技术领域technical field
本发明属于湿法冶金和电化学工业技术领域，具体涉及用于金属电积、电解、电镀的一种设有铂金属或含铂氧化锡中间层的氧化物涂层钛电极及其制备方法。The invention belongs to the technical field of hydrometallurgy and electrochemical industry, and specifically relates to an oxide-coated titanium electrode provided with a platinum metal or platinum-containing tin oxide intermediate layer for metal electrowinning, electrolysis and electroplating and a preparation method thereof.
背景技术Background technique
金属电积是金属湿法提取、金属箔材制备和金属镀层制备工艺重要的单元过程。目前金属电积工业普遍采用酸性硫酸盐溶液体系，阳极一般采用铅基二元合金阳极，如锌电积普遍使用Pb-Ag电极。该类阳极存在的主要问题为：（1）阳极析氧电位高，增加了无用电耗；（2）阳极表面的二氧化铅氧化膜疏松多孔，造成阳极基体腐蚀速率快，从而导致阳极寿命短、铅污染阴极产品和阴极电效降低等问题；（3）阳极机械强度低，易弯曲蠕变，导致阴阳极短路，进而出现阳极损坏等问题。Metal electrowinning is an important unit process of metal wet extraction, metal foil preparation and metal coating preparation. At present, the metal electrowinning industry generally adopts an acidic sulfate solution system, and the anode generally adopts a lead-based binary alloy anode, such as zinc electrowinning generally uses a Pb-Ag electrode. The main problems of this type of anode are: (1) The oxygen evolution potential of the anode is high, which increases the useless power consumption; (2) The lead dioxide oxide film on the surface of the anode is loose and porous, resulting in a fast corrosion rate of the anode substrate, resulting in a short life of the anode , Lead polluted cathode products and the reduction of cathode electric efficiency; (3) The mechanical strength of the anode is low, and it is easy to bend and creep, resulting in a short circuit between the cathode and the anode, and then the anode is damaged.
为克服铅基二元合金阳极的以上不足，国内外大致形成了两种技术路线，一种是对铅阳极合金化（刘良坤等，Pb-Ag-Ca三元合金机械性能的研究,《矿冶工程》, 1995, 15(4)：61-63），制成铅基多元合金，另一种是采用涂层钛电极代替铅基合金阳极（MasatsuguM, Naoyuki O. Accelerated oxygen evolution and suppressed MnOOH deposition onamorphous IrO2-Ta2O5 Coatings. Chemistry Letters, 2009, 38(8):821-822）。以Pb-Ag-Ca电极为代表的铅基多元合金阳极，虽然机械强度较Pb-Ag电极有所提高，腐蚀率降低，但阳极回收时银钙的损失大，高能耗、铅污染的问题仍未解决，实际上并没有获得工业应用。In order to overcome the above shortcomings of lead-based binary alloy anodes, two technical routes have been roughly formed at home and abroad, one is alloying of lead anodes (Liu Liangkun et al., Research on the mechanical properties of Pb-Ag-Ca ternary alloys, "Mining and Metallurgy Engineering", 1995, 15(4): 61-63), made of lead-based multi-element alloys, and the other is to use coated titanium electrodes instead of lead-based alloy anodes (MasatsuguM, Naoyuki O. Accelerated oxygen evolution and suppressed MnOOH deposition onamorphous IrO2 -Ta2 O5 Coatings. Chemistry Letters, 2009, 38(8):821-822). The lead-based multi-element alloy anode represented by Pb-Ag-Ca electrode has higher mechanical strength and lower corrosion rate than Pb-Ag electrode, but the loss of silver and calcium is large when the anode is recycled, and the problems of high energy consumption and lead pollution remain. Unresolved and practically did not gain industrial application.
目前，金属电积用涂层钛电极由基体Ti和涂层铱钽氧化物IrO2-Ta2O5组成。该涂层钛电极的析氧电位较低，在采用高纯溶液体系的电镀工业上有所应用，但因锌电积液等工业电解液中普遍含有F--、Mn2+等杂质，而导致耐腐蚀性能变差，服役寿命较短。因此目前铅基三元合金电极和铱钽涂层钛电极，都仍不能根本上解决铅基二元合金阳极存在的问题。At present, coated titanium electrodes for metal electrowinning are composed of substrate Ti and coating iridium-tantalum oxide IrO2 -Ta2 O5 . The oxygen evolution potential of the coated titanium electrode is low, and it has been used in the electroplating industry using high-purity solution systems. However, industrial electrolytes such as zinc electrolysis solutions generally contain impurities such as F-- and Mn2+ Lead to poor corrosion resistance and shorter service life. Therefore, the current lead-based ternary alloy electrodes and iridium-tantalum-coated titanium electrodes still cannot fundamentally solve the problems existing in lead-based binary alloy anodes.
发明内容Contents of the invention
针对铅基合金阳极和涂层钛电极存在的以上不足，本发明的一个目的是提供适用于含F--、Mn2+等硫酸体系的一种析氧电位低、使用寿命长和机械强度高等综合性能优异的涂层钛电极。For the above deficiencies that lead- based alloyanodes and coated titanium electrodes exist, an object of the present invention is to provide a kind of low oxygen evolution potential, long service life and high mechanical strength, etc. Coated titanium electrode with excellent comprehensive performance.
本发明的另一个目的提供上述涂层钛电极的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned coated titanium electrode.
本发明所述的金属电积用涂层钛电极由基体1、中间层2和外涂层3构成，其中基体1为纯钛板、纯钛包铝层状复合板或者焊接于钛板框架表面的纯钛网，优选纯钛板；中间层2为金属铂或含铂氧化锡层，如铂镀层或铂涂层，其对F--表现出极高的耐受性，起到保护基体1作用，同时防止氧扩散至基体1，延缓基体1的钝化，中间层2中铂负载量为0.5~10g/m2，厚度为0.05~1μm，含铂氧化锡中间层2中锡与铂的摩尔比为1:9~5:5；外涂层3为活性催化涂层，由贵金属氧化物和非贵金属氧化物组成，贵金属氧化物为氧化铱或者氧化铱与氧化钌的混合物，非贵金属氧化物由氧化锰、氧化锡或氧化铋中的一种或多种组成。外涂层3对酸性溶液中的析氧反应有较强的电催化作用，对酸性溶液中的F--、Mn2+等无机杂质表现出极高的耐受性，外涂层3中贵金属的负载量5~20g/m2，贵金属与非贵金属的摩尔比为1:9~5:5，厚度为5~20μm。The coated titanium electrode for metal deposition according to the present invention is composed of a substrate 1, an intermediate layer 2 and an outer coating 3, wherein the substrate 1 is a pure titanium plate, a pure titanium-clad aluminum-clad layered composite plate or is welded on the surface of a titanium plate frame A pure titanium mesh, preferably a pure titanium plate; the middle layer 2 is metal platinum or a platinum-containing tin oxide layer, such as a platinum coating or a platinum coating, which exhibits extremely high tolerance to F--and plays a role in protecting the substrate 1 At the same time, it prevents oxygen from diffusing to the substrate 1 and delays the passivation of the substrate 1. The platinum loading in the intermediate layer 2 is 0.5~10g/m2 , the thickness is 0.05~1μm, and the tin and platinum in the platinum-containing tin oxide intermediate layer 2 The molar ratio is 1:9~5:5; the outer coating 3 is an active catalytic coating, composed of noble metal oxides and non-noble metal oxides, the noble metal oxides are iridium oxide or a mixture of iridium oxide and ruthenium oxide, and the non-noble metal oxides are The compound is composed of one or more of manganese oxide, tin oxide or bismuth oxide. The outer coating 3 has a strong electrocatalytic effect on the oxygen evolution reaction in the acidic solution, and exhibits extremely high tolerance to inorganic impurities such as F-- , Mn2+ in the acidic solution, and the noble metal in the outer coating 3 The loading capacity is 5~20g/m2 , the molar ratio of noble metal to non-noble metal is 1:9~5:5, and the thickness is 5~20μm.
上述涂层钛电极的制备方法由以下步骤组成：The preparation method of the above-mentioned coated titanium electrode consists of the following steps:
（1）基体1：用5%纯碱水溶液煮沸1h，水洗，再浸入5%~10%草酸溶液中煮沸2~4h，水洗，用去离子水冲净，80~120℃下干燥；(1) Substrate 1: Boil with 5% soda ash aqueous solution for 1 hour, wash with water, then immerse in 5%~10% oxalic acid solution, boil for 2~4 hours, wash with water, rinse with deionized water, and dry at 80~120°C;
（2）中间层2：采用化学镀、热分解、电镀或者磁控溅射法中的一种或它们的组合；(2) Intermediate layer 2: one or a combination of chemical plating, thermal decomposition, electroplating or magnetron sputtering;
（3）外涂层3：将步骤（2）的带有中间层2的基体1浸入外层涂液中浸涂，或者用软毛刷将外层涂液均匀地刷涂在中间层2上，在温度为50~120℃下烘干10min，然后在热空气温度为450~520℃中氧化10~15min，冷却后再浸入外层涂液或者刷涂外层涂液，再干燥、氧化、冷却，重复上述过程，次数为4~25次，最后在450~520℃下热处理1h，外涂层3已沉积在中间层2上，即制成所述设有铂中间层2或含铂氧化锡中间层2的金属电积用涂层钛电极。(3) Outer coating 3: Dip the substrate 1 with the intermediate layer 2 in step (2) into the outer layer coating liquid for dip coating, or brush the outer layer coating liquid evenly on the intermediate layer 2 with a soft brush , drying at a temperature of 50~120°C for 10 minutes, then oxidizing in a hot air temperature of 450~520°C for 10~15 minutes, after cooling, immerse in the outer layer coating liquid or brush the outer layer coating liquid, and then dry, oxidize, Cool, repeat the above process, the number of times is 4~25 times, and finally heat treatment at 450~520°C for 1h, the outer coating 3 has been deposited on the middle layer 2, that is, the platinum middle layer 2 or platinum-containing oxidation Coated titanium electrode for metal deposition of tin interlayer 2.
因为化学镀法沉积的镀层均匀、致密，因此，优选的制备中间层2的方法是化学镀法，步骤如下：将步骤（1）洁净的基体1浸入化学镀液中，50~60℃下施镀1~15min，水洗，用去离子水冲净，80~120℃下干燥。化学镀液的组成为：四醋酸六氨铂配合物溶液（以铂计）2~5g/L，水合肼4~6mL/L，使用醋酸或氨水调节pH9~11。Because the plating layer deposited by the electroless plating method is uniform and dense, therefore, the preferred method for preparing the intermediate layer 2 is the electroless plating method, and the steps are as follows: immerse the clean substrate 1 in step (1) in the electroless plating solution, and apply Plating for 1~15min, washing with water, rinsing with deionized water, and drying at 80~120℃. The composition of the electroless plating solution is: tetraacetic acid hexaamine platinum complex solution (calculated as platinum) 2~5g/L, hydrazine hydrate 4~6mL/L, use acetic acid or ammonia water to adjust the pH to 9~11.
或者采用热分解法，步骤如下：将步骤（1）洗净的基体1浸入铂涂液中浸涂，或者用软毛刷将铂涂液均匀刷涂在基体1上，温度为50~120℃烘干10min，然后移入热空气气氛中氧化10~15min，氧化温度为350~450℃，冷却后再浸入铂涂液或者刷涂铂涂液，再干燥、氧化、冷却，重复上述过程1~9次，最后在350~450℃下热处理0.5~1h，至此中间层2已沉积在基体1上。所述铂涂液为含铂10~20g/L的铂配合物溶液。Or use the thermal decomposition method, the steps are as follows: immerse the substrate 1 cleaned in step (1) into the platinum coating solution for dip coating, or use a soft brush to evenly brush the platinum coating solution on the substrate 1 at a temperature of 50~120°C Dry for 10 minutes, then move into a hot air atmosphere to oxidize for 10-15 minutes, the oxidation temperature is 350-450°C, after cooling, immerse in the platinum coating solution or brush the platinum coating solution, then dry, oxidize and cool, repeat the above process 1-9 times, and finally heat treatment at 350-450°C for 0.5-1h, and the intermediate layer 2 has been deposited on the substrate 1 so far. The platinum coating solution is a platinum complex solution containing 10-20 g/L of platinum.
或者采用电镀法，步骤如下：将步骤（1）洁净的基体1浸入二亚硝基二氨铂电镀液（以铂计）5~10g/L中，在0.01A/cm2条件下，施镀1~20min。Or use the electroplating method, the steps are as follows: immerse the clean substrate 1 in step (1) in 5~10g/L of dinitrosodiammine platinum electroplating solution (calculated as platinum), and apply plating under the condition of 0.01A/cm2 1~20min.
或者采用磁控溅射法，步骤如下：将步骤（1）洁净的基体1在功率100W，真空度为1.0~20MPa，氩气压强为1~50Pa的条件下，磁控溅射沉积1~20min。Or use the magnetron sputtering method, the steps are as follows: deposit the clean substrate 1 in step (1) by magnetron sputtering for 1~20min under the conditions of power 100W, vacuum degree 1.0~20MPa, and argon pressure 1~50Pa. .
所述含铂氧化锡层的制备：将步骤（1）洗净的基体1浸入铂锡涂液中，浸涂后取出，或者用软毛刷将铂锡涂液均匀刷涂在基体1上，接着烘干10min，干燥温度为50~120℃，然后移入热空气氧化气氛中氧化10~15min，氧化温度为400~500℃，冷却后再浸入涂液或者刷涂涂液，再干燥、氧化、冷却，重复上述过程2~9次，最后在400~500℃下热处理1h，至此中间层2已沉积在基体1上。所述铂锡涂液为含铂10~20g/L和含锡0.6~12g/L的氯铂酸和氯化亚锡或氯化锡的≤C4的醇溶液。Preparation of the platinum-containing tin oxide layer: immerse the substrate 1 cleaned in step (1) into the platinum-tin coating solution, take it out after dipping, or evenly brush the platinum-tin coating solution on the substrate 1 with a soft brush, Then dry for 10 minutes, the drying temperature is 50~120°C, and then move into the hot air oxidation atmosphere for oxidation for 10~15 minutes, the oxidation temperature is 400~500°C, after cooling, immerse in the coating liquid or brush the coating liquid, and then dry, oxidize, Cooling, repeat the above process 2~9 times, and finally heat treatment at 400~500°C for 1h, so far the intermediate layer 2 has been deposited on the substrate 1. The platinum-tin coating solution is an alcohol solution of ≤C4 containing platinum 10-20g/L and tin 0.6-12g/L chloroplatinic acid and stannous chloride or tin chloride.
所述外层涂液由铱或钌贵金属氯化物与锰、锡或铋贱金属氯化物配制而成，溶剂为乙醇、异丙醇和正丁醇中的一种或者两种。The outer layer coating solution is prepared from iridium or ruthenium noble metal chloride and manganese, tin or bismuth base metal chloride, and the solvent is one or two of ethanol, isopropanol and n-butanol.
由于涂层钛电极的基体和涂层IrO2-Ta2O5中的Ta2O5均在含F--酸性溶液中的耐腐蚀性能差，所以导致服役寿命较短，实用价值不高。为此，一方面，本发明在基体1与外涂层3间增设铂金属或含铂氧化锡中间层2，以保护基体1；另一方面，本发明外涂层3选择贵金属氧化物和耐蚀非贵金属氧化物是为了提高外涂层3的耐腐蚀性能，延长其使用寿命。Because the substrate of the coated titanium electrode and the Ta2 O5 in the coating IrO2 -Ta2 O5 have poor corrosion resistancein acidic solutions containing F-, the service life is short and the practical value is not high. For this reason, on the one hand, the present invention adds a platinum metal or a platinum-containing tin oxide intermediate layer 2 between the substrate 1 and the outer coating 3 to protect the substrate 1; The purpose of etching non-precious metal oxides is to improve the corrosion resistance of the outer coating 3 and prolong its service life.
与现有技术相比，本发明的用于金属电积的涂层钛电极有如下优点：Compared with the prior art, the coated titanium electrode for metal electrowinning of the present invention has the following advantages:
1.与Pb-Ag电极相比，氧析出电位低，基体强度高，不易短路，阴极电流效率高，涂层的化学稳定性高，对阴极产品无污染；1. Compared with the Pb-Ag electrode, the oxygen evolution potential is low, the matrix strength is high, it is not easy to short circuit, the cathode current efficiency is high, the chemical stability of the coating is high, and there is no pollution to the cathode product;
2.与Ti/IrO2-Ta2O5电极相比，涂层的化学稳定性高，使用寿命显著延长，具有实用性。2. Compared with the Ti/IrO2 -Ta2 O5 electrode, the coating has high chemical stability, significantly prolonged service life, and is practical.
本发明的涂层钛电极的结构及其制备方法制备的涂层钛电极与现有技术相比综合性能优良，适用于硫酸溶液体系中电积金属，特别适用于含F--、Mn2+等杂质的硫酸溶液体系中电积金属。The structure of the coated titanium electrode of the present invention and its preparation method The coated titanium electrode prepared by the coating titanium electrode has better overall performance compared with the prior art, and is suitable for electrodepositing metals in sulfuric acid solution systems, especially suitable for containing F-- , Mn2+ Electrodeposit metals in sulfuric acid solution system with other impurities.
附图说明Description of drawings
图1为本发明的涂层钛电极结构图。Fig. 1 is a structure diagram of the coated titanium electrode of the present invention.
1.基体，2.中间层，3.外涂层。1. Substrate, 2. Intermediate layer, 3. Outer coating.
具体实施方式detailed description
用以下实施例对本发明进行详细描述。The present invention is described in detail with the following examples.
实施例1Example 1
基体1：将纯钛板用5%纯碱水溶液煮沸1h，水洗，再浸入8%草酸溶液中煮沸3h，水洗，用去离子水冲净，100℃下干燥；Substrate 1: Boil the pure titanium plate with 5% soda ash aqueous solution for 1 hour, wash with water, then immerse in 8% oxalic acid solution, boil for 3 hours, wash with water, rinse with deionized water, and dry at 100°C;
中间层2：接着将纯钛板浸入含四醋酸六氨铂配合物溶液（以铂计5g/L），水合肼5mL/L的化学镀液中，镀液温度55℃，施镀8min，控制镀液pH为10，水洗，用去离子水冲净，110℃干燥，制得铂负载量为5g/m2的中间层2；Intermediate layer 2: Then immerse the pure titanium plate in the electroless plating solution containing tetraacetate hexammonium platinum complex solution (5g/L as platinum) and hydrazine hydrate 5mL/L. The pH of the plating solution is 10, washed with water, rinsed with deionized water, and dried at 110° C. to obtain an intermediate layer 2 with a platinum loading of 5 g/m2 ;
外涂层3：用18g氯铱酸、50g五水四氯化锡、2.68g氯化铋、225mL乙醇和250mL正丁醇的外层涂液。利用软毛刷将上述外层涂液均匀地刷涂在纯钛板的中间层2上，温度80℃烘干10min，然后移入热空气温度480℃中氧化10min，冷却后再刷涂涂液，再干燥、氧化、冷却，重复上述过程14次，最后480℃下热处理1h，即制得铂负载量5g/m2的中间层2、外涂层3铱负载量15g/m2的铱锡铋氧化物的涂层钛电极。Outer coating 3: use an outer coating liquid of 18g of chloroiridic acid, 50g of tin tetrachloride pentahydrate, 2.68g of bismuth chloride, 225mL of ethanol and 250mL of n-butanol. Use a soft brush to evenly brush the above outer layer coating solution on the middle layer 2 of the pure titanium plate, dry it at 80°C for 10 minutes, then move it into hot air at a temperature of 480°C for 10 minutes, and then brush the coating solution after cooling. Then dry, oxidize, and cool down, repeat the above process 14 times, and finally heat-treat at 480°C for 1 hour to prepare the middle layer2 with a platinum loading of 5g/m2 and the outer coating3 with an iridium loading of 15g/m2. Oxide-coated titanium electrodes.
在室温条件下，在50g/LH2SO4水溶液中，测定5A/dm2下涂层钛电极的析氧电位。分别在H2SO4150g/L水溶液（溶液①）和含F-20mg/L、Mn2+10g/L、H2SO4150g/L水溶液（溶液②）中，电流密度为2A/cm2、40℃条件下，测定涂层钛电极的强化寿命（人为规定槽电压升至10V所用时间）。在含Zn2+50g/L、H2SO4170g/L的模拟锌电解液中，以涂层钛电极为阳极，以纯铝板为阴极，异名极间距为5.5cm，在4A/dm2下进行电解试验，并测定槽电压和阴极电流效率。为便于对照比较，也测试了背景技术中Ti/IrO2-Ta2O5电极（铱负载量约15g/m2）和Pb-0.75%Ag电极的相应数据，结果见表1。At room temperature, in 50g/LH2 SO4 aqueous solution, the oxygen evolution potential of the coated titanium electrode was measured at 5A/dm2 . In H2 SO4 150g/L aqueous solution (solution ①) and F- 20mg/L, Mn2+ 10g/L, H2 SO4 150g/L aqueous solution (solution ②), the current density is 2A/cm2 , Under the condition of 40°C, the enhanced life of the coated titanium electrode was measured (the time it takes for the cell voltage to rise to 10V is artificially specified). In the simulated zinc electrolyte containing Zn2+ 50g/L, H2 SO4 170g/L, with the coated titanium electrode as the anode and the pure aluminum plate as the cathode, the distance between the different electrodes is 5.5cm, under 4A/dm2 Electrolysis tests were performed and cell voltage and cathodic current efficiency were determined. For the convenience of comparison, the corresponding data of Ti/IrO2 -Ta2 O5 electrodes (iridium loading about 15g/m2 ) and Pb-0.75%Ag electrodes in the background technology were also tested, and the results are shown in Table 1.
在溶液②中，本发明的涂层钛电极的强化寿命为765h，根据电极通过电量可估算其工作寿命为3年以上，而Pb-0.75%Ag电极的寿命仅为2年。In the solution ②, the enhanced life of the coated titanium electrode of the present invention is 765h, and its working life can be estimated to be more than 3 years according to the electricity passing through the electrode, while the life of the Pb-0.75%Ag electrode is only 2 years.
表1Table 1
实施例2Example 2
基体1：将纯钛包铝层状复合板用5%纯碱水溶液煮沸1h，水洗，再浸入10%草酸溶液中煮沸2.5h，水洗，用去离子水冲净，120℃下干燥；Substrate 1: Boil the pure titanium-clad aluminum layered composite board with 5% soda ash aqueous solution for 1 hour, wash with water, then immerse in 10% oxalic acid solution, boil for 2.5 hours, wash with water, rinse with deionized water, and dry at 120°C;
中间层2：接着将洗净的纯钛包铝层状复合板浸入铂涂液中，浸涂后取出，温度80℃烘干10min，然后移入热空气温度400℃中氧化10min，冷却后再浸入铂涂液，再干燥、氧化、冷却，重复上述过程3次，最后热处理400℃下0.5h，所述铂涂液为铂浓度12g/L的氯铂酸正丁醇溶液，制得铂负载量为4g/m2的中间层2；Intermediate layer 2: Then immerse the cleaned pure titanium-clad aluminum laminated composite plate in the platinum coating solution, take it out after dipping, and dry it at 80°C for 10 minutes, then move it into hot air at 400°C for oxidation for 10 minutes, and then immerse it after cooling Platinum coating solution, then dry, oxidize, and cool, repeat the above process 3 times, and finally heat-treat at 400°C for 0.5h. The platinum coating solution is a chloroplatinic acid n-butanol solution with a platinum concentration of 12g/L to obtain a platinum loading Intermediate layer 2 of 4 g/m2 ;
外涂层3：用10g氯铱酸、3.23g三氯化钌、21.40g四氯化锡、150mL乙醇和280mL正丁醇的外层涂液。利用软毛刷将上述外层涂液均匀地刷涂在复合板的中间层2上，温度90℃烘干10min，然后移入热空气温度500℃中氧化15min，冷却后再刷涂涂液，再干燥、氧化、冷却，重复上述过程19次，最后500℃下热处理1h，即制得铂负载量4g/m2的中间层2、外涂层3铱负载量20g/m2的铱钌锡氧化物的涂层钛电极。Outer coating 3: use an outer coating liquid of 10 g of chloroiridic acid, 3.23 g of ruthenium trichloride, 21.40 g of tin tetrachloride, 150 mL of ethanol and 280 mL of n-butanol. Use a soft brush to evenly brush the above outer layer coating solution on the middle layer 2 of the composite board, dry it at 90°C for 10 minutes, then move it into hot air at a temperature of 500°C for oxidation for 15 minutes, and then brush the coating solution after cooling down. Drying, oxidation, cooling, repeat the above process 19 times, and finally heat treatment at 500 ° C for 1 hour, that is, the intermediate layer 2 with a platinum loading of 4 g/m2 and the outer coating 3 iridium ruthenium tin oxide with an iridium loading of 20 g/m2 coated titanium electrodes.
按照实施例1的方法，测试了Ti/IrO2-Ta2O5电极（铱负载量约20g/m2）和Pb-0.75%Ag电极的相应数据，结果见表2。According to the method of Example 1, the corresponding data of Ti/IrO2 -Ta2 O5 electrode (iridium loading about 20g/m2 ) and Pb-0.75%Ag electrode were tested, and the results are shown in Table 2.
表2Table 2
实施例3Example 3
基体1：将纯钛包铝层状复合板用5%纯碱水溶液煮沸1h，水洗，再浸入10%草酸溶液中煮沸2.5h，水洗，用去离子水冲净，120℃下干燥；Substrate 1: Boil the pure titanium-clad aluminum layered composite board with 5% soda ash aqueous solution for 1 hour, wash with water, then immerse in 10% oxalic acid solution, boil for 2.5 hours, wash with water, rinse with deionized water, and dry at 120°C;
中间层2：接着将洗净的纯钛包铝层状复合板在功率100W、真空度为2.0MPa，氩气压强为2Pa的条件下，溅射沉积16min，制得铂负载量为8g/m2的中间层2；Intermediate layer 2: Next, the cleaned pure titanium-clad aluminum layered composite plate is sputter-deposited for 16 minutes under the conditions of power 100W, vacuum degree 2.0MPa, and argon pressure 2Pa, to obtain a platinum loading of 8g/m middle layer2 of 2;
外涂层3：用18g氯铱酸、19.15g四氯化锡、4.32g四水氯化锰、150mL乙醇和290mL正丁醇的外层涂液。利用软毛刷将上述外层涂液均匀地刷涂在复合板的中间层2上，温度90℃烘干10min，然后移入热空气温度500℃中氧化15min，冷却后再刷涂涂液，再干燥、氧化、冷却，重复上述过程24次，最后500℃下热处理1h，即制得铂负载量8g/m2的中间层2、外涂层3铱负载量25g/m2的铱锡锰氧化物的涂层钛电极。Outer coating 3: use an outer coating solution of 18g of chloroiridic acid, 19.15g of tin tetrachloride, 4.32g of manganese chloride tetrahydrate, 150mL of ethanol and 290mL of n-butanol. Use a soft brush to evenly brush the above outer layer coating solution on the middle layer 2 of the composite board, dry it at 90°C for 10 minutes, then move it into hot air at a temperature of 500°C for oxidation for 15 minutes, and then brush the coating solution after cooling down. Dry, oxidize, cool, repeat the above process 24 times, and finally heat-treat at 500°C for 1 hour to obtain an intermediate layer2 with a platinum loading of 8g/m2 and an outer coating3 with an iridium loading of 25g/m2. coated titanium electrodes.
按照实施例1的方法，测定的铱锡锰氧化物涂层钛电极的强化寿命是铱钽氧化物涂层钛电极的8倍。According to the method of Example 1, the measured strengthening life of the titanium electrode coated with iridium tin manganese oxide is 8 times that of the titanium electrode coated with iridium tantalum oxide.
实施例4Example 4
基体1：将焊接于钛板框架表面的纯钛网用5%纯碱水溶液煮沸1h，水洗，再浸入10%草酸溶液中煮沸4h，水洗，用去离子水冲净，110℃下干燥；Substrate 1: Boil the pure titanium mesh welded on the surface of the titanium plate frame with 5% soda ash aqueous solution for 1 hour, wash with water, then immerse in 10% oxalic acid solution, boil for 4 hours, wash with water, rinse with deionized water, and dry at 110°C;
中间层2：将洗净的纯钛网浸入铂锡涂液中，铂锡涂液为氯铂酸和四氯化锡正丁醇溶液，含铂为15g/L和含锡为9.12g/L，浸涂后取出，温度80℃，烘干10min，然后移入热空气温度400℃中氧化10min，冷却后再浸入铂锡涂液，再干燥、氧化、冷却，重复上述过程2次，最后400℃下热处理0.5h，制得铂负载量为3g/m2的含铂氧化锡中间层2；Intermediate layer 2: Immerse the cleaned pure titanium mesh in the platinum tin coating solution, which is chloroplatinic acid and tin tetrachloride n-butanol solution, containing 15g/L of platinum and 9.12g/L of tin , take out after dipping, temperature 80°C, dry for 10min, then move into hot air at 400°C to oxidize for 10min, then immerse in platinum tin coating solution after cooling, then dry, oxidize, cool, repeat the above process twice, and finally 400°C Under heat treatment for 0.5h, the platinum-containing tin oxide intermediate layer2 with a platinum loading of 3g/m2 was prepared;
外涂层3：用10g氯铱酸、6.70g四水氯化锰、100mL乙醇和100mL正丁醇的外层涂液。利用软毛刷将上述外层涂液均匀地刷涂在纯钛网的含铂氧化锡中间层2上，温度80℃烘干10min，然后移入热空气温度480℃中氧化10min，冷却后再刷涂涂液，再干燥、氧化、冷却，重复上述过程16次，最后480℃下热处理1h，即制得铂负载量32g/m2的中间层2、外涂层3铱负载量15g/m2的铱锰摩尔比为3.5:6.5的铱锰氧化物涂层钛电极。Outer coating 3: use an outer coating liquid of 10 g of chloroiridic acid, 6.70 g of manganese chloride tetrahydrate, 100 mL of ethanol and 100 mL of n-butanol. Use a soft brush to evenly brush the above outer layer coating solution on the platinum-containing tin oxide intermediate layer 2 of the pure titanium mesh, dry it at 80°C for 10 minutes, then move it into hot air at 480°C for oxidation for 10 minutes, and then brush it after cooling Apply the coating solution, then dry, oxidize, and cool, repeat the above process 16 times, and finally heat-treat at 480°C for 1 hour to obtain the middle layer 2 with a platinum loading of 32g/m2 and the outer coating 3 with an iridium loading of 15g/m2 The iridium-manganese oxide-coated titanium electrode with an iridium-manganese molar ratio of 3.5:6.5.
按照实施例1的方法，测定的铱锰氧化物涂层钛电极的强化寿命是铱钽氧化物涂层钛电极的5倍。According to the method of Example 1, the strengthened life of the iridium-manganese oxide-coated titanium electrode measured is 5 times that of the iridium-tantalum oxide-coated titanium electrode.
实施例5Example 5
基体1：将纯钛板用5%纯碱水溶液煮沸1h，水洗，再浸入8%草酸溶液中煮沸3h，水洗，用去离子水冲净，110℃下干燥；Substrate 1: Boil the pure titanium plate with 5% soda ash aqueous solution for 1 hour, wash with water, then immerse in 8% oxalic acid solution, boil for 3 hours, wash with water, rinse with deionized water, and dry at 110°C;
中间层2：洁净的基体1浸入二亚硝基二氨铂电镀液（以铂计）10g/L中，在0.01A/cm2条件下，施镀10min，制得铂负载量为5g/m2的铂镀层中间层2；Intermediate layer 2: The clean substrate 1 is immersed in 10g/L of dinitrosodiammine platinum electroplating solution (calculated as platinum), and plated for 10min under the condition of 0.01A/cm2 to obtain a platinum loading of 5g/m Platinum-coated intermediate layer2 of 2;
外涂层3：用18g氯铱酸、50g五水四氯化锡、2.68g氯化铋、225mL乙醇和250mL正丁醇的外层涂液。利用软毛刷将上述外层涂液均匀地刷涂在纯钛板的中间层2上，温度80℃烘干10min，然后移入热空气温度480℃中氧化10min，冷却后再刷涂涂液，再干燥、氧化、冷却，重复上述过程14次，最后480℃下热处理1h，即制得铂负载量5g/m2的中间层2、外涂层3铱负载量15g/m2的铱锡铋氧化物涂层钛电极。Outer coating 3: use an outer coating liquid of 18g of chloroiridic acid, 50g of tin tetrachloride pentahydrate, 2.68g of bismuth chloride, 225mL of ethanol and 250mL of n-butanol. Use a soft brush to evenly brush the above outer layer coating solution on the middle layer 2 of the pure titanium plate, dry it at 80°C for 10 minutes, then move it into hot air at a temperature of 480°C for 10 minutes, and then brush the coating solution after cooling. Then dry, oxidize, and cool down, repeat the above process 14 times, and finally heat-treat at 480°C for 1 hour to prepare the middle layer2 with a platinum loading of 5g/m2 and the outer coating3 with an iridium loading of 15g/m2. Oxide-coated titanium electrodes.
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