Engineering eg Orbital Occupancy of Pt with Au Alloying Enables Reversible Li−O2 Batteries

Constructing well‐designed catalysts to accelerate OER catalytic activity and alleviate the charge overpotential is prevailing for achieving sophisticated Li−O2 batteries. Herein, we report a concept for engineering the eg occupancy of Pt with M alloying (M=Au, Ru) to tune the charge overpotentials...

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Bibliographic Details
Published in:Angewandte Chemie 2022-06, Vol.134 (26), p.n/a
Main Authors: Zhou, Yin, Gu, Qianfeng, Yin, Kun, Li, Yiju, Tao, Lu, Tan, Hao, Yang, Yong, Guo, Shaojun
Format: Article
Language:English
Subjects:
Adsorption Strength
Alloying
Antibonding Orbital
Catalysts
Catalytic activity
Cathodes
Chemistry
Density functional theory
eg Occupancy
Electronegativity
Electrons
Gold
Intermediates
Li−O2 Batter
Noble metals
Occupancy
Photoelectron spectroscopy
Photoelectrons
Platinum
PtAu Nanocrystals
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Summary:Constructing well‐designed catalysts to accelerate OER catalytic activity and alleviate the charge overpotential is prevailing for achieving sophisticated Li−O2 batteries. Herein, we report a concept for engineering the eg occupancy of Pt with M alloying (M=Au, Ru) to tune the charge overpotentials for achieving high‐performance Li−O2 batteries. The X‐ray photoelectron spectroscopy results coupled with density functional theory (DFT) calculations reveal that the highly electronegative Au can capture more eg electrons from Pt, leading to less eg electrons of Pt in PtAu than that in PtRu. The lower eg 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 (LiO2), thereby decreasing the OER energy barrier. As a consequence, the Li−O2 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. Engineering the eg occupancy of Pt with M alloying (M=Au, Ru) is reported to tune the charge overpotentials for achieving high‐performance Li−O2 batteries. Lowering eg occupancy of Pt in PtAu can elevate the antibonding orbitals and enhance the adsorption strength towards LiO2, resulting in high‐performance Li−O2 batteries with a low overpotential.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202201416