Regulating f orbital of Tb electronic reservoir to activate stepwise and dual‐directional sulfur conversion reaction. Issue 1 (13th October 2022)

• Record Type: Journal Article
• Authors: Yu, Shuang; Yang, Shuo; Cai, Dong; Nie, Huagui; Zhou, Xuemei; Li, Tingting; Liang, Ce; Wang, Haohao; Dong, Yangyang; Xu, Rui; Fang, Guoyong; Qian, Jinjie; Ge, Yongjie; Hu, Yue; Yang, Zhi
• Is Part Of: InfoMat. Volume 5:Issue 1(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-10-13
• Subjects: electronic reservoir -- lithium–sulfur battery -- sulfur redox reaction kinetics -- unfilled f orbital; Materials -- Periodicals; Information technology -- Periodicals; Smart materials -- Periodicals; 620.11
• DOI: 10.1002/inf2.12381
• Languages: English
• ISSNs: 2567-3165

Abstract

Abstract: The sluggish kinetics in multistep sulfur redox reaction with different energy requirements for each step, is considered as the crucial handicap of lithium–sulfur (Li–S) batteries. Designing an electron reservoir, which can dynamically release electron to/accept electron from sulfur species during discharge/charge, is the ideal strategy for realizing stepwise and dual‐directional polysulfide electrocatalysis. Herein, a single Tb 3+/4+ oxide with moderate unfilled f orbital is synthetized as an electron reservoir to optimize polysulfide adsorption via Tb–S and N···Li bonds, reduce activation energy barrier, expedite electron/Li + transport, and selectively catalyze both long‐chain and short‐chain polysulfide conversions during charge and discharge. As a result, Tb electron reservoir enables stable operation of low‐capacity decay (0.087% over 500 cycles at 1 C), high sulfur loading (5.2 mg cm −2 ) and electrolyte‐starved (7.5 μL mg −1 ) Li–S batteries. This work could unlock the potential of f orbital engineering for high‐energy battery systems. Abstract : A single mixed‐valence Tb oxide with moderate unfilled f orbital as electron reservoir is introduced to optimize polysulfide adsorption, reduce activation energy barrier, expedite electron/Li + transport, and selectively catalyze both long‐chain and short‐chain polysulfide conversions during charge and discharge with passing through an important intermediate S5 2−, thus achieving outstanding electrochemical performance of high sulfur loading and electrolyte‐starved Li–S batteries.