Statistical thermodynamics of supercapacitors and blue engines
Statistical thermodynamics of supercapacitors and blue engines
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超级电容器和蓝色发动机的统计热力学
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发表时间：
2012
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通讯作者：
R. Roij
中科院分区：
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作者：
R. Roij
我们研究电极电解质系统的热力学，例如充满离子液体的超级电容器或充满河流或海水的蓝色能源设备。通过适当的热力学变量映射，我们发现了与经典热机的强烈类比。我们介绍几个勒让德变换和麦克斯韦关系。我们认为，人们应该区分恒定离子数和恒定离子化学势下的微分容量，并推导它们之间的关系，类似于恒定体积和恒定压力下热容之间的标准关系。最后，我们考虑给定电极电势下电极电荷的概率分布，其标准差由微分电容给出。
We study the thermodynamics of electrode-electrolyte systems, for instance supercapacitors filled with an ionic liquid or blue-energy devices filled with river- or sea water. By a suitable mapping of thermodynamic variables, we identify a strong analogy with classical heat engines. We introduce several Legendre transformations and Maxwell relations. We argue that one should distinguish between the differential capacity at constant ion number and at constant ion chemical potential, and derive a relation between them that resembles the standard relation between heat capacity at constant volume and constant pressure. Finally, we consider the probability distribution of the electrode charge at a given electrode potential, the standard deviation of which is given by the differential capacity.