Kinetics of Lithium Intercalation in Titanium Disulfide Single Crystals

Abstract

Abstract Single crystals of titanium disulfide TiS2 were synthesized by chemical vapor synthesis and subsequently intercalated with n-butyl lithium (BuLi) in n-hexane. Experiments were carried out using a butyl lithium concentration between 0.8 and 10 mol L-1 and the temperature range was from 248 K to 328 K. The duration of the intercalation was varied from 2 h to 30 d. After the intercalation experiments concentration profiles of lithium, titanium and sulfur were measured parallel to the ab-plane of the crystal by LA-ICP-OES (LASER Ablation — Inductively Coupled Plasma - Optical Emission Spectroscopy). Chemical diffusion coefficients (D) were determined by fitting of the profiles to the specific solution of Fick's 2 nd law for the given boundary conditions. The measured diffusivity in the ab-plane (D|| a/b ) varies between 10-13 and 10-15 m2 s-1 at room temperature. These variations of D cannot be correlated to the reaction time. On the other hand a systematic increase of D|| a/b with the concentration of butyl lithium (cBuLi ) was observed, with a corresponding decrease in activation energy from 59.6 ± 7.6 kJ mol-1 (cBuLi=1.6 mol L-1 ) to 42.6 ± 11.7 kJ mol-1 (cBuLi=10 mol L-1 ). Furthermore, profiles measured on the same crystals reveal D|| a/b values differing by up to a factor of 3. ToF-SIMS (Time-of-Flight Secondary Ion Mass Spectromety) images gave evidence of inhomogenous insertion of lithium along crystal edges. These findings indicate that stress induced by widening of the crystal layers plays a crucial role in the intercalation kinetics. SIMS profiling perpendicular to the ab-plane gives evidence that D⊥ a/b is at least four orders of magnitude lower than D|| a/b .