Liu Jianfeng, He Qiu, Zou Wanjuan, Wu Mingwei, Rego Celso Ricardo Caldeira, Xia Chenxi, Xiong Yan, Zhao Yan
The Institute of Technological Sciences, Wuhan University, Wuhan 430072, China.
College of Materials Synthesis and Engineering, Sichuan University, Chengdu 610065, China.
ACS Appl Mater Interfaces. 2024 Nov 6;16(44):60180-60188. doi: 10.1021/acsami.4c11523. Epub 2024 Oct 22.
Modulating the electronic structure is essential for improving the anchoring and catalytic capabilities of catalysts in lithium-sulfur batteries (LSBs). This study delves into the modulation of -orbitals in transition metal dual-atom catalysts (DACs) supported by boron nitride and graphene (BNC) hybrid sheets for LSBs. This study reveals that the -band center of the DACs, a key determinant of material chemical properties, is primarily determined by the electronic configuration of the and orbitals. Furthermore, the interaction between of transition metals and S_3 orbitals is critical for the binding strength of LiPSs. By understanding these interactions, the functionality of DACs can be customized for optimal performance in LSBs. For example, the MnCrBNC catalyst with 10 -electrons exhibits the optimal -band center and demonstrates exceptional LiPSs binding capability, the lowest LiS decomposition energy barrier, and the lowest Gibbs free energy of reaction for the rate-determining step of sulfur reduction. This study elucidates the fundamental mechanisms for designing high-performance LSB catalysts through electronic structure modulation.
调节电子结构对于提高锂硫电池（LSB）中催化剂的锚定和催化能力至关重要。本研究深入探讨了由氮化硼和石墨烯（BNC）混合片负载的过渡金属双原子催化剂（DAC）中π轨道的调制，用于锂硫电池。本研究表明，DAC的π带中心是材料化学性质的关键决定因素，主要由d和p轨道的电子构型决定。此外，过渡金属的d轨道与S_3 p轨道之间的相互作用对于多硫化锂（LiPSs）的结合强度至关重要。通过理解这些相互作用，可以定制DAC的功能，以在锂硫电池中实现最佳性能。例如，具有10个d电子的MnCrBNC催化剂表现出最佳的π带中心，并展示出卓越的LiPSs结合能力、最低的Li_2S分解能垒以及硫还原速率决定步骤的最低反应吉布斯自由能。本研究阐明了通过电子结构调制设计高性能锂硫电池催化剂的基本机制。
