New Perspectives on the Charging Mechanisms of Supercapacitors
Journal of the American Chemical Society
American Chemical Society
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Forse, A., Merlet, C., Griffin, J. M., & Grey, C. (2016). New Perspectives on the Charging Mechanisms of Supercapacitors. Journal of the American Chemical Society, 138 5731-5744. https://doi.org/10.1021/jacs.6b02115
Supercapacitors (or electric double-layer capacitors) are high power energy storage devices that store charge at the interface between porous carbon electrodes and an electrolyte solution. These devices are already employed in heavy electric vehicles and electronic devices, and can complement batteries in a more sustainable future. Their widespread application could be facilitated by the development of devices that can store more energy, without compromising their fast charging and discharging times. In situ characterization methods and computational modeling techniques have recently been developed to study the molecular mechanisms of charge storage, with the hope that better devices can be rationally designed. In this perspective article, we bring together recent findings from a range of experimental and computational studies to give a detailed picture of the charging mechanisms of supercapacitors. Nuclear magnetic resonance experiments and molecular dynamics simulations have revealed that the electrode pores contain a considerable number of ions in the absence of an applied charging potential. Experiments and computer simulations have shown that different charging mechanisms can then operate when a potential is applied, going beyond the traditional view of charging by counter-ion adsorption. It is shown that charging almost always involves ion exchange (swapping of co-ions for counter-ions), and rarely occurs by counter-ion adsorption alone. We introduce a charging mechanism parameter that quantifies the mechanism and allows comparisons between different systems. The mechanism is found to depend strongly on the polarization of the electrode, and the choice of the electrolyte and electrode materials. In light of these advances we identify new directions for supercapacitor research. Further experimental and computational work is needed to explain the factors that control supercapacitor charging mechanisms, and to establish the links between mechanisms and performance. Increased understanding and control of charging mechanisms should lead to new strategies for developing next generation supercapacitors with improved performances.
The authors acknowledge the Sims Scholarship Cambridge (A.C.F.), the School of the Physical Sciences of the University of Cambridge (via an Oppenheimer Research Fellowship, C.M.), EPSRC (via the Supergen consortium, A.C.F. and J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. We thank Nicole Trease, Andrew Ilott, Phoebe Allan, Elizabeth Humphreys, Paul Bayley, Hao Wang, Patrice Simon, Wan-Yu Tsai, Yury Gogotsi, Mathieu Salanne, Benjamin Rotenberg, Alexei Kornyshev, Svyatoslav Kondrat and Volker Presser for collaboration, and stimulating discussions and insights into supercapacitors over the course of our research on this subject.
UNIVERSITY OF OXFORD (FB EPSRC) (EP/L019469/1)
EPSRC (via Imperial College London) (EP/K002252/1)
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External DOI: https://doi.org/10.1021/jacs.6b02115
This record's URL: https://www.repository.cam.ac.uk/handle/1810/255009