梁玉冬等：Fe-TB,/Al,O,复合阴极的电解性能及元素迁移行为 ·1051· 生成并保持也是复合阴极材料能否长期高效使用的 [4]Alton T,Jim B,Ivan E,et al.The operational performance of 70 一个关键所在. kA prebake cells retrofitted with TiB,-G cathode elements / Light Metals 1998:Proceedings of the Technical Sessions Presented 3结论 by the Tms Aluminum Committee at the 127th Tms Annual Meeting. San Antonio,1998:257 (1)以氧化铝溶胶作为黏结剂，Fe金属为烧结 [5]Alcom T R,Tabereaux A T,Richards N E.Operational results of 助剂在冷压烧结的条件下制备出Fe-TiB,/AL,O,阴 pilot cell test with cermet inert anodes /Light Metals 1998:Pro- 极材料.氧化铝溶胶的加入使相对密度值达到 ceedings of the Technical Sessions Presented by the Tms Aluminum 94.17%.较TiB2/A山，03复合材料高1.73%，相对于 Committee at the 127th Tms Annual Meeting.San Antonio,1998:433 [6]Liao X A,Oye H A.Effects of carbon-bonded coatings on sodium Fe-TiB,复合阴极提高了3.07%. expansion of the cathode in aluminum electrolysis/Light Metals (2)通过20A电解实验研究Fe-TB,/AL,03复 1999:Proceedings of the Technical Sessions Presented by the Tms A- 合阴极的电解性能.整个电解过程电压运行平稳， luminum Committee at the 128th Tms Annual Meeting.San Diego, 电流效率93.2%，原铝中A1元素的质量分数为 1999:629 [7]Kang S H,Kim D J,Kang E S,et al.Pressureless sintering and 99.47%,杂质元素质量分数为0.53%.在电解试验 properties of titanium diboride ceramics containing chromium and 后，铝液能有效润湿阴极表面，表明Fe-TB2/AL2O3 iron.J Am Ceram Soc,2001,84(4):893 复合阴极材料具有较理想的可润湿性. [8]Finch C B,Tannery V J.Crack formation and swelling of TiB,- (3)碱金属元素对Fe-TiB,/AL,O,复合阴极材 Ni ceramics in liquid aluminum.J Am Ceram Soc,1982,65(7): 料的渗透作用主要通过电解质对材料孔隙的渗透， c100 [9]Escribano S,Blachot J F,Etheve J,et al.Characterization of 进而渗透进入黏结剂相中，K元素的渗透深度显著 PEMFCs gas diffusion layers properties.Power Sources,2006, 强于Na元素：Al元素通过阴极材料内部的空隙渗 156(1):8 透进入阴极材料的金属相中，而Fe金属也会通过空 [10]Sekhar JA,de Nora,Liu J,et al.TiBz/colloidal alumina car- 隙进行反向扩散至铝液中，直至达到相对平衡 bon cathode coatings in Hall-Heroult and drained cells /Light Metals 1998:Proceedings of the Technical Sessions Presented by 参考文献 the Tms Aluminum Committee at the 127th Tms Annual Meeting. [1]Viswanath R P.A patent for generation of electrolytic hydrogen by San Antonio,1998:605 a cost effective and cheaper route.Int J Hydrogen Energy,2004, [11]Oye HA,de Nora V.Duruz J J.et al.Properties of a colloidal 29(11):1191 alumina-bonded TiB:coating on cathode carbon materials/ [2]Hryn J N,Pellin M J.A dynamic inert metal anode /Light Met- Light Metals1997:Proceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 126th Tms Annual Meet- als 1999:Proceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 128th Tms Annual Meeting.San ing.Orlando,1997:1171 [12]Han S,Li J,Zhang K,et al.Sintering and properties of TiBz/ Diego,1999:377 Al2O composite cathode for aluminum electrolysis.Nonferrous [3]Espen 0,Jomar T.The behavior of Feckel ferrite cermet materials Met (Extr Metall),2011(9):13 as inert anodes /Light Metals 1996:Proceedings of the Technical (韩硕，李劫，张凯，等.铝电解用TB2/A山2O3复合阴极的 Sessions Presented by the Tms Aluminum Committee at the 125th 烧结与性能研究.有色金属（冶炼部分），2011(9)：13) Tms Annual Meeting.Anaheim,1996:249梁玉冬等: Fe鄄鄄TiB2 / Al 2O3复合阴极的电解性能及元素迁移行为 生成并保持也是复合阴极材料能否长期高效使用的 一个关键所在. 3 结论 (1)以氧化铝溶胶作为黏结剂,Fe 金属为烧结 助剂在冷压烧结的条件下制备出 Fe鄄鄄 TiB2 / Al 2O3阴 极材料. 氧化铝溶胶的加入使相对密度值达到 94郾 17% . 较 TiB2 / Al 2O3复合材料高 1郾 73% ,相对于 Fe鄄鄄TiB2复合阴极提高了 3郾 07% . (2)通过 20 A 电解实验研究 Fe鄄鄄 TiB2 / Al 2O3复 合阴极的电解性能. 整个电解过程电压运行平稳, 电流效率 93郾 2% ,原铝中 Al 元素的质量分数为 99郾 47% ,杂质元素质量分数为 0郾 53% . 在电解试验 后,铝液能有效润湿阴极表面,表明 Fe鄄鄄 TiB2 / Al 2O3 复合阴极材料具有较理想的可润湿性. (3)碱金属元素对 Fe鄄鄄 TiB2 / Al 2 O3 复合阴极材 料的渗透作用主要通过电解质对材料孔隙的渗透, 进而渗透进入黏结剂相中,K 元素的渗透深度显著 强于 Na 元素;Al 元素通过阴极材料内部的空隙渗 透进入阴极材料的金属相中,而 Fe 金属也会通过空 隙进行反向扩散至铝液中,直至达到相对平衡. 参 考 文 献 [1] Viswanath R P. A patent for generation of electrolytic hydrogen by a cost effective and cheaper route. Int J Hydrogen Energy, 2004, 29(11): 1191 [2] Hryn J N, Pellin M J. A dynamic inert metal anode / / Light Met鄄 als 1999: Proceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 128th Tms Annual Meeting. San Diego, 1999: 377 [3] Espen O, Jomar T. The behavior of Feckel ferrite cermet materials as inert anodes / / Light Metals 1996: Proceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 125th Tms Annual Meeting. Anaheim, 1996: 249 [4] Alton T, Jim B, Ivan E, et al. The operational performance of 70 kA prebake cells retrofitted with TiB2 鄄鄄 G cathode elements / / Light Metals 1998: Proceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 127th Tms Annual Meeting. San Antonio, 1998: 257 [5] Alcom T R, Tabereaux A T, Richards N E. Operational results of pilot cell test with cermet inert anodes / / Light Metals 1998: Pro鄄 ceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 127th Tms Annual Meeting. San Antonio, 1998: 433 [6] Liao X A, 覫ye H A. Effects of carbon鄄bonded coatings on sodium expansion of the cathode in aluminum electrolysis / / Light Metals 1999: Proceedings of the Technical Sessions Presented by the Tms A鄄 luminum Committee at the 128th Tms Annual Meeting. San Diego, 1999: 629 [7] Kang S H, Kim D J, Kang E S, et al. Pressureless sintering and properties of titanium diboride ceramics containing chromium and iron. J Am Ceram Soc, 2001, 84(4): 893 [8] Finch C B, Tannery V J. Crack formation and swelling of TiB2 鄄鄄 Ni ceramics in liquid aluminum. J Am Ceram Soc, 1982, 65(7): c100 [9] Escribano S, Blachot J F, Eth侉ve J, et al. Characterization of PEMFCs gas diffusion layers properties. J Power Sources, 2006, 156(1): 8 [10] Sekhar J A, de Nora, Liu J, et al. TiB2 / colloidal alumina car鄄 bon cathode coatings in Hall鄄鄄Heroult and drained cells / / Light Metals 1998: Proceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 127th Tms Annual Meeting. San Antonio, 1998: 605 [11] 覫ye H A, de Nora V, Duruz J J, et al. Properties of a colloidal alumina鄄bonded TiB2 coating on cathode carbon materials / / Light Metals 1997: Proceedings of the Technical Sessions Presented by the Tms Aluminum Committee at the 126th Tms Annual Meet鄄 ing. Orlando, 1997: 1171 [12] Han S, Li J, Zhang K, et al. Sintering and properties of TiB2 / Al2O3 composite cathode for aluminum electrolysis. Nonferrous Met (Extr Metall), 2011(9): 13 (韩硕, 李劼, 张凯, 等. 铝电解用 TiB2 / Al2O3 复合阴极的 烧结与性能研究. 有色金属(冶炼部分), 2011(9): 13) ·1051·