Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation.

In this study, silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. Here we present an electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46-y for the anode material in lithium-ion batteries. Post-cycling characterization with NMR and XRD show no discernible structural or volume changes even after electrochemical insertion of 44 Li into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from larger volume changes. The lithiation/delithiation processes are proposed to occur in single phase reactions at approximately 0.2 and 0.4 V vs. Li/Li+, respectively, distinct from other diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g-1 at a 5 mA g-1 rate were observed for silicon clathrate with composition Ba8Al8.54Si37.46, corresponding to Li:Si of 1.18:1. The results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.