Structural evolution at the oxidative and reductive limits in the first electrochemical cycle of Li1.2Ni0.13Mn0.54Co0.13O2

Wei Yin (1) , Alexis Grimaud (2) , Gwenaëlle Rousse (3) , Artem Abakumov (4) , Anatoliy Senyshyn (5) , Leiting Zhang (6) , Sigita Trabesinger , Antonella Iadecola (7) , Dominique Foix (8, 9) , Domitille Giaume (10) , Jean‐marie Tarascon (3, 1)

1 Collège de France - Chaire Chimie du solide et énergie
2 RS2E - Réseau sur le stockage électrochimique de l'énergie
3 SU - Sorbonne Université
4 Skoltech - Skolkovo Institute of Science and Technology [Moscow]
5 TUM - Technische Universität Munchen - Université Technique de Munich [Munich, Allemagne]
6 PSI - Paul Scherrer Institute
7 SSOLEIL - Synchrotron SOLEIL
8 ALISTORE-ERI - Advanced Lithium Energy Storage Systems - ALISTORE-ERI
9 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
10 LPMC - Laboratoire de physique de la matière condensée

High-energy-density lithium-rich materials are of significant interest for advanced lithium-ion batteries, provided that several roadblocks, such as voltage fade and poor energy efficiency are removed. However, this remains challenging as their functioning mechanisms during first cycle are not fully understood. Here we enlarge the cycling potential window for Li1.2Ni0.13Mn0.54Co0.13O2 electrode, identifying novel structural evolution mechanism involving a structurally-densified single-phase A’ formed under harsh oxidizing conditions throughout the crystallites and not only at the surface, in contrast to previous beliefs. We also recover a majority of first-cycle capacity loss by applying a constant-voltage step on discharge. Using highly reducing conditions we obtain additional capacity via a new low-potential P” phase, which is involved into triggering oxygen redox on charge. Altogether, these results provide deeper insights into the structural-composition evolution of Li1.2Ni0.13Mn0.54Co0.13O2 and will help to find measures to cure voltage fade and improve energy efficiency in this class of material.

Keywords: battery

Domains: Polymers; Material chemistry; Theoretical and/or physical chemistry; Analytical chemistry

Wei Yin, Alexis Grimaud, Gwenaëlle Rousse, Artem Abakumov, Anatoliy Senyshyn, et al.. Structural evolution at the oxidative and reductive limits in the first electrochemical cycle of Li1.2Ni0.13Mn0.54Co0.13O2. Nature Communications, 2020, 11 (1), ⟨10.1038/s41467-020-14927-4⟩. ⟨hal-02515164⟩