Institute for Condensed Matter Physics of the National Academy of Sciences of Ukraine, 1 Svientsitskii St., 79011 Lviv, Ukraine.
Department of Complex Systems, Institute of Physical Chemistry, PAS, Kasprzaka 44/52, Warsaw, Poland.
J Chem Phys. 2019 Nov 14;151(18):184105. doi: 10.1063/1.5127851.
We develop a theory of charge storage in ultranarrow slitlike pores of nanostructured electrodes. Our analysis is based on the Blume-Capel model in an external field, which we solve analytically on a Bethe lattice. The obtained solutions allow us to explore the complete phase diagram of confined ionic liquids in terms of the key parameters characterizing the system, such as pore ionophilicity, interionic interaction energy, and voltage. The phase diagram includes the lines of first- and second-order, direct and re-entrant phase transitions, which are manifested by singularities in the corresponding capacitance-voltage plots. Testing our predictions experimentally requires monodisperse, conducting ultranarrow slit pores, to permit only one layer of ions, and thick pore walls, to prevent interionic interactions across the pore walls. However, some qualitative features, which distinguish the behavior of ionophilic and ionophobic pores and their underlying physics, may emerge in future experimental studies of more complex electrode structures.
我们提出了一种关于纳米结构电极中超窄狭缝中电荷存储的理论。我们的分析基于外场中的 Blume-Capel 模型，并在 Bethe 格子上进行了分析。所得到的解允许我们根据表征系统的关键参数，如孔亲水性、离子间相互作用能和电压，探索受限离子液体的完整相图。相图包括一级和二级、直接和重入相变的线，这在相应的电容-电压图中表现为奇点。为了实验验证我们的预测，需要具有单分散性、导电性的超窄狭缝孔，以仅允许一层离子，并且需要厚的孔壁，以防止离子穿过孔壁相互作用。然而，一些定性特征，如亲水性和疏水性孔的行为及其潜在物理，可能会在未来对更复杂电极结构的实验研究中显现出来。
