ABSTRACT
Ti2Nb2O9 with a tunnel-type structure is considered as a perspective negative electrode material for Li-ion batteries (LIBs) with theoretical capacity of 252 mAh g-1 corresponding to one-electron reduction/oxidation of Ti and Nb, but only ≈160 mAh g-1 has been observed practically. In this work, highly reversible capacity of 200 mAh g-1 with the average (de)lithiation potential of 1.5 V vs Li/Li+ is achieved for Ti2Nb2O9 with pseudo-2D layered morphology obtained via thermal decomposition of the NH4TiNbO5 intermediate prepared by K+â H+â NH4+ cation exchange from KTiNbO5. Using operando synchrotron powder X-ray diffraction (SXPD), single-phase (de)lithiation mechanism with 4.8% unit cell volume change is observed. Operando X-ray absorption near-edge structure (XANES) experiment revealed simultaneous Ti4+/Ti3+ and Nb5+/Nb4+ reduction/oxidation within the whole voltage range. Li+ migration barriers for Ti2Nb2O9 along [010] direction derived from density functional theory (DFT) calculations are within the 0.15-0.4 eV range depending on the Li content that is reflected in excellent C-rate capacity retention. Ti2Nb2O9 synthesized via the ion-exchange route appears as a strong contender to widely commercialized Ti-based negative electrode material Li4Ti5O12 in the next generation of high-performance LIBs.
ABSTRACT
Sodium-ion batteries are emerging as promising candidates for grid energy storage because of the abundant sodium resources and low cost. However, the identification and development of suitable anode materials is far from being satisfactory. Here, it is demonstrated that the Ti2 Nb2 O9 nanosheets with tunnel structure can be used as suitable anode materials for sodium-ion batteries. Ti2 Nb2 O9 nanosheets are synthesized by liquid exfoliation combined with topotactic dehydration, delivering a high reversible capacity of 250 mAh g-1 at 50 mA g-1 at a suitable average voltage of ≈0.7 V. It is found that a low energy diffusion barrier, enlarged interlayer spacing, and exceptional nanoporosity together give rise to high rate performance characterized by pseudocapacitive behavior. The observed high reversible capacity, excellent rate capability, and good cyclability of Ti2 Nb2 O9 nanosheets make this material competitive when compared to other sodium insertion anode materials.