This talk highlights recent work, which establishes a picture of the driving forces that govern material transformations and degradation in electrochemical environments to enable the ab initio design of electrochemical materials. Using select prototype systems, how the interplay between materials properties such as crystal field splitting, band edge energies, surface termination, material length scale, dielectric constant, and isoelectric point, and electrolyte properties such as pH and ion type, impacts electrochemical behavior—i.e., redox potentials, reaction enthalpies, reactivity, and decoupled ionic, and electronic processes is described. We show that the ab initio modeling of charged defects and intercalants within the grand canonical unified electrochemical band diagram (UEB) framework enables the quantitative prediction of electrochemical materials behavior. UEB combines electrochemical theory, charged defect theory, and band diagram descriptions and can be used both for materials discovery and development. First, a pedagogical description of the UEB framework is presented, followed by examples of the application of this framework to reveal mechanisms for high rate electronic charge storage in cation-incorporated α-MnO2 and λ-MnO2. Finally, suggestions of new prospects for the application of the UEB framework to electrolyte design, interfacial engineering, and catalysis are given.

Unified electrochemical band diagram framework: Understanding the driving forces of material electrochemistry

2019 Spring National Meeting

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.