The lithium–tin alloy electrode,
as an artificial solid–electrolyte
interphase (SEI) material with outstanding electrochemical properties,
is promising to realize advanced next-generation lithium batteries.
Experimental explorations on Li–Sn alloy have already achieved
great success, while theoretical understanding on the mechanism of
lithium-ion transport is still lacking. In this work, we carried out
first-principles simulations and developed a theoretical methodology
to reveal how a lithium ion diffuses in different lithium–tin
phases and further elaborated the origin of low diffusion barriers.
The simulation results indicate that two kinds of diffusion modes,
interstitial and vacancy diffusion, will compete with each other with
the increase in lithium concentration. Furthermore, the underlying
mechanisms of direct hopping and coordinate process are also different
in different Li–Sn/In phases. It is interesting to discover
that during the lithiation process of alloy phases, the high-rate
transport channel will gradually transform from the interstitial direct-hopping
to vacancy mechanism and finally to the interstitial knock-off mechanism.
This work provides a thorough theoretical understanding on lithium-ion
transportation, further opening up the possibility of synthesizing
or modifying SEI materials with enhanced Li conductivity in novel
Li-ion battery designs.