Ionic Intercalation in Two-Dimensional van der Waals Materials: In Situ Characterization and Electrochemical Control of the Anisotropic Thermal Conductivity of Black Phosphorus

Two-dimensional van der Waals materials have shown novel fundamental properties and promise for wide applications. Here, we report for the first time an experimental demonstration of the in situ characterization and highly reversible control of the anisotropic thermal conductivity of black phosphorus. We develop a novel platform based on lithium ion batteries that integrates ultrafast optical spectroscopy and electrochemical control to investigate the interactions between lithium ions and the lattices of the black phosphorus electrode. We discover a strong dependence of the thermal conductivity on battery charge states (lithium concentrations) during the discharge/charge process. The thermal conductivity of black phosphorus is reversibly tunable over a wide range of 2.45–3.86, 62.67–85.80, and 21.66–27.58 W·m–1·K–1 in the cross-plan, zigzag, and armchair directions, respectively. The modulation in thermal conductivity is attributed to phonon scattering introduced by the ionic intercalation in between the ...