Abstract

The inability of graphite to store Na⁺ ions at low potentials necessitates the use of disordered materials as anodes in Na-ion batteries, wherein complex degradative pathways limit cycle life. This study delineates the influence of synthetically induced material disorder in facilitating stable, high-rate sodium ion storage in a series of anatase titania analogs. The degree of disorder in the titanium oxyhydroxide (TiO_x(OH)_y-T_anneal) materials, synthesized via a simple, solution-phase sol–gel protocol employing a Ti(III) precursor, is systematically varied by tuning the postsynthesis annealing temperature (T_anneal). The variable disorder in TiO_x(OH)_y-T_anneal stems from the distribution of residual Ti(III), N-dopants, and O-vacancies in these materials as a function of T_anneal, as mapped by XPS, bulk-sensitive resonance inelastic X-ray scattering (RIXS), and EPR spectroscopy. In terms of electrochemical performance, we observe a unique, nonmonotonic dependence of Na⁺ storage capacity on the synthetically induced degree of disorder in TiO_x(OH)_y-T_anneal, instead of a simple inverse size dependence, as normally seen in the case of fully crystalline anatase materials. Further in contrast to crystalline anatase, the disorder in TiO_x(OH)_y-T_anneal opens up a bulk mode of Na⁺ storage instead of a purely surface confined or capacitive mode, as determined by scan rate-dependent cyclic voltammetry. TiO_x(OH)_y-400, with an intermediary amount of disorder in the prepared series of materials, shows the highest specific capacity (∼188 mAh/g) and cycling stability for Na⁺ storage at elevated rates. These results are in agreement with our first-principles simulated data exhibiting a higher number of possible sites that Na⁺ can occupy at an intermediate degree of disorder in a TiO_x(OH)_y structure.