Self-Modifying Nanointerface Driving Ultrahigh Bidirectional Thermal Conductivity Boron Nitride-Based Composite Flexible Films.

While boron nitride (BN) is widely recognized as the most promising thermally conductive filler for rapidly developing high-power electronic devices due to its excellent thermal conductivity and dielectric properties, a great challenge is the poor vertical thermal conductivity when embedded in composites owing to the poor interfacial interaction causing severe phonon scattering. Here, we report a novel surface modification strategy called the "self-modified nanointerface" using BN nanocrystals (BNNCs) to efficiently link the interface between BN and the polymer matrix. Combining with ice-press assembly method, an only 25 wt% BN-embedded composite film can not only possess an in-plane thermal conductivity of 20.3 W m-1 K-1 but also, more importantly, achieve a through-plane thermal conductivity as high as 21.3 W m-1 K-1, which is more than twice the reported maximum due to the ideal phonon spectrum matching between BNNCs and BN fillers, the strong interaction between the self-modified fillers and polymer matrix, as well as ladder-structured BN skeleton. The excellent thermal conductivity has been verified by theoretical calculations and the heat dissipation of a CPU. This study provides an innovative design principle to tailor composite interfaces and opens up a new path to develop high-performance composites.

Anomalous Redox Features Induced by Strong Covalency in Layered NaTi1-y Vy S2 Cathodes for Na-Ion Batteries.

The rising demand for energy density of cathodes means the need to raise the voltage or capacity of cathodes. Transition metal (TM) doping has been employed to enhance the electrochemical properties in multiple aspects. The redox voltage of doped cathodes usually falls in between the voltage of undoped layered cathodes. However, we found anomalous redox features in NaTi1-y Vy S2 . The first discharge platform potential (2.4 V) is significantly higher than that of undoped NaTiS2 and NaVS2 (both around 2.2 V), and the energy density is raised by 15 %. We speculate that the anomalous voltage is mainly attributed to the strong hybridization in the Ti-V-S system. Ti3+ and V3+ undergo charge transfer and form a more stable Ti (t2g 0 eg 0 ) and V (t2g 3 eg 0 ) electronic configuration. Our results indicate that higher voltage of cathode materials could be achieved by strong TM-ligand covalency, and this conclusion provides possible opportunities to explore high voltage materials for future layered cathodes.

Anionic Redox Regulated via Metal-Ligand Combinations in Layered Sulfides.

The increasing demand for energy storage is calling for improvements in cathode performance. In traditional layered cathodes, the higher energy of the metal 3d over the O 2p orbital results in one-band cationic redox; capacity solely from cations cannot meet the needs for higher energy density. Emerging anionic redox chemistry is promising to access higher capacity. In recent studies, the low-lying O nonbonding 2p orbital was designed to activate one-band oxygen redox, but they are still accompanied by reversibility problems like oxygen loss, irreversible cation migration, and voltage decay. Herein, by regulating the metal-ligand energy level, both extra capacities provided by anionic redox and highly reversible anionic redox process are realized in NaCr1- y Vy S2 system. The simultaneous cationic and anionic redox of Cr/V and S is observed by in situ X-ray absorption near edge structure (XANES). Under high d-p hybridization, the strong covalent interaction stabilizes the holes on the anions, prevents irreversible dimerization and cation migration, and restrains voltage hysteresis and voltage decay. The work provides a fundamental understanding of highly reversible anionic redox in layered compounds, and demonstrates the feasibility of anionic redox chemistry based on hybridized bands with d-p covalence.