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Atomistic Insight on the Charging Energetics in Subnanometer Pore Supercapacitors

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College of Engineering and Science, Clemson University, Clemson, South Carolina 29634-0921, United States, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6367, United States, and Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, New York 12180-3590 United States
* To whom correspondence should be addressed. E-mail: [email protected]
†Clemson University.
‡Oak Ridge National Laboratory.
§Rensselaer Polytechnic Institute.
Cite this: J. Phys. Chem. C 2010, 114, 41, 18012–18016
Publication Date (Web):September 29, 2010
https://doi.org/10.1021/jp107125m
Copyright © 2010 American Chemical Society
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    Abstract

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    Electrodes featuring subnanometer pores are favorable to the capacitance and energy density of supercapacitors. However, there is an energy penalty to enter subnanometer pores as ions have to shed part of their solvation shell. The magnitude of such an energy penalty plays a key role in determining the accessibility and charging/discharging of these subnanometer pores. Here, we report on the atomistic simulation of Na+ and Cl− ions entering a polarizable slit pore with a center-to-center 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 ions and pore walls, the image charge effects, the moderate (19−26%) dehydration of the ions inside the pore, and the strengthened interactions between ions and their hydration water molecules in the subnanometer pore. The results provide strong impetus for further developing nanoporous electrodes featuring subnanometer pores.

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