LiF-SmF_3-Sm_2O_3熔盐中Sm(Ⅲ)的电化学行为研究
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摘要
以SmF_3-LiF-Sm_2O_3为熔盐体系,Sm_2O_3为原料,分别采用循环伏安法、方波伏安法、计时电位法研究钐离子在惰性钨电极和活性铜电极上的电化学行为.结果表明,在惰性钨电极上,Sm(Ⅲ)离子的还原反应是通过2步电子转移完成,其反应为准可逆反应且扩散系数为4. 05×10~(-5)cm~2·s~(-1).根据活性电极Cu上循环伏安曲线可见,电解可获得2种Sm-Cu金属间化合物,对应的电流密度分别为-0. 231A·cm~(-2)和-0. 782 A·cm~(-2).
The electrochemical behaviors of samarium ions on inert tungsten electrode and active copper electrode were studied by cyclic voltammetry,square wave voltammetry and chronopotentiometry in SmF_3-LiF-Sm_2O_3 molten salt system. The results indicated that the reduction reaction of Sm(Ⅲ) ions on the inert tungsten electrode was completed by two-step electron transfer,and the reaction was quasi-reversible. The diffusion coefficient of Sm(Ⅲ) was 4. 05 × 10~(-5) cm~2·s~(-1) which obtained by the chronopotentiometry. There are two kinds of Sm-Cu intermetallic compounds could be obtained According to the cyclic voltammetry curve of the active electrode Cu,and the corresponding current densities were -0. 231 A·cm~(-2) and-0. 782 A·cm~(-2),respectively.
The electrochemical behaviors of samarium ions on inert tungsten electrode and active copper electrode were studied by cyclic voltammetry,square wave voltammetry and chronopotentiometry in SmF_3-LiF-Sm_2O_3 molten salt system. The results indicated that the reduction reaction of Sm(Ⅲ) ions on the inert tungsten electrode was completed by two-step electron transfer,and the reaction was quasi-reversible. The diffusion coefficient of Sm(Ⅲ) was 4. 05 × 10~(-5) cm~2·s~(-1) which obtained by the chronopotentiometry. There are two kinds of Sm-Cu intermetallic compounds could be obtained According to the cyclic voltammetry curve of the active electrode Cu,and the corresponding current densities were -0. 231 A·cm~(-2) and-0. 782 A·cm~(-2),respectively.
引文
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[3] M. Krishnan,P. Predeep,D. V. Sridhara Rao,et al. Chowdhury. High coercivity Sm-Co thin films from elemental Sm/Co multilayer deposition and their microstructural aspects[J]. Journal of Magnetism and Magnetic Materials. 2017,430:47-51.
[4] K. J. Li,Q. A. Li,X. T. Jing,et al. Effects of Sm addition on microstructure and mechanical properties of Mg-6Al-0. 6 Zn alloy[J]. Scripta Materialia,2009,60(12):1101-1104.
[5] Q. A. Li,Q. Zhang,Y. G. Wang,et al. Effects of Sm addition on microstructure and mechanical properties of a Mg-10Y alloy[J]. Research&Development,2014,11(1).
[6] Y. Castrillejo,P. Fernandez,J. Medina,et. al. Electrochemical extraction of samarium from molten chlorides in pyrochemical processes[J].Electrochimica Acta. 2011,56:8638-8644.
[7] Y. Castrillejo,C. de la Fuenta,M. Vega,et al. Cathodic behaviour and oxoacidity reactions of samarium(III)in two molten chlorides with different acidity properties:The eutectic Li Cl-KCl and the equimolar CaCl2-Na Cl melt[J]. Electrochimica Acta. 2013,97:120-131.
[8] L. Massot,P. Chamelot,P. Taxil. Cathodic behaviour of samarium(III)in Li F-CaF2media on molybdenum and nickel electrodes[J]. Electrochimica Acta,2005,50:5510-5517.
[9] G. Cordoba,C. Caravacan. Electrochemical study of samarium ions in the molten eutectic Li Cl+KCl[J]. Journal of Electroanalytical Chemistry,2004,572:145-151.
[10] Y. Castrillejo,P. Fernández,J. Medina,et al. Electrochemical extraction of samarium from molten chlorides in pyrochemical processes[J].Electrochimica Acta,2011,56:8638-8644.
[11] D. B. Ji,Y. D. Yan,M. L. Zhang,et al. Thomas Hartmann. Electrochemical preparation of Al-Sm intermetallic compound whisker in Li Cl-KCl Eutectic Melts[J]. Electrochimica Acta,2015,165:211-220.
[12] 薛云,王倩,颜永得.在Li Cl-KCl-AlCl3熔盐中直接电化学还原Sm2O3及得Al-Sm合金的形成[J].无机化学学报,2013,29(9):1947-1951.
[13] Q. Chen,W. Han,Y. S. Yang. A new electrochemical preparation method for formation Sm-Al alloys on inert Mo electrode from Sm2O3in Li ClKCl-MgCl2-KF molten salts[J]. Metallurgica sinica. 2012,25(2):102-110.
[14] Y. Gao,Y. K. Shi,X. L. Liu,et al. Cathodic Behavior of Samarium(III)and Sm-Al alloys Preparation in Fluorides Melts[J]. Electrochimica Acta,2016,190:208-214.
[15] L. Massot,P. Chamelot,P. Taxil,Cathodic behaviour of samarium(III)in Li F-CaF2media on molybdenum and nickel electrodes[J]. Electrochimica Acta,2005,50:5510-5517.