CN101894675B - Method for preparing titanium-based super capacitor membrane electrode - Google Patents

Abstract

The invention discloses a method for preparing a titanium-based super capacitor membrane electrode, which is characterized by comprising the following steps: 1) spraying sands; 2) removing oil; 3) carrying out acid-washing and etching; 4) adding an interlayer; and 5) electrochemically depositing an active MnO2 coating. The method has the advantages that: the interlayer of the prepared electrode is firmly combined with the matrix of the electrode, and the MnO2 coating is provided with a plurality of micropores which facilitate exchanging active substances, and is not easy to fall off; the electrode has good cyclical stability, and is high in specific capacity, long in service life and good in adhesion of the coating; and the electrolyte is neutral Na2SO4 solution, which is convenient to promote and apply in industry.

Description

Translated fromChinese

一种钛基超级电容器薄膜电极的制作方法A kind of fabrication method of titanium-based supercapacitor film electrode

技术领域technical field

本发明涉及一种电极的制作方法，尤其涉及一种钛基超级电容器薄膜电极的制作方法。The invention relates to a method for manufacturing an electrode, in particular to a method for manufacturing a thin film electrode of a titanium-based supercapacitor.

背景技术Background technique

当前，电子领域的发展趋势是便携式电子器件的体积在大幅降低，但是能量消耗却在增长。传统的电池越来越难以应付日益增长的能耗要求。电池的充电速度比较慢，因为其以化学方式存储能量。比较而言，在电子领域应用普遍的电容器可以在瞬间充电，但是容纳的电量却很少。近年来，超级电容器由于其超高充放电性能和储能性能(即高能量密度和功率密度)以被广泛应用于电子设备及复合能量汽车的备用电源或辅助装置，以满足现实中需要瞬间提供大功率大电流的需要。并且超级电容器的使用材料无毒无污染，对环境友好。以上诸多优点已经受到世界各国的科研工作者的关注和研究，其广阔的应用前景毋庸质疑。Currently, the development trend in the electronic field is that the volume of portable electronic devices is greatly reduced, but the energy consumption is increasing. Conventional batteries are becoming more and more difficult to cope with the increasing energy consumption requirements. Batteries charge slowly because they store energy chemically. In comparison, capacitors, which are widely used in electronics, can be charged in an instant, but hold very little power. In recent years, due to its ultra-high charge and discharge performance and energy storage performance (that is, high energy density and power density), supercapacitors have been widely used in backup power supplies or auxiliary devices for electronic equipment and hybrid energy vehicles to meet the needs of real-world instant supply. The need for high power and high current. Moreover, the materials used in the supercapacitor are non-toxic and pollution-free, and are friendly to the environment. Many of the above advantages have been paid attention to and researched by researchers from all over the world, and its broad application prospects are beyond doubt.

目前用于超级电容器的电极材料主要有：炭材料，过渡金属氧化物和导电聚合物。其中金属氧化物先后出现了以下一些氧化物电极材料：RuO₂、MnO₂、NiO、CoO₂等。众所周知，RuO₂比电容很高，是理想的超级电容器材料，但其价格昂贵，污染环境且不容易获取。而MnO₂的生产成本低、来源广、电化学性能稳定、毒性小、对环境友好，近年来成为超级电容器电极材料的研究焦点。然而制备MnO₂的方法有很多，如热分解法、溶胶凝胶法、电解法、电沉积法等。其中电沉积法是近年来发展较为迅速的制备MnO₂薄膜电极的方法。电沉积法所得的沉积层具有独特的高密度和低空隙率；工艺上易通过改变电参数、电解液成分等条件来控制材料的化学成分、结晶组织和晶粒大小；同时现有的电镀和电铸业已为其提供了广泛的基础，将该技术从实验室转向现有的电镀和电铸工业所需要克服的技术障碍小，成本低。The electrode materials currently used in supercapacitors mainly include: carbon materials, transition metal oxides and conductive polymers. Among them, metal oxides have appeared in the following oxide electrode materials: RuO₂ , MnO₂ , NiO, CoO₂ and so on. As we all know,_RuO2 has a high specific capacitance and is an ideal supercapacitor material, but it is expensive, pollutes the environment and is not easy to obtain. However, MnO₂ has low production cost, wide sources, stable electrochemical performance, low toxicity, and environmental friendliness, and has become the research focus of supercapacitor electrode materials in recent years. However, there are many ways to prepare MnO₂ , such as thermal decomposition, sol-gel method, electrolysis, electrodeposition and so on. Among them, the electrodeposition method is a method for preparing MnO₂ thin film electrodes that has developed rapidly in recent years. The deposited layer obtained by the electrodeposition method has a unique high density and low porosity; it is easy to control the chemical composition, crystal structure and grain size of the material by changing the electrical parameters, electrolyte composition and other conditions in the process; at the same time, the existing electroplating and The electroforming industry has provided it with a broad base, and the technical barriers that need to be overcome to transfer this technology from the laboratory to the existing electroplating and electroforming industries are small and low-cost.

在石墨等炭基体上阳极电沉积MnO₂则有可能出现由于基体强度不足所产生的种种问题，而金属Ti则具有较高的机械强度和延展性能。由于其近年来氯碱工业上的广泛应用也验证了Ti作为基体的优越性。同时由于在电沉积活性物质MnO₂的时候阳极极化后，基体与镀层的界面处容易生成导电性差的TiO₂，使得镀层容易脱落，并影响电极寿命。为改善镀层与基体结合不牢固，阳极寿命短等缺点，为提升镀层与Ti基体的结合力，研究人员采用的往基体和镀层之间添加中间层的方法。单纯MnO₂是半导体其导电性不好，同时其疏松的结构也使得电极寿命缩短。在电沉积过程中掺杂其它物质是改变电沉积MnO₂的有效方法。Mo，Fe的掺入有利于提高MnO₂的导电性，使结构更紧密，有效的提高电极的比电容。Anodic electrodeposition of MnO₂ on graphite and other carbon substrates may cause various problems due to insufficient substrate strength, while metal Ti has high mechanical strength and ductility. Due to its extensive application in the chlor-alkali industry in recent years, the superiority of Ti as a matrix has also been verified. At the same time, due to the anodic polarization during electrodeposition of the active material MnO₂ , TiO₂ with poor conductivity is easily formed at the interface between the substrate and the coating, which makes the coating easy to fall off and affects the life of the electrode. In order to improve the shortcomings such as weak bonding between the coating and the substrate and short anode life, and to improve the bonding force between the coating and the Ti substrate, the researchers adopted the method of adding an intermediate layer between the substrate and the coating. Pure MnO₂ is a semiconductor and its conductivity is not good, and its loose structure also shortens the life of the electrode. Doping other substances during electrodeposition is an effective way to modify electrodeposited_MnO2 . The doping of Mo and Fe is beneficial to improve the conductivity of_MnO2 , make the structure more compact, and effectively improve the specific capacitance of the electrode.

发明内容Contents of the invention

本发明的目的在于提供一种钛基超级电容器薄膜电极的制作方法，该方法使用纯金属钛作为基体，先在基体上采用热分解法涂覆IrO₂、IrO₂+MnO₂、IrO₂-Ta₂O₅、IrO₂-Ta₂O₅-SnO₂或IrO₂-Ta₂O₅-SiO₂中间层，再通过电化学沉积在钛基体上获得掺杂Mo，Fe的MnO₂镀层从而获得成品。The object of the present invention is to provide a method for making a titanium-based supercapacitor film electrode. The method uses pure metal titanium as a substrate, and first coats the substrate with IrO₂ , IrO₂ +MnO₂ , and IrO₂ -Ta by thermal decomposition.₂ O₅ , IrO₂ -Ta₂ O₅ -SnO₂ or IrO₂ -Ta₂ O₅ -SiO₂ interlayer, and then electrochemically deposited on the titanium substrate to obtain Mo, Fe-doped MnO₂ coating to obtain the finished product .

本发明是这样来实现的，其特征是方法步骤为：The present invention is realized like this, it is characterized in that method step is:

1)喷砂：将加工好的纯钛板进行喷砂处理使表面粗糙度加大，保证镀层与基体结合更为牢固；1) Sandblasting: Sandblasting the processed pure titanium plate to increase the surface roughness and ensure a firmer bond between the coating and the substrate;

2)除油：将加工好的纯钛板放入烧杯中，加入除油液超声清洗20～30min，加热温度控制在30℃～65℃，清洗完成后再用自来水和去离子水分别冲洗，再吹干，除油液的配方为：NaOH 30～80g/L，Na₂CO₃ 20～40g/L；2) Degreasing: Put the processed pure titanium plate into a beaker, add a degreasing solution for ultrasonic cleaning for 20-30 minutes, control the heating temperature at 30°C-65°C, and rinse with tap water and deionized water after cleaning. Then blow dry, the formula of degreasing liquid is: NaOH 30～80g/L, Na₂ CO₃ 20～40g/L;

3)酸洗刻蚀：将碱洗后的钛板放入15％～50％的硫酸中浸泡，然后用浓度为98％的浓硫酸进一步刻蚀，刻蚀温度70-90℃保持1.5h，直到溶液呈深紫色后取出试样冲洗再晾干；3) Pickling and etching: soak the titanium plate after alkali washing in 15% to 50% sulfuric acid, and then further etch it with concentrated sulfuric acid with a concentration of 98%, and keep the etching temperature at 70-90°C for 1.5h, Take out the sample until the solution turns dark purple, rinse and dry it;

4)添加中间层：(1)采用热分解法在经过处理的钛板上涂覆烧结IrO₂中间层，配制浓度为0.15～0.30mol·dm^-3氯铱酸异丁醇溶液为涂敷液，将涂敷液涂敷于处理好的钛板上，再置于烘箱内70～100℃烘干10～30min，然后于马弗炉内300～600℃进行热分解10min，取出空冷，重复三次，最后一次300～600℃热分解时间为40～90min，获得均匀的钛基IrO₂中间层；4) Adding the middle layer: (1) Coating the sintered_IrO2 middle layer on the treated titanium plate by the thermal decomposition method, and preparing a concentration of 0.15～0.30mol dm^-3 chloroiridic acid isobutanol solution as the coating solution , apply the coating solution on the treated titanium plate, then place it in an oven for 10-30 minutes at 70-100°C, then decompose it in a muffle furnace at 300-600°C for 10 minutes, take it out and air-cool it, repeat three times , the last thermal decomposition time at 300-600 ° C is 40-90 minutes, and a uniform titanium-based IrO₂ intermediate layer is obtained;

5)电化学沉积活性MnO₂镀层：首先把无水MnSO₄与H₂SO₄按摩尔比为2∶5配制成500ml水溶液后将溶液加热到80～100℃，再将封装好的试样置于其中浸泡约2～5min，之后可以通上直流电流，电流密度为2～60mA/cm²，电沉积1～20min后取出清洗晾干，电极制作完毕。5) Electrochemical deposition of active MnO₂ coating: first prepare anhydrous MnSO₄ and H₂ SO₄ with a molar ratio of 2:5 to make 500ml aqueous solution, heat the solution to 80-100°C, and then place the packaged sample in Soak in it for about 2-5 minutes, then apply direct current with a current density of 2-60mA/cm² , take it out after 1-20 minutes of electrodeposition, wash and dry, and the electrode is finished.

所述的添加中间层还可以是：采用热分解法在经过处理的钛板上涂敷烧结SnO₂+SbOx中间层，涂液的溶质为SnCl₄和SbCl₃，溶剂为盐酸和正丁醇的混合溶液，其中Sn、Sb原子比为2～9∶3，总离子浓度0.2～0.8mol·dm^-3，盐酸和正丁醇体积比为1～5∶1，将涂液均匀地涂刷在处理后的钛板上，70～100℃烘干后在450～700℃下热分解10min，重复涂覆3次，最后在500℃下热分解60min，获得均匀的钛基锡锑氧化物中间层。The adding of the intermediate layer can also be: adopting the thermal decomposition method to coat the sintered SnO₂ +SbOx intermediate layer on the treated titanium plate, the solute of the coating solution is SnCl₄ and SbCl₃ , and the solvent is a mixture of hydrochloric acid and n-butanol Solution, in which the atomic ratio of Sn and Sb is 2-9:3, the total ion concentration is 0.2-0.8mol·dm^-3 , the volume ratio of hydrochloric acid and n-butanol is 1-5:1, and the coating liquid is evenly applied after treatment After drying at 70-100°C, thermally decompose at 450-700°C for 10 minutes, repeat the coating for 3 times, and finally thermally decompose at 500°C for 60 minutes to obtain a uniform titanium-based tin antimony oxide intermediate layer.

所述的添加中间层还可以是：采用热分解法在经过处理的钛板上涂敷烧结IrO₂-Ta₂O₅中间层，配制铱钽的乙醇异丙醇涂液，其中铱钽原子比为7∶3，总离子浓度为0.2mol·dm^-3，乙醇和异丙醇体积比为1∶1，将涂敷液均匀地涂刷在钛板上，100℃烘干10min，450℃下热分解15min，重复上述涂刷和热分解过程5次，最后一次450℃烧结60min，获得均匀的钛基铱钽氧化物中间层。The adding of the intermediate layer can also be: adopting thermal decomposition method to coat the sintered IrO₂ -Ta₂ O₅ intermediate layer on the treated titanium plate, and prepare the ethanol isopropanol coating solution of iridium tantalum, wherein the atomic ratio of iridium tantalum to 7:3, the total ion concentration is 0.2mol·dm^-3 , and the volume ratio of ethanol and isopropanol is 1:1. Apply the coating solution evenly on the titanium plate, dry at 100°C for 10min, and then dry at 450°C Thermally decompose for 15 minutes, repeat the above brushing andthermal decomposition process 5 times, and sinter at 450°C for 60 minutes for the last time to obtain a uniform titanium-based iridium-tantalum oxide intermediate layer.

所述的添加中间层还可以是：采用热分解法在经过处理的钛板上涂覆烧结IrO₂+MnO₂中间层，涂敷液为IrMn原子比1∶9～9∶1的HIrC₁₄和Mn(NO₃)₂的水溶液，总金属离子浓度为0.15～0.4mol/L，将涂覆液均匀地涂刷在进过预处理的钛基体上，70～100℃下烘干5～20min，350～550℃下热分解8～25min，重复以上涂刷和热分解步骤，涂覆1～3层，最后一次在350～550℃烧结0.5～3h，即获得钛基锰铱复合氧化物涂层阳极，涂层复合氧化物的担载量为0.5～3g/m²。The adding of the intermediate layer can also be: coating the sintered IrO₂ +MnO₂ intermediate layer on the treated titanium plate by the thermal decomposition method, and the coating solution is HIrC₁₄ with an IrMn atomic ratio of 1:9 to 9:1 and The aqueous solution of Mn(NO₃ )₂ , the total metal ion concentration is 0.15~0.4mol/L, the coating solution is evenly painted on the pretreated titanium substrate, and dried at 70~100°C for 5~20min, Thermally decompose at 350-550°C for 8-25 minutes, repeat the above brushing and thermal decomposition steps, coat 1-3 layers, and sinter at 350-550°C for 0.5-3 hours for the last time to obtain titanium-based manganese-iridium composite oxide coating For the anode, the loading amount of the coated composite oxide is 0.5 to 3 g/m² .

所述的添加中间层还可以是：采用热分解法在经过处理的钛板上涂敷烧结IrO₂-Ta₂O₅-SnO₂中间层：配制铱钽锡原子比为3～7∶4～8∶0.5～1的TaCl₅，H₂IrCl₆，SnCl₂·2H₂O盐酸异丙醇溶液，将涂覆液均匀地涂刷在钛板上，100℃烘干10min，450℃下热分解15min，重复上述涂刷和热分解过程1～5次，最后一次350～550℃热分解0.5～3h，获得均匀的钛基铱钽锡氧化物中间层。The addition of the intermediate layer can also be: apply a sintered IrO₂ -Ta₂ O₅ -SnO₂ intermediate layer on the treated titanium plate by thermal decomposition method: prepare the atomic ratio of iridium, tantalum and tin to 3-7:4- 8: 0.5~1 TaCl₅ , H₂ IrCl₆ , SnCl₂ 2H₂ O hydrochloric acid isopropanol solution, brush the coating liquid evenly on the titanium plate, dry at 100°C for 10min, and thermally decompose at 450°C 15 minutes, repeat the above brushing and thermal decomposition process 1 to 5 times, the last thermal decomposition at 350-550 ° C for 0.5-3 hours, to obtain a uniform titanium-based iridium-tantalum-tin oxide intermediate layer.

本发明的优点是：制成的电极中间层与基体结合牢固、MnO₂镀层微空隙多，便于活性物质交换，不易脱落；在表现出很好的循环稳定性，电极比容量高、寿命长、镀层结合力好；电解液为中性的Na₂SO₄溶液，便于在工业上推广应用。The advantages of the present invention are: the formed electrode middle layer is firmly bonded to the substrate, and the_MnO2 coating has many micro-voids, which facilitates the exchange of active materials and is not easy to fall off; it shows good cycle stability, high electrode specific capacity, long life, The coating has good binding force; the electrolyte is neutral Na₂ SO₄ solution, which is convenient for popularization and application in industry.

附图说明Description of drawings

图1为本发明以Ir-Mn、Ir-Ta、Ir-Ta-Si、Ir-Ta-Sn为中间层的四种MnO₂电极在20mv/s的扫描速率下在0～1.0V的电位窗口内的循环伏安图。Fig. 1 is that four kinds of_MnO electrodes of the present invention take Ir-Mn, Ir-Ta, Ir-Ta-Si, Ir-Ta-Sn as the intermediate layer at a scan rate of 20mv/s in the potential window of 0～1.0V The cyclic voltammogram inside.

图2为本发明以Ir-Mn、Ir-Ta、Ir-Ta-Si、Ir-Ta-Sn为中间层的四种MnO₂电极在以5mA的充放电电流在0～1.0V的电位窗口内的充放电曲线。Fig. 2 is that four kinds of_MnO2 electrodes of the present invention take Ir-Mn, Ir-Ta, Ir-Ta-Si, Ir-Ta-Sn as interlayer in the potential window of 0～1.0V with the charging and discharging current of 5mA charge-discharge curve.

具体实施方式Detailed ways

本发明是这样实现的，如图1、图2所示，The present invention is realized like this, as shown in Figure 1, Figure 2,

实施例1：Example 1:

首先将加工好的纯钛板进行喷砂处理，再将钛板在NaOH80g/L，NaCO₃40g/L的混合液中进行碱洗，进一步除油。之后要用浓硫酸在(80℃1.5h)下进行刻蚀。再采用热分解法在经过处理的钛板上涂覆烧结IrO₂+MnO₂中间层。涂敷液为IrMn原子比3∶7的HIrC₁₄和Mn(NO₃)₂的水溶液，总金属离子浓度为0.2mol/L。将涂覆液均匀地涂刷在进过预处理的钛基体上。100℃下烘干15min，450℃下热分解10min，重复以上涂刷和热分解步骤，涂覆10层，最后一次在350～550℃烧结1.5h，即获得钛基铱锰复合氧化物涂层阳极，涂层复合氧化物的担载量为10g/m²。最后一步就是电化学沉积活性MnO₂镀层了。其具体步骤为：首先把无水Na₂SO₄与H₂SO₄按摩尔比为2∶5配制成500ml水溶液后将溶液加热到98℃，再将封装好的试样置于其中浸泡约3min。之后可以通上直流电流(电流密度为20mA/cm²)。电沉积10min后取出清洗晾干，电极制作完毕。First, the processed pure titanium plate is subjected to sand blasting, and then the titanium plate is subjected to alkali washing in a mixture of NaOH 80g/L and NaCO₃ 40g/L to further remove oil. After that, it should be etched with concentrated sulfuric acid (80°C 1.5h). Then, a sintered IrO₂ +MnO₂ intermediate layer is coated on the treated titanium plate by a thermal decomposition method. The coating solution is an aqueous solution of HIrC₁₄ and Mn(NO₃ )₂ with an IrMn atomic ratio of 3:7, and the total metal ion concentration is 0.2 mol/L. Brush the coating liquid evenly on the pretreated titanium substrate. Dry at 100°C for 15 minutes, thermally decompose at 450°C for 10 minutes, repeat the above brushing and thermal decomposition steps, coat 10 layers, and sinter at 350-550°C for 1.5 hours for the last time to obtain a titanium-based iridium-manganese composite oxide coating For the anode, the loading amount of the coated composite oxide was 10 g/m² . The last step is the electrochemical deposition of active MnO₂ coating. The specific steps are as follows: first prepare 500ml of aqueous solution by anhydrous Na₂ SO₄ and H₂ SO₄ with a molar ratio of 2:5, then heat the solution to 98°C, and then soak the packaged sample in it for about 3 minutes . Then a direct current (current density 20mA/cm² ) can be applied. After 10 minutes of electrodeposition, take it out, wash and dry it, and the electrode is finished.

实施例2：Example 2:

按实施例1所说明处理钛板，采用热分解法在经过处理的钛板上涂敷烧结IrO₂-Ta₂O₅中间层：配制铱钽的乙醇异丙醇涂液，其中铱钽原子比为7∶6，总离子浓度为0.2mol·dm^-3，乙醇和异丙醇体积比为1∶1。将涂敷液均匀地涂刷在钛板上，100℃烘干10min，450℃下热分解15min，重复上述涂刷和热分解过程5次，最后一次450℃烧结60min，获得均匀的钛基铱钽氧化物中间层。最后一步如实施例1所述，电化学沉积活性MnO₂镀层。Treat the titanium plate as described in Example 1, and apply a thermal decomposition method on the treated titanium plate to coat the sintered IrO₂ -Ta₂ O₅ intermediate layer: prepare the ethanol isopropanol coating solution of iridium tantalum, wherein the atomic ratio of iridium tantalum to is 7:6, the total ion concentration is 0.2mol·dm^-3 , and the volume ratio of ethanol and isopropanol is 1:1. Apply the coating solution evenly on the titanium plate, dry it at 100°C for 10 minutes, and thermally decompose it at 450°C for 15 minutes. Repeat the above process of painting and thermal decomposition for 5 times, and sinter at 450°C for 60 minutes for the last time to obtain a uniform titanium-based iridium. Tantalum oxide interlayer. The final step was the electrochemical deposition of an active_MnO2 coating as described in Example 1.

实施例3：Example 3:

按实施例1所说明处理钛板，采用热分解法在经过处理的钛板上涂敷烧结IrO₂-Ta₂O₅-SnO₂中间层：配制铱钽锡原子比为7∶6∶1的TaCl₅，H₂IrCl₆，SnCl₂·2H₂O盐酸异丙醇溶液，将涂覆液均匀地涂刷在钛板上，100℃烘干10min，450℃下热分解15min，重复上述涂刷和热分解过程5次，最后一次450℃烧结60min，获得均匀的钛基铱钽锡氧化物中间层。最后一步如实施例1所述，电化学沉积活性MnO₂镀层。The titanium plate is processed as described in Example 1, and the sintered IrO₂ -Ta₂ O₅ -SnO₂ intermediate layer is coated on the treated titanium plate by thermal decomposition method: the iridium tantalum tin atomic ratio is prepared to be 7: 6: 1 TaCl₅ , H₂ IrCl₆ , SnCl₂ 2H₂ O hydrochloric acid isopropanol solution, paint the coating solution evenly on the titanium plate, dry at 100°C for 10min, thermally decompose at 450°C for 15min, repeat the above brushing andthermal decomposition process 5 times, the last sintering at 450° C. for 60 minutes to obtain a uniform titanium-based iridium-tantalum-tin oxide intermediate layer. The final step was the electrochemical deposition of an active_MnO2 coating as described in Example 1.

实施例4：Example 4:

按实施例1所说明处理钛板，配制的IrO₂-Ta₂O₅溶液与实例1相同。在其中加入0.227ml浓度为25.5％的酸性硅溶胶溶液，使SiO₂在其中的重量百分比为7％，制成IrO₂-Ta₂O₅-SiO₂涂覆溶液。用软毛绒笔将涂液刷涂在钛板两面，置烘箱中于90℃下烘干5min，然后在马弗炉中350℃下烧结5min，取出后空冷至室温，重复以上步骤至涂覆3层。然后，在烘箱中仍是于90℃下烘干5min，但是在马弗炉中350℃下烧结10min，如此反复至涂覆3层。最后一步如实施例1所述，电化学沉积活性MnO₂镀层。The titanium plate was treated as described in Example 1, and the prepared IrO₂ -Ta₂ O₅ solution was the same as in Example 1. 0.227ml of 25.5% acidic silica sol solution was added therein so that the weight percentage of SiO₂ in it was 7%, to prepare an IrO₂ -Ta₂ O₅ -SiO₂ coating solution. Brush the coating solution on both sides of the titanium plate with a soft plush pen, dry it in an oven at 90°C for 5 minutes, then sinter it in a muffle furnace at 350°C for 5 minutes, take it out and air cool to room temperature, repeat the above steps until coating 3 floors. Then, it was still dried in an oven at 90°C for 5 minutes, but sintered in a muffle furnace at 350°C for 10 minutes, and so on until three layers were applied. The final step was the electrochemical deposition of an active_MnO2 coating as described in Example 1.

通过充放电测试测得实施例中4种电极比电容如下表所示The specific capacitance of 4 kinds of electrodes in the embodiment measured by charge and discharge test is shown in the following table

中间层成分middle layer composition    Ir-MnIr-Mn    Ir-TaIr-Ta    Ir-Ta-Si Ir-Ta-Si    Ir-Ta-Sn Ir-Ta-Sn

Claims (5)

Translated fromChinese

1.一种钛基超级电容器薄膜电极的制作方法，其特征是方法步骤为：1. A method for making a titanium-based supercapacitor film electrode, characterized in that the method steps are:1)喷砂：将加工好的纯钛板进行喷砂处理使表面粗糙度加大，保证镀层与基体结合更为牢固；1) Sandblasting: Sandblasting the processed pure titanium plate to increase the surface roughness and ensure a firmer bond between the coating and the substrate;2)除油：将加工好的纯钛板放入烧杯中，加入除油液超声清洗20～30min，加热温度控制在30℃～65℃，清洗完成后再用自来水和去离子水分别冲洗，再吹干，除油液的配方为：NaOH 30～80g/L，Na₂CO₃ 20～40g/L；2) Degreasing: Put the processed pure titanium plate into a beaker, add a degreasing solution for ultrasonic cleaning for 20-30 minutes, control the heating temperature at 30°C-65°C, and rinse with tap water and deionized water after cleaning. Then blow dry, the formula of degreasing liquid is: NaOH 30～80g/L, Na₂ CO₃ 20～40g/L;3)酸洗刻蚀：将碱洗后的钛板放入15％～50％的硫酸中浸泡，然后用浓度为98％的浓硫酸进一步刻蚀，刻蚀温度70-90℃保持1.5h，直到溶液呈深紫色后取出试样冲洗再晾干；3) Pickling and etching: soak the titanium plate after alkali washing in 15% to 50% sulfuric acid, and then further etch it with concentrated sulfuric acid with a concentration of 98%, and keep the etching temperature at 70-90°C for 1.5h, Take out the sample until the solution turns dark purple, rinse and dry it;4)添加中间层：采用热分解法在经过处理的钛板上涂覆烧结IrO₂中间层，配制浓度为0.15～0.30mol·dm^-3氯铱酸异丁醇溶液为涂敷液，将涂敷液涂敷于处理好的钛板上，再置于烘箱内70～100℃烘干10～30min，然后于马弗炉内300～600℃进行热分解10min，取出空冷，重复三次，最后一次300～600℃热分解时间为40～90min，获得均匀的钛基IrO₂中间层；4) Adding the intermediate layer: Coating the sintered_IrO2 intermediate layer on the treated titanium plate by thermal decomposition method, preparing a concentration of 0.15～0.30mol·dm^-3 chloroiridic acid isobutanol solution as the coating liquid, and coating Apply the application liquid on the treated titanium plate, then place it in an oven for 10-30 minutes at 70-100°C, then decompose it in a muffle furnace at 300-600°C for 10 minutes, take it out and air-cool, repeat three times, and the last time The thermal decomposition time at 300-600°C is 40-90 minutes, and a uniform titanium-based IrO₂ intermediate layer is obtained;5)电化学沉积活性MnO₂镀层：首先把无水MnSO₄与H₂SO₄按摩尔比为2∶5配制成500ml水溶液后将溶液加热到80～100℃，再将封装好的试样置于其中浸泡2～5min，之后通上直流电流，电流密度为2～60mA/cm²，电沉积1～20min后取出清洗晾干，电极制作完毕。5) Electrochemical deposition of active MnO₂ coating: first prepare anhydrous MnSO₄ and H₂ SO₄ with a molar ratio of 2:5 to make 500ml aqueous solution, heat the solution to 80-100°C, and then place the packaged sample in Soak in it for 2-5 minutes, then apply a direct current with a current density of 2-60mA/cm² , take it out after 1-20 minutes of electrodeposition, wash and dry, and the electrode is finished.2.根据权利要求1所述的一种钛基超级电容器薄膜电极的制作方法，其特征是所述的添加中间层的制作可以替换为以下步骤：采用热分解法在经过处理的钛板上涂敷烧结SnO₂+SbOx中间层，涂液的溶质为SnCl₄和SbCl₃，溶剂为盐酸和正丁醇的混合溶液，其中Sn、Sb原子比为2～9∶3，总离子浓度0.2～0.8mol·dm^-3，盐酸和正丁醇体积比为1～5∶1，将涂液均匀地涂刷在处理后的钛板上，70～100℃烘干后在450～700℃下热分解10min，重复涂覆3次，最后在500℃下热分解60min，获得均匀的钛基锡锑氧化物中间层。2. the manufacture method of a kind of titanium-based supercapacitor film electrode according to claim 1 is characterized in that the making of described adding intermediate layer can be replaced by the following steps: adopt thermal decomposition method to coat on the treated titanium plate Apply sintered SnO₂ +SbOx intermediate layer, the solutes of the coating solution are SnCl₄ and SbCl₃ , the solvent is a mixed solution of hydrochloric acid and n-butanol, in which the atomic ratio of Sn and Sb is 2-9:3, and the total ion concentration is 0.2-0.8mol dm^-3 , the volume ratio of hydrochloric acid and n-butanol is 1-5:1, apply the coating solution evenly on the treated titanium plate, dry it at 70-100°C, and then thermally decompose it at 450-700°C for 10 minutes, Repeat the coating for 3 times, and finally thermally decompose it at 500°C for 60 minutes to obtain a uniform titanium-based tin antimony oxide intermediate layer.3.根据权利要求1所述的一种钛基超级电容器薄膜电极的制作方法，其特征是所述的添加中间层的制作可以替换为以下步骤：采用热分解法在经过处理的钛板上涂敷烧结IrO₂-Ta₂O₅中间层，配制铱钽的乙醇异丙醇涂液，其中铱钽原子比为7∶3，总离子浓度为0.2mol·dm^-3，乙醇和异丙醇体积比为1∶1，将涂敷液均匀地涂刷在钛板上，100℃烘干10min，450℃下热分解15min，重复上述涂刷和热分解过程5次，最后一次450℃烧结60min，获得均匀的钛基铱钽氧化物中间层。3. the manufacture method of a kind of titanium-based supercapacitor film electrode according to claim 1, it is characterized in that the making of described adding intermediate layer can be replaced by following steps: adopt thermal decomposition method to coat on the treated titanium plate Apply the sintered IrO₂ -Ta₂ O₅ intermediate layer, and prepare the ethanol-isopropanol coating solution of iridium-tantalum, in which the atomic ratio of iridium-tantalum is 7:3, the total ion concentration is 0.2mol·dm^-3 , the volume of ethanol and isopropanol The ratio is 1:1. Apply the coating solution evenly on the titanium plate, dry at 100°C for 10 minutes, and thermally decompose at 450°C for 15 minutes. Repeat the above-mentioned brushing and thermal decomposition process for 5 times, and sinter at 450°C for 60 minutes for the last time. A uniform intermediate layer of titanium-based iridium-tantalum oxide is obtained.4.根据权利要求1所述的一种钛基超级电容器薄膜电极的制作方法，其特征是所述的添加中间层的制作可以替换为以下步骤：采用热分解法在经过处理的钛板上涂覆烧结IrO₂+MnO₂中间层，涂敷液为IrMn原子比1∶9～9∶1的HIrC₁₄和Mn(NO₃)₂的水溶液，总金属离子浓度为0.15～0.4mol/L，将涂覆液均匀地涂刷在进过预处理的钛基体上，70～100℃下烘干5～20min，350～550℃下热分解8～25min，重复以上涂刷和热分解步骤，涂覆1～3层，最后一次在350～550℃烧结0.5～3h，即获得钛基锰铱复合氧化物涂层阳极，涂层复合氧化物的担载量为0.5～3g/m²。4. the manufacture method of a kind of titanium-based supercapacitor film electrode according to claim 1 is characterized in that the making of described adding intermediate layer can be replaced by following steps: adopt thermal decomposition method to coat on the treated titanium plate Cover and sinter the IrO₂ +MnO₂ intermediate layer, the coating solution is an aqueous solution of HIrC₁₄ and Mn(NO₃ )₂ with an IrMn atomic ratio of 1:9 to 9:1, and the total metal ion concentration is 0.15 to 0.4mol/L. Apply the coating liquid evenly on the pretreated titanium substrate, dry at 70-100°C for 5-20 minutes, and thermally decompose at 350-550°C for 8-25 minutes, repeat the above brushing and thermal decomposition steps, and coat 1-3 layers, the final sintering at 350-550° C. for 0.5-3 hours to obtain a titanium-based manganese-iridium composite oxide coated anode, and the loading amount of the coated composite oxide is 0.5-3 g/m² .5.根据权利要求1所述的一种钛基超级电容器薄膜电极的制作方法，其特征是所述的添加中间层的制作可以替换为以下步骤：采用热分解法在经过处理的钛板上涂敷烧结IrO₂-Ta₂O₅-SnO₂中间层：配制铱钽锡原子比为3～7∶4～8∶0.5～1的TaCl₅，H₂IrCl₆，SnCl₂·2H₂O盐酸异丙醇溶液，将涂覆液均匀地涂刷在钛板上，100℃烘干10min，450℃下热分解15min，重复上述涂刷和热分解过程1～5次，最后一次350～550℃热分解0.5～3h，获得均匀的钛基铱钽锡氧化物中间层。5. the manufacture method of a kind of titanium-based supercapacitor film electrode according to claim 1 is characterized in that the making of described adding intermediate layer can be replaced by the following steps: adopt thermal decomposition method to coat on the treated titanium plate Laying and sintering IrO₂ -Ta₂ O₅ -SnO₂ intermediate layer: prepare TaCl₅ , H₂ IrCl₆ , SnCl₂ ·2H₂ O hydrochloric acid iso Propanol solution, paint the coating liquid evenly on the titanium plate, dry it at 100°C for 10 minutes, and thermally decompose it at 450°C for 15 minutes. Decompose for 0.5-3 hours to obtain a uniform intermediate layer of titanium-based iridium-tantalum-tin oxide.

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