浓差电池法用于铝液脱测氢的研究

doi:10.15541/jim20150527

无机材料学报 ›› 2016, Vol. 31 ›› Issue (5): 505-509.DOI: 10.15541/jim20150527

浓差电池法用于铝液脱测氢的研究

王东¹, 刘春明², 李胜利¹, 李维娟¹, 陈树江¹, 杨博威¹

(1. 辽宁科技大学材料与冶金学院, 鞍山114051; 2. 东北大学材料科学与工程学院, 沈阳110819)

收稿日期:2015-10-29 修回日期:2015-12-09 出版日期:2016-05-20 网络出版日期:2016-04-25
作者简介:王东(1980–), 男, 副教授. E-mail: chickwong@163.com
基金资助:
国家自然科学基金(51204095)

Determination of Hydrogen Content and Dehydrogenation in Molten Aluminum by Concentration Cell Method

WANG Dong¹, LIU Chun-Ming², LI Sheng-Li¹, LI Wei-Juan¹, CHEN Shu-Jiang¹, YANG Bo-Wei¹

(1. School of Materials and Metallurgy, University of Science and Technology, Anshan 114051, China; 2. School of Metallurgy, Northeastern University, Shenyang 110819, China)

Received:2015-10-29 Revised:2015-12-09 Published:2016-05-20 Online:2016-04-25
About author:WANG Dong. E-mail: chickwong@163.com
Supported by:
National Natural Science Foundation of China (51204095)

摘要/Abstract

摘要：

利用固相反应法制备了纯度较高、粒度较小的CaZr_0.9In_0.1O_3-_α质子导体管, 将其作为电解质组装成浓差电池型氢泵和氢传感器, 并对760℃铝液进行了脱氢过程和氢含量的测定, 研究了氢传感器的探头组装方式、参比气体流量和压力等对电动势曲线和阻抗谱的影响, 以及氢泵在改善物理条件下的脱氢效果。结果表明: 倒置式探头的电动势曲线变化较平滑, 约经13 min达到较稳定状态, 其传感性能优于正置式探头; 参比气体的流量或压力增加时, 电动势也将随之迅速增大, 其原因与电动势受Nernst方程控制有关, 反之则减小。同时, 参比气体流量的增加, 会延长电动势达到平衡所需的时间, 并使电极/电解质界面的电荷转移电阻降低。因此, 为了获得快速、准确的测氢结果, 组装传感器时探头应倒置, 并根据气体管路特点, 确定合适的参比气体流量并对其进行精确控制。此外, 实验证明了浓差电池型氢泵在铝液脱氢方面具有可行性和实用价值, 有深入研究的必要。

关键词: 质子导体, 参比气体, 浓差电池, 氢泵, 氢传感器, 阻抗谱

Abstract:

The CaZr_0.9In_0.1O_3-α proton conductor was prepared by solid reaction method with high purity and small particle size. Two types hydrogen sensors and pump based on the proton conductor were fabricated for monitoring the hydrogen content and dehydrogenation in molten aluminum at 760℃. The electromotive force (EMF) and time of hydrogen sensor with the inverted-U electrolyte tube followed a smooth curve in which the EMF tended to be stable after about 13 min whose sensing performance was superior to that with the upright-U electrolyte tube. The sensor EMF increased with the pressure or flow rate of referent gas according to Nernst equation. The equilibrium time of EMF increased and the transferring resistance between the Pt electrode and proton conductor’s transfer resistance decreased with the flow rate of reference gas. Therefore, inverted-U type tube and flow rate value of reference gas were very important to acquire the sensitive and accurate hydrogen content values in molten aluminum. In addition, hydrogen pump based on concentration cell had feasibility and actual using value for the dehydrogenation of molten aluminum.

Key words: proton conductor, reference gas, concentration cell, hydrogen pump, hydrogen sensor, impedance spectrum

中图分类号:

TB321

王东, 刘春明, 李胜利, 李维娟, 陈树江, 杨博威. 浓差电池法用于铝液脱测氢的研究[J]. 无机材料学报, 2016, 31(5): 505-509.

WANG Dong, LIU Chun-Ming, LI Sheng-Li, LI Wei-Juan, CHEN Shu-Jiang, YANG Bo-Wei. Determination of Hydrogen Content and Dehydrogenation in Molten Aluminum by Concentration Cell Method[J]. Journal of Inorganic Materials, 2016, 31(5): 505-509.

图/表 9

图1 混合粉末经1400℃×8 h煅烧产物的XRD图谱

Fig. 1 XRD pattern of the mixed powders after calcinated at 1400℃ for 8 h

图2 倒置式氢传感器的结构示意图

Fig. 2 Diagram of structure of hydrogen sensor with inverted- U electrolyte tube

图3 倒置式(a)和正置式(b)探头的电动势变化

Fig. 3 EMF of hydrogen probe with inverted-U (a) and upright-U (b) electrolyte tube

图4 参比气体压力对传感器电动势的影响

Fig. 4 Dependence of EMF on different pressure of gas

图5 参比气体流量对传感器电动势的影响

Fig. 5 Dependence of EMF on different gas flow rates

图6 参比气体流量对电动势平衡时间的影响

Fig. 6 Dependence of equilibrium time of EMF on different gas flow rates

图7 传感器的阻抗谱(a)及其等效电路(RcQc)(RtQd)(b)

Fig. 7 Impedance spectra (a) and equivalent electrical circuit (b) obtained from hydrogen sensor (20 mL/min of flow rate of reference gas)

图8 参比气体流量对阻抗谱的影响

Fig. 8 Dependence of impedance spectra on different gas flow rates Gas cylinder pressure 0.12 MPa (a) and 0.20 MPa (b)

图9 短路真空抽取或气流携带脱氢法的氢含量曲线

Fig. 9 Relationship between hydrogen content by extracting or gas carrying hydrogen and time at 760℃

参考文献 15

[1]	IWAHARA H, ESAKA T, UCHIDA H, et al. Proton conduction in sintered oxides and its application to steam electrolysis for hydrogen production. Solid State Ionics, 1981, 3-4: 359-363.
[2]	MATSUSHITA E, SASAKI T.Theoretical approach for protonic conduction in perovskite-type oxides.Solid State Ionics, 1999, 125(1-4): 31-37.
[3]	王东, 范建华, 刘春明, 等. BaCe1-xYxO3-α及BaCe0.9Sm0.1O3-α质子导体的表征及组成氢泵对铝熔体的脱氢. 金属学报, 2007, 43(17): 1228-1232.
[4]	王东, 史苍际, 刘春明, 等. CaZr0.9In0.1O3-α高温质子导体管的制备及性质表征. 金属学报, 2007, 44(2): 177-182.
[5]	XU J H, XIANG J, DING H, et al.Synthesis and electrical properties of BaCeO3-based proton conductors by calcinations of metal-polyvinyl alcohol gel.J. Alloys Compd., 2013, 551: 333-337.
[6]	ANANYEV M, MEDVEDEV D, GAVRILYUK A, et al.Cu and Gd co-doped BaCeO3 proton conductors: experimental vs SEM image algorithmic-segmentation results.Electrochimica Acta, 2014, 125(10): 371-379.
[7]	Medvedev D A, GORBOVA E V, DEMIN A K, et al.Conductivity of Gd-doped BaCeO3 protonic conductor in Н2-Н2О-О2 atmospheres.Int. J. Hydrogen Energy, 2014, 39(36): 21547-21552.
[8]	KOKKOFITIS C, OUZOUNIDOU M, SKODRA A, et al.High temperature proton conductors: applications in catalytic processes.Solid State Ionics, 2007, 178(7): 507-513.
[9]	SUKSAMAI W, METCALFE I S.Measurement of proton and oxide ion fluxes in a working Y-doped BaCeO3 SOFC.Solid State Ionics, 2007, 178(7-10): 627-634.
[10]	STUART P A, UNNO T, KILNER J A, et al.Solid oxide proton conducting steam electrolysers.Solid State Ionics, 2008, 179(21-26): 1120-1124.
[11]	ZHANG J C, WEN Z Y, CHI X W, et al.Proton conducting CaZr0.9In0.1O3-δ ceramic membrane prepared by tape casting.Solid State Ionics, 2012, 225(1): 291-296.
[12]	MATSUMOTO H, SHIMURA T, IWAHARA H, et al. Hydrogen separation using proton-conducting perovskites. J. Alloys Compd., 2006, 408-412: 456-462.
[13]	XIA T, HE C H, YANG H G, et al.Hydrogen extraction characteristics of high-temperature proton conductor ceramics for hydrogen isotopes purification and recovery.Fusion Engineering & Design, 2014, 89(7/8): 1500-1504.
[14]	NOTORP KYHS-A2 Hydrogen Analyzer for Molten Aluminium Alloys, TYK Corporation, Tokyo, Japan, 1997.
[15]	FUKATSU N, KURITA N, OHASHI T.Hydrogen Sensor for Molten Metals and Its Application to Materials Processing. Second International Conference on Properties on Processing Materials for Properties. Pennsylvania, 2000: 357-363.

浓差电池法用于铝液脱测氢的研究

Determination of Hydrogen Content and Dehydrogenation in Molten Aluminum by Concentration Cell Method

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