Thermal synthesis of conversion-type bismuth fluoride cathodes for high-energy-density Li-ion batteries

Towards enhancement of the energy density of Li-ion batteries, BiF3 has recently attracted considerable attention as a compelling conversion-type cathode material due to its high theoretical capacity of 302 mAh g−1, average discharge voltage of ca. 3.0 V vs. Li+/Li, the low theoretical volume change of ca. 1.7% upon lithiation, and an intrinsically high oxidative stability. Here we report a facile and scalable synthesis of phase-pure and highly crystalline orthorhombic BiF3via thermal decomposition of bismuth(III) trifluoroacetate at T = 300 °C under inert atmosphere. The electrochemical measurements of BiF3 in both carbonate (LiPF6-EC/DMC)- and ionic liquid-based (LiFSI-Pyr1,4TFSI) Li-ion electrolytes demonstrated that ionic liquids improve the cyclic stability of BiF3. In particular, BiF3 in 4.3 M LiFSI-Pyr1,4TFSI shows a high initial capacity of 208 mA g−1 and capacity retention of ca. 50% over at least 80 cycles at a current density of 30 mA g−1.

Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge 1–3. This is particularly true in the context of accessing non-natural reactions by bioinspired approaches, which offer intriguing possibilities for benign and affordable chemical synthesis 4. Exploiting the untapped potential of inorganic solids by translating complex knowledge in (bio)molecular-based systems may constitute a potentially useful strategy for such purpose 5, but efforts to capitalize on the minimum catalytic unit of a versatile solid matrix have been largely unsuccessful. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighboured single cobalt site/pyridinic-N site (Co-N4/Py-N) pairs can act cooperatively as an oxidase mimic, which renders an engaged coupling of oxygen (O2) reduction with synthetically beneficial chemical transformations. By developing this broadly applicable platform, the scalable synthesis of greater than 100 industrially and pharmaceutically appealing O-silylated compounds via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated. Moreover, this heterogeneous oxidase mimic also offers potential for expanding the catalytic scope of enzymatic synthesis. We anticipate that the strategy demonstrated here will pave a new avenue for understanding the underlying nature of redox enzymes and open up a new class of material systems for artificial biomimetics.

Synthesis of Atomically Thin h-BN Layers Using BCl3 and NH3 by Sequential-Pulsed Chemical Vapor Deposition on Cu Foil

The chemical vapor deposition of hexagonal boron nitride layers from BCl3 and NH3 is highly beneficial for scalable synthesis with high controllability, yet multiple challenges such as corrosive reaction or by-product formation have hindered its successful demonstration. Here, we report the synthesis of polycrystalline hexagonal boron nitride (h-BN) layers on copper foil using BCl3 and NH3. The sequential pulse injection of precursors leads to the formation of atomically thin h-BN layers with a polycrystalline structure. The relationship between growth temperature and crystallinity of the h-BN film is investigated using transmission electron microscopy and Raman spectroscopy. Investigation on the initial growth mode achieved by the suppression of precursor supply revealed the formation of triangular domains and existence of preferred crystal orientations. The possible growth mechanism of h-BN in this sequential-pulsed CVD is discussed.