Lithium Bond Chemistry in Lithium–Sulfur Batteries
Ting-Zheng Hou
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
University of California Berkeley, Berkeley, CA, 94720 USA
These authors contributed equally to this work.
Search for more papers by this authorWen-Tao Xu
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
University of California Berkeley, Berkeley, CA, 94720 USA
These authors contributed equally to this work.
Search for more papers by this authorXiang Chen
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
These authors contributed equally to this work.
Search for more papers by this authorHong-Jie Peng
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
Search for more papers by this authorProf. Jia-Qi Huang
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
Search for more papers by this authorCorresponding Author
Prof. Qiang Zhang
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
Search for more papers by this authorTing-Zheng Hou
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
University of California Berkeley, Berkeley, CA, 94720 USA
These authors contributed equally to this work.
Search for more papers by this authorWen-Tao Xu
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
University of California Berkeley, Berkeley, CA, 94720 USA
These authors contributed equally to this work.
Search for more papers by this authorXiang Chen
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
These authors contributed equally to this work.
Search for more papers by this authorHong-Jie Peng
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
Search for more papers by this authorProf. Jia-Qi Huang
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
Search for more papers by this authorCorresponding Author
Prof. Qiang Zhang
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, 100084 P.R. China
Search for more papers by this authorAbstract
The lithium–sulfur (Li–S) battery is a promising high-energy-density storage system. The strong anchoring of intermediates is widely accepted to retard the shuttle of polysulfides in a working battery. However, the understanding of the intrinsic chemistry is still deficient. Inspired by the concept of hydrogen bond, herein we focus on the Li bond chemistry in Li–S batteries through sophisticated quantum chemical calculations, in combination with 7Li nuclear magnetic resonance (NMR) spectroscopy. Identified as Li bond, the strong dipole–dipole interaction between Li polysulfides and Li–S cathode materials originates from the electron-rich donors (e.g., pyridinic nitrogen (pN)), and is enhanced by the inductive and conjugative effect of scaffold materials with π-electrons (e.g., graphene). The chemical shift of Li polysulfides in 7Li NMR spectroscopy, being both theoretically predicted and experimentally verified, is suggested to serve as a quantitative descriptor of Li bond strength. These theoretical insights were further proved by actual electrochemical tests. This work highlights the importance of Li bond chemistry in Li–S cell and provides a deep comprehension, which is helpful to the cathode materials rational design and practical applications of Li–S batteries.
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