Spontaneous and mass-conserved formation of continuous Si frameworks

Controlled formation of porous silicon has been of primary importance for numerous landmark applications such as light emitting sources, sensors, actuators, drug delivery systems, and energy storage applications. Frequently explored methods to form the structures have long relied on selective etching of silicon, which still stands as the most controllable and reliable methods to highlight essence of the applications. Here, we demonstrate an unprecedented approach to form silicon framework, which is spontaneously formed with atomistic arrangement of silicon without gravimetric loss via single electrochemical (de)alloying with lithium. Carefully controlling bare crystallinity of Si and composite/electrode designs, we reveal that the key prerequisite to forming the structure lies in using unique dealloying dynamics of crystalline-amorphous phase transformations at room temperature. Using the feature, we clearly highlight that commercially available nano-structured silicon particles can abruptly yet uniformly transform into continuous sub-2 nm spherical silicon frameworks with size-tunable pores.