Engineering egOrbital Occupancy of Pt with Au Alloying Enables Reversible Li−O2Batteries

作     者：Yin Zhou Qianfeng Gu Kun Yin Yiju Li Lu Tao Hao Tan Yong Yang Prof. Shaojun Guo 

作者机构：School of Materials Science and Engineering Peking University Beijing 100871 China Department of Materials Science and Engineering City University of Hong Kong Tat Chee Avenue 83 Kowloon Hong Kong 999077 China Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications School of Materials Science & Engineering Beijing Institute of Technology Beijing 10081 China State Key Laboratory of Solidification Processing Center of Advanced Lubrication and Seal Materials Northwestern Polytechnical University Xi'an 710072 China 

出 版 物：《Angewandte Chemie》 

年 卷 期：2022年第134卷第26期

学科分类：081704[工学-应用化学] 08[工学] 0817[工学-化学工程与技术] 

主　　题：Adsorption Strength Antibonding Orbital eg Occupancy Li−O2 Batter PtAu Nanocrystals 

摘      要：Constructing well-designed catalysts to accelerate OER catalytic activity and alleviate the charge overpotential is prevailing for achieving sophisticated Li−O 2 batteries. Herein, we report a concept for engineering the e g occupancy of Pt with M alloying (M=Au, Ru) to tune the charge overpotentials for achieving high-performance Li−O 2 batteries. The X-ray photoelectron spectroscopy results coupled with density functional theory (DFT) calculations reveal that the highly electronegative Au can capture more e g electrons from Pt, leading to less e g electrons of Pt in PtAu than that in PtRu. The lower e g occupancy of Pt atoms in PtAu alloys entails the upward shift of the Pt d band, which causes a strong binding strength towards the intermediates (LiO 2 ), thereby decreasing the OER energy barrier. As a consequence, the Li−O 2 battery with a PtAu cathode delivers a low charge overpotential of 0.36 V and superior cycle life of 220 cycles at a cutoff capacity of 1000 mAh g −1 , which is among the best in the reported noble metal-based cathodes.