Oxygen-Loss-Induced Structural Degradation in ε-LiVOPO₄

The ε-LiVOPO4 cathode for Li-ion batteries has attracted wide attention with its multivalent electronic states and improved discharge capacity of over 300 mAh/g. Oxygen loss stands as a potential cause for structural degradations of the ε-LiVOPO4 cathode and its derivatives but has been barely studied. Through in situ environmental transmission electron microscopy, we probe lattice oxygen loss and the associated structural degradations by spatially and temporally resolving the atomic-scale structural dynamics and phase transformation pathways in ε-LiVOPO4. We demonstrate that the mild oxygen loss at 400 °C induces a topotactic phase transformation of ε-LiVOPO4 → α-Li3V2(PO4)3 in the particle surface via a nucleation and growth mechanism, leading to the formation of a core–shell configuration. The phase transformation can be reversed by switching to an oxidizing environment, in which the α-Li3V2(PO4)3 is reoxidized to ε-LiVOPO4. By contrast, oxygen loss at higher temperatures of 500 and 600 °C results in a high concentration of oxygen vacancies that subsequently induces irreversible structural damages including lattice amorphization and formation of nanocavities. This work illustrates the fundamental mechanisms governing the structural failure of oxide cathodes and underlines possible strategies to overcome such issues by exploiting environmental constraints.