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Atomistic Insight on the Charging Energetics in Sub-nanometer Pore Supercacitors

Journal Article · · Journal of Physical Chemistry C
OSTI ID:991682

Electrodes featuring sub-nanometer pores can significantly enhance the capacitance and energy density of supercapacitors. However, ions must pay an energy penalty to enter sub-nanometer pores as they have to shed part of their solvation shell. The magnitude of such energy penalty plays a key role in determining the accessibility and charging/discharging of these sub-nanometer pores. Here we report on the atomistic simulation of Na+ and Cl ions entering a polarizable slit pore with a width of 0.82 nm. We show that the free energy penalty for these ions to enter the pore is less than 14 kJ/mol for both Na+ and Cl ions. The surprisingly small energy penalty is caused by the van der Waals attractions between ion and pore walls, the image charge effects, the moderate (19-26%) de-hydration of the ions inside the pore, and the strengthened interactions between ions and their hydration water molecules in the sub-nanometer pore. The results provide strong impetus for further developing nanoporous electrodes featuring sub- nanometer pores.

Research Organization:
Oak Ridge National Laboratory (ORNL); Center for Nanophase Materials Sciences; Center for Computational Sciences
Sponsoring Organization:
SC USDOE - Office of Science (SC)
DOE Contract Number:
AC05-00OR22725
OSTI ID:
991682
Journal Information:
Journal of Physical Chemistry C, Journal Name: Journal of Physical Chemistry C Journal Issue: 41 Vol. 114; ISSN 1932-7447
Country of Publication:
United States
Language:
English

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