Transition-Metal Phosphorus Trisulfides and its Vacancy Defects: Emergence of a New Class of Anode Material for Li-Ion Batteries.

In the search of suitable anode candidates with high specific capacity, favorable potential, and structural stability for lithium-ion batteries (LIBs), transition-metal phosphorus trisulfides (TMPS3 ) can be considered as one of the most promising alternatives to commercial graphite. Here, it was demonstrated that the limitations of commercial anode materials (i.e., low specific capacity, large volume change, and high lithium diffusion barrier as well as nucleation) can be circumvented by using TMPS3 monolayer surfaces. The study revealed that lithium binds strongly to TMPS3 monolayers (-2.31 eV) without any distortion of the surface, with Li@TMPS3 exhibiting enhanced stability compared with other 2D analogues (graphene, phosphorene, MXenes, transition-metal sulfides and phosphides). The binding energy of lithium was overwhelmingly enhanced with vacancy defects. The vacancy-mediated TMPS3 surfaces showed further amplification of Li binding energy from -2.03 to -2.32 eV and theoretical specific capacity of 441.65 to 484.34 mAh g-1 for MnPS3 surface. Most importantly, minimal change in volume (less than 2 %) after lithiation makes TMPS3 monolayers a very effective candidate for LIBs. Additionally, the ultralow lithium diffusion barrier (0.08 eV) compared with other existing commercial anode material proves the superiority of TMPS3 .