RESUMEN
This study explores the relationships between material quench rate during processing and the resulting structural and electrochemical properties of Li[Ni0.25 Li0.167 Mn0.583 ]O2 . Samples of this lithium-rich material are prepared with highly contrasting postfiring cooling methods: a rapid water emersion quench or closed-door oven cooling. The contrasting approaches result in samples with different structural, chemical, and electrochemical behaviors; after cycling the rapidly quenched material yields greater capacity, greater stability, and initially lower, but more stable voltages than the slower cooled samples. Through the use of scanning tunneling electron microscopy, X-Ray Diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) it is demonstrated that rapidly quenched powders are more structurally uniform and chemically homogenous before cycling. By comparing these precycling sample to postcycling samples, it is then examined how this increased structural uniformity and chemical homogeneity leads to the superior electrochemical properties of the rapidly quenched samples.
RESUMEN
Developing high-energy and efficient battery technologies is a crucial aspect of advancing the electrification of transportation and aviation. However, battery innovations can take years to deliver. In the case of non-aqueous battery electrolyte solutions, the many design variables in selecting multiple solvents, salts and their relative ratios make electrolyte optimization time-consuming and laborious. To overcome these issues, we propose in this work an experimental design that couples robotics (a custom-built automated experiment named "Clio") to machine-learning (a Bayesian optimization-based experiment planner named "Dragonfly"). An autonomous optimization of the electrolyte conductivity over a single-salt and ternary solvent design space identifies six fast-charging non-aqueous electrolyte solutions in two work-days and forty-two experiments. This result represents a six-fold time acceleration compared to a random search performed by the same automated experiment. To validate the practical use of these electrolytes, we tested them in a 220 mAh graphiteâ£â£LiNi0.5Mn0.3Co0.2O2 pouch cell configuration. All the pouch cells containing the robot-developed electrolytes demonstrate improved fast-charging capability against a baseline experiment that uses a non-aqueous electrolyte solution selected a priori from the design space.
RESUMEN
We use correlated confocal and wide-field fluorescence microscopy to probe the interplay between local variations in charge carrier recombination and charge carrier transport in methylammonium lead triiodide perovskite thin films. We find that local photoluminescence variations present in confocal imaging are also observed in wide-field imaging, while intensity-dependent confocal measurements show that the heterogeneity in nonradiative losses observed at low excitation powers becomes less pronounced at higher excitation powers. Both confocal and wide-field images show that carriers undergo anisotropic diffusion due to differences in intergrain connectivity. These data are all qualitatively consistent with trap-dominated variations in local photoluminescence intensity and with grain boundaries that exhibit varying degrees of opacity to carrier transport. We use a two-dimensional kinetic model to simulate and compare confocal time-resolved photoluminescence decay traces with experimental data. The simulations further support the assignment of local variations in nonradiative recombination as the primary cause of photoluminescence heterogeneity in the films studied herein. These results point to surface passivation and intergrain connectivity as areas that could yield improvements in perovskite solar cells and optoelectronic device performance.
