Understanding the pseudocapacitance of RuO2 from joint density functional theory

Zhan, Cheng; Jiang, De-en

doi:10.1088/0953-8984/28/46/464004

Understanding the pseudocapacitance of RuO₂ from joint density functional theory

Journal Article · Wed Sep 14 04:00:00 EDT 2016 · Journal of Physics. Condensed Matter

DOI:https://doi.org/10.1088/0953-8984/28/46/464004· OSTI ID:1346657

Zhan, Cheng ^[1]; Jiang, De-en ^[1]

Univ. of California, Riverside, CA (United States). Department of Chemistry

Pseudocapacitors have been experimentally studied for many years in electric energy storage. However, first principles understanding of the pseudocapacitive behavior is still not satisfactory due to the complexity involved in modeling electrochemistry. In this paper, we applied joint density functional theory (JDFT) to simulate the pseudocapacitive behavior of RuO₂, a prototypical material, in a model electrolyte. Additionally, we obtained from JDFT a capacitive curve which showed a redox peak position comparable to that in the experimental cyclic voltammetry (CV) curve. We found that the experimental turning point from double-layer to pseudocapacitive charge storage at low scan rates could be explained by the hydrogen adsorption at low coverage. As the electrode voltage becomes more negative, H coverage increases and causes the surface-structure change, leading to bended –OH bonds at the on-top oxygen atoms and large capacitance. This H coverage-dependent capacitance can explain the high pseudocapacitance of hydrous RuO₂. In conclusion, our work here provides a first principles understanding of the pseudocapacitance for RuO₂ in particular and for transition-metal oxides in general.

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1346657

Journal Information:: Journal of Physics. Condensed Matter, Journal Name: Journal of Physics. Condensed Matter Journal Issue: 46 Vol. 28; ISSN 0953-8984

Publisher:: IOP Publishing

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
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Understanding the pseudocapacitance of RuO2 from joint density functional theory

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Understanding the pseudocapacitance of RuO₂ from joint density functional theory