电解二氧化锰复合涂层修饰钛基阳极的制备与性能
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摘要
在电解二氧化锰体系中,使用的阳极板通常具有易变型,电流密度低,电耗高等缺点。为了解决这些问题,文中选用工业纯钛作为基体,二氧化锰和二氧化锡作为复合活性涂层,采用简易的热分解方法制备出钛基复合涂层阳极。通过SEM测试涂层表面形貌,发现该阳极的涂层致密、呈较平整的层状。采用循环伏安曲线测试并计算积分面积和极化曲线对涂层配方进行研究,发现烧结温度为450℃,锡/锰比为6∶4时的阳极性能最优。与铅阳极和铅银合金阳极对比,用该复合涂层阳极电解得到的二氧化锰纯度更高,但其槽压比其它阳极低了约0.2 V左右,电流效率得到了提高,从而节约了电解过程中的能耗。因此,该复合涂层阳极适合做大型电极的阳极板。
Anode plates have some disadvantages in the electrolysis, such as easy distortion, low current density, high power consumption, et al. In order to solve these problems, the composite coating of MnO_2 and SnO_2 was prepared on titanium anode by a simple thermal decomposition method. The surface morphology of the composite coating was characterized by SEM.Results show that the coating is dense and smooth with a layer structure. The properties of composite coating are studied by testing the polarization curve, cyclic voltammetry curves and calculating the voltammetry curve integral area. It is showed that the optimum coating is Sn/Mn with a ratio 6∶4 sintering at 450 ℃. The composite coating anode has much obvious advantages, compared with lead anode, lead silver alloy anode and the titanium anode. Higher purity MnO_2 has obtained by using the composite coating anode. The voltage is reduced about 0.2 V improved the current efficiency. Therefore, the composite coating anode is suitable for the anode plate of large electrodes.
Anode plates have some disadvantages in the electrolysis, such as easy distortion, low current density, high power consumption, et al. In order to solve these problems, the composite coating of MnO_2 and SnO_2 was prepared on titanium anode by a simple thermal decomposition method. The surface morphology of the composite coating was characterized by SEM.Results show that the coating is dense and smooth with a layer structure. The properties of composite coating are studied by testing the polarization curve, cyclic voltammetry curves and calculating the voltammetry curve integral area. It is showed that the optimum coating is Sn/Mn with a ratio 6∶4 sintering at 450 ℃. The composite coating anode has much obvious advantages, compared with lead anode, lead silver alloy anode and the titanium anode. Higher purity MnO_2 has obtained by using the composite coating anode. The voltage is reduced about 0.2 V improved the current efficiency. Therefore, the composite coating anode is suitable for the anode plate of large electrodes.
引文
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[2]廖先杰,翟玉春,谢宏伟,等.低温熔盐电解法制备金属Ti及其动力学[J].材料研究学报,2012(6):590-596.LIAO X J,ZHAI Y C,XIE H W,et al.Preparation of Ti by direct electrochemical deoxidation in low temperature molten salt[J].Journal of Materials Research,2012(6):590-596(in Chinese).
[3]YANG H T,LIU H R,GUO Z C,et al.Electrochemical behavior of rolled Pb-0.8%Ag anodes[J].Hydrometallurgy,2013,140:144-150.
[4]杨海涛,陈步明,郭忠诚.铅基合金阳极在有色金属湿法冶炼中的研究与发展[J].中国有色冶金,2012,41(2):20-24.YANG H T,CHEN B M,GUO Z C,et al.Research and development of lead-based alloy anodes in non-ferrous metal smelting[J].China Nonferrous Metallurgy,2012,41(2):20-24(in Chinese).
[5]SHI Y,MENG H,SUN D,et al.Effect of SbO_x+SnO_2 intermediate layer on the properties of Ti-based MnO_2 anode[J].Acta Physico-chimica Sinica,2007,23(10):1553-1559.
[6]张恒,吴元花.制备二氧化锰大型Ti-Mn合金阳极性能的研究[J].稀有金属,2014,38(4):574-580.ZHANG H,WU Y H.Performance of large Ti-Mn alloy anode for preparation of manganese dioxide[J].Rare Metal,2014,38(4):574-580(in Chinese).
[7]ZHOU M H,LIU L,JIAO Y L,et al.Treatment of high-salinity reverse osmosis concentrate by electrochemical oxidation on BDD and DSA electrodes[J].Desalination,2011,277(1-3):201-206.
[8]ZHANG Q L,GUO X Y,CAO X D,et al.Facile preparation of a Ti/α-PbO_2/β-PbO_2 electrode for the electrochemical degradation of 2-chlorophenol[J].Chinese Journal of Catalysis,2015,36(7):975-981.
[9]YONGLE N,HUIMIN M,DONG C,et al.Preparation of IrO_2+MnO_2 coating anodes and their application in NaCIO production[J].Journal of University of Science and Technology Beijing,Mineral,Metallurgy,Material,2008,15(4):461-467.
[10]史艳华,孟惠民,孙冬柏,等.阳极电沉积法制备锰类氧化物涂层电极的研究[J].热处理技术与装备,2008,29(1):39-42.SHI Y H,MENG H D,SUN D B,et al.The research of manganese oxide coating electrodeby anode electrodepos it process[J].Heat Treatment Technology and Equipment,2008,29(1):39-42(in Chinese).
[11]SUN Y,TIAN X K,HE B B,et al.Studies of the reduction mechanism of selenium dioxide and its impact on the microstructure of manganese electrodeposit[J].Electrochimica Acta,2011,56(24):8305-8310.
[12]SUN W,LEE J W,YEO I H,et al.The role of cations of the electrolyte for the pseudocapacitive behavior of metal oxide electrodes,MnO_2 and RuO_2[J].Electrochimica Acta,2004,50:849-855.
[13]HU C C,WANG C W,WU T H,et al.Anodic composite deposition of hydrous RuO_2-TiO_2 nanocomposites for electrochemical capacitors[J].Electrochimica Acta,2012,85:90-98.
[14]王清泉,刘贵昌,刘坤.稀土La掺杂对Ru-La-Ti涂层阳极电催化性能的影响[J].材料保护,2007,40(5):1-3.WANG Q Q,LIU G C,LIU K,et al.Effect of rare earth La doping on electrocatalytic performance of Ru-La-Ti coating anodes[J].Material Protection,2007,40(5):1-3(in Chinese).
[15]范农杰,竺培显,韩朝辉,等.稀土La对RuO_2-TiO_2涂层钛阳极表面结构和性能的影响[J].材料保护,2015,36(8):217-221.FAN N J,ZHU P X,HAN C H,et al.Effects of La on microstructure and properties of RuO_2-TiO_2 titanium anode coating[J].Materials Protection,2015,36(8):217-221(in Chinese).
[16]翟东.Ru-Ir-Ti/Ti氧化物涂层阳极的制备工艺与表面改性研究[D].昆明:昆明理工大学.2012.ZHAID.Study on preparation process and surface modification of Ru-Ir-Ti/Ti oxide anodes[D].Kunming:Kunming University of Science and Technology,2012(in Chinese).
[17]ALEXANDRA P,ANNETT R,SANDRA E T,et al.Pt/IrO_2-TiO_2 cathode catalyst for low temperature polymer electrolyte fuel cell-application in MEAs,performance and stability issues[J].Catalysis Today,2016,262:161-169.
[18]MOHAMMAD M N,SEYEDEH M H.Highly dispersed PtO_2 on layered Mn oxide as water-oxidizing catalysts[J].International Journal of Hydrogen Energy,2016,41(16):6798-6804.
[19]YAN Z W,LI G,WANG J S,et al.Electro-catalytic study of IrO_2-Ta_2O_5 coated anodes with pretreated titanium substrates[J].Journal of Alloys and Compounds,2016,680:60-66.
[20]王雅琼,许文林,陆路德,等.MnO活性层制备条件对Ti/SnO+SbO/MnO电极性能的影响[J].无机材料学报,2006,21(6):1362-1366.WANG Y Q,XU W L,LU L D,et al.MnO two active layer preparation conditions for Ti/SnO+SbO/MnO electrode performance[J].Journal of Inorganic Materials,2006,21(6):1362-1366(in Chinese).
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