Pushing the Detection Limit of Static Wideline NMR Spectroscopy Using Ultrafast Frequency-Swept Pulses.

We report a simple design strategy for wideband uniform-rate smooth truncation (WURST) pulses that enables ultrafast frequency sweeps to maximize the sensitivity of Carr-Purcell-Meiboom-Gill (CPMG) acquisition in static wideline nuclear magnetic resonance (NMR). Three compelling examples showcase the advantage of ultrafast frequency sweeps over currently employed WURST-CPMG protocols, demonstrating the potential of investigating materials that are typically inaccessible to static wideline NMR techniques, e.g., paramagnetic solids with short homogeneous transverse relaxation times.

Advanced Dual-Ion Batteries with High-Capacity Negative Electrodes Incorporating Black Phosphorus.

Dual-graphite batteries (DGBs), being an all-graphite-electrode variation of dual-ion batteries (DIBs), have attracted great attention in recent years as a possible low-cost technology for stationary energy storage due to the utilization of inexpensive graphite as a positive electrode (cathode) material. However, DGBs suffer from a low specific energy limited by the capacity of both electrode materials. In this work, a composite of black phosphorus with carbon (BP-C) is introduced as negative electrode (anode) material for DIB full-cells for the first time. The electrochemical behavior of the graphite || BP-C DIB cells is then discussed in the context of DGBs and DIBs using alloying anodes. Mechanistic studies confirm the staging behavior for anion storage in the graphite positive electrode and the formation of lithiated phosphorus alloys in the negative electrode. BP-C containing full-cells demonstrate promising electrochemical performance with specific energies of up to 319 Wh kg-1 (related to masses of both electrode active materials) or 155 Wh kg-1 (related to masses of electrode active materials and active salt), and high Coulombic efficiency. This work provides highly relevant insights for the development of advanced high-energy and safe DIBs incorporating BP-C and other high-capacity alloying materials in their anodes.

Exploiting the Degradation Mechanism of NCM523 ∥ Graphite Lithium-Ion Full Cells Operated at High Voltage.

Layered oxides, particularly including Li[Nix Coy Mnz ]O2 (NCMxyz) materials, such as NCM523, are the most promising cathode materials for high-energy lithium-ion batteries (LIBs). One major strategy to increase the energy density of LIBs is to expand the cell voltage (>4.3 V). However, high-voltage NCM ∥ graphite full cells typically suffer from drastic capacity fading, often referred to as "rollover" failure. In this study, the underlying degradation mechanisms responsible for failure of NCM523 ∥ graphite full cells operated at 4.5 V are unraveled by a comprehensive study including the variation of different electrode and cell parameters. It is found that the "rollover" failure after around 50 cycles can be attributed to severe solid electrolyte interphase growth, owing to formation of thick deposits at the graphite anode surface through deposition of transition metals migrating from the cathode to the anode. These deposits induce the formation of Li metal dendrites, which, in the worst cases, result in a "rollover" failure owing to the generation of (micro-) short circuits. Finally, approaches to overcome this dramatic failure mechanism are presented, for example, by use of single-crystal NCM523 materials, showing no "rollover" failure even after 200 cycles. The suppression of cross-talk phenomena in high-voltage LIB cells is of utmost importance for achieving high cycling stability.