An acid-resistant high-activity ruthenium-based mixed metal oxide titanium anode and its preparation method

Abstract

The present invention discloses an acid-resistant high-activity ruthenium-based mixed metal oxide titanium anode and a preparation method thereof, which relates to the technical field of titanium anode preparation. The preparation method includes the following steps: preparing a modified titanium matrix mixture, preparing a modified titanium anode matrix, preparing a coating solution powder, preparing a ruthenium-based metal oxide coating solution, pre-treating the modified titanium anode matrix, and preparing a ruthenium-based mixed metal oxide titanium anode. By mixing titanium powder with vanadium powder, the activity of the titanium electrode matrix is improved, or by mixing titanium powder with graphene nanopowder or carbon nanotube powder, a preparation mixture of the titanium matrix is obtained, thereby enhancing the electrical conductivity of the titanium electrode. By performing recrystallization annealing treatment on the mixture, the lattice structure of the mixture is changed, the grain size and the connection distribution state are regulated, and the activity of the titanium anode is further enhanced. By coating the ruthenium-based metal oxide coating solution, the acid resistance and corrosion resistance of the titanium anode are improved, thereby prolonging the service life of the titanium anode.

Description

Technical Field

[0001] The present invention relates to the technical field of titanium anode preparation, and specifically to an acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode and a preparation method thereof. Background Art

[0002] The titanium anode, also known as the titanium electrode, is an anode made of metallic titanium and is widely used in many fields such as the chlor-alkali industry, wastewater treatment, electroplating, cathodic protection, electrochemical cells, and energy storage systems. Currently, the commonly used one is generally the coated titanium anode, but there are still problems such as poor activity of the titanium substrate, poor acid and corrosion resistance, and easy coating peeling during long-term use.

[0003] The defects of the existing titanium anodes are as follows:

[0004] 1. In the application document WO2012000440A1, the main consideration is to produce a titanium electrode material and a titanium electrode with a large current density and a small overpotential, without considering the problem of low activity of the titanium electrode metal substrate;

[0005] 2. In the patent document EP3202956A1, the main consideration is to coat a composite material coating on the surface of a titanium substrate to prepare a titanium electrode, without considering the problem that the coating is prone to peeling during long-term use of the electrode;

[0006] 3. In the application document US20110274968A1, the main consideration is to improve the thermal stability of the titanium electrode, without considering the problem of optimizing the coating solution to improve the acid and corrosion resistance of the titanium anode;

[0007] 4. In the patent document CN113120995B, the main consideration is to improve the electrocatalytic activity of the electrode by setting a coating, without considering the problem of uniformly distributing metal catalyst particles on the surface of the titanium electrode substrate. Summary of the Invention

[0008] The purpose of the present invention is to provide an acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode and a preparation method thereof to solve the problems raised in the above background art.

[0009] To achieve the above purpose, the present invention provides the following technical solution: A preparation method of an acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode, comprising the following steps:

[0010] Step 1: Prepare a modified titanium substrate mixture. Add titanium powder and vanadium powder to a blender in proportion, uniformly stir to obtain a mixture, and sinter the mixture to obtain a modified titanium substrate mixture;

[0011] Step 2: Prepare the modified titanium anode substrate. Perform recrystallization annealing on the modified titanium matrix mixture to obtain the titanium substrate raw material. Use a tablet press to press the titanium substrate raw material into shape to obtain the modified titanium anode substrate;

[0012] Step 3: Prepare the coating solution powder. Take ruthenium oxide, tin oxide, and nickel oxide metal powders and dry and crush them separately. Then mix the crushed metal powders to obtain ruthenium-based metal oxide powder. Take carbon black particles and cobalt hydroxide powder, crush them separately and then mix them to obtain the modified activator. Add the modified activator to the ruthenium-based metal oxide powder, stir and mix evenly to obtain the coating solution powder;

[0013] Step 4: Prepare the ruthenium-based metal oxide coating solution. Take the coating solution powder from Step 3 and mix and stir it with an organic solvent to obtain the ruthenium-based metal oxide coating solution;

[0014] Step 5: Pretreatment of the modified titanium anode substrate. Take the modified titanium anode substrate from Step 2 and perform pretreatment on the modified titanium anode substrate. Take a metal catalyst and dissolve it in an organic solvent, and add a catalyst dispersant and mix to obtain a catalyst solution. Coat the catalyst solution on the surface of the pretreated titanium anode substrate and dry it to obtain the titanium substrate;

[0015] Step 6: Prepare the ruthenium-based mixed metal oxide titanium anode. Take the ruthenium-based metal oxide coating solution from Step 4 and evenly coat it on the surface of the titanium substrate in Step 5 to obtain the ruthenium-based mixed metal oxide titanium anode precursor. Then perform sintering heat treatment on the precursor to obtain the ruthenium-based metal oxide titanium anode.

[0016] Preferably, in Step 1, the average particle size of the titanium powder and the vanadium powder is 80 - 130 μm, the ratio of the titanium powder to the vanadium powder is (8 - 16):1, the sintering temperature is 300 - 800 °C, the sintering time is 5 - 15 min, the heat preservation time is 10 - 25 min, and the sintering is carried out in an inert gas environment. The inert gas is one of nitrogen, argon, and helium.

[0017] Preferably, in Step 2, the heating temperature of the recrystallization annealing is 800 - 1200 °C, the heating time is 5 - 25 min, and the cooling time is 5 - 25 min.

[0018] Preferably, in Step 3, the mass ratio of ruthenium oxide, tin oxide, and nickel oxide in the ruthenium-based metal oxide powder is 1:(0.2 - 0.5):(0.2 - 0.4), the average particle size of ruthenium oxide, tin oxide, and nickel oxide is 50 - 110 μm, the average particle size of the carbon black particles and the cobalt hydroxide powder in the modified activator is 40 - 70 μm, and the mass ratio of the carbon black particles to the cobalt hydroxide powder is 1:(0.3 - 0.5).

[0019] Preferably, the mass ratio of the ruthenium-based metal oxide powder to the modified activator in the step 3 is 1:(0.1-0.5).

[0020] Preferably, the organic solvent in the step 4 is one of ethyl acetate, acetone, and methanol, the organic solvent in the step 5 is one of polyvinyl alcohol, methanol, ethanol, and toluene, the metal catalyst is one or more of palladium-based metal catalysts and platinum-based metal catalysts, and the catalyst dispersant is one of polyethylene glycol and polyethyleneimine.

[0021] Preferably, the steps for pre-treating the modified titanium anode substrate in the step 5 include sandblasting and polishing the modified titanium anode substrate, rinsing and degreasing the polished substrate, acid-etching the degreased substrate with a phosphoric acid solution or an oxalic acid solution for 30-50 min, and then rinsing with deionized water.

[0022] Preferably, the coating method for coating the ruthenium-based mixed metal oxide coating solution on the surface of the titanium substrate in the step 6 includes one of plasma electrophoresis deposition method, chemical vapor deposition method, dip coating method, and spraying method. The sintering temperature for sintering and heat-treating the precursor in the step 6 is 300-700 °C, the sintering time is 5-20 min, and the number of repetitions of coating, sintering, and heat-treating in the step 6 is 3-5 times.

[0023] An acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode is prepared by the above preparation method to obtain a ruthenium-based mixed metal oxide titanium anode.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] 1. In the present invention, by mixing titanium powder and vanadium powder, the activity of the titanium electrode substrate is improved, or by mixing titanium powder with graphene nanoflakes or carbon nanotube powder, a preparation mixture for the titanium substrate is obtained, thereby enhancing the electrical conductivity of the titanium electrode. By performing recrystallization annealing on the mixture, the lattice structure of the mixture is changed, and the grain size and connection distribution state are regulated, further enhancing the activity of the titanium anode.

[0026] 2. In the present invention, by pre-treating the titanium anode substrate through steps of grinding, degreasing, and acid-etching, micro-pits are formed on the surface of the titanium anode substrate. By coating a solution containing a metal catalyst on the surface of the titanium anode substrate, it is beneficial to improve the activity of the titanium anode and enhance the adhesion between the ruthenium-based mixed metal oxide coating and the surface of the titanium anode substrate, avoiding the phenomenon of peeling off of the ruthenium-based mixed metal oxide coating of the titanium anode and extending the service life of the titanium anode.

[0027] 3. The present invention mixes ruthenium-based metal oxides with other metal oxides, and modifies the ruthenium-based metal iron oxide coating powder by adding modified activator powder to prepare a highly active ruthenium-based mixed metal oxide coating solution, which is applied to the surface of the titanium anode substrate to protect the titanium anode, improve the acid resistance and corrosion resistance of the titanium anode, and thus extend the service life of the titanium anode.

[0028] 4. The present invention improves the dispersion uniformity of the metal catalyst in the organic solvent by adding a catalyst dispersant to the organic solvent mixed with the metal catalyst, so that the metal catalyst particles can be evenly distributed on the surface of the titanium anode substrate. DETAILED DESCRIPTION

[0029] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Embodiment 1:

[0031] Step 1: Prepare a modified titanium matrix mixture, add 50 parts of titanium powder and 5 parts of vanadium powder into a mixer, stir evenly to obtain a mixture, sinter the mixture in a nitrogen environment at a temperature of 500° C. for 10 minutes, and keep it warm for 15 minutes to obtain a modified titanium matrix mixture;

[0032] Step 2: preparing a modified titanium anode substrate, heating the modified titanium substrate mixture in step 1 at 900° C. for 8 min, then cooling it to 200-300° C. within 15 min, and performing recrystallization annealing to obtain a titanium substrate raw material, and using a tablet press to press the titanium substrate raw material to obtain a thin sheet-shaped modified titanium anode substrate;

[0033] Step 3: Prepare coating solution powder, take 5 parts of ruthenium oxide, 1.5 parts of tin oxide and 1.5 parts of nickel oxide metal powder and dry and crush them respectively to obtain ruthenium oxide, tin oxide and nickel oxide crushed powders with an average particle size of 60 to 80 μm, mix the crushed metal powders evenly to obtain ruthenium metal oxide powder, take 1 part of carbon black particles and 0.3 parts of cobalt hydroxide powder, crush them respectively and mix them to obtain a modified activator, add the modified activator to the ruthenium metal oxide powder, stir and mix evenly to obtain a coating solution powder;

[0034] Step 4: preparing a ruthenium metal oxide coating solution, taking the coating solution powder in step 3 and mixing it with 65 parts of an organic solvent to obtain a ruthenium metal oxide coating solution, wherein the organic solvent is one of ethyl acetate, acetone, and methanol;

[0035] Step 5: pretreatment of the modified titanium anode substrate, taking the modified titanium anode substrate in step 2, and pretreatment the modified titanium anode substrate, wherein the pretreatment steps are sandblasting and grinding the modified titanium anode substrate, rinsing and degreasing the polished substrate, etching the degreased substrate with a phosphoric acid solution or an oxalic acid solution for 30 to 50 minutes, and then rinsing with deionized water;

[0036] 3 parts of a metal catalyst are dissolved in 25 parts of an organic solvent, and 0.6 parts of a catalyst dispersant are added and mixed to obtain a catalyst solution, the catalyst solution is applied to the surface of the pretreated titanium anode substrate, and the titanium substrate is obtained after drying, wherein the metal catalyst is one or more of a palladium-based metal catalyst and a platinum-based metal catalyst, the organic solvent is one of polyvinyl alcohol, methanol, and ethanol, and the catalyst dispersant is one of polyethylene glycol and polyethyleneimine;

[0037] Step six: prepare a ruthenium-based mixed metal oxide titanium anode, take the ruthenium-based metal oxide coating solution in step four, and evenly coat it on the surface of the titanium substrate in step five, and the coating method is one of plasma electrophoretic deposition, vapor deposition, immersion pulling, and spraying to obtain a ruthenium-based mixed metal oxide titanium anode precursor, and then sinter the precursor at a temperature of 450°C for 10 minutes, and repeat the coating and sintering heat treatment 4 times to obtain a ruthenium-based mixed metal oxide titanium anode.

[0038] Embodiment 2:

[0039] Step 1: Prepare a modified titanium matrix mixture, add 78 parts of titanium powder and 6 parts of vanadium powder into a mixer, stir evenly to obtain a mixture, sinter the mixture in a nitrogen environment at a temperature of 700° C. for 12 minutes, and keep it warm for 20 minutes to obtain a modified titanium matrix mixture;

[0040] Step 2: preparing a modified titanium anode substrate, heating the modified titanium substrate mixture in step 1 at a temperature of 1100° C. for 12 minutes, then cooling to 300-350° C. within 20 minutes, and performing recrystallization annealing treatment to obtain a titanium substrate raw material, and using a tablet press to press the titanium substrate raw material to obtain a thin sheet-shaped modified titanium anode substrate;

[0041] Step 3: Prepare the coating solution powder. Take 6 parts of ruthenium oxide, 2.4 parts of tin oxide and 1.8 parts of nickel oxide metal powder, and dry and crush them respectively to obtain ruthenium oxide, tin oxide and nickel oxide crushed powder with an average particle size of 80 - 100 μm. Mix the crushed metal powders evenly to obtain ruthenium-based metal oxide powder. Take 1.8 parts of carbon black particles and 0.7 parts of cobalt hydroxide powder, crush them respectively and then mix to obtain a modified activator. Add the modified activator to the ruthenium-based metal oxide powder, stir and mix evenly to obtain the coating solution powder;

[0042] Step 4: Prepare the ruthenium-based metal oxide coating solution. Take the coating solution powder in Step 3 and mix and stir it with 110 parts of organic solvent to obtain the ruthenium-based metal oxide coating solution, and the organic solvent is one of ethyl acetate, acetone, and methanol;

[0043] Step 5: Pretreatment of the modified titanium anode substrate. Take the modified titanium anode substrate in Step 2 and perform pretreatment on it. The pretreatment steps are sandblasting and polishing the modified titanium anode substrate, rinsing and degreasing the polished substrate, acid etching the degreased substrate with phosphoric acid solution or oxalic acid solution for 30 - 50 min, and then rinsing with deionized water;

[0044] Take 6 parts of metal catalyst and dissolve it in 38 parts of organic solvent, add 0.8 part of catalyst dispersant and mix to obtain a catalyst solution. Coat the catalyst solution on the surface of the pretreated titanium anode substrate, and dry it to obtain a titanium substrate. The metal catalyst is one or more of palladium-based metal catalysts and platinum-based metal catalysts, the organic solvent is one of polyvinyl alcohol, methanol, and ethanol, and the catalyst dispersant is one of polyethylene glycol and polyethyleneimine;

[0045] Step 6: Prepare the ruthenium-based mixed metal oxide titanium anode. Take the ruthenium-based metal oxide coating solution in Step 4 and evenly coat it on the surface of the titanium substrate in Step 5. The coating method is one of plasma electrophoresis deposition method, chemical vapor deposition method, dip-coating method, and spraying method to obtain a ruthenium-based mixed metal oxide titanium anode precursor. Then, sinter and heat-treat the precursor at a temperature of 500 °C for 15 min, and repeat the coating, sintering and heat-treatment 4 times to obtain the ruthenium-based mixed metal oxide titanium anode.

[0046] Example 3:

[0047] Step 1: Prepare the modified titanium matrix mixture. Take 95 parts of titanium powder and 6 parts of vanadium powder and add them to a mixer, stir evenly to obtain a mixture. Sinter and process the mixture in a nitrogen environment at a temperature of 700 °C for 12 min and keep it warm for 20 min to obtain the modified titanium matrix mixture;

[0048] Step 2: Prepare the modified titanium anode substrate. Heat the modified titanium matrix mixture in Step 1 at 1200 °C for 15 min, and then cool it to 350 - 450 °C within 20 min for recrystallization annealing treatment to obtain the titanium substrate raw material. Use a tablet press to press the titanium substrate raw material into shape to obtain a flaky modified titanium anode substrate;

[0049] Step 3: Prepare the coating solution powder. Take 5 parts of ruthenium oxide, 2.5 parts of tin oxide, and 2 parts of nickel oxide metal powder, and dry and crush them respectively to obtain ruthenium oxide, tin oxide, and nickel oxide crushed powders with an average particle size of 90 - 105 μm. Mix the crushed metal powders evenly to obtain ruthenium-based metal oxide powder. Take 2.2 parts of carbon black particles and 1 part of cobalt hydroxide powder, crush and mix them respectively to obtain a modified activator. Add the modified activator to the ruthenium-based metal oxide powder, stir and mix evenly to obtain the coating solution powder;

[0050] Step 4: Prepare the ruthenium-based metal oxide coating solution. Take the coating solution powder in Step 3 and mix and stir it with 145 parts of an organic solvent to obtain the ruthenium-based metal oxide coating solution, and the organic solvent is one of ethyl acetate, acetone, and methanol;

[0051] Step 5: Pretreatment of the modified titanium anode substrate. Take the modified titanium anode substrate in Step 2 and perform pretreatment on it. The pretreatment steps are sandblasting and polishing the modified titanium anode substrate, rinsing and degreasing the polished substrate, acid etching the degreased substrate with phosphoric acid solution or oxalic acid solution for 30 - 50 min, and then rinsing with deionized water;

[0052] Dissolve 9 parts of a metal catalyst in 45 parts of an organic solvent, add 1.2 parts of a catalyst dispersant and mix to obtain a catalyst solution. Coat the catalyst solution on the surface of the pretreated titanium anode substrate and dry it to obtain the titanium substrate. The metal catalyst is one or more of palladium-based metal catalysts and platinum-based metal catalysts, the organic solvent is one of polyvinyl alcohol, methanol, and ethanol, and the catalyst dispersant is one of polyethylene glycol and polyethyleneimine;

[0053] Step 6: Prepare the ruthenium-based mixed metal oxide titanium anode. Take the ruthenium-based metal oxide coating solution in Step 4 and evenly coat it on the surface of the titanium substrate in Step 5. The coating method is one of plasma electrophoresis deposition method, vapor deposition method, dip coating method, and spraying method to obtain a ruthenium-based mixed metal oxide titanium anode precursor. Then heat-treat the precursor at 550 °C for 17 min, and repeat the coating and heat-treatment 4 times to obtain the ruthenium-based mixed metal oxide titanium anode.

[0054] Example 4:

[0055] Step 1: Prepare the modified titanium matrix mixture. Take 50 parts of titanium powder and 5 parts of graphene nanopowder or carbon nanotube powder and add them to a blender. After uniform stirring, a mixture is obtained. The mixture is sintered at 500 °C for 10 min and kept warm for 15 min in a nitrogen environment to obtain the modified titanium matrix mixture;

[0056] Step 2: Prepare the modified titanium anode matrix. Use a tablet press to press the titanium substrate raw material with the modified titanium matrix mixture in Step 1 to form a flaky modified titanium anode matrix;

[0057] Step 3: Prepare the coating solution powder. Take 5 parts of ruthenium oxide, 1.5 parts of tin oxide and 1.5 parts of nickel oxide metal powder and dry and crush them respectively to obtain ruthenium oxide, tin oxide and nickel oxide crushed powders with an average particle size of 60 - 80 μm. Mix the crushed metal powders evenly to obtain ruthenium-based metal oxide powder. Take 1.2 parts of carbon black particles and 0.5 part of cobalt hydroxide powder, crush and mix them respectively to obtain a modified activator. Add the modified activator to the ruthenium-based metal oxide powder, stir and mix evenly to obtain the coating solution powder;

[0058] Step 4: Prepare the ruthenium-based metal oxide coating solution. Take the coating solution powder in Step 3 and mix and stir it with 70 parts of organic solvent to obtain the ruthenium-based metal oxide coating solution, and the organic solvent is one of ethyl acetate, acetone and methanol;

[0059] Step 5: Pretreatment of the modified titanium anode matrix. Take the modified titanium anode matrix in Step 2 and perform pretreatment on it. The pretreatment steps are sandblasting and polishing the modified titanium anode matrix, rinsing and degreasing the polished matrix, acid etching the degreased matrix with phosphoric acid solution or oxalic acid solution for 30 - 50 min, and then rinsing with deionized water;

[0060] Dissolve 3 parts of metal catalyst in 25 parts of organic solvent, and add 0.6 part of catalyst dispersant and mix to obtain a catalyst solution. Coat the catalyst solution on the surface of the pretreated titanium anode matrix and dry it to obtain the titanium substrate. The metal catalyst is a palladium-based metal catalyst, the organic solvent is one of polyvinyl alcohol, methanol and ethanol, and the catalyst dispersant is one of polyethylene glycol and polyethyleneimine;

[0061] Take 5 parts of polyaniline powder, dissolve it in 25 parts of N-methylpyrrolidone to make a polyaniline precursor solution, and place the flaky modified titanium anode matrix as the positive electrode in the polyaniline precursor solution and apply current to deposit a polyaniline film on the flaky modified titanium anode matrix to obtain the completed modified titanium anode matrix;

[0062] Step 7: Prepare a ruthenium-based mixed metal oxide titanium anode. Take the ruthenium-based metal oxide coating solution in Step 4 and uniformly coat it on the surface of the modified titanium anode substrate completed body in Step 5. The coating method is one of plasma electrophoresis deposition method, chemical vapor deposition method, dip-coating method, and spraying method to obtain a ruthenium-based mixed metal oxide titanium anode precursor. Then, the precursor is sintered and heat-treated at a temperature of 450 °C for 10 min, and the coating, sintering, and heat treatment are repeated 4 times to obtain a ruthenium-based mixed metal oxide titanium anode.

[0063] Performance test: Based on the standard of GB / T 38069-2017 "Test Methods for Electrochemical Properties of Titanium and Titanium Alloys", the electrochemical impedance method is used to test the performance of the titanium anode by measuring the electrochemical impedance and surface state resistance of the titanium anode. According to the test results, the ruthenium-based mixed metal oxide titanium electrode prepared by the preparation method in the embodiment of the present invention has strong acid resistance and corrosion resistance, and has good electrocatalytic activity.

[0064] The raw materials and components required for preparing the ruthenium-based mixed metal oxide titanium electrode in the above Examples 1 to 3 are as follows:

[0065]

[0066] The raw materials and components required for preparing the ruthenium-based mixed metal oxide titanium electrode in the above Example 4 are as follows:

[0067]

[0068] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

Claims

1. A method for preparing an acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode, characterized in that: The following steps are involved: Step 1: preparing a modified titanium matrix mixture, adding titanium powder and vanadium powder in proportion to a mixer, or adding titanium powder and graphene nanopowder or carbon nanotube powder in proportion to a mixer, stirring evenly to obtain a mixture, and sintering the mixture to obtain a modified titanium matrix mixture; Step 2: preparing a modified titanium anode substrate, performing recrystallization annealing treatment on the modified titanium substrate mixture to obtain a titanium substrate raw material, and using a tablet press to press the titanium substrate raw material to obtain a modified titanium anode substrate; Step 3: preparing a coating solution powder, taking ruthenium oxide, tin oxide and nickel oxide powders, drying and crushing them respectively, and then mixing the crushed powders to obtain a ruthenium metal oxide powder, taking carbon black particles and cobalt hydroxide powders, crushing them respectively and mixing them to obtain a modified activator, adding the modified activator to the ruthenium metal oxide powder, stirring and mixing them evenly to obtain a coating solution powder; Step 4: preparing a ruthenium metal oxide coating solution, taking the coating solution powder in step 3 and mixing it with an organic solvent to obtain a ruthenium metal oxide coating solution; Step 5: pretreatment of the modified titanium anode substrate, taking the modified titanium anode substrate in step 2, and pretreatment the modified titanium anode substrate, dissolving the metal catalyst in an organic solvent, and adding a catalyst dispersant to mix to obtain a catalyst solution, coating the catalyst solution on the surface of the pretreated titanium anode substrate, and drying to obtain a titanium substrate; Step 6: preparing a ruthenium-based mixed metal oxide titanium anode, taking the ruthenium-based metal oxide coating solution in step 4, and uniformly coating it on the surface of the titanium substrate in step 5 to obtain a ruthenium-based mixed metal oxide titanium anode precursor, and then sintering the precursor to obtain a ruthenium-based metal oxide titanium anode; In the step 1, the average particle size of the titanium powder and the vanadium powder is 80-130 μm, the mass ratio of the titanium powder to the vanadium powder is (8-16):1, the sintering temperature is 300-800°C, the sintering time is 5-15 minutes, the holding time is 10-25 minutes, and the sintering is carried out under an inert gas environment, wherein the inert gas is one of nitrogen, argon and helium; The heating temperature of the recrystallization annealing in the step 2 is 800-1200° C., the heating time is 5-25 min, and the cooling time is 5-25 min; The mass ratio of ruthenium oxide, tin oxide and nickel oxide in the ruthenium-based metal oxide powder of step 3 is 1: (0.2-0.5): (0.2-0.4), the average particle size of ruthenium oxide, tin oxide and nickel oxide is 50-110 μm, the average particle size of carbon black particles and cobalt hydroxide powder in the modified activator is 40-70 μm, and the mass ratio of carbon black particles to cobalt hydroxide powder is 1: (0.3-0.5); In the step three, the mass ratio of the ruthenium-based metal oxide powder to the modified activator is 1:(0.1-0.5).

2. The method for preparing an acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode according to claim 1, characterized in that: The organic solvent in step 4 is one of ethyl acetate, acetone, and methanol; the organic solvent in step 5 is one of polyvinyl alcohol, methanol, ethanol, and toluene; the metal catalyst is one or both of a palladium-based metal catalyst and a platinum-based metal catalyst; and the catalyst dispersant is one of polyethylene glycol and polyethyleneimine.

3. The method for preparing an acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode according to claim 1, characterized in that: The step of pre-treating the modified titanium anode substrate in step 5 includes sandblasting and polishing the modified titanium anode substrate, rinsing and degreasing the polished substrate, etching the degreased substrate with phosphoric acid solution or oxalic acid solution for 30 to 50 minutes, and then rinsing with deionized water.

4. The method for preparing an acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode according to claim 1, characterized in that: The coating method of coating the ruthenium-based mixed metal oxide coating solution on the surface of the titanium substrate in step six includes one of a plasma electrophoretic deposition method, a vapor deposition method, an immersion pulling method, and a spraying method. The sintering temperature of the precursor for sintering heat treatment in step six is ​​300 to 700° C., the sintering time is 5 to 20 minutes, and the number of repetitions of the coating and sintering heat treatment in step six is ​​3 to 5 times.

5. An acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode, characterized in that: A ruthenium-based mixed metal oxide titanium anode obtained by the method for preparing the acid-resistant and highly active ruthenium-based mixed metal oxide titanium anode according to any one of claims 1 to 4.

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