WO2021017104A1 - Substrate etching method for titanium-based dimension stabilization type anode - Google Patents

Substrate etching method for titanium-based dimension stabilization type anode Download PDF

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WO2021017104A1
WO2021017104A1 PCT/CN2019/105081 CN2019105081W WO2021017104A1 WO 2021017104 A1 WO2021017104 A1 WO 2021017104A1 CN 2019105081 W CN2019105081 W CN 2019105081W WO 2021017104 A1 WO2021017104 A1 WO 2021017104A1
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etching
titanium
substrate
solution
dimensionally stable
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Chinese (zh)
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谢锋
路雨禾
王伟
路殿坤
畅永锋
符岩
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东北大学
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof

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  • the invention belongs to the technical field of electrochemical industrial electrode materials, and specifically relates to a matrix etching method for a titanium-based dimensionally stable anode.
  • DSA has high practical value as an anode with stable dimensions and low OER overpotential.
  • its catalytic oxide coating is limited to IrO 2 , RuO 2 and so on due to the acidic environment. Due to the harsh working conditions of the DSA electrode in the electrodeposition process, most metals or metal oxides cannot meet their use conditions.
  • IrO 2 and RuO 2 can be used as high-efficiency catalyst coatings, DSA electrodes still need to be studied on electrode stability. The service life of DSA electrodes currently used in industrial production is 5-10 years.
  • the current method for coating the oxide coating on the titanium substrate is thermal deposition. This method needs to consume more precious metal salt solution as the original, and the cost is higher.
  • the main reason for the failure of the catalytic electrode is that the catalytic coating gradually dissolves in the electrolyte solution during the oxygen evolution reaction.
  • the acidic electrolyte solution gradually penetrates deeper into the titanium matrix from the coating gap. At higher current densities, the titanium substrate is corroded and further leads to an increase in cell voltage and the shedding of the catalyst coating.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings in the prior art and provide a method for etching the substrate of a titanium-based dimensionally stable anode.
  • the DSA obtained from the titanium-based system has higher OER catalytic activity and a longer working life. It can effectively extend the use time of DSA and reduce the cost caused by the replacement of waste electrodes.
  • This method takes 15-40% sulfuric acid solution as an example to optimize the traditional titanium matrix etching method. That is, nitrogen gas is introduced during the etching process. By exhausting the dissolved oxygen in the etching solution and changing the surface roughness of the titanium substrate, the effect of extending the service life of the DSA is achieved.
  • a method for etching the substrate of a titanium-based dimensionally stable anode includes the following:
  • the etching solution reaches the set temperature, put in the dried titanium substrate and etch to obtain the etched titanium substrate, which can be used as the titanium-based dimensionally stable anode substrate, wherein the etching time is 0.5-3h, and during the etching process, keep the etching solution temperature at 80-100°C and continue to blow in nitrogen.
  • the industrial titanium substrate is TA1 titanium substrate or TA2 titanium substrate.
  • the cleaning process is: cleaning with deionized water and absolute ethanol for 5-20 minutes respectively to complete the cleaning.
  • the drying operation is carried out in the air or in an oven at 40-80°C.
  • the acid solution is sulfuric acid, oxalic acid or hydrochloric acid.
  • the sealed container is provided with an air inlet and an air outlet.
  • the method of introducing nitrogen gas is as follows: when the etching solution is heated to 20-70°C, the gas inlet of the container penetrates into the liquid, and nitrogen gas is introduced into the solution.
  • the nitrogen gas flow rate is 2-5ml/s to ensure that when the etching solution rises to the etching temperature, the air in the container is completely discharged from the air outlet.
  • the titanium substrate will be etched to prepare a titanium-based dimensionally stable anode, which has a current density of 25-45 A/cm 2 under a cell voltage of 1.65V.
  • the oxygen dissolved in the etching solution will cause the surface of the titanium substrate to form an oxide layer at the etching temperature, the composition of which is TiO 2 or other Ti oxides.
  • the formation of this oxide layer hinders the etching process of the titanium matrix to a certain extent.
  • the morphology of the etched substrate is generally larger (50-200 ⁇ m in diameter) etch pits.
  • nitrogen is introduced during the etching process to inhibit the formation of such an oxide layer, and at the same time, the continuous blowing of nitrogen bubbles can prevent uneven etching caused by excessively high local sulfuric acid concentration on the surface of the substrate. Therefore, the titanium substrate processed by the etching method mentioned in the present invention has etch pits with a smaller size (5-15 ⁇ m in diameter) and a larger roughness.
  • the process of preparing DSA from the etched titanium substrate in the present invention is a traditional thermal deposition method.
  • the prepared DSA can be used for life test experiments and compared with traditional DSA.
  • the present invention only adds the step of introducing nitrogen gas, thereby increasing the cost of preparation relatively low.
  • the introduction of nitrogen gas during the etching process of the present invention improves the roughness of the titanium substrate, and the Rq value (root mean square of the surface etching pit depth) of the substrate obtained by the atomic force microscope test can be increased from 43nm to 189nm at the highest.
  • the electrode active area per square centimeter of DSA can be increased from 26.8cm 2 to 44.4cm 2 .
  • the current density of the electrode can be increased from 20A/cm 2 to 45A/cm 2 at the highest, thus effectively improving the electrodeposition efficiency.
  • Figure 1 is a scanning electron microscope (SEM) picture of a titanium substrate after etching obtained in Example 1 of the present invention
  • Example 2 is a comparison diagram of the accelerated failure experiment results of the DSA electrode prepared in Example 1 of the present invention and the conventional DSA in Comparative Example 1;
  • Example 3 is a comparison diagram of the polarization curves of the DSA electrode prepared in Example 1 of the present invention and the DSA electrode prepared in Comparative Example 1.
  • the thickness of the titanium substrate is 0.5-1mm;
  • the method of preparing titanium-based dimensionally stable anode DSA by etching the titanium substrate is as follows:
  • Steps 3 and 4 are repeated fifteen times, that is, a total of 15 coating processes are performed, and the last heat treatment process is performed for 1 hour;
  • Example 1 and Comparative Example 1 adopts chronopotentiometric test under high current density, and the conditions are: (1) Current density is 10mA/cm 2 ; (2) The test environment is 1mol/L sulfuric acid solution; (3) ) The test temperature is 80°C.
  • the TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 15% sulfuric acid solution as the etching solution. Place it in a sealed container with air inlets and outlets. The etching solution is heated in a water bath and the temperature is maintained at 85°C. When the temperature of the etching solution reached 30°C, nitrogen was introduced into the solution at a rate of 2ml/s.
  • the etching solution When the etching solution reaches 85°C, it is put into the dried titanium substrate with an area of 10cm 2 , and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas was introduced to obtain the etched titanium substrate.
  • the scanning electron microscope (SEM) image of the titanium substrate after the etching is shown in Figure 1.
  • the Rq value (root mean square of the surface etch pit depth) of the substrate was 189 nm through the atomic force microscope test.
  • the titanium-based dimensionally stable anode DSA was prepared by etching the titanium substrate.
  • the active area of the electrode per square centimeter of the DSA was 44.4 cm 2 , and the current density of 45 A/cm 2 was obtained at a cell voltage of 1.65V.
  • the TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 85°C. When the etching solution reaches 85°C, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1h to obtain the etched titanium substrate.
  • the Rq value of the substrate is obtained by the atomic force microscope test (the depth of the surface etching pits is equal root) is 43nm, the etching of the titanium-based preparation yl dimensionally stable titanium anodes DSA, DSA per square centimeter of active electrode area 26.8cm 2, the current density obtainable 25A / cm 2 at a cell voltage of 1.65V.
  • the TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 15 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 800ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 85°C. When the temperature of the etching solution reached 70°C, nitrogen was introduced into the solution at a rate of 4ml/s.
  • the etching solution When the etching solution reaches 85°C, it is put into the dried titanium substrate with an area of 10cm 2 , and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas is introduced to obtain an etched titanium substrate, and the etched titanium substrate is used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 35A/cm 2 can be obtained at a cell voltage of 1.65V.
  • the TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 10 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in an oven at 60°C for 20 minutes. Prepare 900 ml of sulfuric acid solution with a mass fraction of 30% as the etching solution. Heat the etching solution in a water bath and keep the temperature at 90°C. When the temperature of the etching solution reached 30°C, nitrogen was introduced into the solution at a rate of 3ml/s.
  • the etching solution When the etching solution reaches 90°C, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas is introduced to obtain an etched titanium substrate.
  • the etched titanium substrate is used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 25A/cm 2 can be obtained at a cell voltage of 1.65V.
  • the TA2 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 80°C. When the temperature of the etching solution reaches 50°C, nitrogen is introduced into the solution at a rate of 2ml/s. When the etching solution reaches 80°C, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas was introduced to obtain an etched titanium substrate, and the etched titanium substrate was used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 42A/cm 2 was obtained at a cell voltage of 1.65V.
  • the TA2 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 25% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 80°C. When the temperature of the etching solution reaches 50° C., nitrogen gas is introduced into the solution at a rate of 2 ml/s.
  • the etching solution When the etching solution reaches 80°C, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1.5 hours to ensure that there is no oxygen in the container at the beginning of the etching, and it will continue during the etching process. Nitrogen gas is introduced to obtain an etched titanium substrate, and the etched titanium substrate is used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 43A/cm 2 can be obtained at a cell voltage of 1.65V.
  • the TA2 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 60 minutes. Prepare 1000ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 85°C. When the temperature of the etching solution reaches 40°C, nitrogen gas is introduced into the solution at a rate of 5 ml/s.
  • the etching solution When the etching solution reaches 85°C, it is put into the dried titanium substrate with an area of 10cm 2 , and the etching process is carried out for 1.5 hours to ensure that there is no oxygen in the container when the etching starts, and the etching process is still continuous Nitrogen gas was introduced to obtain an etched titanium substrate, and the etched titanium substrate was used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 45A/cm 2 was obtained at a cell voltage of 1.65V.

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Abstract

The present invention provides a substrate etching method for a titanium-based dimension stabilization type anode. In the etching process, optimization on the titanium substrate surface micro morphology is achieved by using a nitrogen introduction method. The effect of enhancing the bonding force of a substrate and a coating is achieved by improving the surface roughness of the substrate, and therefore the purposes of effectively prolonging the working life of the titanium-based dimension stabilization type anode and improving the working efficiency of electrodes to a certain extent are achieved. Compared with a conventional titanium substrate, the method can achieve the purposes of saving electrodeposition energy consumption, reducing electrode damage and reducing the replacement cost, and satisfies the industrial application demands for less electrode preparation processes and low cost.

Description

一种钛基尺寸稳定型阳极的基体刻蚀方法Matrix etching method for titanium-based dimensionally stable anode 技术领域Technical field
本发明属于电化学工业电极材料技术领域，具体涉及一种钛基尺寸稳定型阳极的基体刻蚀方法。The invention belongs to the technical field of electrochemical industrial electrode materials, and specifically relates to a matrix etching method for a titanium-based dimensionally stable anode.
背景技术Background technique
目前湿法冶金技术仍广泛应用于铜、锌等金属的生产，电沉积过程为其中重要的一步。电沉积过程中，金属在阴极析出，阳极则发生氧析出反应(OER)。这一过程需要消耗大量电能。电能的消耗主要来自于较高的阳极OER过电位，因此制备较高活性OER阳极在节能减排，降低成本方面至关重要。以往工业中常使用铅基阳极进行电沉积，然而因其易蠕变，OER过电位较高，易引入Pb元素导致阴极产物污染，在生产中的使用受到限制。DSA作为一种尺寸稳定且OER过电位低的阳极具有较高实用价值，然而其催化性氧化物涂层因使用环境为酸性，仅局限于IrO 2，RuO 2等。由于DSA电极在电沉积过程中的工作条件较苛刻，大多数金属或金属氧化物无法满足其使用条件。尽管IrO 2，RuO 2可作为高效率催化剂涂层使用，DSA电极仍需要进行电极稳定性相关的研究。目前工业生产中使用的DSA电极使用寿命在5-10年。同时目前将氧化物涂层涂敷在钛基体上的方法为热沉积法。这一方法需要耗费较多贵金属盐溶液作为原来，成本较高。且过程中需要进行多次热处理增强涂层结合力，工序繁琐，催化电极的失效原因主要为催化剂涂层在析氧反应过程中逐渐溶解在电解质溶液中。酸性电解质溶液由涂层缝隙逐渐渗透到更深处直至钛基体。在较高电流密度下，钛基体受到腐蚀并进一步导致槽电压的升高以及催化剂涂层的脱落。 At present, hydrometallurgical technology is still widely used in the production of metals such as copper and zinc, and the electrodeposition process is an important step. During the electrodeposition process, the metal is precipitated at the cathode and the oxygen evolution reaction (OER) occurs at the anode. This process requires a lot of power consumption. The power consumption mainly comes from the higher anode OER overpotential. Therefore, the preparation of higher active OER anode is very important in terms of energy saving, emission reduction and cost reduction. In the past, lead-based anodes were often used for electrodeposition in the industry. However, due to its easy creep and high OER overpotential, it is easy to introduce Pb elements to cause cathode product pollution, and its use in production is restricted. DSA has high practical value as an anode with stable dimensions and low OER overpotential. However, its catalytic oxide coating is limited to IrO 2 , RuO 2 and so on due to the acidic environment. Due to the harsh working conditions of the DSA electrode in the electrodeposition process, most metals or metal oxides cannot meet their use conditions. Although IrO 2 and RuO 2 can be used as high-efficiency catalyst coatings, DSA electrodes still need to be studied on electrode stability. The service life of DSA electrodes currently used in industrial production is 5-10 years. At the same time, the current method for coating the oxide coating on the titanium substrate is thermal deposition. This method needs to consume more precious metal salt solution as the original, and the cost is higher. In addition, multiple heat treatments are required to enhance the bonding force of the coating during the process, and the process is complicated. The main reason for the failure of the catalytic electrode is that the catalytic coating gradually dissolves in the electrolyte solution during the oxygen evolution reaction. The acidic electrolyte solution gradually penetrates deeper into the titanium matrix from the coating gap. At higher current densities, the titanium substrate is corroded and further leads to an increase in cell voltage and the shedding of the catalyst coating.
发明概述Summary of the invention
技术问题technical problem
问题的解决方案The solution to the problem
技术解决方案Technical solutions
本发明的目的是克服上述现有技术存在的不足，提供一种钛基尺寸稳定型阳极 的基体刻蚀方法。由该钛基体制得的DSA具有较高的OER催化活性，并且具有更长的工作寿命。可以有效延长DSA使用时间，减少废旧电极更换导致的成本，该方法以15-40％质量分数的硫酸溶液为例，对传统钛基体刻蚀方法进行优化。即在刻蚀过程中通入氮气。通过排出刻蚀溶液中溶解的氧气，以及改变钛基体的表面粗糙度，达到延长DSA使用寿命的效果。The purpose of the present invention is to overcome the above-mentioned shortcomings in the prior art and provide a method for etching the substrate of a titanium-based dimensionally stable anode. The DSA obtained from the titanium-based system has higher OER catalytic activity and a longer working life. It can effectively extend the use time of DSA and reduce the cost caused by the replacement of waste electrodes. This method takes 15-40% sulfuric acid solution as an example to optimize the traditional titanium matrix etching method. That is, nitrogen gas is introduced during the etching process. By exhausting the dissolved oxygen in the etching solution and changing the surface roughness of the titanium substrate, the effect of extending the service life of the DSA is achieved.
为实现上述目的，本发明采用以下技术方案：In order to achieve the above objectives, the present invention adopts the following technical solutions:
一种钛基尺寸稳定型阳极的基体刻蚀方法，具体步骤包括如下：A method for etching the substrate of a titanium-based dimensionally stable anode. The specific steps include the following:
步骤1，钛基体制备：Step 1. Preparation of titanium substrate:
(1)将工业用钛基体进行清洗，去除其表面油污；(1) Clean the industrial titanium substrate to remove oil stains on its surface;
(2)将清洁后钛基体干燥10-60min，获得干燥后钛基体；(2) Dry the cleaned titanium substrate for 10-60 minutes to obtain a dried titanium substrate;
步骤2，刻蚀：Step 2. Etching:
(1)配制质量分数为15-40％的酸溶液，作为刻蚀溶液，放置于密封容器中，所述的刻蚀溶液量以保证每cm 2钛基体进行刻蚀过程时，刻蚀液体积为10-100ml为准； (1) Prepare an acid solution with a mass fraction of 15-40%, and place it in a sealed container as an etching solution. The amount of the etching solution is to ensure that the volume of the etching solution per cm 2 of the titanium substrate during the etching process 10-100ml shall prevail;
(2)加热刻蚀溶液，使溶液温度升至刻蚀温度80-100℃，并在刻蚀溶液升温过程中，向溶液中持续通入氮气，以保证刻蚀溶液升至刻蚀温度时，容器内无空气存在；(2) Heat the etching solution to raise the temperature of the solution to the etching temperature of 80-100°C. During the heating process of the etching solution, continue to pour nitrogen into the solution to ensure that when the etching solution rises to the etching temperature, There is no air in the container;
(3)刻蚀溶液达到设定温度时，放入烘干后的钛基体，进行刻蚀，获得刻蚀钛基体，作为钛基尺寸稳定型阳极基体用，其中，所述的刻蚀时间为0.5-3h，并在刻蚀过程中，使刻蚀溶液温度保持在80-100℃，并持续通入氮气。(3) When the etching solution reaches the set temperature, put in the dried titanium substrate and etch to obtain the etched titanium substrate, which can be used as the titanium-based dimensionally stable anode substrate, wherein the etching time is 0.5-3h, and during the etching process, keep the etching solution temperature at 80-100°C and continue to blow in nitrogen.
所述的步骤1(1)中，工业用钛基体为TA1钛基体或TA2钛基体。In the step 1 (1), the industrial titanium substrate is TA1 titanium substrate or TA2 titanium substrate.
所述的步骤1(1)中，清洗过程为：用去离子水、无水乙醇分别清洗5-20min，完成清洗。In the step 1 (1), the cleaning process is: cleaning with deionized water and absolute ethanol for 5-20 minutes respectively to complete the cleaning.
所述的步骤1(2)中，干燥操作在空气中进行，或在40-80℃烘箱中进行。In the step 1 (2), the drying operation is carried out in the air or in an oven at 40-80°C.
所述的步骤2(1)中，酸溶液为硫酸溶液，草酸溶液或盐酸溶液。In the step 2 (1), the acid solution is sulfuric acid, oxalic acid or hydrochloric acid.
所述的步骤2(1)中，密封容器设有进气口和出气口。In the step 2 (1), the sealed container is provided with an air inlet and an air outlet.
所述的步骤2(2)中，氮气通入方式为：当刻蚀溶液升温至20-70℃时，由容器进气口，深入液体内，向溶液内通入氮气，氮气通入流速为2-5ml/s，以保证以保 证刻蚀溶液升至刻蚀温度时，容器内空气完全由出气口排出。In the step 2(2), the method of introducing nitrogen gas is as follows: when the etching solution is heated to 20-70°C, the gas inlet of the container penetrates into the liquid, and nitrogen gas is introduced into the solution. The nitrogen gas flow rate is 2-5ml/s to ensure that when the etching solution rises to the etching temperature, the air in the container is completely discharged from the air outlet.
所述的步骤2(3)中，将将刻蚀钛基体制备钛基尺寸稳定型阳极，该钛基尺寸稳定型阳极在1.65V槽电压下获得电流密度25-45A/cm 2。 In the step 2 (3), the titanium substrate will be etched to prepare a titanium-based dimensionally stable anode, which has a current density of 25-45 A/cm 2 under a cell voltage of 1.65V.
当使用传统刻蚀方法时，溶解于刻蚀溶液中的氧气会使钛基体表面在刻蚀温度下形成氧化层，其成分为TiO 2或其他Ti的氧化物。这种氧化层的形成一定程度上阻碍钛基体的刻蚀过程。刻蚀后的基体形貌普遍为尺寸较大(直径50-200μm)的刻蚀坑。本发明的刻蚀方法在刻蚀过程中通入氮气可以抑制这种氧化层的形成，同时氮气气泡的不断鼓入可以防止基体表面局部硫酸浓度过高而导致的刻蚀不均匀情况。因此由本发明提及的刻蚀方法处理的钛基体具有尺寸较小(直径5-15μm)的刻蚀坑，并具有更大粗糙度。 When using the traditional etching method, the oxygen dissolved in the etching solution will cause the surface of the titanium substrate to form an oxide layer at the etching temperature, the composition of which is TiO 2 or other Ti oxides. The formation of this oxide layer hinders the etching process of the titanium matrix to a certain extent. The morphology of the etched substrate is generally larger (50-200μm in diameter) etch pits. In the etching method of the present invention, nitrogen is introduced during the etching process to inhibit the formation of such an oxide layer, and at the same time, the continuous blowing of nitrogen bubbles can prevent uneven etching caused by excessively high local sulfuric acid concentration on the surface of the substrate. Therefore, the titanium substrate processed by the etching method mentioned in the present invention has etch pits with a smaller size (5-15 μm in diameter) and a larger roughness.
由本发明中刻蚀的钛基体制备DSA过程为传统热沉积法。制备的DSA可用于寿命测试实验，并与传统DSA进行比较，本发明与现有DSA基体刻蚀技术相比，仅仅添加氮气通入的步骤，由此增加的制备成本相对低廉。The process of preparing DSA from the etched titanium substrate in the present invention is a traditional thermal deposition method. The prepared DSA can be used for life test experiments and compared with traditional DSA. Compared with the existing DSA matrix etching technology, the present invention only adds the step of introducing nitrogen gas, thereby increasing the cost of preparation relatively low.
发明的有益效果The beneficial effects of the invention
有益效果Beneficial effect
本发明刻蚀过程中氮气的通入提升了钛基体的粗糙度，通过原子力显微镜测试得到基体Rq值(表面刻蚀坑深度均方根)最高可由43nm提升到189nm。每平方厘米DSA的电极活性面积最高可由26.8cm 2提升为44.4cm 2。槽电压为1.65V时，电极的电流密度最高可由20A/cm 2提升至45A/cm 2，因此有效提升电沉积效率。 The introduction of nitrogen gas during the etching process of the present invention improves the roughness of the titanium substrate, and the Rq value (root mean square of the surface etching pit depth) of the substrate obtained by the atomic force microscope test can be increased from 43nm to 189nm at the highest. The electrode active area per square centimeter of DSA can be increased from 26.8cm 2 to 44.4cm 2 . When the cell voltage is 1.65V, the current density of the electrode can be increased from 20A/cm 2 to 45A/cm 2 at the highest, thus effectively improving the electrodeposition efficiency.
并且，通过本发明方法能够获得更高的基体粗糙度，增强了涂层与基体之间的结合力。在电沉积过程中有效延迟了电极涂层的脱落，从而延长电极使用寿命。In addition, higher substrate roughness can be obtained by the method of the present invention, and the bonding force between the coating and the substrate can be enhanced. During the electrodeposition process, the peeling off of the electrode coating is effectively delayed, thereby prolonging the service life of the electrode.
对附图的简要说明Brief description of the drawings
附图说明Description of the drawings
图1为本发明实施例1获得的刻蚀后钛基体扫描电镜(SEM)图片；Figure 1 is a scanning electron microscope (SEM) picture of a titanium substrate after etching obtained in Example 1 of the present invention;
图2为本发明实施例1制备DSA电极与对比例1传统DSA的加速失效实验结果对比图；2 is a comparison diagram of the accelerated failure experiment results of the DSA electrode prepared in Example 1 of the present invention and the conventional DSA in Comparative Example 1;
图3为本发明实施例1制备DSA与对比例1制备的DSA电极的极化曲线对比图。3 is a comparison diagram of the polarization curves of the DSA electrode prepared in Example 1 of the present invention and the DSA electrode prepared in Comparative Example 1.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
下面结合实施例对本发明作进一步的详细说明。The present invention will be further described in detail below in conjunction with the embodiments.
以下实施例与对比例中：In the following examples and comparative examples:
钛基体厚度为0.5-1mm；The thickness of the titanium substrate is 0.5-1mm;
由刻蚀钛基体制备钛基尺寸稳定型阳极DSA的方法过程为：The method of preparing titanium-based dimensionally stable anode DSA by etching the titanium substrate is as follows:
(1)称量氯铱酸(H 2IrCl 6·6H 2O)、TaCl 5，二者摩尔比为7∶3，且保证Ir元素的负载量为1.5mg/cm 2； (1) Weigh chloroiridic acid (H 2 IrCl 6 ·6H 2 O) and TaCl 5 , the molar ratio of the two is 7:3, and ensure that the loading amount of Ir element is 1.5 mg/cm 2 ;
(2)将两种物质混合均匀，并加入体积比为1∶1的乙醇/异丙醇混合溶液，配置成前驱体溶液。其中Ir元素浓度为5mg/ml；(2) Mix the two substances uniformly, and add a mixture solution of ethanol/isopropanol with a volume ratio of 1:1 to prepare a precursor solution. The concentration of Ir element is 5mg/ml;
(3)用刷子将前驱体溶液均匀涂覆在处理好的钛基体表面，并进行15min120℃的烘干；(3) Use a brush to evenly coat the precursor solution on the surface of the treated titanium substrate, and dry it at 120°C for 15 minutes;
(4)对电极进行450℃，10min的热处理过程；(4) Heat the electrode at 450℃ for 10min;
(5)步骤3、4重复十五次，即共进行15次涂敷过程，最后一次热处理过程进行1h；(5) Steps 3 and 4 are repeated fifteen times, that is, a total of 15 coating processes are performed, and the last heat treatment process is performed for 1 hour;
(6)待电极随炉冷却至室温后即可取出进行测试或使用。(6) After the electrode is cooled to room temperature with the furnace, it can be taken out for testing or use.
实施例1与对比例1的加速实验测试采用高电流密度下的计时电位测试，其条件为：(1)电流密度为10mA/cm 2；(2)测试环境为1mol/L硫酸溶液；(3)测试温度为80℃。 The accelerated experiment test of Example 1 and Comparative Example 1 adopts chronopotentiometric test under high current density, and the conditions are: (1) Current density is 10mA/cm 2 ; (2) The test environment is 1mol/L sulfuric acid solution; (3) ) The test temperature is 80°C.
实施例1：Example 1:
将TA1钛基体用去离子水、无水乙醇分别进行5min清洗，去除基体表面的油污。随后，将清洁后的钛基体在空气中风干30min。配制质量分数为15％的硫酸溶液500ml作为刻蚀溶液.放置于密封容器中，密封容器设有进气口和出气口，水浴加热刻蚀溶液并使其温度保持在85℃。在刻蚀溶液温度达到30℃时，以2ml/s的速度向溶液中通入氮气。刻蚀溶液达到85℃时放入烘干后的钛基体，其面积为10cm 2，进行1h的刻蚀过程，保证刻蚀开始时，容器内无氧气存在，并在刻蚀过程中仍不断通入氮气，获得刻蚀钛基体，该刻蚀后钛基体扫描电镜(SEM)图如图1所示，通过原子力显微镜测试得到基体Rq值(表面刻蚀坑深度均方根)为189nm 。将该刻蚀钛基体制备钛基尺寸稳定型阳极DSA，每平方厘米DSA的电极活性面积为44.4cm 2，在1.65V槽电压下可获得电流密度45A/cm 2。 The TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 15% sulfuric acid solution as the etching solution. Place it in a sealed container with air inlets and outlets. The etching solution is heated in a water bath and the temperature is maintained at 85°C. When the temperature of the etching solution reached 30°C, nitrogen was introduced into the solution at a rate of 2ml/s. When the etching solution reaches 85℃, it is put into the dried titanium substrate with an area of 10cm 2 , and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas was introduced to obtain the etched titanium substrate. The scanning electron microscope (SEM) image of the titanium substrate after the etching is shown in Figure 1. The Rq value (root mean square of the surface etch pit depth) of the substrate was 189 nm through the atomic force microscope test. The titanium-based dimensionally stable anode DSA was prepared by etching the titanium substrate. The active area of the electrode per square centimeter of the DSA was 44.4 cm 2 , and the current density of 45 A/cm 2 was obtained at a cell voltage of 1.65V.
对比例1Comparative example 1
将TA1钛基体用去离子水、无水乙醇分别进行5min清洗，去除基体表面的油污。随后，将清洁后的钛基体在空气中风干30min。配制质量分数为15％的硫酸溶液500ml作为刻蚀溶液.水浴加热刻蚀溶液并使其温度保持在85℃。刻蚀溶液达到85℃时放入烘干后的钛基体，其面积为10cm 2，进行1h的刻蚀过程，获得刻蚀钛基体，通过原子力显微镜测试得到基体Rq值(表面刻蚀坑深度均方根)为43nm，将该刻蚀钛基体制备钛基尺寸稳定型阳极DSA，每平方厘米DSA的电极活性面积为26.8cm 2，在1.65V槽电压下可获得电流密度25A/cm 2。 The TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 85°C. When the etching solution reaches 85℃, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1h to obtain the etched titanium substrate. The Rq value of the substrate is obtained by the atomic force microscope test (the depth of the surface etching pits is equal root) is 43nm, the etching of the titanium-based preparation yl dimensionally stable titanium anodes DSA, DSA per square centimeter of active electrode area 26.8cm 2, the current density obtainable 25A / cm 2 at a cell voltage of 1.65V.
上述实施例1制备DSA电极与对比例1传统DSA的加速失效实验结果对比图如图2所示，实施例1制备DSA与对比例1制备的DSA电极的极化曲线对比图如图3所示，图中，“本专利刻蚀方法制备DSA”即为实施例制备DSA，“传统DSA”即为对比例1制备的DSA。The comparison diagram of the accelerated failure experiment results of the DSA electrode prepared in Example 1 and the conventional DSA in Comparative Example 1 is shown in Figure 2, and the polarization curve comparison diagram of the DSA electrode prepared in Example 1 and the DSA electrode prepared in Comparative Example 1 is shown in Figure 3. In the figure, "Preparation of DSA by the etching method of this patent" is the DSA prepared in the example, and "conventional DSA" is the DSA prepared in Comparative Example 1.
实施例2：Example 2:
将TA1钛基体用去离子水、无水乙醇分别进行15min清洗，去除基体表面的油污。随后，将清洁后的钛基体在空气中风干30min。配制质量分数为15％的硫酸溶液800ml作为刻蚀溶液.水浴加热刻蚀溶液并使其温度保持在85℃。在刻蚀溶液温度达到70℃时，以4ml/s的速度向溶液中通入氮气。刻蚀溶液达到85℃时放入烘干后的钛基体，其面积为10cm 2，进行1h的刻蚀过程，保证刻蚀开始时，容器内无氧气存在，并在刻蚀过程中仍不断通入氮气，获得刻蚀钛基体，将该刻蚀钛基体制备钛基尺寸稳定型阳极DSA，在1.65V槽电压下可获得电流密度35A/cm 2。 The TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 15 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 800ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 85°C. When the temperature of the etching solution reached 70°C, nitrogen was introduced into the solution at a rate of 4ml/s. When the etching solution reaches 85℃, it is put into the dried titanium substrate with an area of 10cm 2 , and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas is introduced to obtain an etched titanium substrate, and the etched titanium substrate is used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 35A/cm 2 can be obtained at a cell voltage of 1.65V.
实施例3：Example 3:
将TA1钛基体用去离子水、无水乙醇分别进行10min清洗，去除基体表面的油污。随后，将清洁后的钛基体在60℃烘箱中烘干20min。配制质量分数为30％的硫酸溶液900ml作为刻蚀溶液.水浴加热刻蚀溶液并使其温度保持在90℃。在刻蚀溶液温度达到30℃时，以3ml/s的速度向溶液中通入氮气。刻蚀溶液达到90℃时 放入烘干后的钛基体，其面积为10cm 2，进行1h的刻蚀过程，保证刻蚀开始时，容器内无氧气存在，并在刻蚀过程中仍不断通入氮气，获得刻蚀钛基体，将该刻蚀钛基体制备钛基尺寸稳定型阳极DSA，在1.65V槽电压下可获得电流密度25A/cm 2。 The TA1 titanium substrate was cleaned with deionized water and absolute ethanol for 10 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in an oven at 60°C for 20 minutes. Prepare 900 ml of sulfuric acid solution with a mass fraction of 30% as the etching solution. Heat the etching solution in a water bath and keep the temperature at 90°C. When the temperature of the etching solution reached 30°C, nitrogen was introduced into the solution at a rate of 3ml/s. When the etching solution reaches 90℃, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas is introduced to obtain an etched titanium substrate. The etched titanium substrate is used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 25A/cm 2 can be obtained at a cell voltage of 1.65V.
实施例4：Example 4:
将TA2钛基体用去离子水、无水乙醇分别进行5min清洗，去除基体表面的油污。随后，将清洁后的钛基体在空气中风干30min。配制质量分数为15％的硫酸溶液500ml作为刻蚀溶液.水浴加热刻蚀溶液并使其温度保持在80℃。在刻蚀溶液温度达到50℃时，以2ml/s的速度向溶中通入氮气。刻蚀溶液达到80℃时放入烘干后的钛基体，其面积为10cm 2，进行1h的刻蚀过程，保证刻蚀开始时，容器内无氧气存在，并在刻蚀过程中仍不断通入氮气，获得刻蚀钛基体，将该刻蚀钛基体制备钛基尺寸稳定型阳极DSA，在1.65V槽电压下可获得电流密度42A/cm 2。 The TA2 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 80°C. When the temperature of the etching solution reaches 50°C, nitrogen is introduced into the solution at a rate of 2ml/s. When the etching solution reaches 80℃, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1 hour to ensure that there is no oxygen in the container at the beginning of the etching, and it is still continuously connected during the etching process. Nitrogen gas was introduced to obtain an etched titanium substrate, and the etched titanium substrate was used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 42A/cm 2 was obtained at a cell voltage of 1.65V.
实施例5：Example 5:
将TA2钛基体用去离子水、无水乙醇分别进行5min清洗，去除基体表面的油污。随后，将清洁后的钛基体在空气中风干30min。配制质量分数为25％的硫酸溶液500ml作为刻蚀溶液.水浴加热刻蚀溶液并使其温度保持在80℃。在刻蚀溶液温度达到50℃时，以2ml/s的速度向溶液中通入氮气。刻蚀溶液达到80℃时放入烘干后的钛基体，其面积为10cm 2，进行1.5h的刻蚀过程，保证刻蚀开始时，容器内无氧气存在，并在刻蚀过程中仍不断通入氮气，获得刻蚀钛基体，将该刻蚀钛基体制备钛基尺寸稳定型阳极DSA，在1.65V槽电压下可获得电流密度43A/cm 2。 The TA2 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 30 minutes. Prepare 500ml of 25% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 80°C. When the temperature of the etching solution reaches 50° C., nitrogen gas is introduced into the solution at a rate of 2 ml/s. When the etching solution reaches 80℃, it is put into the dried titanium substrate with an area of 10cm 2 and the etching process is carried out for 1.5 hours to ensure that there is no oxygen in the container at the beginning of the etching, and it will continue during the etching process. Nitrogen gas is introduced to obtain an etched titanium substrate, and the etched titanium substrate is used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 43A/cm 2 can be obtained at a cell voltage of 1.65V.
实施例6：Example 6:
将TA2钛基体用去离子水、无水乙醇分别进行5min清洗，去除基体表面的油污。随后，将清洁后的钛基体在空气中风干60min。配制质量分数为15％的硫酸溶液1000ml作为刻蚀溶液.水浴加热刻蚀溶液并使其温度保持在85℃。在刻蚀溶液温度达到40℃时，以5ml/s的速度向溶液中通入氮气。刻蚀溶液达到85℃时放入烘干后的钛基体，其面积为10cm 2，进行1.5h的刻蚀过程，保证刻蚀开始时，容器内无氧气存在，并在刻蚀过程中仍不断通入氮气，获得刻蚀钛基体，将该刻 蚀钛基体制备钛基尺寸稳定型阳极DSA，在1.65V槽电压下可获得电流密度45A/cm 2。 The TA2 titanium substrate was cleaned with deionized water and absolute ethanol for 5 minutes to remove oil stains on the surface of the substrate. Subsequently, the cleaned titanium substrate was dried in air for 60 minutes. Prepare 1000ml of 15% sulfuric acid solution as the etching solution. Heat the etching solution in a water bath and keep the temperature at 85°C. When the temperature of the etching solution reaches 40°C, nitrogen gas is introduced into the solution at a rate of 5 ml/s. When the etching solution reaches 85℃, it is put into the dried titanium substrate with an area of 10cm 2 , and the etching process is carried out for 1.5 hours to ensure that there is no oxygen in the container when the etching starts, and the etching process is still continuous Nitrogen gas was introduced to obtain an etched titanium substrate, and the etched titanium substrate was used to prepare a titanium-based dimensionally stable anode DSA, and a current density of 45A/cm 2 was obtained at a cell voltage of 1.65V.

Claims (7)

  1. 一种钛基尺寸稳定型阳极的基体刻蚀方法，其特征在于，具体步骤包括如下：A method for etching the substrate of a titanium-based dimensionally stable anode, which is characterized in that the specific steps include the following:
    步骤1，钛基体制备：Step 1. Preparation of titanium substrate:
    (1)将工业用钛基体进行清洗，去除其表面油污；(1) Clean the industrial titanium substrate to remove oil stains on its surface;
    (2)将清洁后钛基体干燥10-60min，获得干燥后钛基体；(2) Dry the cleaned titanium substrate for 10-60 minutes to obtain a dried titanium substrate;
    步骤2，刻蚀：Step 2. Etching:
    (1)配制质量分数为15-40％的酸溶液，作为刻蚀溶液，放置于密封容器中，所述的刻蚀溶液量以保证每cm 2钛基体进行刻蚀过程时，刻蚀液体积为10-100ml为准； (1) Prepare an acid solution with a mass fraction of 15-40%, and place it in a sealed container as an etching solution. The amount of the etching solution is to ensure that the volume of the etching solution per cm 2 of the titanium substrate during the etching process 10-100ml shall prevail;
    (2)加热刻蚀溶液，使溶液温度升至刻蚀温度80-100℃，并在刻蚀溶液升温过程中，向溶液中持续通入氮气，以保证刻蚀溶液升至刻蚀温度时，容器内无空气存在；(2) Heat the etching solution to raise the temperature of the solution to the etching temperature of 80-100°C. During the heating process of the etching solution, continue to pour nitrogen into the solution to ensure that when the etching solution rises to the etching temperature, There is no air in the container;
    (3)刻蚀溶液达到设定温度时，放入烘干后的钛基体，进行刻蚀，获得刻蚀钛基体，作为钛基尺寸稳定型阳极基体用，其中，所述的刻蚀时间为0.5-3h，并在刻蚀过程中，使刻蚀溶液温度保持在80-100℃，并持续通入氮气。(3) When the etching solution reaches the set temperature, put in the dried titanium substrate and etch to obtain the etched titanium substrate, which can be used as the titanium-based dimensionally stable anode substrate, wherein the etching time is 0.5-3h, and during the etching process, keep the etching solution temperature at 80-100°C and continue to blow in nitrogen.
  2. 根据权利要求1所述的钛基尺寸稳定型阳极的基体刻蚀方法，其特征在于，所述的步骤1(1)中，工业用钛基体为TA1钛基体或TA2钛基体。The substrate etching method for a titanium-based dimensionally stable anode according to claim 1, wherein in the step 1 (1), the industrial titanium substrate is TA1 titanium substrate or TA2 titanium substrate.
  3. 根据权利要求1所述的钛基尺寸稳定型阳极的基体刻蚀方法，其特征在于，所述的步骤1(2)中，干燥操作在空气中进行，或在40-80℃烘箱中进行。The substrate etching method of titanium-based dimensionally stable anode according to claim 1, characterized in that, in the step 1 (2), the drying operation is carried out in air or in an oven at 40-80°C.
  4. 根据权利要求1所述的钛基尺寸稳定型阳极的基体刻蚀方法，其特征在于，所述的步骤2(1)中，酸溶液为硫酸溶液，草酸溶液或盐酸溶液。The substrate etching method for a titanium-based dimensionally stable anode according to claim 1, wherein in the step 2 (1), the acid solution is a sulfuric acid solution, an oxalic acid solution or a hydrochloric acid solution.
  5. 根据权利要求1所述的钛基尺寸稳定型阳极的基体刻蚀方法，其特征在于，所述的步骤2(1)中，密封容器设有进气口和出气口。The substrate etching method for a titanium-based dimensionally stable anode according to claim 1, wherein in the step 2 (1), the sealed container is provided with an air inlet and an air outlet.
  6. 根据权利要求5所述的钛基尺寸稳定型阳极的基体刻蚀方法，其特征在于，所述的步骤2(2)中，氮气通入方式为：当刻蚀溶液升温至20-70℃时，由容器进气口向溶液内通入氮气，氮气通入流速为2-5ml/s，以保证以保证刻蚀溶液升至刻蚀温度时，容器内空气完全由出气口排出。The method for etching the substrate of a titanium-based dimensionally stable anode according to claim 5, characterized in that, in the step 2 (2), the way of introducing nitrogen gas is: when the etching solution is heated to 20-70°C , Nitrogen is introduced into the solution from the air inlet of the container, and the nitrogen flow rate is 2-5ml/s to ensure that when the etching solution rises to the etching temperature, the air in the container is completely discharged from the air outlet.
  7. 根据权利要求1所述的钛基尺寸稳定型阳极的基体刻蚀方法，其特征在于，所述的步骤2(3)中，将刻蚀钛基体制备钛基尺寸稳定型阳极，该钛基尺寸稳定型阳极在1.65V槽电压下获得电流密度25-45A/cm 2。 The method for etching a titanium-based dimensionally stable anode substrate according to claim 1, wherein in step 2(3), the titanium substrate is etched to prepare a titanium-based dimensionally stable anode, and the size of the titanium substrate is The stable anode has a current density of 25-45A/cm 2 at a cell voltage of 1.65V.
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