Abstract
Black phosphorus intercalation compounds (BPICs) with alkali metals (namely: K and Na) have been synthesized in bulk by solid‐state as well as vapor‐phase reactions. By means of a combination of in situ X‐ray diffraction, Raman spectroscopy, and DFT calculations the structural behavior of the BPICs at different intercalation stages has been demonstrated for the first time. Our results provide a glimpse into the very first steps of a new family of intercalation compounds, with a distinct behavior as compared to its graphite analogues (GICs), showing a remarkable structural complexity and a dynamic behavior.
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