Electrochemical Thin Layers in Nanostructures for Energy Storage

This Account summarizes recent findings related to thin electrode materials synthesized by atomic layer deposition (ALD) and electrochemical deposition (ECD), including nanowires, nanotubes, and thin films. Throughout the Account, we will show how these techniques enabled us to synthesize electrodes of interest with precise control over the structure and composition of the material. We will illustrate and discuss how the electrochemical response of thin electrodes made by these techniques can facilitate new mechanisms for ion storage, mediate the interfacial electrochemical response of the electrode, and address issues related to electrode degradation over time. The effects of nanosizing materials and their electrochemical response will be mechanistically reviewed through two categories of ion storage: (1) pseudocapacitance and (2) ion insertion. Additionally, we will show how electrochemical processes that are more complicated because of accompanying volumetric changes and electrode degradation pathways can be mediated and controlled by application of thin functional materials on the electrochemically active interface; examples include conversion electrodes, reactive lithium metal anodes, and complex reactions in a Li/O₂ cathode system. The goal of this Account is to illustrate how careful design of thin materials either as active electrodes or as mediating layers can facilitate desirable interfacial electrochemical activity and resolve or shed light on mechanistic limitations of electrochemical processes related to micrometer size particles currently used in energy storage electrodes.