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A rechargeable lithium–oxygen battery with dual mediators stabilizing the carbon cathode

Nature Energy volume 2, Article number: 17118 (2017) Cite this article

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Abstract

At the cathode of a Li–O2 battery, O2 is reduced to Li2O2 on discharge, the process being reversed on charge. Li2O2 is an insulating and insoluble solid, leading ultimately to low rates, low capacities and early cell death if formed on the cathode surface. Here we show that when using dual mediators, 2,5-Di-tert-butyl-1,4-benzoquinone [DBBQ] on discharge and 2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO] on charge, the electrochemistry at the cathode surface is decoupled from Li2O2 formation/decomposition in solution. Capacities of 2 mAh cmareal−2 at 1 mA cmareal−2 with low polarization on charge/discharge are demonstrated, and up to 40 mAh cmareal−2 at rates ≫1 mA cmareal−2 are anticipated if suitable gas diffusion electrodes can be devised. One of the major barriers to the progress of Li–O2 cells is decomposition of the carbon cathode. By forming/decomposing Li2O2 in solution and avoiding high charge potentials, the carbon instability is significantly mitigated (<0.008% decomposition per cycle compared with 0.12% without mediators).

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Figure 1: Discharge–charge curves of GDL-based porous carbon electrodes with and without mediators.
Figure 2: SEM images of the GDL-based porous carbon electrodes after cycling in a dual-mediator Li–O2 cell.
Figure 3: FTIR spectra of GDL-based porous carbon electrodes after cycling in a dual-mediator Li–O2 cell.
Figure 4: Amounts of Li213CO3 in the 13C-carbon cathodes at the end of discharge on each cycle.
Figure 5: Schematics of positive electrode reactions on discharge and charge in the presence of DBBQ and TEMPO.
Figure 6: Cycling profile of a dual-mediator Li–O2 cell with a Li metal anode protected with Ohara glass.

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Acknowledgements

P.G.B. is indebted to the EPSRC, including the SUPERGEN programme, for financial support.

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  1. Xiangwen Gao and Yuhui Chen: These authors contributed equally to this work.

Authors and Affiliations

  1. Departments of Materials and Chemistry, Parks Road, University of Oxford, Oxford, OX1 3PH, UK

    Xiangwen Gao, Yuhui Chen, Lee R. Johnson, Zarko P. Jovanov & Peter G. Bruce

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Contributions

X.G. and Y.C. designed experiments and analysed the data. X.G. performed electrochemical performance tests and characterizations with contributions from Z.P.J. Y.C. performed the 13C-carbon experiments and analysed the data. P.G.B., X.G., Y.C., L.R.J. and Z.P.J. interpreted the data. P.G.B. wrote the paper.

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Correspondence to Peter G. Bruce.

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Gao, X., Chen, Y., Johnson, L. et al. A rechargeable lithium–oxygen battery with dual mediators stabilizing the carbon cathode. Nat Energy 2, 17118 (2017). https://doi.org/10.1038/nenergy.2017.118

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