Bidirectional Superionic Conduction in Surface-Engineered 2D Hexagonal Boron Nitrides.

We designed functionalized hexagonal boron nitride (FhBN) nanoflakes with high proton conductivity in both in- and through-plane directions as next generation polymer electrolyte membranes (PEMs) for energy storage and conversion systems. The synthesis and functionalization of hBN nanoflakes with sulfonic acid (SA) groups are obtained by one-step and in situ liquid-phase exfoliation with excellent dispersibility and stability over a period of three months. The physico/chemical properties of FhBN nanoflakes were investigated by different spectroscopic and microscopic characterization, confirming chemical interactions between hBN lattice and SA groups. High concentrations (65 and 75 wt %) of FhBN nanoflakes composed with Nafion solution formed stable FhBN-Nafion nanocomposite PEMs, offering extra proton conduction sites, doubling ion-exchange capacity, and reducing the swelling ratio compared to those of Nafion. Our results demonstrate that both the in-plane and through-plane proton conductivities of FhBN-Nafion PEMs significantly improve under various conditions comparative to that of Nafion. The maximum values of both in- and through-plane conductivities for FhBN75%-Nafion PEM at 80% of humidity and 80 °C are 0.41 and 0.1 S·cm-1, respectively, which are 7 and 14 times higher than those of Nafion. The bidirectional superionic transport in highly concentrated FhBN PEMs is responsible for outstanding properties, useful for electrochemical energy devices.