Metal valence state-regulated Li bond chemistry for efficient lithium–sulfur battery catalysis: A case study of cupric and cuprous oxides

IF 4.1 2区 材料科学 Q2 ENGINEERING, CHEMICAL
Hao-Bo Zhang , Bo-Bo Zou , Xian Zhong , Xin-He Liu , Kai-Xi You , Xinyan Liu , Hong-Jie Peng
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引用次数: 0

Abstract

Valence state is identified as a key property of transition metal-based catalysts in conventional heterogeneous catalysis research. For a specific monometal element, however, the regulatory role of valence state has seldom explored in emerging energy catalytic applications such as rechargeable lithium–sulfur batteries suffering from sluggish sulfur cathode conversion kinetics. In this study, two monometal oxides with distinct valence states, cupric oxide (CuO) and cuprous oxide (Cu2O), were investigated, revealing valence-state-dependent interactions between oxides and sulfur species, as well as the modulated sulfur reduction reaction (SRR) kinetics. In addition to the inherent Cu2+-enabled surface (poly)thiosulfate redox, divalent Cu2+ and monovalent Cu+ were found to steer the oxygen reactivity and so indirectly tune the lithium bond strength that dictates the surface chemisorption of lithium (poly)sulfides. The stronger interactions between CuO and sulfur species promoted SRR conversion kinetics, enabling enhanced lithium–sulfur battery performance under kinetically demanding conditions such as high-rate capability at 2 C with a moderate sulfur loading of 1.3 mg cm−2 and cycling stability for over 110 cycles at a high sulfur loading of 4.8 mg cm−2. This work is expected to expand the scope of metal-valence-state effect on heterogeneous catalysis and offer an unconventional “indirect” way to regulate lithium-bond chemistry for battery research.

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来源期刊
Particuology
Particuology 工程技术-材料科学:综合
CiteScore
6.70
自引率
2.90%
发文量
1730
审稿时长
32 days
期刊介绍: The word ‘particuology’ was coined to parallel the discipline for the science and technology of particles. Particuology is an interdisciplinary journal that publishes frontier research articles and critical reviews on the discovery, formulation and engineering of particulate materials, processes and systems. It especially welcomes contributions utilising advanced theoretical, modelling and measurement methods to enable the discovery and creation of new particulate materials, and the manufacturing of functional particulate-based products, such as sensors. Papers are handled by Thematic Editors who oversee contributions from specific subject fields. These fields are classified into: Particle Synthesis and Modification; Particle Characterization and Measurement; Granular Systems and Bulk Solids Technology; Fluidization and Particle-Fluid Systems; Aerosols; and Applications of Particle Technology. Key topics concerning the creation and processing of particulates include: -Modelling and simulation of particle formation, collective behaviour of particles and systems for particle production over a broad spectrum of length scales -Mining of experimental data for particle synthesis and surface properties to facilitate the creation of new materials and processes -Particle design and preparation including controlled response and sensing functionalities in formation, delivery systems and biological systems, etc. -Experimental and computational methods for visualization and analysis of particulate system. These topics are broadly relevant to the production of materials, pharmaceuticals and food, and to the conversion of energy resources to fuels and protection of the environment.
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