Enabling Increased Delithiation Rates in Silicon‐Based Anodes through Alloying with Phosphorus

Abstract The capability of battery materials to deliver not only high lithium storage capacity, but also the ability to operate at high charge/discharge rates is an essential property for development of new batteries. In the present work, the influence on the charge/discharge rate behaviour of substoichiometric concentrations of phosphorus (P) in silicon (Si) nanoparticles was studied. The results revealed an increase in rate capability as a function of the P concentration between 0 and 5.2 at %, particularly during delithiation. The stoichiometry of the nanoparticles was found to strongly affect the formation of the Li 3.5 Si phase during lithiation. Cyclic stability experiments demonstrated an initial increase in capacity for the SiP x materials. Galvanostatic intermittent titration technique and electrochemical impedance spectroscopy demonstrated the increased lithium diffusivity with inclusion of P. Density functional theory and ab initio molecular dynamics were deployed to provide a rationale for the electrochemical behaviour of SiP x .