Halide-free synthesis of metastable graphitic BC3.

Layered BC3, a metastable phase within the binary boron-carbon system that is composed of graphite-like sheets with hexagonally symmetric C6B6 units, has never been successfully crystallized. Instead, poorly-crystalline BC3-like materials with significant stacking disorder have been isolated, based on the co-pyrolysis of a boron trihalide precursor with benzene at around 800 °C. The halide leaving group (-X) is a significant driving force of these reactions, but the subsequent evolution of gaseous HX species at such high temperatures hampers their scaling up and also prohibits their further use in the presence of hard-casting templates such as ordered silicates. Herein, we report a novel halide-free synthesis route to turbostratic BC3 with long-range in-plane ordering, as evidenced by multi-wavelength Raman spectroscopy. Judicious pairing of the two molecular precursors is crucial to achieving B-C bond formation and preventing phase-segregation into the thermodynamically favored products. A simple computational method used herein to evaluate the compatibility of bottom-up molecular precursors can be generalized to guide the future synthesis of other metastable materials beyond the boron-carbon system.

Hydrogen-Type Binding Sites in Carbonaceous Electrodes for Rapid Lithium Insertion.

Direct pyrolysis of coronene at 800 °C produces low-surface-area, nanocrystalline graphitic carbon containing a uniquely high content of a class of lithium binding sites referred to herein as "hydrogen-type" sites. Correspondingly, this material exhibits a distinct redox couple under electrochemical lithiation that is characterized as intermediate-strength, capacitive lithium binding, centered at ∼0.5 V vs Li/Li+. Lithiation of hydrogen-type sites is reversible and electrochemically distinct from capacitive lithium adsorption and from intercalation-type binding between graphitic layers. Hydrogen-type site lithiation can be fully retained even up to ultrafast current rates (e.g., 15 A g-1, ∼40 C) where intercalation is severely hampered by ion desolvation kinetics; at the same time, the bulk nature of these sites does not require a large surface area, and only minimal electrolyte decomposition occurs during the first charge/discharge cycle, making coronene-derived carbon an exceptional candidate for high-energy-density battery applications.