)The acidic electroplating solution uses sulfamic acid as a buffer and a complexing agent, uses sulfuric acid as a conductive agent, uses OP-10 as a wetting agent and a dispersing agent, and uses benzotriazole as a brightener and a corrosion inhibitor, wherein the sulfamic acid can form a complex with platinum ions to improve the solubility of platinum, so that platinum can be uniformly deposited in the electroplating process; the sulfuric acid as a strong electrolyte can improve the conductivity of the electroplating solution and the stability of current conduction, thereby promoting the uniform reduction of platinum ions, improving the compactness and adhesion of the plating layer, and improving the uniformity and quality of the plating layer; the OP-10 can reduce the surface tension of the liquid, improve the coverage of the electroplating solution on the substrate surface, reduce the formation of bubbles, and further promote the uniform deposition of metal ions, so that the platinum plating layer prepared by the acidic electroplating solution has the advantages of uniformity, compactness, surface brightness, high coverage, no cracking and peeling, low porosity and excellent plating quality.

[0074] (3)The pH of the acidic platinum plating solution is stable, wherein the sulfuric acid and the sulfamic acid form a mixed buffer system due to the similar pKa values and the significant overlap of the effective buffer range, and the pH is stable through the synergistic effect of the respective ionization equilibrium and the conjugate acid-base pair, so that the pH does not need to be continuously adjusted, the stable pH can promote the uniform reduction of platinum ions, effectively avoid the unstable plating layer quality caused by pH fluctuation, and improve the controllability and efficiency of the deposition process.

[0075] (4)Before electroplating platinum, the application carries out acid treatment in two steps, first, a mixed acid A solution composed of hydrofluoric acid, nitric acid and polyethylene glycol is used to carry out demolding treatment on the surface of the titanium plate, so as to remove the oxides on the surface of the titanium plate, and then a mixed acid B solution composed of hydrochloric acid and phosphoric acid is used to carry out surface activation treatment on the titanium plate, so as to increase the surface area and roughness of the titanium plate, thereby greatly improving the adhesion of the platinum plating layer to the titanium plate, so that the prepared platinum plating layer does not fall off obviously in a strong acidic acid corrosion solution and has excellent corrosion resistance.

[0076] (5) The acid plating platinum solution of the present application has a lower platinum dosage, but the platinum plating layer prepared on the surface of the titanium plate by the electroplating method of the present application has a higher platinum content (the proportion can reach 53.66%), a thinner thickness (which can be controlled within 20-0.30 μm), a uniform thickness, a thickness standard deviation of 0.01-0.02, and a difference between the maximum and minimum thicknesses of no more than 40 nm, indicating that the acid plating platinum solution of the present application has excellent uniform plating performance and excellent deep plating capacity.

[0077] (6) The platinum particles in the platinum plating layer prepared by the present application are significantly reduced in size, and the particles are more closely arranged, thereby optimizing the particle refinement degree of the platinum layer, reducing the porosity of the platinum plating layer, and improving the conductivity of the titanium plate after plating platinum, and the contact resistance of the titanium plate after plating platinum is within the range of 3.5-5.0 mΩ / cm 2 The degree of fineness of the particles of the titanium plate after plating platinum can greatly improve the efficiency and yield of the catalytic reaction.

[0078] (7) The plating solution of the present application has stable pH, uniform plating performance and deep plating capacity, and is prepared by direct current deposition, which is simple to operate. The platinum plating layer prepared has excellent quality, has an ultrathin thickness, and still has excellent conductivity and corrosion resistance. The plating solution of the present application is more environmentally friendly, has a lower dosage of harmful chemicals and platinum in the plating solution, and is helpful to reduce environmental pollution. Therefore, the present application is more conducive to industrial production, and has the potential for wide application in the fields of electronics, energy and catalysis. BRIEF DESCRIPTION OF DRAWINGS

[0079] Figure 1 The scanning electron microscope image of the surface of the titanium plate of Example 1 after acid treatment (demolding + surface activation) with a magnification of 500 times.

[0080] Figure 2 The scanning electron microscope image of the surface of the titanium plate of Example 2 after acid treatment (demolding + surface activation) with a magnification of 500 times.

[0081] Figure 3 The surface photograph of the platinum-plated titanium plate prepared in Example 1.

[0082] Figure 4 The scanning electron microscope image of the surface of the platinum-plated titanium plate prepared in Example 1 with a magnification of 10,000 times.

[0083] Figure 5 The element content diagram of the platinum-plated titanium plate prepared in Example 1 under EDS surface scanning.

[0084] Figure 6 The element interval distribution diagram of the platinum-plated titanium plate prepared in Example 1 under EDS surface scanning.

[0085] Figure 7 Figure 1 is a surface point graph of the sample plate for thickness testing of the platinum content in the platinum plating layer of the sample plate using the XRF device. Figure 7 (a) is the front surface, Figure 7 (b) is the back surface.

[0086] Figure 8 Figure 2 is a physical comparison graph of Example 2 and Comparative Example 1.

[0087] Figure 9 Figure 3 is a physical comparison graph of Example 2 and Comparative Example 2.

[0088] Figure 10 Figure 4 is a physical comparison graph of the anti-falling experiment of Example 2 and Comparative Example 2. DETAILED DESCRIPTION

[0089] The present embodiment is implemented on the basis of the technical scheme of the present application, and gives a detailed implementation mode and specific operation process, but the protection scope of the present application is not limited to the following examples.

[0090] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present application are conventional reagents, methods, instruments and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0091] The present application provides an acidic platinum plating solution for preparing a platinum plating layer on the surface of a titanium plate, which is an aqueous solution comprising 1-50 g / L of a platinum source, 30-90 g / L of sulfamic acid, 2-20 ml / L of sulfuric acid, 0.1-5.0 g / L of OP-10, and 0.1-5.0 g / L of benzotriazole, calculated as platinum, the pH value of the acidic platinum plating solution is 0.5-3.0, and the platinum source is selected from one or more of dinitrosyl diamino platinum, potassium tetranitro platinum sulfate, chloroplatinic acid, dinitrosyl platinous sulfate, and platinum nitrate, which is prepared by adding the platinum source, sulfamic acid, sulfuric acid, OP-10, and benzotriazole into deionized water according to the proportion and heating to dissolve.

[0092] The present application also provides an electroplating method for preparing a platinum plating layer on the surface of a titanium plate using the acidic platinum plating solution, comprising the following steps:

[0093] S1: oil removal and degreasing treatment of the titanium plate;

[0094] S2: acid treatment of the titanium plate after oil removal and degreasing treatment: sequentially performing film removal treatment and surface activation treatment;

[0095] S3: placing the titanium plate after acid treatment in the acidic platinum plating solution and electroplating platinum by direct current deposition method;

[0096] S4: The titanium plate after electroplating is sequentially cleaned, dried, and high-temperature treated to obtain a platinum-plated titanium plate.

[0097] The application will be described in detail below with reference to the drawings and specific examples.

[0098] Example 1

[0099] In this example, an acidic platinum plating solution is first prepared, which comprises the following components:

[0100] 10 g / L chloroplatinic acid, 30 g / L sulfamic acid, 2 ml / L sulfuric acid, 0.1 g / L OP-10, 0.5 g / L benzotriazole, and the rest is deionized water. The platinum source and each additive component are added to deionized water in a proportioning amount, and then the raw materials are stirred at 95°C using a magnetic heating stirrer to completely dissolve and form a stable solution state.

[0101] The pH value of the obtained platinum plating solution is in the range of 0.5-3.0. Since the acidic platinum plating solution body electrolyte is stable, the pH is stable and does not need to be continuously adjusted.

[0102] In this example, the method for electroplating platinum on the surface of a titanium plate using the acidic platinum plating solution described above is as follows:

[0103] (1) Oil removal and degreasing: Before electroplating, the titanium plate is ultrasonically cleaned with anhydrous ethanol solution for 20 minutes, and then 3 wt.% metal oil removal and degreasing agent is used to remove oil and grease from the titanium plate at 60°C for 15 minutes; then 20 ml / L of acetone solution is used for ultrasonic cleaning for 5 minutes, and then deionized water is used for cleaning and drying for standby;

[0104] (2) Acid treatment: 5 mL of hydrofluoric acid, 15 mL of nitric acid, 5 mL of polyethylene glycol, and 100 mL of deionized water are prepared into a mixed acid A solution, the treated titanium plate is placed in the mixed acid A solution at room temperature for 4 min of film removal treatment to achieve the film removal effect, and then 5 mL of hydrochloric acid, 5 mL of phosphoric acid, and 100 mL of deionized water are prepared into a mixed acid B solution for surface activation treatment at 40°C for 40 min. Through acid treatment, the titanium plate surface has a certain roughness;

[0105] (3) Platinum plating: The titanium plate after acid treatment is repeatedly washed with deionized water several times to remove the residual mixed acid solution on the surface, and then placed in the platinum plating solution for electroplating, with the electroplating conditions being: current density 1 A / dm 2 , plating solution temperature 65°C, electroplating time 8 min, and area ratio of anode to cathode 1:4;

[0106] (4) Cleaning: The titanium plate after platinum plating is rinsed with deionized water at room temperature for 10 s, and then placed in a 100°C drying oven for 15 min;

[0107] (5) Post-processing: After drying, the titanium plate is placed in a vacuum furnace at 400°C for high-temperature baking for 120 min to obtain a platinum-coated titanium plate.

[0108] Example 2

[0109] This example first prepares an acidic platinum plating solution containing the following components:

[0110] 15 g / L chloroplatinic acid, 40 g / L sulfamic acid, 3.5 ml / L sulfuric acid, 0.3 g / L OP-10, 1.0 g / L benzotriazole, and the balance is deionized water. The platinum source and additives are added to the deionized water in the specified amounts, and then the raw materials are stirred to completely dissolve to form a solution at 95°C using a magnetic heating stirrer.

[0111] The pH of the obtained platinum plating solution is in the range of 0.5-3.0. Since the acidic platinum plating solution is stable, the pH is stable and does not need to be continuously adjusted.

[0112] In this example, the method for electroplating platinum on the surface of a titanium plate using the acidic platinum plating solution described above is as follows:

[0113] (1) Oil removal and degreasing: Before electroplating, the titanium plate is ultrasonically cleaned with anhydrous ethanol solution for 20 minutes, then 3 wt.% metal oil removal and degreasing agent is used to remove oil and grease from the titanium plate at 60°C for 15 minutes; then 20 ml / L of acetone solution is used for ultrasonic cleaning for 5 minutes, and then deionized water is used for washing and drying for standby;

[0114] (2) Acid treatment: 5 ml of hydrofluoric acid, 15 ml of nitric acid, 5 ml of polyethylene glycol, and 100 ml of deionized water are mixed to prepare a mixed acid A solution, the treated titanium plate is placed in the mixed acid A solution at room temperature for 5 min of film removal treatment to achieve the film removal effect, then 10 ml of hydrochloric acid, 10 ml of phosphoric acid, and 80 ml of deionized water are mixed to prepare a mixed acid B solution, and the surface activation treatment is carried out at 40°C for 30 min, through acid treatment so that the titanium plate surface has a certain roughness;

[0115] (3) Platinum plating: The titanium plate after acid treatment is repeatedly rinsed with deionized water to remove the residual mixed acid solution on the surface, and then placed in the platinum plating solution for electroplating, the electroplating conditions are: current density is 2 A / dm 2 , the plating solution temperature is 65°C, the electroplating time is 4 min, and the area ratio of the anode to the cathode is 1:4;

[0116] (4) Cleaning: After platinum plating, the titanium plate is rinsed with deionized water at room temperature for 10 s, and then placed in a 100°C drying oven for 15 min;

[0117] (5) Post-processing: the dried titanium plate is placed in a vacuum furnace at 500°C for high-temperature baking for 90 min to obtain a platinum-coated titanium plate.

[0118] Example 3

[0119] This example first prepares an acidic platinum plating solution containing the following components:

[0120] 20 g / L chloroplatinic acid, 50 g / L sulfamic acid, 5 ml / L sulfuric acid, 0.5 g / L OP-10, 1.5 g / L benzotriazole, and the balance is deionized water. The platinum source and additives are added to the deionized water in the proportioning amount, and then the raw materials are stirred to completely dissolve to form a solution state at 95°C using a magnetic heating stirring table.

[0121] The pH value of the obtained platinum plating solution is in the range of 0.5-3.0, and because the acidic platinum plating solution body electrolyte is stable, the pH is stable and does not need to be continuously adjusted.

[0122] In this example, the method for electroplating platinum on the surface of a titanium plate using the acidic platinum plating solution described above is as follows:

[0123] (1) Oil removal and degreasing: before electroplating, the titanium plate is ultrasonically cleaned with anhydrous ethanol solution for 20 minutes, and then 3 wt.% metal oil removal and degreasing agent is used to remove oil and grease from the titanium plate at 60°C for 15 minutes; then 20 ml / L of acetone solution is used for ultrasonic cleaning for 5 minutes, and then deionized water is used for washing and drying for standby;

[0124] (2) Acid treatment: 5 ml of hydrofluoric acid, 15 ml of nitric acid, 5 ml of polyethylene glycol, and 100 ml of deionized water are prepared into a mixed acid A solution, the treated titanium plate is placed in the mixed acid A solution at room temperature for 6 min of acid etching treatment to achieve the effect of removing the film, and then 15 ml of hydrochloric acid, 15 ml of phosphoric acid, and 100 ml of deionized water are prepared into a mixed acid B solution for surface activation treatment at 40°C for 20 min to achieve a certain roughness of the titanium plate surface by acid etching;

[0125] (3) Platinum plating: the titanium plate after acid treatment is repeatedly rinsed with deionized water to remove the residual mixed acid solution on the surface, and then placed in the platinum plating solution for electroplating, with the electroplating conditions being: current density of 3 A / dm 2 , plating solution temperature of 66°C, time of 3 min, and area ratio of anode to cathode of 1:4;

[0126] (4) Cleaning: the titanium plate after plating is rinsed with deionized water at room temperature for 10 s, and then placed in a 100°C drying oven for 15 min;

[0127] (5) Post-processing: the dried titanium plate is placed in a vacuum furnace at 600°C for high-temperature baking for 60 min to obtain a platinum-coated titanium plate.

[0128] Comparative Example 1

[0129] The comparative example comprises the following components: 15 g / L chloroplatinic acid, 10 g / L sulfamic acid, 3.5 ml / L sulfuric acid, 0.3 g / L OP-10, 1.0 g / L benzotriazole, and the balance is deionized water. The platinum source and additives are added to deionized water in the proportioning amount, and then the raw materials are stirred to completely dissolve to form a solution at 95°C using a magnetic heating stirrer.

[0130] The pH value of the obtained plating platinum solution is in the range of 0.5-3.0, and because the acidic plating platinum solution is stable, the pH value is stable and does not need to be continuously adjusted.

[0131] In the example, the method for electroplating platinum on the surface of a titanium plate using the acidic plating platinum solution described above is as follows:

[0132] (1) Oil removal and degreasing: Before electroplating, the titanium plate is ultrasonically cleaned with anhydrous ethanol solution for 20 minutes, and then oil removal and degreasing are performed on the titanium plate using a 3 wt.% metal oil removal and degreasing agent at 60°C for 15 minutes; then the titanium plate is ultrasonically cleaned with 20 ml / L of acetone solution for 5 minutes, and then deionized water is used for washing and drying for standby;

[0133] (2) Acid treatment: 5 ml of hydrofluoric acid, 15 ml of nitric acid, and 5 ml of polyethylene glycol are prepared into a mixed acid A solution of 100 ml of deionized water, the treated titanium plate is placed in the mixed acid A solution at room temperature for 5 min of demolding treatment to achieve the demolding effect, and then 10 ml of hydrochloric acid, 10 ml of phosphoric acid, and 80 ml of deionized water are prepared into a mixed acid B solution for surface activation treatment at 40°C for 30 min, so that the titanium plate surface has a certain roughness through the surface activation treatment;

[0134] (3) Plating platinum: The titanium plate after acid treatment is repeatedly washed with deionized water to remove the residual mixed acid solution on the surface, and then placed in the plating platinum solution for electroplating, the electroplating conditions are: current density is 2 A / dm 2 , the plating solution temperature is 65°C, the electroplating time is 4 min, and the area ratio of the anode to the cathode is 1:4;

[0135] (4) Cleaning: the titanium plate after plating platinum is rinsed with deionized water at room temperature for 10 s, and then placed in a drying oven at 100°C for 15 min;

[0136] (5) Post-treatment: the dried titanium plate is placed in a vacuum furnace at 500°C for high-temperature baking for 90 min to obtain a platinum-plated titanium plate.

[0137] Comparative Example 2

[0138] This comparative example contains the following components: 15g / L chloroplatinic acid, 40g / L sulfamic acid, 3.5ml / L sulfuric acid, 0.3g / L OP-10, and 1.0g / L benzotriazole, with the remainder added in deionized water. The platinum source and additives were added to the deionized water in the appropriate proportions, and the materials were stirred at 95°C using a magnetic heating stirrer to completely dissolve the ingredients and form a solution.

[0139] The pH value of the platinum plating solution is measured to be in the range of 0.5 to 3.0. Since the acidic platinum plating liquid electrolyte is stable, the pH is stable and does not need to be continuously adjusted.

[0140] In this embodiment, the method of electroplating platinum on the surface of the titanium plate using the acidic platinum plating solution as described above is as follows:

[0141] (1) Degreasing: Before electroplating, the titanium plate was ultrasonically cleaned with anhydrous ethanol solution for 20 minutes, and then degreased with a 3 wt.% metal degreasing agent at 60°C for 15 minutes; then ultrasonically cleaned with a 20 ml / L acetone solution for 5 minutes, and then rinsed with deionized water and dried for later use;

[0142] (2) Acid treatment: 5 ml of hydrofluoric acid, 15 ml of nitric acid, 5 ml of polyethylene glycol and 100 ml of deionized water are prepared into a mixed acid A solution. The treated titanium plate is placed in the mixed acid A solution at room temperature for 5 minutes to achieve the demolding effect.

[0143] (3) Platinum plating: The titanium plate after the stripping treatment is repeatedly rinsed with deionized water to remove the residual mixed acid solution on the surface, and then placed in the platinum plating solution for electroplating. The electroplating conditions are: current density 2A / dm 2 , the plating temperature is 65℃, the plating time is 4min, and the area ratio of the electroplating anode to the cathode is 1:4;

[0144] (4) Cleaning: Rinse the platinum-plated titanium plate with deionized water at room temperature for 10 seconds, then place it in a drying oven at 100°C and dry it for 15 minutes;

[0145] (5) Post-treatment: The dried titanium plate was placed in a vacuum furnace at 500°C for high-temperature baking for 90 minutes to obtain a platinum-coated titanium plate.

[0146] The titanium plates of Examples 1 and 2 were placed under a scanning electron microscope for observation after acid treatment (demolding + surface activation treatment). Figure 1 and Figure 2 As shown in Figure 2, the surface of the titanium plate after treatment with different concentrations of acid has a certain degree of roughness, so the acid treatment as a pretreatment can enhance the bonding strength between the titanium plate and the platinum coating, such as Figure 2 As shown in the figure, the surface roughness of the titanium plate after acid etching is Figure 1The adhesion between the titanium plate and the plating layer is improved.

[0147] The titanium plate after electroplating in Example 1 is shown in FIG. Figure 3 The surface of the titanium plate after electroplating is dense, without peeling and cracking, and the plating layer surface is closely arranged, indicating that the acidic electroplating solution and the electroplating method in the application are beneficial to forming a dense and closely distributed platinum plating layer on the surface of the titanium plate.

[0148] The platinum-plated titanium plate after electroplating in Example 1 is observed under a scanning electron microscope, and the scanning electron microscope image of the platinum-plated titanium plate surface magnified by 10,000 times is shown in FIG. Figure 4 As can be seen from the figure, the platinum particles in the platinum plating layer have a small particle size of 150-250 nm, and the particles are closely arranged, and the porosity of the platinum plating layer is also low.

[0149] The platinum-plated titanium plate prepared in Example 1 is subjected to EDS surface scanning under an X-ray energy spectrometer to obtain the surface element composition content distribution information of the platinum-plated titanium plate. Figures 5-6 Table 1 is the element content diagram of the platinum-plated titanium plate prepared in Example 1 under EDS point scanning. As can be seen from Table 1 and Figures 5-6 It can be seen from Table 1 and

[0150] Table 1: Element content diagram of the platinum-plated titanium plate prepared in Example 1 under EDS point scanning

[0151]

[0152]

[0153] The detection depth of EDS is in the nanometer to micrometer level, which is suitable for surface analysis and micron-level element distribution research. Since the platinum plating layer is thin, the EDS measurement result contains the platinum plating layer and the titanium element in the titanium substrate within microns, and the preparation of a thinner platinum plating layer can effectively reduce the process cost and provide the possibility for commercial mass production.

[0154] The platinum plating solution formula and the selected parameters in the platinum plating step of Examples 1-3 and Comparative Examples 1 and 2 are shown in Table 2 and Table 3:

[0155] Table 2: Platinum plating solution formula of Examples 1-3 and Comparative Examples 1-2

[0156] Component Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Chloroplatinic acid 5 g / L 7.5 g / L 10 g / L 7.5 g / L 7.5 g / L Sulfamic acid 30 g / L 40 g / L 50 g / L 10 g / L 40 g / L Sulfuric acid 2 ml / L 3.5 ml / L 5 ml / L 3.5 ml / L 3.5 ml / L OP-10 0.1 g / L 0.3 g / L 0.5 g / L 0.3 g / L 0.3 g / L Benzotriazole 0.5 g / L 1.0 g / L 1.5 g / L 1.0 g / L 1.0 g / L

[0157] Table 3: Selected parameters in the platinum plating step of Examples 1-3 and Comparative Examples 1-2

[0158]

[0159]

[0160] The platinum-plated titanium plates prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to coating thickness measurement using an X-ray fluorescence spectrometer (XRF) instrument model XAU, and the thickness of 10 points on the front and back surfaces of the platinum-plated titanium plates was tested (the points were taken as shown in Figure 7 The thickness distribution of the platinum coating on the platinum-plated titanium plates prepared in Examples 1-3 and Comparative Examples 1-2 is shown in Table 4 by comparing the average value and standard deviation data to systematically characterize the thickness distribution of the platinum coating on the sample plates.

[0161] Table 4: Average value of the coating thickness on the surface of the platinum-plated sample plates measured using XRF for the platinum coating of Examples 1-3 and Comparative Examples 1-2

[0162]

[0163] As can be seen from Table 4, in Examples 1-3 and Comparative Examples 1-2, the thickness of the platinum coating on the platinum-plated titanium plates prepared in Example 1-3 is less than 0.30 μm, the standard deviation is 0.01-0.02, and the difference between the maximum and minimum thickness in Example 1-3 is not more than 40 nm, indicating that the acidic platinum plating solution of the present application has excellent uniform plating performance and excellent deep plating capacity, the stable formula ensures the long-term stability of the plating solution, and at the same time has excellent electroplating performance, can uniformly and high-quality deposit platinum coating, and produce products with excellent high and low temperature acid corrosion resistance and excellent adhesion, meeting the needs of industrial production. However, compared with Example 2, the concentration of sulfamic acid in Comparative Example 1 is 10 g / L, which is 1 / 4 of the concentration of Example 2, and as a buffer, the buffering capacity is weakened during electroplating, and the local pH change is difficult to buffer, resulting in uneven plating, and the adhesion of the coating is weakened and roughness occurs, as shown in Figure 8 The surface color after high temperature treatment is uniform and the adhesion has no peeling and falling phenomenon, and the standard deviation of the thickness test is 0.05, indicating that the platinum layer thickness is uneven. In Comparative Example 2, only the titanium plate surface was subjected to demolding treatment, and the titanium exposed to the air will form a dense oxide film (TiO2) instantaneously, resulting in failure to plate on the coating, and the adhesion is very weak. As shown in Figure 9 Macroscopic observation shows that only demolding cannot guarantee the surface adhesion.

[0164] Table 5: Conductive performance of the platinum-plated titanium plates in Examples 1-3 and Comparative Examples 1-2

[0165]

[0166] The conductive property of the platinum plated titanium plates of Examples 1-3 and Comparative Examples 1-2 was examined by testing the contact resistance of the platinum plated titanium plates using a direct current low resistance tester JK2511, and the results are shown in Table 5. The contact resistance of the platinum plated titanium plates of Examples 1-3 was in the range of 3.5-5.0 mΩ / cm, while the contact resistance of the platinum plated titanium plates of Comparative Examples 1 and 2 was in the range of 5.0 mΩ / cm or more, and the contact resistance of the titanium plates without plating after the pre-treatment was maintained at 8 mΩ / cm or more. 2 2 2 The above results show that the conductive property of the platinum plated titanium plates of the present application is improved.

[0167] The platinum plated titanium plates prepared in Examples 1-3 and Comparative Examples 1-2 were immersed in an acid corrosion solution for 7 days, and an anti-falling test was performed to examine the corrosion resistance of the plated layer, and the test results are shown in Table 6. The test results of Examples 2 and Comparative Example 1 are shown in the photographs of Figure 10

[0168] Table 5: Corrosion resistance of the platinum plated titanium plates of Examples 1-3 and Comparative Examples 1-2

[0169]

[0170] According to the results of Table 6, Figure 10 it can be seen that there is almost no falling in the strong acidic acid corrosion solution in Examples 1-3, while there is obvious falling in Comparative Examples 1-2, which shows that the ultra-thin coating prepared using the plating bath formulation and the plating method of the present application has a strong binding force with the titanium plate and has good corrosion resistance.

[0171] The above description of the examples is for the purpose of enabling one of ordinary skill in the art to understand and use the present application. It will be apparent to those skilled in the art that various modifications and variations can be made to the examples without departing from the spirit and scope of the present application. Thus, it is intended that the present application cover modifications and variations of this application provided they come within the scope of the appended claims and their equivalents.​​​

Claims

1. An acidic platinum plating solution for preparing a platinum coating on a titanium plate surface, characterized in that: The acidic platinum plating solution is an aqueous solution comprising the following components: 1-50 g / L platinum source, 30-90 g / L aminosulfonic acid, 2-20 ml / L sulfuric acid, 0.1-5.0 g / L O-10, and 0.1-5.0 g / L benzotriazole, based on platinum. The pH value of the acidic platinum plating solution is 0.5-3.

0.

2. The acidic platinum plating solution for preparing a platinum coating on a titanium plate surface according to claim 1, characterized in that: The platinum source is selected from one or more of dinitrosodiammineplatinum, potassium tetranitroplatinate, chloroplatinic acid, dinitrosoplatinous acid sulfate or platinum nitrate.

3. The acidic platinum plating solution for preparing a platinum coating on a titanium plate surface according to claim 1, characterized in that: According to the ratio, platinum source, aminosulfonic acid, sulfuric acid, OP-10 and benzotriazole are added to deionized water and heated to dissolve, wherein aminosulfonic acid serves as a buffer and complexing agent, sulfuric acid serves as a conductive agent, benzotriazole serves as a brightener and corrosion inhibitor, and OP-10 serves as a wetting agent and dispersant.

4. An electroplating method for preparing a platinum coating on a titanium plate surface using the acidic platinum plating solution according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1: Degreasing and degreasing the titanium plate; S2: Acid treatment is performed on the titanium plate after degreasing and deoiling: demolding treatment and surface activation treatment are performed in sequence: S3: placing the acid-treated titanium plate in an acidic platinum plating solution and electroplating platinum using a direct current electrodeposition method; S4: The electroplated titanium plate is sequentially cleaned, dried, and subjected to high-temperature heat treatment to obtain a platinum-plated titanium plate.

5. The electroplating method according to claim 4, wherein: In step S1, the degreasing treatment refers to cleaning the titanium plate with anhydrous ethanol, then degreasing the titanium plate with a metal degreasing and degreasing agent, and then washing the titanium plate with an acetone aqueous solution and deionized water in sequence and drying; Among them, the use of anhydrous ethanol for cleaning refers to ultrasonic cleaning for 15-25 minutes, the concentration of the metal degreasing and degreasing agent is 2-5wt.%, the degreasing treatment refers to degreasing and degreasing the titanium plate at 50-70°C for 10-20 minutes, and the use of acetone aqueous solution for cleaning refers to ultrasonic cleaning with 15-25ml / L acetone aqueous solution for 3-8 minutes.

6. The electroplating method according to claim 4, wherein: In step S2, the demolding treatment refers to placing the titanium plate in a mixed acid A solution for demolding treatment at room temperature for 4-8 minutes; The mixed acid A solution includes hydrofluoric acid, nitric acid, polyethylene glycol, and deionized water, and the volume ratio of hydrofluoric acid, nitric acid, polyethylene glycol, and deionized water is 5-20 mL: 10-50 mL: 1-10 mL: 90-110 mL.

7. The electroplating method according to claim 4, wherein: In step S2, the surface activation treatment refers to placing the titanium plate after the demolding treatment in a mixed acid B solution and treating it at 40-60° C. for 20-40 minutes; The mixed acid B solution includes hydrochloric acid, phosphoric acid, and deionized water, and the volume ratio of hydrochloric acid, phosphoric acid, and deionized water is 5-30 mL: 5-30 mL: 80-110 mL.

8. The electroplating method according to claim 4, wherein: In step S3, a pure platinum mesh is used as an anode and an acid-treated titanium plate is used as a cathode. The area ratio of the anode to the cathode is 1:2-6. The temperature of the acidic platinum plating solution is 40-70°C. The current density during the platinum electroplating is 1.0-5.0 A / dm 2 , the electroplating time is 1-8min.

9. The electroplating method according to claim 4, wherein: In step S4, the cleaning refers to rinsing with deionized water at room temperature for 10-20 seconds, the drying temperature is 60-120°C and the time is 10-30 minutes, and the high-temperature heat treatment refers to heat treatment at 400-600°C under vacuum conditions for 60-120 minutes.

10. A platinum-plated titanium plate, obtained by preparing a platinum coating on the surface of a titanium plate using the acidic platinum plating solution according to any one of claims 1 to 3, the platinum-plated titanium plate comprising a titanium plate and a platinum coating thereon, the platinum coating having a thickness of 0.20 to 0.30 μm, and the platinum coating being obtained by closely arranging platinum particles on the titanium plate, the particle size of the platinum particles being 150 nm to 250 nm.

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