Lithiation of phosphorus at the nanoscale: a computational study of Li n P m clusters

• Published in: Nanoscale Vol. 16; no. 3; pp. 1197 - 1205
• Main Authors: Rybkovskiy, Dmitry V, Lepeshkin, Sergey V, Mikhailova, Anastasiia A, Baturin, Vladimir S, Oganov, Artem R
• Format: Journal Article
• Language: English
• Published: England 18.01.2024
• ISSN: 2040-3364; 2040-3372
• DOI: 10.1039/D3NR05166H

Systematic structure prediction of Li P nanoclusters was performed for a wide range of compositions (0 ≤ ≤ 10, 0 ≤ ≤ 20) using the evolutionary global optimization algorithm USPEX coupled with density functional calculations. With increasing Li concentration, the number of P-P bonds in the cluster reduces and the phosphorus backbone undergoes the following transformations: elongated tubular → multi-fragment (with mainly P rings and P cages) → cyclic topology → branched topology → P-P dumbbells → isolated P ions. By applying several stability criteria, we determined the most favorable Li P clusters and found that they are located in the compositional area between ≈ /3 and ≈ /3 + 6. For instance, the Li P cluster has the highest stability and is known to be the structural basis of the corresponding bulk crystal. The obtained results provide valuable insights into the lithiation mechanism of nanoscale phosphorus which is of interest for development of novel phosphorus-based anode materials.