Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.

Local equilibrium of the Gibbs interface in two-phase systems

We analyze the local equilibrium assumption for interfaces from the perspective of gauge transformations, which are the small displacements of Gibbs' dividing surface. The gauge invariance of thermodynamic properties turns out to be equivalent to conditions for jumps of bulk densities across the interface. This insight strengthens the foundations of the local equilibrium assumption for interfaces and can be used to characterize nonequilibrium interfaces in a compact and consistent way, with a clear focus on gauge-invariant properties. Using the principle of gauge invariance, we show that the validity of Clapeyron equations can be extended to nonequilibrium interfaces, and an additional jump condition for the momentum density is recognized to be of the Clapeyron type. © 2012 Europhysics Letters Association.