Weijie Chen, Yue Yu, Yu Du, Yu Wang, Yan Zhao, Kai Guo, Pengfei Yuan, Jia-Nan Zhang, Gan Qu
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引用次数: 0
摘要
锂多硫化物(LiPSs)的催化转化是提高锂硫(Li-S)电池氧化还原动力学和抑制穿梭效应的关键方法。然而,由于结构的复杂性,典型的异质催化剂的作用并不容易确定。与单原子催化剂(SAC)的不同位点相比,单位点催化剂(SSC)的每个活性位点在空间能量、结合模式和配位球等方面都是相同和统一的。利用这种定义明确的结构,铁酞菁(FePc)被共价键接在氧化铜纳米片上,制备出低自旋态的铁单位点催化剂,作为锂-S 电化学的模型催化剂。在硫氧化还原反应过程中,通过原位拉曼光谱探测了 Fe-N 键的周期性极化演化。理论分析表明,轴向点击限制后,Fe 的 d 波段中心间隙(Δd)减小,dxz/dyz 脱域。因此,使用铁 SSC 的锂-S 电池在 2 C 下的容量衰减率为每周期 0.029%。一系列具有类似电子构型变化的 M SSC(M = Mn、Co 和 Ni)证明了这种方法的普遍性。这项工作为锂-S 电池中高效电催化的设计提供了指导。
A Click Chemistry Strategy Toward Spin-Polarized Transition-Metal Single Site Catalysts for Dynamic Probing of Sulfur Redox Electrocatalysis
Catalytic conversion of lithium polysulfides (LiPSs) is a crucial approach to enhance the redox kinetics and suppress the shuttle effect in lithium–sulfur (Li–S) batteries. However, the roles of a typical heterogenous catalyst cannot be easily identified due to its structural complexity. Compared with the distinct sites of single atom catalysts (SACs), each active site of single site catalysts (SSCs) is identical and uniform in their spatial energy, binding mode, and coordination sphere, etc. Benefiting from the well-defined structure, iron phthalocyanine (FePc) is covalently clicked onto CuO nanosheet to prepare low spin-state Fe SSCs as the model catalyst for Li–S electrochemistry. The periodic polarizability evolution of Fe-N bonding is probed during sulfur redox reaction by in situ Raman spectra. Theoretical analysis shows the decreased d-band center gap of Fe (Δd) and delocalization of dxz/dyz after the axial click confinement. Consequently, Li–S batteries with Fe SSCs exhibit a capacity decay rate of 0.029% per cycle at 2 C. The universality of this methodological approach is demonstrated by a series of M SSCs (M = Mn, Co, and Ni) with similar variation of electronic configuration. This work provides guidance for the design of efficient electrocatalysis in Li–S batteries.
期刊介绍:
Advanced Materials, one of the world's most prestigious journals and the foundation of the Advanced portfolio, is the home of choice for best-in-class materials science for more than 30 years. Following this fast-growing and interdisciplinary field, we are considering and publishing the most important discoveries on any and all materials from materials scientists, chemists, physicists, engineers as well as health and life scientists and bringing you the latest results and trends in modern materials-related research every week.