Journal
JOURNAL OF PHYSICS-CONDENSED MATTER
Volume 23, Issue 2, Pages -Publisher
IOP PUBLISHING LTD
DOI: 10.1088/0953-8984/23/2/022201
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Funding
- Engineering and Physical Science Research Council [EP/H004319/1]
- Engineering and Physical Sciences Research Council [EP/H004319/1] Funding Source: researchfish
- EPSRC [EP/H004319/1] Funding Source: UKRI
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In recent experiments (Chmiola et al 2006 Science 313 1760; Largeot et al 2008 J. Am. Chem. Soc. 130 2730) an anomalous increase of the capacitance with a decrease of the pore size of a carbon-based porous electric double-layer capacitor has been observed. We explain this effect by image forces which exponentially screen out the electrostatic interactions of ions in the interior of a pore. Packing of ions of the same sign becomes easier and is mainly limited by steric interactions. We call this state 'superionic' and suggest a simple model to describe it. The model reveals the possibility of a voltage-induced first order transition between a cation(anion)-deficient phase and a cation(anion)-rich phase which manifests itself in a jump of capacitance as a function of voltage.
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