The Electrochemical and Structural Changes of Phosphorus-Doped TiO2 through In Situ Raman and In Situ X-Ray Diffraction Analysis.

Doping is a widely employed technique to enhance the functionality of lithium-ion battery materials, tailoring their performance for specific applications. In our study, we employed in situ Raman and in situ X-ray diffraction (XRD) spectroscopic techniques to examine the structural alterations and electrochemical behavior of phosphorus-doped titanium dioxide (TiO2) nanoparticles. This investigation revealed several notable changes: an increase in structural defects, enhanced ionic and electronic conductivity, and a reduction in crystallite size. These alterations facilitated higher lithiation rates and led to the first observed appearance of LiTiO2 in the Raman spectra due to anatase lithiation, resulting in a reversible double-phase transition during the charging and discharging processes. Furthermore, doping with 2, 5, and 10 wt % phosphorus resulted in an initial increase in specific capacity compared to undoped TiO2. However, higher doping levels were associated with diminished capacity retention, pinpointing an optimal doping level for phosphorus. These results underscore the critical role of in situ characterization techniques in understanding doping effects, thereby advancing the performance of anode materials, particularly TiO2, in lithium-ion batteries.

Limiting voltage and capacity fade of lithium-rich, low cobalt Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 by controlling the upper cut-off voltage.

A new Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 material with a higher content of Fe and lower content of Co was designed via a simple sol-gel method. Moreover, the effect of upper cut-off voltage on the structural stability, capacity and voltage retention was studied. The Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 electrode delivers a discharge capacity of 250 mA h g-1 with good capacity retention and coulombic efficiency at 4.6 V cut-off voltage. Importantly, improved voltage retention of 94% was achieved. Ex situ XRD and Raman proved that the electrodes cycled at 4.8 V cut-off voltage showed huge structural conversion from layered-to-spinel explaining the poor capacity and voltage retention at this cut-off voltage. In addition, ex situ FT-IR demonstrates that the upper cut-off voltage of 4.8 V exhibits a higher intensity of SEI-related peaks than 4.6 V, suggesting that reducing the upper cut-off voltage can inhibit the growth of the SEI layer. In addition, when the Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 cathode was paired with a synthesized phosphorus-doped TiO2 anode (P-doped TiO2) in a complete battery cell, it exhibits good capacity and cycling stability at 1C rate. The material developed in this study represents a promising approach for designing high-performance Li-rich, low cobalt cathodes for next-generation lithium-ion batteries.