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.