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Triple ionic–electronic conducting oxides for next-generation electrochemical devices

Nature Materials volume 20, pages 301–313 (2021)Cite this article

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Abstract

Triple ionic–electronic conductors (TIECs) are materials that can simultaneously transport electronic species alongside two ionic species. The recent emergence of TIECs provides intriguing opportunities to maximize performance in a variety of electrochemical devices, including fuel cells, membrane reactors and electrolysis cells. However, the potential application of these nascent materials is limited by lack of fundamental knowledge of their transport properties and electrocatalytic activity. The goal of this Review is to summarize and analyse the current understanding of TIEC transport and electrochemistry in single-phase materials, including defect formation and conduction mechanisms. We particularly focus on the discovery criteria (for example, crystal structure and ion electronegativity), design principles (for example, cation and anion substitution chemistry) and operating conditions (for example, atmosphere) of materials that enable deliberate tuning of the conductivity of each charge carrier. Lastly, we identify important areas for further advances, including higher chemical stability, lower operating temperatures and discovery of n-type TIEC materials.

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Fig. 1: Typical structure of TIEC materials.
Fig. 2: TIECs as protonic ceramic fuel cell positrodes.
Fig. 3: Transport in TIECs.
Fig. 4: Factors that influence TIEC performance.
Fig. 5: Composition effects on electronic conductivity, oxygen non-stoichiometry, and proton uptake.
Fig. 6: Conceptual band diagram of an n-type TIEC.

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Acknowledgements

This work was supported by the Army Research Office under grant number W911NF-17-1-0051. Additional support was provided by the Advanced Research Projects Agency–Energy (ARPA-E) through the REFUEL (award DE-AR0000808) and REBELS programmes (award DEAR0000493). A.Z. was supported by the US Department of Energy (DOE), under contract no. DEAC36-08GO28308 with the Alliance for Sustainable Energy LLC, the manager and operator of the National Renewable Energy Laboratory (NREL), with funding provided by the Office of Energy Efficiency and Renewable Energy (EERE), under Hydrogen and Fuel Cell Technologies Office (HFCO), as a part of HydroGEN Energy Materials Network (EMN) consortium. The views expressed in the article do not necessarily represent the views of the DOE or the US government.

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  1. Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, CO, USA

    Meagan Papac, Vladan Stevanović, Andriy Zakutayev & Ryan O’Hayre

  2. Materials Science Center, National Renewable Energy Laboratory, Golden, CO, USA

    Meagan Papac, Vladan Stevanović & Andriy Zakutayev

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M.P. prepared the manuscript. V.S. provided content related to n-type TIEC materials and assisted with revisions. A.Z. assisted with revisions. R.O. assisted with the manuscript scope and development, contributed to revisions, and provided introductory content.

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Correspondence to Ryan O’Hayre.

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Papac, M., Stevanović, V., Zakutayev, A. et al. Triple ionic–electronic conducting oxides for next-generation electrochemical devices. Nat. Mater. 20, 301–313 (2021). https://doi.org/10.1038/s41563-020-00854-8

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