La-Mg-Ni-H体系相平衡及其吸放氢动力学机理研究
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摘要
La-Mg-Ni三元系中存在多种类型的储氢合金。然而，这些储氢合金却有着动力学性能差，或储氢量小等缺点。研究者们进行了大量研究以期开发出综合性能良好的储氢合金，但大多数的实验研究由于缺乏理论指导收获甚微。基于此，本论文从热力学相平衡的基础理论研究入手，首先建立了La-Mg-Ni-H四元体系热力学数据库，在此基础上建立并验证了PCT统计热力学模型和吸放氢反应动力学模型，以期为材料设计提供指导。论文主要研究内容包含三个部分：
(1)利用Rietveld精修的方法确认了La_5Ni_(19)的存在，并在考虑了La_5Ni_(19)、(La,Mg)_5Ni_(19)、Mg_2NiH_4同型转变和LaNi_5-H垂直截面相关系的基础上，建立了La-Mg-Ni-H体系相平衡热力学，并采用ICP、HR XRD、HP DSC、BSE/EDS等方法验证了从热力学相平衡计算得到的La-Ni、La-Mg-Ni、Mg-Ni-H和La-Ni-H体系的相平衡关系，实验研究的结果表明：
在623K检测到了La_5Ni_(19)相，并在1276K发生包晶反应L+LaNi_5La_5Ni_(19)。
LaNi_5、MgNi_2和LaMg_2Ni_9在非平衡状态下可共存，在均匀化处理中，MgNi_2逐渐消失，最终平衡态的相组成为LaNi_5和LaMg_2Ni_9。
LaNi_5H7在1和3MPa恒压下的分解温度分别为343和379K。
(2)分三段推导了PCT统计热力学模型。根据金属吸氢形成的α、α+β和β三个相区，将PCT曲线分为三段。考虑了每个相区中H原子的个数、单胞作用能、吸氢能和H-H相互作用能。依据统计热力学原理和真实气体的化学势与H在金属中的化学势相等建立了PCT统计热力学模型。将此模型应用于La-Mg-Ni系储氢合金中，计算结果与实验结果有很好的一致性。
(3)在Chou模型的基础上，考虑了吸放氢后颗粒尺寸变化(R_(PB))，推导了扩散控速动力学模型。讨论了温度和压力对吸放氢动力学的影响，曲线末端形状以及吸氢量与R_(PB)的关系。本模型可以较为准确地描述La-Mg-Ni系合金的吸氢反应动力学过程。
There are several hydrogen storage alloys in the La-Mg-Ni system. Somedisadvantages have been found in these alloys, for example, slow kinetics and hightemperature for hydriding/dehydriding of Mg-based alloys, and small hydrogencapacity in the La-Ni-based alloys. A great number of studies were carried out inorder to develop alloys in the La-Mg-Ni system with excellent hydrogen storageproperties, but little achievement was obtained due to lack of theoretical guidance.Therefore, the present work focused on theoretical study. The thermodynamicdatabase of La-Mg-Ni-H system was constructed, and PCT statistic thermodynamicmodel and kinetic model were established to provide the theoretical guidance for thehydrogen storage materials design in the La-Mg-Ni system. Present work consists ofthe following three parts:
(1) The existence of La_5Ni_(19)was identified by Rietveld refinement method. Thethermodynamic database of La-Mg-Ni-H system was constructed taking into accountof La_5Ni_(19),(La, Mg)5Ni19, phase transformation of Mg_2NiH_4and phase relationshipsin LaNi_5-H vertical section. The phase equilibrium relationships in the La-Ni,La-Mg-Ni, Mg-Ni-H and La-Ni-H systems were experimentally validated, by themeans of ICP, HR XRD, HP DSC, BSE/EDS. The experimental results showed that
La_5Ni_(19)existed at the temperature range of room temperature to1276K andthe invariant reaction,L+LaNi_5La_5Ni_(19), took place at1276K.
LaNi_5, MgNi_2and LaMg_2Ni_9could coexist in one sample in thenonequilibrium state. However, MgNi_2would disappear gradually duringannealing treatment, and the final phases were LaNi_5and LaMg_2Ni_9.
LaNi_5H7decomposed at343and379K when the pressure was kept under1and3MPa, respectively.
(2) The PCT curve was devided into three stages, i.e. α, α+β and β. A statistic thermodynamic model was dedveloped to describe the PCT curves. The modelassumes the equivalent of hydrogen chemical potential in both the real gas and the Hin metal, takes into the account of the amount of H, the contribution of each unit cellto the total energy, the energy of absorbed hydrogen and interaction energy of H-H.The model was used to analyze the PCT curves of La-Mg-Ni hydrogen alloys, whichshown a good agreement with the experimental data.
(3) A new diffusion kinetic model was developed on the basis of Chou modeland with the consideration of R_(PB).The effects of temperature and pressure on thekinetic process, the shape of the end of the kinetic curve, and the relationshipbetween hydrogen capacity and R_(PB)were discussed. The kinetic model was used todescribe the hydriding reaction of La-Mg-Ni alloys, and agreed well with theexperimental data.
(1)利用Rietveld精修的方法确认了La_5Ni_(19)的存在，并在考虑了La_5Ni_(19)、(La,Mg)_5Ni_(19)、Mg_2NiH_4同型转变和LaNi_5-H垂直截面相关系的基础上，建立了La-Mg-Ni-H体系相平衡热力学，并采用ICP、HR XRD、HP DSC、BSE/EDS等方法验证了从热力学相平衡计算得到的La-Ni、La-Mg-Ni、Mg-Ni-H和La-Ni-H体系的相平衡关系，实验研究的结果表明：
在623K检测到了La_5Ni_(19)相，并在1276K发生包晶反应L+LaNi_5La_5Ni_(19)。
LaNi_5、MgNi_2和LaMg_2Ni_9在非平衡状态下可共存，在均匀化处理中，MgNi_2逐渐消失，最终平衡态的相组成为LaNi_5和LaMg_2Ni_9。
LaNi_5H7在1和3MPa恒压下的分解温度分别为343和379K。
(2)分三段推导了PCT统计热力学模型。根据金属吸氢形成的α、α+β和β三个相区，将PCT曲线分为三段。考虑了每个相区中H原子的个数、单胞作用能、吸氢能和H-H相互作用能。依据统计热力学原理和真实气体的化学势与H在金属中的化学势相等建立了PCT统计热力学模型。将此模型应用于La-Mg-Ni系储氢合金中，计算结果与实验结果有很好的一致性。
(3)在Chou模型的基础上，考虑了吸放氢后颗粒尺寸变化(R_(PB))，推导了扩散控速动力学模型。讨论了温度和压力对吸放氢动力学的影响，曲线末端形状以及吸氢量与R_(PB)的关系。本模型可以较为准确地描述La-Mg-Ni系合金的吸氢反应动力学过程。
There are several hydrogen storage alloys in the La-Mg-Ni system. Somedisadvantages have been found in these alloys, for example, slow kinetics and hightemperature for hydriding/dehydriding of Mg-based alloys, and small hydrogencapacity in the La-Ni-based alloys. A great number of studies were carried out inorder to develop alloys in the La-Mg-Ni system with excellent hydrogen storageproperties, but little achievement was obtained due to lack of theoretical guidance.Therefore, the present work focused on theoretical study. The thermodynamicdatabase of La-Mg-Ni-H system was constructed, and PCT statistic thermodynamicmodel and kinetic model were established to provide the theoretical guidance for thehydrogen storage materials design in the La-Mg-Ni system. Present work consists ofthe following three parts:
(1) The existence of La_5Ni_(19)was identified by Rietveld refinement method. Thethermodynamic database of La-Mg-Ni-H system was constructed taking into accountof La_5Ni_(19),(La, Mg)5Ni19, phase transformation of Mg_2NiH_4and phase relationshipsin LaNi_5-H vertical section. The phase equilibrium relationships in the La-Ni,La-Mg-Ni, Mg-Ni-H and La-Ni-H systems were experimentally validated, by themeans of ICP, HR XRD, HP DSC, BSE/EDS. The experimental results showed that
La_5Ni_(19)existed at the temperature range of room temperature to1276K andthe invariant reaction,L+LaNi_5La_5Ni_(19), took place at1276K.
LaNi_5, MgNi_2and LaMg_2Ni_9could coexist in one sample in thenonequilibrium state. However, MgNi_2would disappear gradually duringannealing treatment, and the final phases were LaNi_5and LaMg_2Ni_9.
LaNi_5H7decomposed at343and379K when the pressure was kept under1and3MPa, respectively.
(2) The PCT curve was devided into three stages, i.e. α, α+β and β. A statistic thermodynamic model was dedveloped to describe the PCT curves. The modelassumes the equivalent of hydrogen chemical potential in both the real gas and the Hin metal, takes into the account of the amount of H, the contribution of each unit cellto the total energy, the energy of absorbed hydrogen and interaction energy of H-H.The model was used to analyze the PCT curves of La-Mg-Ni hydrogen alloys, whichshown a good agreement with the experimental data.
(3) A new diffusion kinetic model was developed on the basis of Chou modeland with the consideration of R_(PB).The effects of temperature and pressure on thekinetic process, the shape of the end of the kinetic curve, and the relationshipbetween hydrogen capacity and R_(PB)were discussed. The kinetic model was used todescribe the hydriding reaction of La-Mg-Ni alloys, and agreed well with theexperimental data.
引文
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