Following the Transient Reactions in Lithium–Sulfur Batteries Using an In Situ Nuclear Magnetic Resonance Technique

• Published in: Nano letters Vol. 15; no. 5; pp. 3309 - 3316
• Main Authors: Xiao, Jie, Hu, Jian Zhi, Chen, Honghao, Vijayakumar, M, Zheng, Jianming, Pan, Huilin, Walter, Eric D, Hu, Mary, Deng, Xuchu, Feng, Ju, Liaw, Bor Yann, Gu, Meng, Deng, Zhiqun Daniel, Lu, Dongping, Xu, Suochang, Wang, Chongmin, Liu, Jun
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.05.2015
• Subjects: Charge; Cycles; Lithium isotopes; Lithium sulfur batteries; Nuclear magnetic resonance; Polysulfides; Reactions (nuclear); Real time; in situ NMR; radicals; Li−S batteries; energy storage
• ISSN: 1530-6984; 1530-6992
• DOI: 10.1021/acs.nanolett.5b00521

A fundamental understanding of electrochemical reaction pathways is critical to improving the performance of Li–S batteries, but few techniques can be used to directly identify and quantify the reaction species during disharge/charge cycling processes in real time. Here, an in situ 7Li NMR technique employing a specially designed cylindrical microbattery was used to probe the transient electrochemical and chemical reactions occurring during the cycling of a Li–S system. In situ NMR provides real time, semiquantitative information related to the temporal evolution of lithium polysulfide allotropes during both discharge/charge processes. This technique uniquely reveals that the polysulfide redox reactions involve charged free radicals as intermediate species that are difficult to detect in ex situ NMR studies. Additionally, it also uncovers vital information about the 7Li chemical environments during the electrochemical and parasitic reactions on the Li metal anode. These new molecular-level insights about transient species and the associated anode failure mechanism are crucial to delineating effective strategies to accelerate the development of Li–S battery technologies.