1723K下熔渣中Ni^(2+)和Fe^(2+)离子共存时的电化学行为  

Electrochemical behaviors of coexisting Ni^(2+) and Fe^(2+) ions in molten slag

作　　者：张灿磊[1] 高运明[1] 杨高[1] 秦庆伟[1] 

机构地区：[1]武汉科技大学钢铁冶金及资源利用省部共建教育部重点实验室,湖北武汉430081

出　　处：《钢铁研究学报》2017年第6期459-467,共9页Journal of Iron and Steel Research

基　　金：国家自然科学基金资助项目(51174148);国家自然科学基金委员会-辽宁省人民政府联合基金资助项目(U1508214)

摘　　要：利用MgO部分稳定的ZrO_2固体电解质管集成构建以Pt,O_2(空气)|ZrO_2作为参比电极的新型可控氧流电解池,采用循环伏安CV、方波伏安SWV、恒电位电解PE等方法,并结合热力学计算与显微观察、能谱分析,研究1 723K高温下SiO_2-CaO-MgO-Al_2O_3熔渣中共存的Ni^(2+)、Fe^(2+) 离子在Ir电极上的电化学行为。结果表明:熔渣系中FeO与NiO之间存在较弱的相互作用,但镍离子以Ni^(2+)存在,铁离子基本以Fe^(2+) 存在。进行方波伏安分析时,Ni^(2+)、Fe^(2+) 离子的还原峰电流对频率呈现不同的规律。Ni^(2+)在Ir电极上的电化学还原是扩散控制的一步两电子转移反应过程;Fe^(2+) 到Fe的电化学还原也是一步两电子转移反应过程,但Fe^(2+) 的还原明显受到Ni^(2+)还原的影响。基于循环伏安法,计算得到NiO、FeO的质量分数分别为3%、5%的熔渣中Ni^(2+)离子在1 723K下的扩散系数为(9.2±0.2)×10-6cm2/s。stabilized zirconia solid electrolyte tube with Pt, O2（air）｜ZrO2 used as reference electrode. Combined with thermodynamic calculation, SEM observation and EDS analysis, electrochemical behaviors of coexisting Ni^2＋ and Fe^2＋ ions in SiO2-CaO-MgO- Al2O3 molten slag were investigated on the iridium electrode at 1723K by means of electrochemical techniques including cyclic voltammetry （CV）, square wave voltammetry （SWV） and potentiostatic electrolysis （PE）. The results show that there is weak interaction between FeO and NiO in the molten slag system, but nickel ions exist in the form of Ni^2＋ and iron ions exist basically in Fe^2＋. When SWV is performed, the reduction peak currents of Fe^2＋ and Ni^2＋ ions exhibit different rules for the scan frequency. The electrochemical reduction of Ni^2＋ on the iridium electrode in the molten slag is a single two-electron transfer step, and the rate of the electrochemical reduction of Ni^2＋ is controlled by diffusion. The electrochemical reduction of Fe^2＋ is also a single two-electron transfer step, but the process is obviously affected by the reduction of Ni^2＋. The diffusion coefficient value of Ni^2＋ ions derived from CVs is （9.2±0.2）×10^-6 cm^2/s in the molten slag containing 3 mass% NiO and 5mass% FeO at 1723K.

关 键 词：NI^2+ FE^2+ 熔渣 电化学行为 固体电解质 可控氧流电解池 

分 类 号：TF111.52[冶金工程—冶金物理化学]