Intercalating Ti2 Nb14 O39 Anode Materials for Fast-Charging, High-Capacity and Safe Lithium-Ion Batteries.

Ti-Nb-O binary oxide materials represent a family of promising intercalating anode materials for lithium-ion batteries. In additional to their excellent capacities (388-402 mAh g-1 ), these materials show excellent safety characteristics, such as an operating potential above the lithium plating voltage and minimal volume change. Herein, this study reports a new member in the Ti-Nb-O family, Ti2 Nb14 O39 , as an advanced anode material. Ti2 Nb14 O39 porous spheres (Ti2 Nb14 O39 -S) exhibit a defective shear ReO3 crystal structure with a large unit cell volume and a large amount of cation vacancies (0.85% vs all cation sites). These morphological and structural characteristics allow for short electron/Li+ -ion transport length and fast Li+ -ion diffusivity. Consequently, the Ti2 Nb14 O39 -S material delivers significant pseudocapacitive behavior and excellent electrochemical performances, including high reversible capacity (326 mAh g-1 at 0.1 C), high first-cycle Coulombic efficiency (87.5%), safe working potential (1.67 V vs Li/Li+ ), outstanding rate capability (223 mAh g-1 at 40 C) and durable cycling stability (only 0.032% capacity loss per cycle over 200 cycles at 10 C). These impressive results clearly demonstrate that Ti2 Nb14 O39 -S can be a promising anode material for fast-charging, high capacity, safe and stable lithium-ion batteries.

Charging Reactions Promoted by Geometrically Necessary Dislocations in Battery Materials Revealed by In Situ Single-Particle Synchrotron Measurements.

Crystallographic defects exist in many redox active energy materials, e.g., battery and catalyst materials, which significantly alter their chemical properties for energy storage and conversion. However, there is lack of quantitative understanding of the interrelationship between crystallographic defects and redox reactions. Herein, crystallographic defects, such as geometrically necessary dislocations, are reported to influence the redox reactions in battery particles through single-particle, multimodal, and in situ synchrotron measurements. Through Laue X-ray microdiffraction, many crystallographic defects are spatially identified and statistically quantified from a large quantity of diffraction patterns in many layered oxide particles, including geometrically necessary dislocations, tilt boundaries, and mixed defects. The in situ and ex situ measurements, combining microdiffraction and X-ray spectroscopy imaging, reveal that LiCoO2 particles with a higher concentration of geometrically necessary dislocations provide deeper charging reactions, indicating that dislocations may facilitate redox reactions in layered oxides during initial charging. The present study illustrates that a precise control of crystallographic defects and their distribution can potentially promote and homogenize redox reactions in battery materials.