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Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3−x

Nature Materials volume 16, pages 454–460 (2017)Cite this article

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Abstract

The short charging times and high power capabilities associated with capacitive energy storage make this approach an attractive alternative to batteries. One limitation of electrochemical capacitors is their low energy density and for this reason, there is widespread interest in pseudocapacitive materials that use Faradaic reactions to store charge. One candidate pseudocapacitive material is orthorhombic MoO3 (α-MoO3), a layered compound with a high theoretical capacity for lithium (279 mA h g−1 or 1,005 C g−1). Here, we report on the properties of reduced α-MoO3−x(R-MoO3−x) and compare it with fully oxidized α-MoO3 (F-MoO3). The introduction of oxygen vacancies leads to a larger interlayer spacing that promotes faster charge storage kinetics and enables the α-MoO3 structure to be retained during the insertion and removal of Li ions. The higher specific capacity of the R-MoO3−x is attributed to the reversible formation of a significant amount of Mo4+ following lithiation. This study underscores the potential importance of incorporating oxygen vacancies into transition metal oxides as a strategy for increasing the charge storage kinetics of redox-active materials.

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Figure 1: Structural analysis of as-prepared α-MoO3.
Figure 2: Characterization of oxygen vacancies in α-MoO3.
Figure 3: Electrochemical analysis of thin-film MoO3 electrodes.
Figure 4: Structural characterization of F-MoO3 and R-MoO3−x associated with electrochemical cycling.
Figure 5: Effect of oxygen vacancies on the presence of Mo4+ and Mo5+ oxidation states during electrochemical cycling.

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Acknowledgements

This work was supported as part of the Center for Molecularly Engineered Energy Materials, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under award DE-SC001342 and through individual DOE grant DE-SC0014213 (S.H.T.). The XPS instrument used in this work was obtained with support from the NSF, award number 0840531. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231. H.L. and V.O. acknowledge financial support from the U.S. DOE under grant DE-FG02-07ER46433. Additional support was provided by the Office of Naval Research. We thank E. D. Gaspera for his experimental insights.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, UCLA, Los Angeles, California 90095-1595, USA

    Hyung-Seok Kim, Hao Lin, Jesse S. Ko, Sarah H. Tolbert, Vidvuds Ozolins & Bruce Dunn

  2. Department of Chemistry and Biochemistry, UCLA, Los Angeles, California 90095-1569, USA

    John B. Cook & Sarah H. Tolbert

  3. The California NanoSystems Institute, UCLA, Los Angeles, California 90095, USA

    John B. Cook, Sarah H. Tolbert & Bruce Dunn

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H.-S.K., J.S.K. and J.B.C.: experimental work and data analysis. H.L.: computational study. S.H.T., V.O. and B.D.: project planning and data analysis.

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Correspondence to Sarah H. Tolbert, Vidvuds Ozolins or Bruce Dunn.

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Kim, HS., Cook, J., Lin, H. et al. Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3−x. Nature Mater 16, 454–460 (2017). https://doi.org/10.1038/nmat4810

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