Yan Min, Dong Wenda, Liu Fu, Chen Lihua, Hasan Tawfique, Li Yu, Su Bao-Lian
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China.
School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China.
Natl Sci Rev. 2022 Apr 21;9(7):nwac078. doi: 10.1093/nsr/nwac078. eCollection 2022 Jul.
The shuttle effect and excessive volume change of the sulfur cathode severely impede the industrial implementation of Li-S batteries. It is still highly challenging to find an efficient way to suppress the shuttle effect and volume expansion. Here, we report, for the first time, an innovative atomic orbital hybridization concept to construct the hierarchical hollow sandwiched sulfur nanospheres with double-polyaniline layers as the cathode material for large-scale high-performance Li-S batteries. This hierarchically 3D, cross-linked and stable sulfur-polyaniline backbone with interconnected disulfide bonds provides a new type and strong intrinsic chemical confinement of sulfur owing to the atomic orbital hybridization of Li 2s, S 3p, C 2p and N 2p. Crucially, such atomic orbital hybridization of sulfur sandwiched in the double sulfur-polyaniline network is highly reversible during the discharge/charge process and can very efficiently suppress the shuttle effect and volume expansion, contributing to a very high capacity of 1142 mAh g and an excellent stabilized capacity of 886 mAh g at 0.2 C after 500 cycles with a suppressed volume expansion and an unprecedented electrode integrity. This innovative atomic orbital hybridization concept can be extended to the preparation of other electrode materials to eliminate the shuttle effect and volume expansion in battery technologies. The present work also provides a commercially viable and up-scalable cathode material based on this strong and highly reversible atomic orbital hybridation for large-scale high-performance Li-S batteries.
硫正极的穿梭效应和过大的体积变化严重阻碍了锂硫电池的工业化应用。找到一种有效的方法来抑制穿梭效应和体积膨胀仍然极具挑战性。在此，我们首次报道了一种创新的原子轨道杂化概念，用于构建具有双聚苯胺层的分级中空夹心硫纳米球，作为大规模高性能锂硫电池的正极材料。这种具有相互连接的二硫键的分级三维、交联且稳定的硫-聚苯胺骨架，由于Li 2s、S 3p、C 2p和N 2p的原子轨道杂化，为硫提供了一种新型且强大的内在化学限制。至关重要的是，夹在双硫-聚苯胺网络中的硫的这种原子轨道杂化在充放电过程中具有高度可逆性，能够非常有效地抑制穿梭效应和体积膨胀，在500次循环后，在0.2 C下实现了1142 mAh g的非常高的容量和886 mAh g的优异稳定容量，同时抑制了体积膨胀并保持了前所未有的电极完整性。这种创新的原子轨道杂化概念可以扩展到其他电极材料的制备，以消除电池技术中的穿梭效应和体积膨胀。本工作还基于这种强大且高度可逆的原子轨道杂化，为大规模高性能锂硫电池提供了一种具有商业可行性且可扩大规模的正极材料。
