Lithium transport at silicon thin film: barrier for high-rate capability anode.

The major hurdle that retards the practical application of nanostructured silicon anode in rechargeable Li-ion batteries is the capacity retention during lithiation/delithiation processes, especially at high current rate (e.g., >5 C). Since fast Li transport in the electrode is the essential of high-rate capability, the rate-limiting step exists during Li transport process and needs to be determined. We here investigate Li transport properties of Si thin film anode by first-principles calculation and find that high intrinsic energy barrier (0.88 eV) of Li surface intercalation retards fast Li transport. However, this energy barrier can be efficiently reduced by surface modification, e.g., P or Al doping. The present results should shed light on designing Si anode of Li-ion batteries with high-rate capability.