水化壳对原始模型的扩展及其对双电层建立过程中可逆产热的影响
Extension of the primitive model by hydration shells and its impact on the reversible heat production during the buildup of the electric double layer
摘要：
最近，实验测量了在氯化钠溶液中双电层（EDL）累积期间的可逆热产生[Janssen等人，物理修订信函119，166002（2017）]并与来自密度泛函理论和分子动力学模拟的理论预测相匹配[Glatzel et al.，J. Chem.Phys.154，064901（2021）]。在后者中，发现离子与电极壁的空间相互作用（导致所谓的Stern层）足以解释实验结果。由于仅检查了受限原始模型中的对称离子尺寸，因此调查导致修改的Stern层的不相等离子尺寸的系统是有益的。在这项工作中，我们探讨了离子不对称性对每个电极的可逆产热的影响。在这种情况下，我们进一步研究了原始模型的扩展，其中离子的水化壳可以逃避在电极的壁附近。我们发现一个强烈的依赖系统参数，如颗粒的大小和总体积所采取的颗粒。在这里，我们甚至发现了在充电期间一个电极被加热而另一个电极同时被冷却的情况，而总的来说，两个电极一起表现得与已经提到的实验结果非常相似。因此，在实验中也应该分别测量每个电极的热产生。通过这种方式，我们提出的模拟电解质的某些成分的重要性可以在实验上得到证实或排除，最终导致对EDLs物理学的更深入理解。
英文摘要：
Recently the reversible heat production during the electric double layer (EDL) buildup in a sodium chloride solution was measured experimentally [Janssen et al., Phys. Rev. Lett. 119, 166002 (2017)] and matched with theoretical predictions from density functional theory and molecular dynamics simulations [Glatzel et al., J. Chem. Phys. 154, 064901 (2021)]. In the latter, it was found that steric interactions of ions with the electrode's walls, which result in the so-called Stern layer, are sufficient to explain the experimental results. As only symmetric ion sizes in a restricted primitive model were examined, it is instructive to investigate systems of unequal ion sizes that lead to modified Stern layers. In this work, we explore the impact of ion asymmetry on the reversible heat production for each electrode separately. In this context, we further study an extension of the primitive model where hydration shells of ions can evade in the vicinity of electrode's walls. We find a strong dependence on system parameters such as the particle sizes and the total volume taken by particles. Here, we even found situations where one electrode was heated and the other electrode was cooled at the same time during charging, while, in sum, both electrodes together behaved very similarly to the already mentioned experimental results. Thus, heat production should also be measured in experiments for each electrode separately. By this, the importance of certain ingredients that we proposed to model electrolytes could be confirmed or ruled out experimentally, finally leading to a deeper understanding of the physics of EDLs.
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