Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite

Spinel transition metal oxides (TMOs) have emerged as promising anode materials for lithium-ion batteries. It has been shown that reducing their particle size to nanoscale dimensions benefits overall electrochemical performance. Here, we use in situ transmission electron microscopy to probe the lithiation behavior of spinel ZnFe₂O₄ as a function of particle size. We have found that ZnFe₂O₄ undergoes an intercalation-to-conversion reaction sequence, with the initial intercalation process being size dependent. Larger ZnFe₂O₄ particles (40 nm) follow a two-phase intercalation reaction. In contrast, a solid-solution transformation dominates the early stages of discharge when the particle size is about 6-9 nm. Using a thermodynamic analysis, we find that the size-dependent kinetics originate from the interfacial energy between the two phases. Furthermore, the conversion reaction in both large and small particles favors {111} planes and follows a core-shell reaction mode. These results elucidate the intrinsic mechanism that permits fast reaction kinetics in smaller nanoparticles.