Amorphization-Driven Lithium Ion Storage Mechanism Change for Anomalous Capacity Enhancement

Capacity fading as a function of lithiation/delithiation cycles is a major limitation of Li-ion batteries. Most Li storage materials are susceptible to this phenomenon due to the degradation of the crystal structure and particle integrity as a result of volume changes associated with lithiation/delithiation processes and/or irreversible redox reactions. However, some Li storage materials show an increase in capacity with an increase in cycles; this phenomenon has been termed "negative fading." Negative fading in Li host materials is usually associated with the additional charge storage at the particle/solid-electrolyte interface (SEI) layer, decomposition/formation of the SEI layer, or redox reactions of various Li species at the interface. In this work, we report the observation of negative fading in a newly discovered anode material, TiNbO₄ (TNO), and reveal amorphization as a new mechanism for negative fading in Li host materials. This assertion was confirmed via a close relationship between changes in the crystal structure and the Li storage mechanism in TNO. Given that other titanium niobium oxide analogues (e.g., TiNb₂O₇) suffer from capacity loss due to amorphization, this unique electrochemical behavior of TNO may provide an interesting new direction to tune the titanium niobium oxides for high-performance, stable battery anodes.