P₄S₁₀ Modification for Lithium Metal Anode Surface

Abstract

P4S10 molecule is a modification material that has important application value in lithium–sulfur batteries. It could modify lithium metal electrode and improve the performance of lithium–sulfur batteries. The mechanism of P4S10 modifying Li (100) surface is investigated with the first‐principles calculation based on density functional theory. The structure and electronic properties of P4S10, freestanding Li (100) surface, and modified Li (100) surface are researched. P4S10 is adsorbed strongly on Li (100) surface and then dissociated completely, which accelerates the redox of P4S10, and finally produces new substances. Density of states shows that newly formed substances could passivate Li (100) surface. It is deduced that it could act as a protective layer to protect Li (100) surface from the other parasitic reaction, polysulfide corrosion, and possibly inhibit the growth of lithium dendrites. There are large charge redistributions between P4S10 and Li (100) surface, improving the interface wettability. The reaction Gibbs free energy is proximately of −20.50 eV per molecule, due to the interaction of occupied orbitals and unoccupied orbitals. The electrons from Li‐s orbitals partially transfer to π* orbitals of P4S10. This work provides theoretical guidance to understand the modification mechanism and the formation of protective layers from P4S10 in lithium–sulfur batteries.