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Magnesium hydride for energy storage applications: The kinetics of dehydrogenation under different working conditions

机译:储能应用的氢化镁:在不同工作条件下的脱氢动力学

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摘要

A new approach to the kinetics of magnesium hydride dehydrogenation is considered. A model able to predict the dehydrogenation under different experimental conditions has been proposed. A new combined kinetic analysis method, which considers the thermodynamic of the process according to the microreversibility principle, has been used for performing the kinetic analysis of data obtained under different thermal schedules at hydrogen pressures ranging from high vacuum up to 20 bar. The kinetic analysis shows that the dehydrogenation mechanism of magnesium hydride depends on the experimental conditions. Thus, the reaction follows a first order kinetics, equivalent to an Avarmi-Erofeev kinetic model with an Avrami coefficient equal to 1, when carried out under high vacuum, while a mechanism of tridimensional growth of nuclei previously formed (A3) is followed under hydrogen pressure. An explanation of the change of mechanism is given. It has been shown that the activation energy is closed to the Mg-H bond breaking energy independently of the hydrogen pressure surrounding the sample, which suggests that the breaking of this bond would be the rate limiting step of the process. The reliability of the calculated kinetic parameters is tested by comparing simulated and experimental curves.
机译:考虑了一种氢化镁脱氢动力学的新方法。提出了能够预测不同实验条件下脱氢的模型。一种新的组合动力学分析方法,该方法根据微可逆性原理考虑了工艺的热力学,已用于对在不同的热工况下在高真空至20 bar的氢气压力下获得的数据进行动力学分析。动力学分析表明,氢化镁的脱氢机理取决于实验条件。因此,当在高真空下进行时,该反应遵循一级动力学,该动力学等效于Avrami系数等于1的Avarmi-Erofeev动力学模型,而在氢气下遵循先前形成的核的三维生长机理(A3)压力。给出了机制变化的解释。已经表明,活化能与Mg-H键的断裂能无关,与样品周围的氢气压力无关,这表明该键的断裂将是该方法的速率限制步骤。通过比较模拟曲线和实验曲线来测试计算出的动力学参数的可靠性。

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