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Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes

Nature Materials volume 13, pages 726–732 (2014)Cite this article

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Abstract

Perovskite oxides have attracted significant attention as energy conversion materials for metal–air battery and solid-oxide fuel-cell electrodes owing to their unique physical and electronic properties. Amongst these unique properties is the structural stability of the cation array in perovskites that can accommodate mobile oxygen ions under electrical polarization. Despite oxygen ion mobility and vacancies having been shown to play an important role in catalysis, their role in charge storage has yet to be explored. Herein we investigate the mechanism of oxygen-vacancy-mediated redox pseudocapacitance for a nanostructured lanthanum-based perovskite, LaMnO3. This is the first example of anion-based intercalation pseudocapacitance as well as the first time oxygen intercalation has been exploited for fast energy storage. Whereas previous pseudocapacitor and rechargeable battery charge storage studies have focused on cation intercalation, the anion-based mechanism presented here offers a new paradigm for electrochemical energy storage.

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Figure 1: Nanocrystal morphology of LaMnO3.09.
Figure 2: Electrochemical characterization of LaMnO3±δ.
Figure 3: Effect of electrolyte concentration on redox reactions for LaMnO3±δ.
Figure 4: Electrolyte studies of LaMnO3.09.
Figure 5: Mechanism of oxygen intercalation into LaMnO3±δ.
Figure 6: Symmetric cell cyclic voltammetry of r-LaMnO2.91.

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Acknowledgements

Financial support for this work was provided by the R. A. Welch Foundation (grants F-1529 and F-1319). S.D. was supported as part of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences.

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Author notes

  1. J. Tyler Mefford and William G. Hardin: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, The University of Texas at Austin, 1 University Station, Austin, Texas 78712, USA

    J. Tyler Mefford & Keith J. Stevenson

  2. Texas Materials Institute, The University of Texas at Austin, 1 University Station, Austin, Texas 78712, USA

    William G. Hardin, Keith P. Johnston & Keith J. Stevenson

  3. Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    Sheng Dai

  4. Department of Chemical Engineering, The University of Texas at Austin, 1 University Station, Austin, Texas 78712, USA

    Keith P. Johnston

  5. Center for Electrochemistry, The University of Texas at Austin, 1 University Station, Austin, Texas 78712, USA

    Keith P. Johnston & Keith J. Stevenson

Authors
  1. J. Tyler Mefford
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  2. William G. Hardin
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  3. Sheng Dai
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Contributions

J.T.M. and W.G.H. performed the experimental work and data analysis. S.D. contributed the carbon support. K.P.J. and K.J.S. planned the experiment and analysed the data.

Corresponding authors

Correspondence to Keith P. Johnston or Keith J. Stevenson.

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The authors declare no competing financial interests.

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Mefford, J., Hardin, W., Dai, S. et al. Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes. Nature Mater 13, 726–732 (2014). https://doi.org/10.1038/nmat4000

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