Operando monitoring the nanometric morphological evolution of TiO₂ nanoparticles in a Na-ion battery

Na-ion batteries are nowadays receiving renewed attention because of its propitiousness for large-scale stationary applications. Although the Na storage mechanism is still not completely understood, TiO₂ nanoparticles are very promising active anode materials in Na-ion batteries provided that a correct dispersion is achieved within the battery electrode. Whilst the structural changes, either in crystallinity or crystalline phase, that occur during operation are receiving much recent attention, the nanometric morphological evolution of the TiO₂ nanoparticles within the electrode is yet to be thoroughly addressed, despite its implication in battery efficiency. In the present work, operando small-angle x-ray scattering studies on TiO₂/Na-ion batteries show that whereas the nanoparticle size is preserved during the discharge-charge cycles, the mean distance between nanoparticles increases. The observed morphological changes are consistent with electrode swelling and nanoparticle aggregation during operation, being one phenomenon dominant over the other depending on the applied density current; thus, depending on the differences in ion diffusion within the electrode.