4 research outputs found
Defect-Driven Anomalous Transport in Fast-Ion Conducting Solid Electrolytes
Solid-state ionic conduction is a key enabler of electrochemical energy
storage and conversion. The mechanistic connections between material
processing, defect chemistry, transport dynamics, and practical performance are
of considerable importance, but remain incomplete. Here, inspired by studies of
fluids and biophysical systems, we re-examine anomalous diffusion in the iconic
two-dimensional fast-ion conductors, the - and
-aluminas. Using large-scale simulations, we reproduce
the frequency dependence of alternating-current ionic conductivity data. We
show how the distribution of charge-compensating defects, modulated by
processing, drives static and dynamic disorder, which lead to persistent
sub-diffusive ion transport at macroscopic timescales. We deconvolute the
effects of repulsions between mobile ions, the attraction between the mobile
ions and charge-compensating defects, and geometric crowding on ionic
conductivity. Our quantitative framework based on these model solid
electrolytes connects their atomistic defect chemistry to macroscopic
performance with minimal assumptions and enables mechanism-driven
'atoms-to-device' optimization of fast-ion conductors.Comment: 45 pages, 23 figures. Additional code is available at
https://github.com/apoletayev/anomalous_ion_conductio
Control of the pH-Dependence of the Band Edges of Si(111) Surfaces Using Mixed Methyl/Allyl Monolayers
The open-circuit potentials of p-Si/((MV^(2+)/MV^(+))(aq)) junctions with Si(111) surfaces functionalized with H−, CH_(3)−, CH_(2)CHCH_(2)−, or mixed CH_(3)−/CH_(2)CHCH_(2)− monolayers have been investigated as the solution pH was changed from 2.5 to 11. The pH sensitivity of the open-circuit potentials, and therefore the band-edge positions, was anticorrelated with the total fraction of Si atop sites that were terminated by Si−C bonds. This behavior is consistent with the hypothesis that the non Si−C terminated atop sites were initially H-terminated and were unstable to oxide growth under aqueous conditions with the oxidation-product inducing a pH-dependent dipole. Metal-semiconductor junctions between Hg and CH_(3)-, CH_(2)CHCH_(2)-, or mixed CH_(3)-/CH_(2)CHCH_(2)-terminated n-Si(111) surfaces formed rectifying Hg/Si Schottky junctions and exhibited mutually similar barrier-heights (~0.9 V), suggesting similar magnitudes and direction of the surface dipoles on all of these functionalized surfaces
Direct Mapping of Band Positions in Doped and Undoped Hematite during Photoelectrochemical Water Splitting
Photoelectrochemical water splitting is a promising pathway for the direct conversion of renewable solar energy to easy to store and use chemical energy. The performance of a photoelectrochemical device is determined in large part by the heterogeneous interface between the photoanode and the electrolyte, which we here characterize directly under operating conditions using interface-specific probes. Utilizing X-ray photoelectron spectroscopy as a noncontact probe of local electrical potentials, we demonstrate direct measurements of the band alignment at the semiconductor/electrolyte interface of an operating hematite/KOH photoelectrochemical cell as a function of solar illumination, applied potential, and doping. We provide evidence for the absence of in-gap states in this system, which is contrary to previous measurements using indirect methods, and give a comprehensive description of shifts in the band positions and limiting processes during the photoelectrochemical reaction