Lewis Acid–Base Interactions between Polysulfides and Metal Organic Framework in Lithium Sulfur Batteries

• Published in: Nano letters Vol. 14; no. 5; pp. 2345 - 2352
• Main Authors: Zheng, Jianming, Tian, Jian, Wu, Dangxin, Gu, Meng, Xu, Wu, Wang, Chongmin, Gao, Fei, Engelhard, Mark H, Zhang, Ji-Guang, Liu, Jun, Xiao, Jie
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 14.05.2014
• Subjects: Condensed matter: structure, mechanical and thermal properties; Confinement; Cycles; Diffusion in nanoscale solids; Diffusion in solids; Environmental Molecular Sciences Laboratory; Exact sciences and technology; Lewis acidic center; Li-S battery; Lithium sulfur batteries; metal organic framework; Metal-organic frameworks; Migration; Nickel; Physics; Polysulfides; polysulfides confinement; Porosity; Sulfur; sulfur composite; Transport properties of condensed matter (nonelectronic); Metal organic framework; polysulfides confinement; sulfur composite; Lewis acidic center; cycle life; lithium sulfur battery; Nickel base alloys; Composite materials; Strong interactions; Benzene; Organometallic compounds; Molecular interaction; Diffusion; Dissolution; Lithium sulfur batteries
• ISSN: 1530-6984; 1530-6992; 1530-6992
• DOI: 10.1021/nl404721h

Lithium–sulfur (Li–S) battery is one of the most promising energy storage systems because of its high specific capacity of 1675 mAh g–1 based on sulfur. However, the rapid capacity degradation, mainly caused by polysulfide dissolution, remains a significant challenge prior to practical applications. This work demonstrates that a novel Ni-based metal organic framework (Ni-MOF), Ni6(BTB)4(BP)3 (BTB = benzene-1,3,5-tribenzoate and BP = 4,4′-bipyridyl), can remarkably immobilize polysulfides within the cathode structure through physical and chemical interactions at molecular level. The capacity retention achieves up to 89% after 100 cycles at 0.1 C. The excellent performance is attributed to the synergistic effects of the interwoven mesopores (∼2.8 nm) and micropores (∼1.4 nm) of Ni-MOF, which first provide an ideal matrix to confine polysulfides, and the strong interactions between Lewis acidic Ni(II) center and the polysulfide base, which significantly slow down the migration of soluble polysulfides out of the pores, leading to the excellent cycling performance of Ni-MOF/S composite.