A method for enhancing the lifespan of coated titanium electrodes with a polymer copolymer-modified coating solution

Abstract

This invention relates to a method for enhancing the lifespan of coated titanium electrodes using a polymer-modified coating solution. Compared to electrodes prepared with conventional coating solutions without polymer modification, the electrode coating prepared with the polymer-modified solution exhibits a 20-50% reduction in crack size, a 0.8-2.4-fold increase in accelerated life testing lifespan, and a 1-2.5-fold increase in lifespan during frequent reverse electrolysis of tap water. The polymer-modified coating solution method is applicable to coated titanium electrodes with various active coatings, including but not limited to RuO2-TiO2 coatings, RuO2-TiO2-IrO2 coatings, RuO2-TiO2-SnO2 coatings, and IrO2-Ta2O5 coatings. Furthermore, the polymer-modified coating solution method is compatible with existing industrial electrode manufacturing processes, namely the surface coating thermal decomposition process, and is easily scaled up for production.

Description

Technical Field

[0001] This invention relates to a method for enhancing the lifespan of coated titanium electrodes with a polymer copolymer-modified coating liquid, belonging to the field of inorganic materials technology. Background Technology

[0002] Coated titanium electrodes are noble metal-based catalytic materials made by coating an active coating, primarily composed of noble metal oxides, onto a titanium substrate. Coated titanium electrodes have wide applications in various industries, including chemical engineering, new energy, advanced electrolytic oxidation, electrodialysis, printed circuit boards, and electrolytic copper foil, and are core and key components in electrochemical reactions across these industries. Surface coating thermal decomposition is currently the most common method for producing coated titanium electrodes both domestically and internationally, with the coating solution being the core of this process. However, during the preparation of traditional coating solutions, repeated thermal cycles result in large cracks in the coating due to the difference in thermal expansion coefficients between the titanium substrate and the coating. These cracks allow electrolyte and molecular oxygen to enter the coating during use, leading to corrosion and passivation of the titanium substrate and ultimately electrode deactivation. Therefore, there is an urgent need to develop methods for modifying the coating solution to reduce crack size and improve electrode lifespan. Summary of the Invention

[0003] This invention provides a method for enhancing the lifespan of coated titanium electrodes using a polymer copolymer-modified coating liquid, resulting in an electrode coating with small crack size and long electrode lifespan.

[0004] The technical solution of the present invention is as follows:

[0005] A method for enhancing the lifespan of coated titanium electrodes using a polymer copolymer-modified coating solution is characterized in that the coating solution used in electrode preparation is obtained by modifying a traditional coating solution with a polymer copolymer. The method of using a polymer copolymer-modified coating solution is applicable to existing industrial electrode preparation processes, namely the surface coating thermal decomposition process, and is easy to scale up for production. Furthermore, the method is applicable to coated titanium electrodes with various active coatings, including but not limited to RuO2-TiO2 coatings, RuO2-TiO2-IrO2 coatings, RuO2-TiO2-SnO2 coatings, and IrO2-Ta2 coatings. O5 coating; the polymer copolymer in the coating solution is composed of a polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymer, which is a Pluronic block copolymer. Due to the presence of hydrophilic EO chains and hydrophobic PO chains in the copolymer, the polymer copolymer self-assembles into micelles during the coating process, resulting in a stable and uniform coating solution. During the drying and calcination process after coating the titanium substrate, the polymer copolymer is slowly burned off, reducing the thermal stress change of the active coating during calcination and minimizing the difference in thermal expansion coefficients between the active coating and the titanium substrate, thereby reducing the size of cracks in the active coating. Therefore, the electrode prepared with the polymer copolymer-modified coating solution has a longer service life. Compared with the electrode prepared with the traditional coating solution without polymer copolymer modification, the electrode prepared with the polymer copolymer-modified coating solution has a 0.8-2.4 times longer accelerated life test life and a 1-2.5 times longer frequent reverse electrolysis of tap water test life.

[0006] A method for enhancing the lifespan of coated titanium electrodes using a polymer copolymer-modified coating solution is as follows:

[0007] (1) Titanium substrate pretreatment: First, the titanium mesh is polished with 200-1000 grit sandpaper to remove the oxide layer on the surface; then, the polished titanium mesh is ultrasonically cleaned in acetone, anhydrous ethanol and deionized water for 10-30 minutes to remove the oil on the surface of the titanium substrate; the degreased titanium mesh is placed in oxalic acid solution (mass fraction of 10%) and heated to 90℃ for acid etching for 1-2 hours; the acid-etched titanium mesh is rinsed with a large amount of deionized water, then dried in an oven and stored in anhydrous ethanol for later use.

[0008] (2) A certain amount of polymer copolymer is added to anhydrous ethanol and stirred at 40℃-60℃ to dissolve it, forming a homogeneous solution. Then, the metal precursor of the active coating is added to the solution. Different metal precursors in the active coating need to be added in a certain molar ratio to obtain a total metal concentration of 0.3-0.6 mol / L. -1A uniform coating solution is applied; the coating solution is applied to the titanium substrate with a brush. After each coating, the coated electrode is first dried under an infrared lamp, and then placed in a muffle furnace for thermal oxidation at 450℃-600℃ in an air atmosphere for 10-20 minutes. After that, it is taken out and cooled to room temperature before the next coating is applied. This process is repeated 5-15 times. After the last coating, the electrode is placed in a muffle furnace for calcination at 450℃-600℃ in an air atmosphere for 0.5-1 hour. After naturally cooling to room temperature in the furnace, it is taken out to obtain the coated titanium electrode.

[0009] (3) Electrode life was evaluated using two methods: accelerated life test and frequent reverse electrolysis of tap water test. Accelerated life test conditions: electrolyte was 1 mol L. -1 Sulfuric acid solution, at 40°C, at 2A cm -2 Electrolysis is performed, and the electrode is considered to be deactivated when the electrode voltage rises to 20V. The experimental conditions for frequent electrode reversal electrolysis of tap water are as follows: the electrolyte is tap water (municipal water), the voltage is 12V, the electrode reversal frequency is to switch the positive and negative electrodes once every 1 minute, and fresh tap water is replaced every hour. The electrode is considered to be deactivated when the current drops to 0.3A.

[0010] According to the method of the present invention, the preferred method is:

[0011] In step (2) above, the type of polymer copolymer is Pluronic block copolymer, which is composed of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblocks, specifically Pluronic F127, or Pluronic F68, or Pluronic P85, or Pluronic P35 or Pluronic P123.

[0012] In step (2) above, the mass fraction of the polymer copolymer in anhydrous ethanol is 0.2wt%-0.5wt%.

[0013] In step (2) above, the precursor of the active coating is determined based on the electrode active coating. The electrode active coating includes, but is not limited to, RuO2-TiO2 coating, RuO2-TiO2-IrO2 coating, RuO2-TiO2-SnO2 coating, and IrO2-Ta2O5 coating. Specifically, the precursor of the RuO2-TiO2 coating is tetrabutyl titanate and RuCl3·3H2O, with a Ti to Ru molar ratio of 7:3 and a total metal concentration of 0.3-0.6 mol / L. -1 The measured amounts of the substances were added to the solution; the precursors for the RuO2-TiO2-IrO2 coating were tetrabutyl titanate, RuCl3·3H2O, and H2IrCl6·6H2O, with a Ti:Ru:Ir molar ratio of 7:2:1 and a total metal concentration of 0.3-0.6 mol / L. -1The measured amounts were added to the solution; the precursors for the RuO2-TiO2-SnO2 coating were tetrabutyl titanate, RuCl3·3H2O, and SnCl2·2H2O, with a Ti:Ru:Sn molar ratio of 7:2:1 and a total metal concentration of 0.3-0.6 mol / L. -1 The measured amounts were added to the solution; the precursors for the IrO2-Ta2O5 coating were H2IrCl6·6H2O and TaCl5, with an Ir:Ta molar ratio of 7:3 and a total metal concentration of 0.3-0.6 mol / L. -1 The measured amount is added to the solution.

[0014] The technical features of this invention are as follows:

[0015] 1. This invention utilizes a method of modifying the coating solution with polymer copolymers to enhance the lifespan of coated titanium electrodes. The selection of the polymer copolymer type plays a crucial role in enhancing electrode lifespan. The polymer copolymer type is a Pluronic block copolymer, composed of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblocks, specifically Pluronic F127, Pluronic F68, Pluronic P85, Pluronic P35, or Pluronic P123. Due to the presence of hydrophilic EO chains and hydrophobic PO chains in the polymer copolymer, it self-assembles into micelles during the coating process in the coating solution, resulting in a stable and uniform coating solution. During the drying and calcination process after coating the titanium substrate, the polymer copolymer is slowly burned off, reducing the thermal stress changes of the active coating during calcination, minimizing the difference in thermal expansion coefficients between the active coating and the titanium substrate, and thus reducing the size of cracks in the active coating.

[0016] 2. The amount of polymer copolymer added in this invention plays a crucial role in the preparation of the electrode. The mass fraction of the polymer copolymer in anhydrous ethanol is 0.2wt%-0.5wt%. When the mass fraction is below 0.2wt%, the polymer copolymer is difficult to self-assemble into micelles during the coating process, and its impact on the thermal stress change of the active coating during calcination is too small to reduce the difference in the coefficient of thermal expansion between the active coating and the titanium substrate, thus making it difficult to reduce the size of the cracks in the active coating. When the mass fraction is above 0.5wt%, the coating solution is too viscous, making it difficult to coat the titanium substrate uniformly, affecting the uniformity of the electrode active coating, and thus affecting the electrode performance. Therefore, the mass fraction of the polymer copolymer in anhydrous ethanol is 0.2wt%-0.5wt%.

[0017] 3. The coating solution used in the electrode preparation of this invention is obtained by modifying a traditional coating solution with a polymer copolymer. The method of modifying the coating solution with a polymer copolymer is applicable to existing industrial electrode preparation processes, namely the surface coating thermal decomposition process, which is easy to scale up for production. At the same time, the method of modifying the coating solution with a polymer copolymer is applicable to coated titanium electrodes with various active coatings, including but not limited to RuO2-TiO2 coating, RuO2-TiO2-IrO2 coating, RuO2-TiO2-SnO2 coating, and IrO2-Ta2O5 coating.

[0018] 4. The coated titanium electrode prepared by the polymer copolymer modified coating solution described in this invention patent has a 20-50% reduction in coating crack size compared to the electrode prepared by the traditional coating solution without polymer copolymer. The electrode life is increased by 0.8-2.4 times and 1-2.5 times, respectively, as evaluated by accelerated life test and frequent reverse electrolysis of tap water test. Attached Figure Description

[0019] Figure 1 The image shown is a scanning electron microscope (SEM) image of the coated titanium electrode in Example 1.

[0020] Figure 2 Here is a scanning electron microscope image of the coated titanium electrode in Comparative Example 1;

[0021] Figure 3 The above are statistical distribution diagrams of coating crack size in Example 1 and Comparative Example 1.

[0022] Figure 4 The results of accelerated life tests on the coated titanium electrodes in Example 2 and Comparative Example 2 are shown.

[0023] Figure 5 The results show the electrolytic tap water life test results of the coated titanium electrodes in Example 2 and Comparative Example 2. Detailed Implementation

[0024] The present invention will now be described in detail with reference to specific embodiments. The illustrative embodiments and descriptions of the present invention are used to explain the present invention, but are not intended to limit the present invention.

[0025] Example 1

[0026] (1) Titanium substrate pretreatment: First, the titanium mesh is polished with 200-grit sandpaper to remove the oxide layer on the surface; then, the polished titanium mesh is ultrasonically cleaned in acetone, anhydrous ethanol and deionized water for 10 minutes to remove the oil on the surface of the titanium substrate; the degreased titanium mesh is placed in oxalic acid solution (mass fraction of 10%) and heated to 90℃ for acid etching for 1 hour; the acid-etched titanium mesh is rinsed with a large amount of deionized water, then dried in an oven and stored in anhydrous ethanol for later use.

[0027] (2) Add 0.12g of polymeric copolymer F127 to 30mL of anhydrous ethanol, stir at 40℃ to dissolve, forming a homogeneous solution, and then add the RuO2-TiO2-SnO2 coated metal precursor tetrabutyl titanate, RuCl3·3H2O, to the solution.

[0028] SnCl2·2H2O, with a Ti:Ru:Sn molar ratio of 7:2:1 and a total metal concentration of 0.5 mol / L. -1 The measured amount of the coating solution was added to obtain a uniform coating solution. The coating solution was then applied to the titanium substrate using a brush. After each coating, the coated electrode was first dried under an infrared lamp, and then placed in a muffle furnace for thermal oxidation at 450°C in air for 10 minutes. After that, it was removed and cooled to room temperature before the next coating was applied. This process was repeated 10 times. After the last coating, the electrode was placed in a muffle furnace for calcination at 450°C in air for 1 hour. After naturally cooling to room temperature in the furnace, it was removed to obtain the coated titanium electrode.

[0029] (3) Accelerated life test: The electrode was cut into 1×1cm pieces. 2 Size, as the anode, pure titanium sheet as the cathode, electrolyte is 1 mol L. -1 Sulfuric acid solution, at 40°C, at 2A cm -2 Electrolysis was performed, and the electrode was considered deactivated when the electrode voltage rose to 20V. The lifespan of the RuO2-TiO2-SnO2 coated titanium electrode prepared with F127 modified coating solution was measured to be 16.3h; under the same conditions, the lifespan of the RuO2-TiO2-SnO2 coated titanium electrode prepared without F127 modified coating solution was 6.8h. The lifespan of the RuO2-TiO2-SnO2 coated titanium electrode prepared with F127 modified coating solution was 1.4 times longer than that of the RuO2-TiO2-SnO2 coated titanium electrode prepared without F127 modified coating solution.

[0030] (4) Experimental conditions for frequent reverse-polarity electrolysis of tap water: Both the anode and cathode were RuO2-TiO2-SnO2 coated titanium electrodes prepared with the F127 modified coating solution, with a size of 3×3cm. 2The electrolyte was 300 mL of tap water (municipal tap water has a chloride ion content of approximately 80 mg / L), the voltage was 12 V, the electrode reversal frequency was once every minute, and fresh tap water was replaced every hour. Electrode deactivation was considered to have occurred when the current dropped to 0.3 A. The lifespan of the RuO2-TiO2-SnO2 coated titanium electrode prepared with F127 modified coating solution was measured to be 345 h; under the same conditions, the lifespan of the RuO2-TiO2-SnO2 coated titanium electrode prepared without F127 modified coating solution was 119 h. The lifespan of the RuO2-TiO2-SnO2 coated titanium electrode prepared with F127 modified coating solution was longer than that of the RuO2-TiO2-SnO2 coated titanium electrode prepared without F127 modified coating solution.

[0031] 1.9 times.

[0032] Example 2

[0033] (1) Titanium substrate pretreatment: First, the titanium mesh is polished with 200-grit sandpaper to remove the oxide layer on the surface; then, the polished titanium mesh is ultrasonically cleaned in acetone, anhydrous ethanol and deionized water for 10 minutes to remove the oil on the surface of the titanium substrate; the degreased titanium mesh is placed in oxalic acid solution (mass fraction of 10%) and heated to 90℃ for acid etching for 1 hour; the acid-etched titanium mesh is rinsed with a large amount of deionized water, then dried in an oven and stored in anhydrous ethanol for later use.

[0034] (2) Add 0.1g of polymer copolymer P123 to 30mL of anhydrous ethanol, stir at 40℃ to dissolve, forming a homogeneous solution. Then add tetrabutyl titanate and RuCl3·3H2O, the metal precursors of RuO2-TiO2 coating, to the solution, according to the following ratio: Ti:

[0035] The Ru molar ratio is 7:3, and the total metal concentration is 0.5 mol / L. -1 The measured amount of the coating solution was added to obtain a uniform coating solution. The coating solution was then applied to the titanium substrate using a brush. After each coating, the coated electrode was first dried under an infrared lamp, and then placed in a muffle furnace for thermal oxidation at 500°C in air for 10 minutes. After that, it was removed and cooled to room temperature before the next coating was applied. This process was repeated 15 times. After the last coating, the electrode was placed in a muffle furnace for calcination at 500°C in air for 1 hour. After naturally cooling to room temperature in the furnace, it was removed to obtain a coated titanium electrode.

[0036] (3) Accelerated life test: The electrode was cut into 1×1cm pieces. 2 Size, as the anode, pure titanium sheet as the cathode, electrolyte is 1 mol L. -1 Sulfuric acid solution, at 40°C, at 2A cm -2Electrolysis was performed, and the electrode was considered deactivated when the electrode voltage rose to 20V. The lifespan of the RuO2-TiO2 coated titanium electrode prepared with P123 modified coating solution was measured to be 29.1h; under the same conditions, the lifespan of the RuO2-TiO2 coated titanium electrode prepared without P123 modified coating solution was 9.5h. The lifespan of the RuO2-TiO2 coated titanium electrode prepared with P123 modified coating solution was 2.06 times longer than that of the RuO2-TiO2 coated titanium electrode prepared without P123 modified coating solution.

[0037] (4) Experimental conditions for frequent reverse-polarity electrolysis of tap water: Both the anode and cathode are RuO2-TiO2 coated titanium electrodes prepared with the P123 modified coating solution, with a size of 3×3cm. 2 The electrolyte was 300 mL of tap water (the chloride ion content in municipal tap water is approximately 80 mg / L), the voltage was 12 V, the reversal frequency was once every minute to switch the positive and negative electrodes, and fresh tap water was replaced every hour. The electrode was considered deactivated when the current dropped to 0.3 A. The lifespan of the RuO2-TiO2 coated titanium electrode prepared with P123 modified coating solution was measured to be 504 h; under the same conditions, the lifespan of the RuO2-TiO2 coated titanium electrode prepared without P123 modified coating solution was 162 h. The lifespan of the RuO2-TiO2 coated titanium electrode prepared with P123 modified coating solution was 2.1 times longer than that of the RuO2-TiO2 coated titanium electrode prepared without P123 modified coating solution.

[0038] Comparative Example 1

[0039] (1) Titanium substrate pretreatment: First, the titanium mesh is polished with 200-grit sandpaper to remove the oxide layer on the surface; then, the polished titanium mesh is ultrasonically cleaned in acetone, anhydrous ethanol and deionized water for 10 minutes to remove the oil on the surface of the titanium substrate; the degreased titanium mesh is placed in oxalic acid solution (mass fraction of 10%) and heated to 90℃ for acid etching for 1 hour; the acid-etched titanium mesh is rinsed with a large amount of deionized water, then dried in an oven and stored in anhydrous ethanol for later use.

[0040] (2) Take 30 mL of anhydrous ethanol and add tetrabutyl titanate, RuCl3·3H2O, and SnCl2·2H2O, the metal precursors of RuO2-TiO2-SnO2 coating, according to a Ti:Ru:Sn molar ratio of 7:2:1 and a total metal concentration of 0.5 mol / L. -1The measured amount of material was added and stirred to obtain a uniform coating solution. The coating solution was then applied to the titanium substrate using a brush. After each coating, the coated electrode was first dried under an infrared lamp, and then placed in a muffle furnace for thermal oxidation at 450°C in air for 10 minutes. After that, it was removed and cooled to room temperature before the next coating was applied. This process was repeated 10 times. After the last coating, the electrode was placed in a muffle furnace for calcination at 450°C in air for 1 hour. After naturally cooling to room temperature in the furnace, it was removed to obtain the coated titanium electrode.

[0041] (3) Accelerated life test: The electrode was cut into 1×1cm pieces. 2 Size, as the anode, pure titanium sheet as the cathode, electrolyte is 1 mol L. -1 Sulfuric acid solution, at 40°C, at 2A cm -2 Electrolysis was performed, and the electrode was considered to be deactivated when the electrode voltage rose to 20V. The lifetime of the RuO2-TiO2-SnO2 coated titanium electrode prepared without F127 modified coating solution was measured to be 6.8h.

[0042] (4) Experimental conditions for frequent reverse-polarity electrolysis of tap water: Both the anode and cathode are RuO2-TiO2-SnO2 coated titanium electrodes, with a size of 3×3cm. 2 The electrolyte was 300 mL of tap water (the chloride ion content in municipal tap water is about 80 mg / L), the voltage was 12 V, the reversal frequency was once every 1 minute to switch the positive and negative electrodes, and the tap water was replaced every hour. When the current dropped to 0.3 A, it was considered that the electrode was deactivated. The lifespan of the RuO2-TiO2-SnO2 coated titanium electrode prepared without F127 modified coating solution was measured to be 119 h.

[0043] Comparative Example 2

[0044] (1) Titanium substrate pretreatment: First, the titanium mesh is polished with 200-grit sandpaper to remove the oxide layer on the surface; then, the polished titanium mesh is ultrasonically cleaned in acetone, anhydrous ethanol and deionized water for 10 minutes to remove the oil on the surface of the titanium substrate; the degreased titanium mesh is placed in oxalic acid solution (mass fraction of 10%) and heated to 90℃ for acid etching for 1 hour; the acid-etched titanium mesh is rinsed with a large amount of deionized water, then dried in an oven and stored in anhydrous ethanol for later use.

[0045] (2) Take 30 mL of anhydrous ethanol, add tetrabutyl titanate and RuCl3·3H2O, the metal precursors of RuO2-TiO2 coating, according to the molar ratio of Ti:Ru of 7:3 and the total metal concentration of 0.5 mol / L. -1The measured amount of material was added and stirred to obtain a uniform coating solution. The coating solution was then applied to the titanium substrate using a brush. After each coating, the coated electrode was first dried under an infrared lamp, and then placed in a muffle furnace for thermal oxidation at 500°C in air for 10 minutes. After that, it was removed and cooled to room temperature before the next coating was applied. This process was repeated 15 times. After the last coating, the electrode was placed in a muffle furnace for calcination at 500°C in air for 1 hour. After naturally cooling to room temperature in the furnace, it was removed to obtain the coated titanium electrode.

[0046] (3) Accelerated life test: The electrode was cut into 1×1cm pieces. 2 Size, as the anode, pure titanium sheet as the cathode, electrolyte is 1 mol L. -1 Sulfuric acid solution, at 40°C, at 2A cm -2 Electrolysis was performed, and the electrode was considered to be deactivated when the electrode voltage rose to 20V. The lifespan of the RuO2-TiO2 coated titanium electrode prepared without P123 modified coating solution was measured to be 9.5h.

[0047] (4) Experimental conditions for frequent reverse-polarity electrolysis of tap water: Both the anode and cathode are RuO2-TiO2 coated titanium electrodes, with a size of 3×3cm. 2 The electrolyte was 300 mL of tap water (the chloride ion content in municipal tap water is about 80 mg / L), the voltage was 12 V, the reversal frequency was to switch the positive and negative electrodes every 1 minute, and the tap water was replaced with fresh water every hour. When the current dropped to 0.3 A, it was considered that the electrode was deactivated. The lifespan of the RuO2-TiO2 coated titanium electrode prepared without P123 modified coating solution was measured to be 162 h.

Claims

1. A method for enhancing the life of a coated titanium electrode by using a high-molecular copolymer modified coating solution, comprising the following steps: (1) Titanium substrate pretreatment: First, the titanium mesh is polished with 200-1000 mesh sandpaper to remove the surface oxide layer; then the polished titanium mesh is sequentially placed in acetone, anhydrous ethanol and deionized water for 10-30 min ultrasonic cleaning to remove oil on the surface of the titanium substrate; the oil-removed titanium mesh is placed in oxalic acid solution (10% by mass fraction) and heated to 90℃ for acid etching for 1-2 h; the acid-etched titanium mesh is rinsed with a large amount of deionized water, then dried in an oven and stored in anhydrous ethanol for standby; (2) a certain amount of high molecular copolymer is added into anhydrous ethanol, stirred and dissolved at 40-60°C to form a uniform solution, then active coating metal precursors are added into the solution, different metal precursors in the active coating are added according to a certain molar ratio, and a uniform coating solution with a total metal concentration of 0.3-0.6 mol / L is obtained; the coating solution is coated onto a titanium substrate by using a brush, after each coating, the coated electrode is dried under an infrared lamp, then the electrode is placed in a muffle furnace and heat-oxidized at 450-600°C under an air atmosphere for 10-20 min, then taken out and cooled to room temperature for the next coating, and the above process is repeated for 5-15 times; the electrode after the last coating is placed in a muffle furnace and calcined at 450-600°C under an air atmosphere for 0.5-1 h, then taken out after natural cooling to room temperature in the furnace, and a coated titanium electrode is obtained, wherein the type of the high molecular copolymer is Pluronic block copolymer, and the copolymer is composed of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) tri-blocks; -1 ​ The active coating precursor is determined in accordance with the electrode active coating, which is selected from the group consisting of RuO2-TiO2coating, RuO2-TiO2-IrO2coating, RuO2-TiO2-SnO2coating, IrO2-Ta2O5coating, wherein, The precursors of the RuO2-TiO2 coating are tetrabutyl titanate and RuCl3·3H2O, and the molar ratio of Ti to Ru is 7:3; the precursors of the RuO2-TiO2-IrO2 coating are tetrabutyl titanate, RuCl3·3H2O and H2IrCl6·6H2O, and the molar ratio of Ti:Ru:Ir is 7:2:1; the precursors of the RuO2-TiO2-SnO2 coating are tetrabutyl titanate, RuCl3·3H2O and SnCl2·2H2O, and the molar ratio of Ti:Ru:Sn is 7:2:1; the precursors of the IrO2-Ta2O5 coating are H2IrCl6·6H2O and TaCl5, and the molar ratio of Ir:Ta is 7:3; (3) Accelerated life test and frequent reversal electrolysis of tap water were used to evaluate the life of the electrode. The accelerated life test was carried out at 40℃ with 1mol / L H2SO4 solution and 2A / cm2 current. The electrode was considered to be deactivated when the voltage rose to 20V. The frequent reversal electrolysis of tap water was carried out at 12V with fresh tap water changed every hour. The electrode was considered to be deactivated when the current dropped to 0.3A. -1 The accelerated life test was carried out at 40℃ with 1mol / L H2SO4 solution and 2A / cm2 current. The electrode was considered to be deactivated when the voltage rose to 20V. The frequent reversal electrolysis of tap water was carried out at 12V with fresh tap water changed every hour. The electrode was considered to be deactivated when the current dropped to 0.3A. -2 The accelerated life test was carried out at 40℃ with 1mol / L H2SO4 solution and 2A / cm2 current. The electrode was considered to be deactivated when the voltage rose to 20V. The frequent reversal electrolysis of tap water was carried out at 12V with fresh tap water changed every hour. The electrode was considered to be deactivated when the current dropped to 0.3A.

2. The method of enhancing the life of a polymer co-polymer modified coating fluid coated titanium electrode as claimed in claim 1, wherein, In the step (2), the high-molecular copolymer is Pluronic F127, or Pluronic F68, or Pluronic P85, or Pluronic P35 or Pluronic P123.

3. The method of enhancing the life of a polymer co-polymer modified coating liquid coated titanium electrode as claimed in claim 1, wherein, In the step (2), the mass fraction of the high-molecular copolymer in anhydrous ethanol is 0.2wt%-0.5wt%.

4. The method of enhancing the life of a polymer co-polymer modified coating liquid coated titanium electrode as claimed in claim 1, wherein, Compared with the electrode prepared by the conventional coating solution without adding the high-molecular copolymer, the coated titanium electrode prepared by the high-molecular copolymer modified coating solution has a coating crack size reduced by 20-50%, and the electrode life evaluated by the accelerated life test and the frequent reverse electrode electrolysis tap water test is respectively increased by 0.8-2.4 times and 1-2.5 times.

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