在LiF-CaF_2-NdF_3熔盐体系中Nd的电化学行为研究及Nd-Fe合金的制备
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摘要
研究了LiF-CaF_2-NdF_3熔盐体系中Nd(Ⅲ)的电化学行为,通过循环伏安法和开路计时电位法研究得出Nd(Ⅲ)的还原反应为两步电子转移过程,在惰性W电极上,两步反应的平衡电位分别为-1.58 V及-1.27 V(vs. Pt)。在活性Fe电极上对Nd(Ⅲ)的电化学行为研究发现,Nd与Fe会在-0.72 V和-1.15 V(vs. Pt)形成两种Nd-Fe合金。采用自耗阴极法制备了液态Nd-Fe合金,通过XRD分析Nd-Fe合金主要是由Nd、Fe_(17)Nd_2和Fe_(17)Nd_5组成。
The electrochemical behavior of neodymium in LiF-CaF_2-NdF_3 molten salt was studied in this paper. A two-step electron transfer process was found for the reduction reaction of Nd(Ⅲ) by cyclic voltammetry and open circuit potential. The equilibrium potentials of two reactions for Nd-2 e→Nd~(2+) and Nd~(2+)-e→Nd~(3+) were obtained to be-1.58 V and-1.27 V(versus Pt) on an inert W electrode, respectively. In addition, neodymium was deposited on an iron electrode forming Fe_(17)Nd_2 and Fe_(17)Nd_5 alloys at-0.72 V and-1.15 V(versus Pt), respectively. The liquid Nd-Fe alloy, which was composed of Nd, Fe_(17)Nd_2 and Fe_(17)Nd_5, was prepared by the consumption of iron cathode.
The electrochemical behavior of neodymium in LiF-CaF_2-NdF_3 molten salt was studied in this paper. A two-step electron transfer process was found for the reduction reaction of Nd(Ⅲ) by cyclic voltammetry and open circuit potential. The equilibrium potentials of two reactions for Nd-2 e→Nd~(2+) and Nd~(2+)-e→Nd~(3+) were obtained to be-1.58 V and-1.27 V(versus Pt) on an inert W electrode, respectively. In addition, neodymium was deposited on an iron electrode forming Fe_(17)Nd_2 and Fe_(17)Nd_5 alloys at-0.72 V and-1.15 V(versus Pt), respectively. The liquid Nd-Fe alloy, which was composed of Nd, Fe_(17)Nd_2 and Fe_(17)Nd_5, was prepared by the consumption of iron cathode.
引文
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[14] 黄超.LiF-NdF3-Nd2O3熔盐体系中Nd电解电流效率和机理的研究 [D].上海:华东理工大学,2016.27-29.Huang C.Study on the current efficiency and mechanism of Nd electrolysis in LiF-NdF3-Nd2O3 melts [D].Shanghai:East China University of Technology,2016.27-29.
[15] Ende M A V,Jung I H.Critical thermodynamic evaluation and optimization of the Fe-B,Fe-Nd,B-Nd and Nd-Fe-B systems[J].Journal of Alloys & Compounds,2013,548(1):133-154.
[16] Stroder U,Duruz J J,Jorda J L.Method for obtaining neodymium or neodymium-iron alloy by electrolysis of melts containing neodymium compounds[P].US:US5346608A,1994-09-14.
[2] 史文范,黄平,李雅民,赖心兰.一种氧化物熔盐电解制备镝铁合金的方法[P].中国:CN102140656A,2011-08-03.Shi W F,Huang P,Li Y M,Lai X L.A method for preparing dysprosium iron alloy by oxide molten salt electrolysis[P].China:CN102140656A,2011-08-03.
[3] 胡宪伟,王兆文,罗旭东,路贵民,崔建忠,陈广华.氟化物熔盐中含钕及钕-氧络合离子存在形式的研究[J].稀土,2008,29(5):58-60.Hu X W,Wang Z W,Luo X D,Lu G M,Cui J Z,Chen G H.Neodymium and neodymium-oxygen containing species in fluoride melts[J].Chinese Rare Earths,2008,29 (5):58-60.
[4] Bertaud Y.Process for the preparation of mother alloys of iron and neodymium by electrolysis of oxygen-bearing salts in a medium of molten fluorides[P].US:US4828658A,1989-05-09.
[5] Tamamura H.Process for preparation of neodymium or neodymium-iron alloy[P].US:US5091065A,1992-02-25.
[6] 陈德宏,颜世宏,李宗安,王志强,庞思明,王祥生,徐立海.NdF3-LiF-Nd2O3熔盐体系中下阴极电解金属钕研究[J].中国稀土学报,2009,27(2):302-305.Chen D H,Yan S H,Li Z A,Wang Z Q,Pang S M,Wang X S,Xue L H.Liquid-cathode cell for neodymium electrolysis in NdF3-LiF-Nd2O3 molten[J].Journal of the Chinese Society of Rare Earths,2009,27(2):302-305.
[7] 庞思明,颜世宏,李宗安,陈德宏,徐立海,赵斌.我国熔盐电解法制备稀土金属及其合金工艺技术进展[J].稀有金属,2011,35(3):440-450.Pang S M,Yan S H,Li Z A,Chen D H,Xue L H,Zhao B.Development on molten salt electrolyic methods and technology for preparing rare earth metals and alloys in China[J].Chinese Journal of Rare Metals,2011,35 (3):440-450.
[8] Hamel C,Chamelot P,Taxil P.Neodymium(Ⅲ) cathodic processes in molten fluorides[J].Electrochimica Acta,2004,49(25):4467-4476.
[9] Chamelot P,Massot L,Hamel C,Nourry C,Taxil P.Feasibility of the electrochemical way in molten fluorides for separating thorium and lanthanides and extracting lanthanides from the solvent[J].Journal of Nuclear Materials,2007,360(1):64-74.
[10] Gibilaro M,Massot L,Chamelot P,Taxil P.Study of neodymium extraction in molten fluorides by electrochemical co-reduction with aluminium[J].Journal of Nuclear Materials,2008,382(1):39-45.
[11] Thudum R,Srivastava A,Nandi S,Nagaraj A,Shekhar R.Molten salt electrolysis of neodymium:electrolyte selection and deposition mechanism[J].Mineral Processing & Extractive Metallurgy,2013,119(2):88-92.
[12] 郭探,王世栋,叶秀深,李权,刘海宁,郭敏,吴志坚.熔盐电解法制备稀土合金研究进展[J].中国科学:化学,2012(9):1328-1336.GUO T,WANG S D,Ye X S,Li Q,Liu H N,Guo M,Wu Z J.Research progress in the preparation of rare earth alloys by molten salt electrolysis method[J].Scientia Sinica Chemistry,2012 (9):1328-1336.
[13] Stefanidaki E,Hasiotis C,Kontoyannis C.Electrodeposition of neodymium from LiF-NdF3-Nd2O3 melts[J].Electrochimica Acta,2001,46(17):2665-2670.
[14] 黄超.LiF-NdF3-Nd2O3熔盐体系中Nd电解电流效率和机理的研究 [D].上海:华东理工大学,2016.27-29.Huang C.Study on the current efficiency and mechanism of Nd electrolysis in LiF-NdF3-Nd2O3 melts [D].Shanghai:East China University of Technology,2016.27-29.
[15] Ende M A V,Jung I H.Critical thermodynamic evaluation and optimization of the Fe-B,Fe-Nd,B-Nd and Nd-Fe-B systems[J].Journal of Alloys & Compounds,2013,548(1):133-154.
[16] Stroder U,Duruz J J,Jorda J L.Method for obtaining neodymium or neodymium-iron alloy by electrolysis of melts containing neodymium compounds[P].US:US5346608A,1994-09-14.
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