Selenium infiltrated hierarchical hollow carbon spheres display rapid kinetics and extended cycling as lithium metal battery (LMB) cathodes

Abstract

Lithium metal–selenium (Li–Se) batteries offer high volumetric energy but are limited in their cycling life and fast charge characteristics. Here a facile approach is demonstrated to synthesize hierarchically porous hollow carbon spheres that host Se (Se@HHCS) and allow for state-of-the-art electrochemical performance in a standard carbonate electrolyte (1 M LiPF₆ in 1 : 1 EC : DEC). The Se@HHCS electrodes display among the most favorable fast charge and cycling behavior reported. For example, they deliver specific capacities of 442 and 357 mA h g⁻¹ after 1500 and 2000 cycles at 5C and 10C, respectively. At 2C, Se@HHCS delivers 558 mA h g⁻¹ after 500 cycles, with cycling coulombic efficiency of 99.9%. Post-mortem microstructural analysis indicates that the structures remain intact during extended cycling. Per GITT analysis, Se@HHCS possesses significantly higher diffusion coefficients in both lithiation and delithiation processes as compared to the baseline. The superior performance of Se@HHCS is directly linked to its macroscopic and nanoscale pore structure: the hollow carbon sphere morphology as well as the remnant open nanoporosity accommodates the 69% volume expansion of the Li to Li₂Se transformation, with the nanopores also providing a complementary fast ion diffusion path.