物理化学学报 >> 2013, Vol. 29 >> Issue (08): 1804-1808.doi: 10.3866/PKU.WHXB201306061

材料物理化学 上一篇    下一篇

KH添加对Na-Al-H配位氢化物可逆放氢性能的影响

王顺葵1, 李志杰2, 肖学章1, 范修林1, 陈志文1, 李寿权1, 葛红卫1, 陈立新1   

  1. 1 浙江大学材料科学与工程学系, 浙江省电池新材料与应用技术研究重点实验室, 杭州 310027;
    2 甘肃工业职业技术学院, 甘肃天水741025
  • 收稿日期:2013-04-18 修回日期:2013-06-06 发布日期:2013-07-09
  • 通讯作者: 肖学章, 陈立新 E-mail:xzxiao@zju.edu.cn; lxchen@zju.edu.cn
  • 基金资助:

    国家重点基础研究发展规划(973) (2010CB631304); 国家自然科学基金(51001090, 51171173); 中国博士后科学基金(20090262, 2012M521167)和浙江省重点科技创新团队(2010R50013)资助项目

Influence of KH on Reversible Dehydriding Performance of Na-Al-H Complex Hydride

WANG Shun-Kui1, LI Zhi-Jie2, XIAO Xue-Zhang1, FAN Xiu-Lin1, CHEN Zhi-Wen1, LI Shou-Quan1, GE Hong-Wei1, CHEN Li-Xin1   

  1. 1 Key Laboratory of Advanced Materials and Applications for Batteries of Zhejiang Province, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, P. R. China;
    2 College of Gansu Vocational Technology, Tianshui 741025, Gansu Province, P. R. China
  • Received:2013-04-18 Revised:2013-06-06 Published:2013-07-09
  • Contact: XIAO Xue-Zhang, CHEN Li-Xin E-mail:xzxiao@zju.edu.cn; lxchen@zju.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2010CB631304), National Natural Science Foundation of China(51001090, 51171173), China Postdoctoral Science Foundation (20090262, 2012M521167), and Key Science & Technology Innovation Team of Zhejiang Province, China (2010R50013).

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摘要：

以NaH粉和Al 粉为合成原料, 分别采用2% (摩尔分数, x) CeCl3和2% CeCl3/y% KH (y=0.02, 0.04)为催化添加剂, 在室温和3 MPa氢压下, 通过反应球磨(NaH/Al+CeCl3)和(NaH/Al+CeCl3/yKH) (y=0.02, 0.04)复合物成功制备出Na-Al-H 配位氢化物. 吸放氢性能测试结果表明, KH的加入能有效改善Na-Al-H 体系中第二步脱氢反应放氢动力学性能. (NaH/Al+CeCl3/0.02KH)复合物170℃放氢时可在20 min内完成脱氢过程, 且在较低温度(100-140℃)下具有良好的可逆吸放氢性能. Kissenger 方法计算表明, 添加KH可降低Na-Al-H 体系第二步脱氢反应的表观活化能, 降低其放氢峰值温度. 相结构分析表明, KH的添加使Na-Al-H 体系中Na3AlH6的晶胞体积发生膨胀, 进而提高体系的第二步放氢动力学性能.

关键词: 配位氢化物, NaAlH4, KH, CeCl3, 放氢动力学

Abstract:

The Na-Al-H complex hydride was prepared by reactive ball milling (NaH/Al+CeCl3) and (NaH/Al+CeCl3/yKH) (y=0.02, 0.04) composites under a hydrogen pressure of 3 MPa at room temperature, using NaH and Al powder as raw materials, as well as 2% (molar fraction) CeCl3 and 2% CeCl3/y% KH (y=0.02, 0.04) as dopant, respectively. The de-/hydrogenation properties show that the addition of KH can effectively improve the dehydrogenation kinetics of second decomposition step for Na-Al-H system. The (NaH/Al+CeCl3/0.02KH) composite can complete dehydrogenation process within 20 min at 170℃, with good de-/hydrogenation cycling performance at relatively low temperature (100-140℃). Calculation by Kissenger method shows that the addition of KH could decrease the apparent activation energy of second decomposition step for Na-Al-H system, resulting in the decrease of desorption peak temperatures. Phase structure analysis shows that the enhanced second step dehydrogenation kinetics of Na-Al-H composite system is mainly ascribed to the lattice volume expansion of Na3AlH6 resulted from the addition of KH.

Key words: Complex hydride, NaAlH4, KH, CeCl3, Dehydrogenation kinetics