On Capacitance Enhancement at Decreasing Pore Width and its Relation with Solvent Concentration and Polarity

Zhou, Shiqi

doi:10.1149/1945-7111/acf95b

Cited by 2 publications

(1 citation statement)

References 73 publications

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“…This is especially true in certain regions of the current system, which belong to a strongly correlated electrostatic regime. The details of the cDFT method employed can be found in the literature [50] and are not reiterated here; however, the principal equations involved are provided below. Given that the system under investigation operates in high concentration and strong confinement regimes, packing effects become overwhelmingly significant.…”

Section: J Stat Mech (2024) 043202mentioning

confidence: 99%

Variability of entropy force and its coupling with electrostatic and steric hindrance interactions

Zhou

2024

J. Stat. Mech.

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We investigated the effective interaction potential (EIP) between charged surfaces in solvent comprised of dipole dimer molecules added with a certain amount of ionic liquid. Using classical density functional theory, the EIP is calculated and decoupled into entropic and energy terms. Unlike the traditional Asakura–Oosawa (AO) depletion model, the present entropic term can be positive or negative, depending on the entropy change associated with solvent molecule migration from bulk into slit pore. This is determined by pore congestion and disruption of the bulk dipole network. The energy term is determined by the free energy associated with hard-core repulsion and electrostatic interactions between surface charges, ion charges, and polarized charges carried by the dipole dimer molecules. The calculations in this article clearly demonstrate the variability of the entropy term, which contrasts sharply with the traditional AO depletion model, and the corrective effects of electrostatic and spatial hindrance interactions on the total EIP; we revealed several non-monotonic behaviors of the EIP and its entropic and energy terms concerning solvent bulk concentration and solvent molecule dipole moment; additionally, we demonstrated the promoting effect of dipolar solvent on the emergence of like-charge attraction, even in 1:1 electrolyte solutions. The microscopic origin of the aforementioned phenomena was analyzed to be due to the non-monotonic change of dipolar solvent adsorption with dipole moment under conditions of low solution dielectric constant. The present findings offer novel approaches and molecular-level guidance for regulating the EIP. This insight has implications for understanding fundamental processes in various fields, including biomolecule-ligand binding, activation energy barriers, ion tunneling transport, as well as the formation of hierarchical structures, such as mesophases, micro-, and nanostructures, and beyond.

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Section: J Stat Mech (2024) 043202mentioning

confidence: 99%