Rational Assembly of Hollow Microporous Carbon Spheres as P Hosts for Long‐Life Sodium‐Ion Batteries

Abstract This paper reports the rational assembly of novel hollow porous carbon nanospheres (HPCNSs) as the hosts of phosphorous (P) active materials for high‐performance sodium‐ion batteries (SIBs). The vaporization‐condensation process is employed to synthesize P/C composites, which is elucidated by both theories and experiments to achieve optimized designs. The combined molecular dynamics simulations and density functional theory calculations indicate that the morphologies of polymeric P4 and the P loading in the P/C composites depend mainly on the pore size and surface condition of carbon supports. Micropores of 1–2 nm in diameter and oxygenated functional groups attached on carbon surface are essential for achieving high P loading and excellent structural stability. In light of these findings, HPCNS/amorphous red phosphorus composites with enhanced structural/functional features are synthesized, which present an extremely low volume expansion of ≈67.3% during cycles, much smaller than the commercial red P's theoretical value of ≈300%. The composite anodes deliver an exceptional sodium storage capacity and remarkable long‐life cyclic stability with capacity retention over 76% after 1000 cycles. This work signifies the importance of rational design of electrode materials based on accurate theoretical predictions and sheds light on future development of cost‐effective P/C composite anodes for commercially viable SIBs.