Design of Sodium Titanate Nanowires as Anodes for Dual Li,Na Ion Batteries

Abstract

The bottleneck in the implementation of hybrid lithium-sodium-ion batteries is the lack of anode materials with a desired rate capability. Herein, we provide an in-depth examination of the Li-storage performance of sodium titanate nanowires as negative electrodes in hybrid Li,Na-ion batteries. Titanate nanowires were prepared by a simple and reproducible hydrothermal method. At a low reaction pressure, the well-isolated nanowires are formed, while by increasing the reaction pressure from 2 to 30 bar, the isolated nanowires tend to bundle. In nanowires, the local coordinations of Na and Ti atoms deviate from those in Na2Ti3O7 and Na2Ti6O13 and slightly depend on the reaction pressure. During the annealing at 350 °C, both Na and Ti coordinations undergo further changes. The nanowires are highly defective, and they easily crystallize into Na2Ti6O13 and Na2Ti3O7 phases. The lithium storage properties are evaluated in lithium-ion cells vs. lithium metal anode and titanate electrodes fabricated with PVDF and carboxymethyl cellulose (CMC) binders. The Li-storage by nanowires proceeds by a hybrid capacitive-diffusive mechanism between 0.1 and 2.5 V, which enables to achieve a high specific capacity. Sodium titanates accommodate Li+ by formation of mixed lithium-sodium-phase Na2−xLixTi6O13, which is decomposed to the distinct lithium phases Li0.54Ti2.86O6 and Li0.5TiO2. Contrary to lithium, the sodium storage is accomplished mainly by the capacitive reactions, and thus the phase composition is preserved during cycling in sodium ion cells. The isolated nanowires outperform bundled nanowires with respect to rate capability.

Keywords

• sodium-ion batteries
• hybrid Li,Na-ion batteries
• lithium intercalation
• capacitive energy storage
• layered sodium titanates
• tunnel-type sodium titanates