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

article Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries published yes Deqing Cao author Xiaoxiao Shen author Aiping Wang author Fengjiao Yu author Yuping Wu author Siqi Shi author Stefan Alexander Freunberger author A8CA28E6-CE23-11E9-AD2D-EC27E66974250000-0003-2902-5319 Yuhui Chen author StFr department 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. Springer Nature2022 eng Process Chemistry and TechnologyBiochemistryBioengineeringCatalysis Nature Catalysis 2520-1158 00076387940000110.1038/s41929-022-00752-z 5193-201 https://research-explorer.ista.ac.at/record/9978 D. Cao, X. Shen, A. Wang, F. Yu, Y. Wu, S. Shi, S.A. Freunberger, Y. Chen, Nature Catalysis 5 (2022) 193–201. Cao, Deqing, et al. “Threshold Potentials for Fast Kinetics during Mediated Redox Catalysis of Insulators in Li–O2 and Li–S Batteries.” Nature Catalysis, vol. 5, Springer Nature, 2022, pp. 193–201, doi:<a href="https://doi.org/10.1038/s41929-022-00752-z">10.1038/s41929-022-00752-z</a>. D. Cao et al., “Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries,” Nature Catalysis, vol. 5. Springer Nature, pp. 193–201, 2022. 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. Nature Catalysis. 2022;5:193-201. doi:<a href="https://doi.org/10.1038/s41929-022-00752-z">10.1038/s41929-022-00752-z</a> Cao D, Shen X, Wang A, Yu F, Wu Y, Shi S, Freunberger SA, Chen Y. 2022. Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries. Nature Catalysis. 5, 193–201. Cao, Deqing, Xiaoxiao Shen, Aiping Wang, Fengjiao Yu, Yuping Wu, Siqi Shi, Stefan Alexander Freunberger, and Yuhui Chen. “Threshold Potentials for Fast Kinetics during Mediated Redox Catalysis of Insulators in Li–O2 and Li–S Batteries.” Nature Catalysis. Springer Nature, 2022. <a href="https://doi.org/10.1038/s41929-022-00752-z">https://doi.org/10.1038/s41929-022-00752-z</a>. Cao, D., Shen, X., Wang, A., Yu, F., Wu, Y., Shi, S., … Chen, Y. (2022). Threshold potentials for fast kinetics during mediated redox catalysis of insulators in Li–O2 and Li–S batteries. Nature Catalysis. Springer Nature. <a href="https://doi.org/10.1038/s41929-022-00752-z">https://doi.org/10.1038/s41929-022-00752-z</a> 108132022-03-04T07:50:10Z2024-10-09T21:01:46Z