Electrochemically Induced Amorphous-to-Rock-Salt Phase Transformation in Niobium Oxide Electrode for Li-Ion Batteries

Intercalation-type metal oxides are promising negative electrode materials for safe rechargeable lithium-ion batteries due to the reduced risk of Li plating at low voltages. Nevertheless, their lower energy and power density along with cycling instability remain bottlenecks for their implementation, especially for fast-charging applications. Here, we report a nanostructured rock-salt Nb2O5 electrode formed through an amorphous-to-crystalline transformation during repeated electrochemical cycling with Li+. This electrode can reversibly cycle three lithiums per Nb2O5, corresponding to a capacity of 269 mAh g−1 at 20 mA g−1, and retains a capacity of 191 mAh g−1 at a high rate of 1 A g−1. It exhibits superb cycling stability with a capacity of 225 mAh g−1 at 200 mA g−1 for 400 cycles, and a Coulombic efficiency of 99.93%. We attribute the enhanced performance to the cubic rock-salt framework, which promotes low-energy migration paths. Our work suggests that inducing crystallization of amorphous nanomaterials through electrochemical cycling is a promising avenue for creating unconventional high-performance metal oxide electrode materials

Electropolishing Valve Metals with Sulfuric Acid-Methanol Electrolyte

To develop uniform oxide nano-structures on the surface of valve metals, via anodization, it is desirable to start with a polished surface. Electropolishing is a common method to produce highly polished surfaces. However, common procedures utilize toxic, fluoride containing electrolytes. This study reports on a novel method for electropolishing titanium and niobium, in a sulfuric acid/methanol electrolyte, at low temperature (-70 oC). Electropolishing at low temperature has a significant effect on reaction kinetics. Experiments show an expansion of the steady-state current density plateau of anodic polarization curves. Additionally, increasing the sulfuric acid concentration led to broadening of the current density plateau. Optimization of conditions produced a root mean squared roughness of 1.64 nm and 0.49 nm for titanium and niobium, respectively. An improvement over results obtained with fluorine-containing electrolytes. We believe it is possible to apply this method to other valve metals, like zirconium and tantalum. Preliminary experiments with zirconium have shown a brightening and smoothing of the surface. However, there is further work required to optimize results with this metal. Additionally, we show that polished valve metal surfaces produce more uniform nano-structures, formed via anodization