In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode

We report the creation of a nanoscale electrochemical device inside a transmission electron microscope-consisting of a single tin dioxide (SnO2) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO2) cathode-and the in situ observation of the lithiation of the SnO2 nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a Medusa zone containing a high density of mobile dislocations, which are continuously nucleated and absorbed at the moving front. This dislocation cloud indicates large in-plane misfit stresses and is a structural precursor to electrochemically driven solid-state amorphization. Because lithiation-induced volume expansion, plasticity, and pulverization of electrode materials are the major mechanical effects that plague the performance and lifetime of high-capacity anodes in lithium-ion batteries, our observations provide important mechanistic insight for the design of advanced batteries.