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Charging a Li–O2 battery using a redox mediator

Nature Chemistry volume 5, pages 489–494 (2013)Cite this article

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Abstract

The non-aqueous Li–air (O2) battery is receiving intense interest because its theoretical specific energy exceeds that of Li-ion batteries. Recharging the Li–O2 battery depends on oxidizing solid lithium peroxide (Li2O2), which is formed on discharge within the porous cathode. However, transporting charge between Li2O2 particles and the solid electrode surface is at best very difficult and leads to voltage polarization on charging, even at modest rates. This is a significant problem facing the non-aqueous Li–O2 battery. Here we show that incorporation of a redox mediator, tetrathiafulvalene (TTF), enables recharging at rates that are impossible for the cell in the absence of the mediator. On charging, TTF is oxidized to TTF+ at the cathode surface; TTF+ in turn oxidizes the solid Li2O2, which results in the regeneration of TTF. The mediator acts as an electron–hole transfer agent that permits efficient oxidation of solid Li2O2. The cell with the mediator demonstrated 100 charge/discharge cycles.

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Figure 1: O2 evolution from the reaction between oxidizing mediators and Li2O2.
Figure 2: First-cycle load curves (constant-current discharge/charge) with and without the redox mediator.
Figure 3: Cycling stability of Li–O2 cathodes that employ a redox mediator.
Figure 4: Vibration spectra at the end of discharge and charge.

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Acknowledgements

P.G.B. is indebted to the Engineering and Physical Sciences Research Council, including Supergen, for financial support. The authors thank K. Dholaki, C. Thomson and P. Ashok for assistance with the SERS equipment.

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Author notes

  1. Stefan A. Freunberger, Zhangquan Peng & Olivier Fontaine

    Present address: Present address: Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria (S.A.F), State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, 130022 Changchun, China (Z.P.), Institut Charles Gerhardt Montpellier, UMR 5253, Equipe Chimie Moléculaire et organisation du Solide, Université Montpellier 2, CC 1700, Place Eugène Bataillon 34095 Montpellier Cedex 5, France (O.F.),

  2. Yuhui Chen and Stefan A. Freunberger: These authors contributed equally to this work

Authors and Affiliations

  1. School of Chemistry, EastChem, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK

    Yuhui Chen, Stefan A. Freunberger, Zhangquan Peng, Olivier Fontaine & Peter G. Bruce

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  1. Yuhui Chen
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Contributions

Y.C. and S.A.F. contributed equally to this work and carried out the experiments. Y.C. and Z.P. measured SERS. P.G.B. wrote the manuscript. All authors contributed to the discussion and interpretation of the results.

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Correspondence to Peter G. Bruce.

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Chen, Y., Freunberger, S., Peng, Z. et al. Charging a Li–O2 battery using a redox mediator. Nature Chem 5, 489–494 (2013). https://doi.org/10.1038/nchem.1646

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