Understanding the MXene Pseudocapacitance

Zhan, Cheng; Naguib, Michael; Lukatskaya, Maria; Kent, Paul R.  C.; Gogotsi, Yury; Jiang, De-en

doi:10.1021/acs.jpclett.8b00200

Title: Understanding the MXene Pseudocapacitance

Journal Article · 20 February 2018 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.8b00200 · OSTI ID:1484259

Zhan, Cheng ^[1];

^[2]; Lukatskaya, Maria ^[3];

^[4];

^[3];

^[1]

Department of Chemistry, University of California, Riverside, California 92521, United States
Department of Physics and Engineering Physics, Tulane University, New Orleans, Louisiana 70118, United States
Department of Materials Science and Engineering and A. J. Drexel Nanomaterials Institute, Drexel University, Philadelphia, Pennsylvania 19104, United States
Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States; Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States

MXenes have attracted great attention as next-generation capacitive energy-storage materials, but the mechanisms underlying their pseudocapacitive behavior are not well understood. Here we provide a theoretical description of the surface redox process of Ti3C2Tx (T = O, OH), a prototypical MXene, in 1 M H2SO4 electrolyte, based on joint density functional theory with an implicit solvation model and the analysis of Gibbs free energy under a constant-electrode potential. From the dependence of the O/OH ratio (or the surface H coverage) and the surface charge on the applied potential, we obtain a clear picture of the capacitive energy-storage mechanism of Ti3C2Tx that shows good agreement with previous experimental findings in terms of the integral capacitance and Ti valence change. We find a voltage-dependent redox/double-layer co-charging behavior: the capacitive mechanism is dominated by the redox process, but the electric double-layer charge works against the redox process. This new insight may be useful in improving the capacitance of MXenes.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center

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

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1484259

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 6 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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