In:
Physical Chemistry Chemical Physics, Royal Society of Chemistry (RSC), Vol. 25, No. 15 ( 2023), p. 10495-10503
Abstract:
The structures and bonding properties of several lithium polysulfide clusters LiS n −/0 ( n = 3–5) and Li 2 S 4 −/0 were investigated by size-selected anion photoelectron spectroscopy coupled with quantum chemistry calculations. The vertical detachment energies of LiS 3 − , LiS 4 − , and LiS 5 − were estimated to be 2.17 ± 0.08, 3.30 ± 0.08 and 3.66 ± 0.08 eV, respectively, and that of Li 2 S 4 − was estimated to be 3.21 ± 0.08 eV. It is found that LiS 3 − and LiS 3 have planar quadrilateral structures, and LiS 4 − and LiS 4 have distorted five-membered ring structures. LiS 5 − has a distorted six-membered ring structure while neutral LiS 5 has a book-shaped structure. The lowest-lying structure of Li 2 S 4 − can be viewed as a S 2 unit connecting to the Li–Li edge of a Li 2 S 2 tetrahedron. The lowest-lying structure of neutral Li 2 S 4 can be viewed as a S 2 unit connecting to the S atoms of a Li 2 S 2 quadrilateral. The natural population analysis (NPA) and electron localization function (ELF) analyses show that the excess electron of LiS n − is mainly localized over the sulfur chains, especially on the S atoms interacting with Li, thus, the most stable structures of LiS n − can be regarded as a Li + cation interacting with a S n 2− dianion. The results may be useful for understanding the formation of lithium polysulfides in lithium sulfur batteries.
Type of Medium:
Online Resource
ISSN:
1463-9076
,
1463-9084
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2023
detail.hit.zdb_id:
1476283-3
detail.hit.zdb_id:
1476244-4
detail.hit.zdb_id:
1460656-2
