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Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries


Redox mediators could catalyse otherwise slow and energy-inefficient cycling of Li–S and Li–O2 batteries by shuttling electrons or holes between the electrode and the solid insulating storage materials. For mediators to work efficiently they need to oxidize the solid with fast kinetics but with the lowest possible overpotential. However, the dependence of kinetics and overpotential is unclear, which hinders informed improvement. Here, we find that when the redox potentials of mediators are tuned via, for example, Li+ concentration in the electrolyte, they exhibit distinct threshold potentials, where the kinetics accelerate several-fold within a range as small as 10 mV. This phenomenon is independent of types of mediator and electrolyte. The acceleration originates from the overpotentials required to activate fast Li+/e extraction and the following chemical step at specific abundant surface facets. Efficient redox catalysis at insulating solids therefore requires careful consideration of the surface conditions of the storage materials and electrolyte-dependent redox potentials, which may be tuned by salt concentrations or solvents.

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Fig. 1: Potential-dependent kinetics of mediated oxidation of Li2S and Li2O2.
Fig. 2: Potential-dependent kinetics of Li2O2 oxidation in various systems.
Fig. 3: The surface structures and energy profiles during oxidation of two Li2O2 facets.
Fig. 4: Kinetics of TEMPO+ oxidizing Li2O2 over a wide potential range.
Fig. 5: In situ DEMS during mediated charging.

Data availability

Source Data for Figs. 15 are provided with the paper. All other data are available from the authors on reasonable request.


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This work was financially supported by the National Natural Science Foundation of China (grant nos. 51773092, 21975124, 11874254, 51802187 and U2030206). It was further supported by Fujian science & technology innovation laboratory for energy devices of China (21C-LAB), Key Research Project of Zhejiang Laboratory (grant no. 2021PE0AC02) and the Cultivation Program for the Excellent Doctoral Dissertation of Nanjing Tech University. S.A.F. is indebted to IST Austria for support.

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Authors and Affiliations



Y.C., S.S. and S.A.F. conceived and directed the project. D.C., X.S., A.W., F.Y., and Y.W. performed experiments and DFT calculations. S.A.F., Y.C. and S.S. wrote the paper. All authors discussed and revised the paper.

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Correspondence to Siqi Shi, Stefan A. Freunberger or Yuhui Chen.

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Supplementary Figs. 1–14, Notes 1–4 and References.

Supplementary Data 1

Atomic coordinates of the optimized computational models.

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Cao, D., Shen, X., Wang, A. et al. Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries. Nat Catal 5, 193–201 (2022).

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