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    Mg-Ni-La-2Mn储氢合金的放氢反应动力学性能研究

    Property study on hydrogen desorption reaction kinetics of the Mg-Ni-La-2Mn hydrogen storage alloy

    • 摘要: 氢能作为一种清洁、高效、可持续的能源,在当今能源转型和可持续发展的背景下具有重要的地位。但是,氢能使用过程中尚存在制取成本高、储存运输困难、基础设施不足以及安全性挑战大等问题。其中,氢能的存储和输运是氢能利用中的核心环节,得到了广泛的关注。在诸多氢能储运方式中,镁基固态储氢材料在常温常压下即可稳定存储氢气,大大降低了对附属设备的要求和安全隐患,是一种具有广阔应用前景的储氢方式。但是镁基储氢合金在吸放氢过程中存在较高的温度和较慢的动力学性能,这在一定程度上限制了镁基储氢材料的规模化推广应用。通过加入Ni、La和Mn等元素能够有效提升Mg基储氢材料的性能。但是,Mg-Ni-La-Mn体系储氢合金的放氢温度及其放氢反应动力学机理尚不清晰。为获得Mg-Ni-La-Mn储氢合金的放氢反应动力学特性,首先使用感应熔炼法制备出了Mg-Ni-La-2Mn储氢合金。而后,搭建了实验系统,对Mg-Ni-La-2Mn储氢合金进行了放氢性能测试。然后,基于实验结果分析获得Mg-Ni-La-2Mn储氢合金放氢的Johnson-Mehl-Avrami(JMA)动力学方程和放氢动力学Arrhenius曲线。最后,将获得的Mg-Ni-La-2Mn储氢合金放氢动力学方程编译进入Comsol软件进行数值模拟研究,验证获得的JMA动力学方程和Arrhenius曲线的可靠性。对Mg-Ni-La-2Mn合金进行放氢实验表明,放氢温度在553 K温度以上时,合金能够在2400 s内实现完全放氢。提高放氢温度能够加速放氢速度,减少放氢所需时间。当放氢温度为593 K时,合金样品的最大放氢量及放氢80%所需要的时间分别为6.19%(质量分数)和232 s。通过分析Mg-Ni-La-2Mn合金的JMA方程和Arrhenius曲线,得出该合金放氢过程中的活化能为66.67 kJ/mol,低于现有文献报道值。对Mg-Ni-La-2Mn合金的放氢过程进行的数值模拟结果与实验数据对比后发现,两者放氢量的最大误差为2.81%,温度的最大相对误差为0.04%,验证了建立的Mg-Ni-La-2Mn储氢合金放氢反应动力学方程的可靠性。

       

      Abstract: Hydrogen energy, as a clean, efficient and sustainable energy source, holds an important position in the current context of energy transition and sustainable development. However, there are still problems such as high production cost, difficult storage and transportation, insufficient infrastructure and significant safety challenges in the use of hydrogen energy. Among them, the storage and transportation of hydrogen are the core links in the utilization of hydrogen energy and have received extensive attention. Among various hydrogen storage methods, magnesium-based solid-state hydrogen storage materials can stably store hydrogen at normal temperature and pressure, greatly reducing the requirements for auxiliary equipment and safety risks, which hold broad application prospects. However, magnesium-based hydrogen storage alloys have high temperatures and slow kinetics during hydrogen absorption and desorption processes, which to some extent limit the application range of magnesium-based hydrogen storage materials. The addition of elements such as Ni, La and Mn can effectively improve the performance of Mg-based hydrogen storage materials. However, the dehydrogenation temperature and reaction kinetics mechanism of Mg-Ni-La-Mn hydrogen storage alloys are still unclear. To obtain the desorption reaction kinetics characteristics of Mg-Ni-La-Mn hydrogen storage alloys, this paper first prepared Mg-Ni-La-2Mn hydrogen storage alloys by induction melting method. Then, an experimental system was built to test the dehydrogenation kinetics performance of Mg-Ni-La-2Mn hydrogen storage alloys. Subsequently, based on the experimental results, the Johnson-Mehl-Avrami (JMA) kinetics equation and the dehydrogenation kinetics Arrhenius curve of Mg-Ni-La-2Mn hydrogen storage alloys were obtained. Finally, the kinetics equation of hydrogen dehydrogenation in Mg-Ni-La-2Mn hydrogen storage alloy was compiled into the Comsol software for numerical simulation to verify the reliability of the obtained JMA kinetics equation and Arrhenius curve. The dehydrogenation experiments of Mg-Ni-La-2Mn showed that when the dehydrogenation temperature was above 553 K, the alloy could achieve complete desorption within 2400 s. Increasing the desorption temperature could accelerate the desorption rate and reduce the desorption time. When the dehydrogenation temperature is 593 K, the maximum dehydrogenation amount and the time required for 80% dehydrogenation of the alloy sample were 6.19% (weight percentage) and 232 s, respectively. By analyzing the JMA equation and Arrhenius curve of Mg-Ni-La-2Mn alloy, the activation energy in the dehydrogenation process was found to be 66.67 kJ/mol, which was much lower than the values reported in the literature. The dehydrogenation process of Mg-Ni-La-2Mn alloy was numerically simulated and compared with the experimental data. The maximum error of hydrogen desorption amount was 2.81%, and the maximum relative error of temperature was only 0.04%, verifying the reliability of the established dehydrogenation reaction kinetics equation of Mg-Ni-La-2Mn hydrogen storage alloy.

       

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