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Reutt-Robey, Janice E.

Publications and source records attributed to Reutt-Robey, Janice E..

Pascalammetry with operando microbattery probes: Sensing high stress in solid-state batteries

Energy storage science calls for techniques to elucidate ion transport over a range of conditions and scales. We introduce a new technique, pascalammetry, in which stress is applied to a solid-state electrochemical device and induced faradaic current transients are measured and analyzed. Stress-step pascalammetry measurements are performed on operando microbattery probes (Li 2 O/Li/W) and Si cathodes, revealing stress-assisted Li + diffusion. We show how non-Cottrellian lithium diffusional kinetics indicates stress, a prelude to battery degradation. An analytical solution to a diffusion/activation equation describes this stress signature, with spatiotemporal characteristics distinct from Cottrell’s classic solution for unstressed systems. These findings create an unprecedented opportunity for quantitative detection of stress in solid-state batteries through the current signature. Generally, pascalammetry offers a powerful new approach to study stress-related phenomena in any solid-state electrochemical system.

25 ENERGY STORAGE↗

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2 , through the saturation monolayer limit, in which these two chemical species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.

2-D phases↗