Fe对(Cu-Ni-Fe)-xNiFe_2O_4复合惰性阳极低温铝电解成膜机制的影响
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摘要
以高温固相合成的NiFe_2O_4和Cu,Ni,Fe金属粉为原料,采用冷压烧结法制备不同合金相含量的(Cu-Ni-Fe)-xNiFe_2O_4(x=50,60,70,80,质量分数/%,下同)金属基复合惰性阳极材料,研究合金相中Fe元素对(Cu-Ni-Fe)-xNiFe_2O_4金属基复合惰性阳极材料烧结和电解过程中基体成分与微观组织的影响,发现合金相中的Ni,Fe及NiFe_2O_4陶瓷相在烧结和电解过程中发生了可逆的氧化还原反应,使得NiFe_2O_4相发生解离和再生成。对(Cu-Ni-Fe)-xNiFe_2O_4金属基复合惰性阳极材料进行了低温电解性能测试,研究其在电解过程中的成膜过程和腐蚀行为。结果表明:(Cu-Ni-Fe)-xNiFe_2O_4金属基复合惰性阳极材料电解过程中电压稳定,铝液杂质含量低于0.7%(质量分数),有望解决金属陶瓷阳极热稳定性差的问题,是理想的惰性阳极材料。
Several(Cu-Ni-Fe)-xNiFe_2O_4(x=50,60,70,80,mass fraction/%) composite inert anodes with different contents of alloy phase were prepared using Cu, Ni, Fe and high-temperature synthetic NiFe_2O_4 by cold-pressing sintering method. The effect of Fe on the composition and microstructure of the(Cu-Ni-Fe)-xNiFe_2O_4 composite inert anodes during sintering and electrolysis process was studied. It is found that the redox reaction between Ni/Fe and NiFe_2O_4 phase occurs, leading to the dissociation and regeneration of NiFe_2O_4. In addition, the film-forming process and corrosion behavior of the(Cu-Ni-Fe)-xNiFe_2O_4 anodes were studied through low-temperature aluminium electrolysis test. The results indicate that the cell voltage is stable during electrolysis and the impurities in the produced aluminium are less than 0.7%(mass fraction), which indicates that(Cu-Ni-Fe)-xNiFe_2O_4 composite inert anode is one of the most promising inert anode materials, and the poor thermal stability of the ceramic anode is expected to be solved.
Several(Cu-Ni-Fe)-xNiFe_2O_4(x=50,60,70,80,mass fraction/%) composite inert anodes with different contents of alloy phase were prepared using Cu, Ni, Fe and high-temperature synthetic NiFe_2O_4 by cold-pressing sintering method. The effect of Fe on the composition and microstructure of the(Cu-Ni-Fe)-xNiFe_2O_4 composite inert anodes during sintering and electrolysis process was studied. It is found that the redox reaction between Ni/Fe and NiFe_2O_4 phase occurs, leading to the dissociation and regeneration of NiFe_2O_4. In addition, the film-forming process and corrosion behavior of the(Cu-Ni-Fe)-xNiFe_2O_4 anodes were studied through low-temperature aluminium electrolysis test. The results indicate that the cell voltage is stable during electrolysis and the impurities in the produced aluminium are less than 0.7%(mass fraction), which indicates that(Cu-Ni-Fe)-xNiFe_2O_4 composite inert anode is one of the most promising inert anode materials, and the poor thermal stability of the ceramic anode is expected to be solved.
引文
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[17] XIAO H,HOVLAND R,ROLSETH S,et al. Studies on the corrosion and the behavior of inert anodes in aluminum electrolysis[J]. Metallurgical and Materials Transactions B,1996,27:185-193.
[18] PENG W P, LIU Y, GUO J, et al. Effect of La on the electrolysis performance of 46Cu-25Ni-19Fe-10Al metal anode[C]// Light Metals 2014. Pittsburgh, PA, US:TMS,2014:1301-1304.
[19] GOUPIL G, HELLE S, DAVIS B, et al. Anodic behavior of mechanically alloyed Cu-Ni-Fe and Cu-Ni-Fe-O electrodes for aluminum electrolysis in low-temperature KF-AlF3 electrolyte[J]. Electrochimica Acta,2013, 112: 176-182.
[20] HELLE S, BRODU B, DAVIS B, et al. Influence of the iron content in Cu-Ni based inert anodes on their corrosion resistance for aluminium electrolysis[J]. Corrosion Science,2011, 53(10): 3248-3253.
[2] 何汉兵,李志友,周科朝. 金属惰性阳极的研究进展[J]. 材料导报, 2007, 21(12): 69-72. HE H B,LI Z Y,ZHOU K C. Research progress in metal inert anodes[J]. Materials Review, 2007, 21(12): 69-72.
[3] 周科朝,陶玉强. 铁酸镍基金属陶瓷惰性阳极材料的研究进展[J]. 中国有色金属学报, 2011, 21(10): 2418-2429. ZHOU K C,TAO Y Q. Research development of nickel ferrite based cermet inert anode materials[J]. The Chinese Journal of Nonferrous Metals, 2011, 21(10): 2418-2429.
[4] MA X X, HE Y D, WANG D R. Inert anode composed of Ni-Cr alloy substrate, intermediate oxide film and α-Al2O3/Au (Au-Pt, Au-Pd, Au-Rh) surface composite coating for aluminium electrolysis[J]. Corrosion Science,2011,53(3): 1009-1017.
[5] CHAPMAN V,WELCH B J,SKYLLAS-KAZACOS M. High temperature oxidation behaviour of Ni-Fe-Co anodes for aluminium electrolysis[J]. Corrosion Science, 2011, 53(9): 2815-2825.
[6] ASSOULI B,PEDRON M,HELLE S,et al. Mechanically alloyed Cu-Ni-Fe based materials as inert anode for aluminum production[C]//Light Metals 2009. Pittsburgh,PA,US:TMS, 2009: 1141-1144.
[7] WELCH B J. Inert anodes-the status of the material science, the opportunities they present and the challenges that need resolving before commercial implementation[C]//Light Metals 2009. Pittsburgh, PA,US: TMS,2009: 971-978.
[8] 吴深,樊江磊,刘建秀,等. NiZnFe2O4包覆铁基软磁复合材料的制备及性能[J]. 材料工程, 2017, 45(7): 60-65. WU S,FAN J L,LIU J X,et al. Fabrication and properties of iron-based soft magnetic composites coated with NiZnFe2O4[J]. Journal of Materials Engineering,2017,45(7): 60-65.
[9] TIAN Z L, LAI Y Q, LI Z Y, et al. Further development on NiFe2O4-based cermet inert anodes for aluminum electrolysis[J]. JOM, 2014, 66(11): 2229-2234.
[10] TAO Y Q, LI Z Y, ZHANG D,et al. Microstructural evolution of a nickel ferrite-copper alloy cermet during sintering and high-temperature oxidation[J]. Journal of the American Ceramic Society,2012, 95(10): 3031-3036.
[11] HE H B. The metal phase selection of 10NiO-NiFe2O4-based cermet anodes for aluminum electrolysis[C]//Light Metals 2014. Pittsburgh, PA, US:TMS,2014: 1321-1325.
[12] LIU J Y,LI Z Y,TAO Y Q,et al. Phase evolution of 17(Cu-10Ni)-(NiFe2O4-10NiO) cermet inert anode during aluminum electrolysis[J]. Transactions of Nonferrous Metals Society of China,2011, 21(3): 566-572.
[13] TIAN Z L,LAI Y Q,YANG S,et al. Anodic corrosion behavior of NiFe2O4-based cermet in Na3AlF6-K3AlF6-AlF3 for aluminium electrolysis[J]. Metallurgical and Materials Transactions B,2015, 46(3): 1257-1261.
[14] OLSEN E,THONSTAD J. Nickel ferrite as inert anodes in aluminium electrolysis: part Ⅰ: material fabrication and preliminary testing[J]. Journal of Applied Electrochemistry,1999,29(3): 293-299.
[15] BAKER H.ASM metals handbook, volume 3: alloy phase diagrams[M]. Ohio,US:ASM International,1992: 1644-1647.
[16] OLSEN E, THONSTAD J. Nickel ferrite as inert anodes in aluminium electrolysis: part Ⅱ: material performance and long-term testing[J]. Journal of Applied Electrochemistry,1999,29(3): 301-311.
[17] XIAO H,HOVLAND R,ROLSETH S,et al. Studies on the corrosion and the behavior of inert anodes in aluminum electrolysis[J]. Metallurgical and Materials Transactions B,1996,27:185-193.
[18] PENG W P, LIU Y, GUO J, et al. Effect of La on the electrolysis performance of 46Cu-25Ni-19Fe-10Al metal anode[C]// Light Metals 2014. Pittsburgh, PA, US:TMS,2014:1301-1304.
[19] GOUPIL G, HELLE S, DAVIS B, et al. Anodic behavior of mechanically alloyed Cu-Ni-Fe and Cu-Ni-Fe-O electrodes for aluminum electrolysis in low-temperature KF-AlF3 electrolyte[J]. Electrochimica Acta,2013, 112: 176-182.
[20] HELLE S, BRODU B, DAVIS B, et al. Influence of the iron content in Cu-Ni based inert anodes on their corrosion resistance for aluminium electrolysis[J]. Corrosion Science,2011, 53(10): 3248-3253.
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