Engineering e g Orbital Occupancy of Pt with Au Alloying Enables Reversible Li−O 2 Batteries

作者：Yin Zhou, Qianfeng Gu, Kun Yin, Yiju Li, Tao Lu, Hao Tan, Yong Yang, Shaojun Guo · 发表于：Angewandte Chemie · 年份：2022 · DOI：10.1002/ange.202201416 · 被引用次数：14 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Electrocatalysts for Energy Conversion

Abstract 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.