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Probing the thermal effects of voltage hysteresis in anionic redox-based lithium-rich cathodes using isothermal calorimetry


The commercialization of high-energy batteries with lithium-rich cathode materials exhibiting combined cationic/anionic redox processes awaits the elimination of certain practical bottlenecks. Among these, large voltage hysteresis remains the most obscure from a fundamental thermochemical perspective. Here, we study this issue by directly measuring, via isothermal calorimetry, the heat generated by Li/Li2Ru0.75Sn0.25O3 (Li/LRSO) cells during various cycling conditions, with LRSO being a ‘model’ Li-rich layered cathode. We show how this heat thermodynamically relates to the lost electrical work that is crucial for practical applications. We further reveal that anionic redox on charging and discharging adopts different metastable paths having non-identical enthalpy potentials, such that the overall Li content no longer remains the unique reaction coordinate, unlike in fully path-reversible cationic redox. We elucidate how quasi-static voltage hysteresis is related to heat dissipated due to non-equilibrium entropy production. Overall, this study establishes the great benefits of isothermal calorimetry for enabling energy-efficient electrode materials in next-generation batteries.

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Fig. 1: Comparison of voltage profiles of Li-rich NMC and LRSO.
Fig. 2: Isothermal calorimetry characterization of the 3.5 V cationic redox step.
Fig. 3: Isothermal calorimetry characterization of the full first cycle.
Fig. 4: Isothermal calorimetry characterization of activated LRSO.
Fig. 5: Isothermal calorimetry for charge voltage window opening of activated LRSO.
Fig. 6: Proposed mechanism for hysteretic bulk anionic redox in activated LRSO.

Data availability

The authors declare that the main data supporting the findings of this study are available within the article and its Supporting Information files. Extra data are available from the corresponding authors on reasonable request.


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J.-M.T. and G.A. acknowledge funding from the European Research Council (FP/2014)/European Research Council Grant-Project 670116-ARPEMA. S.L.G. thanks NSERC and the Walter C. Sumner Foundation for funding. We are grateful to J. Dahn for providing access to some of the equipment used in this work.

Author information




G.A. and S.L.G. conceived the idea. G.A. prepared the electrochemical cells. S.L.G. performed the isothermal calorimetry experiments. G.A. and C.D. performed the thermodynamic analysis. J.-M.T. supervised the project. G.A. wrote the paper, with contributions from all authors.

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Correspondence to Charles Delacourt or Jean-Marie Tarascon.

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Assat, G., Glazier, S.L., Delacourt, C. et al. Probing the thermal effects of voltage hysteresis in anionic redox-based lithium-rich cathodes using isothermal calorimetry. Nat Energy 4, 647–656 (2019).

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