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Selectively anchoring Pd single atoms on specific sites in defective cobalt oxides for efficient lithium-oxygen batteries

缺陷钴氧化物中选择性锚定Pd单原子用于高效锂氧电池

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Abstract

Aprotic Li-O2 batteries, based on the reversible formation of Li2O2 by the reaction between Li metal and oxygen, afford extremely high theoretical energy density. However, the nucleation/delithiation mechanisms of Li2O2 remain ambiguous. Therefore, it is an important issue for developing high performance Li-O2 batteries to construct a catalyst system and deeply understand the catalytic mechanism at the atomic level. Herein, we report a strategy for achieving the site-selectively anchoring of Pd single atoms in oxygen vacancy-rich Co3O4 (Pd1-Co3O4−x). Atomic-level characterization techniques unravel that the Pd atoms are preferably incorporated into the tetrahedral site of defective Co3O4. Theoretical calculations manifest the obvious charge redistribution induced by the selective-anchored Pd single atom coupled with oxygen vacancies can effectively increase the energy band occupancy of Pd 4d orbitals near the Fermi level, which promotes electron transfer and facilitates the adsorption of intermediates. This dual interaction can not only regulate the nucleation-growth procedures of Li2O2 during discharging, but also benefit the delocalization of the electron cloud on Li2O2 and weaken the strength of the Li–O bond, which promotes the decomposition of Li2O2 during charging. This work proposes some insights into the catalytic mechanism at the atomic level and facilitates the rational design of highly efficient catalysts for Li-O2 batteries.

摘要

非质子锂氧电池基于锂金属与氧的可逆反应生成Li2O2, 可提供 极高的理论能量密度. 然而, Li2O2的成核/消除机制仍然不清楚. 因此, 构建能在原子水平上深入了解催化机理的催化剂体系, 是开发高性能 锂氧电池的关键. 在此, 我们报道了一种在富氧空位的Co3O4 (Pd1-Co3O4−x)中实现Pd单原子选择性锚定的策略. 原子水平表征技术 揭示了Pd原子优先地结合到缺陷Co3O4的四面体位点. 理论计算表明, 选择性锚定的Pd单原子与氧空位的耦合引起了明显的电荷重分布, 这 可以有效地提高Pd 4d轨道在费米能级附近的能带占用率, 促进电子转 移, 有利于中间体的吸附. 这种双重相互作用不仅可以调节放电过程中 Li2O2的成核生长过程, 而且有利于Li2O2上的电子云的离域, 减弱Li–O 键的强度, 从而促进Li2O2在充电过程中的分解. 本研究对锂氧电池在原 子水平上的催化机理和高效催化剂的合理设计提出了一些见解.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (11975238 and 11575192), the Scientific Instrument Developing Project (ZDKYYQ20170001), the Strategic Priority Research Program (XDB28000000), and the International Partnership Program (211211KYSB20170060 and 211211KYSB20180020) of the Chinese Academy of Sciences and the University of the Chinese Academy of Sciences. This work was also supported by the Fundamental Research Funds for the Central Universities. Allocation of beamtime at BL14W1 of Shanghai Synchrotron Radiation Facility (SSRF) is gratefully acknowledged. We also acknowledge the 4W1A station in Beijing Synchrotron Radiation Facility (BSRF) for help with nano-CT characterizations.

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Authors and Affiliations

  1. Center of Materials Science and Optoelectronics Engineering, College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, China

    Jian Zheng  (郑健), Wenjing Zhang  (张文静), Taiguang Li  (李泰广), Butian Chen  (陈步天), Chong Liu  (柳冲), Tianran Zhang  (张天然) & Xiangfeng Liu  (刘向峰)

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  1. Jian Zheng  (郑健)
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  2. Wenjing Zhang  (张文静)
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  3. Taiguang Li  (李泰广)
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  4. Butian Chen  (陈步天)
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  5. Chong Liu  (柳冲)
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  6. Tianran Zhang  (张天然)
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  7. Xiangfeng Liu  (刘向峰)
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Contributions

Author contributions Zheng J and Liu X conceived and designed the research; Zheng J, Zhang W, and Li T synthesized the samples; Zheng J, Chen B, and Liu C characterized the samples; Zheng J, Zhang W, and Li T tested the battery performance; Zheng J, Zhang W, Li T, Chen B, and Liu C helped to analyze the data; Zheng J, Zhang T, and Liu X revised the manuscript; Zhang T performed the DFT calculation. All the authors commented on the manuscript and gave approval to the final version of the manuscript.

Corresponding authors

Correspondence to Tianran Zhang  (张天然) or Xiangfeng Liu  (刘向峰).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Supporting data are available in the online version of the paper.

Jian Zheng received his PhD degree in 2023 from the University of Chinese Academy of Sciences. At the same year, he worked as a postdoctoral researcher at Shenzhen Institutes of Advanced Technology of the Chinese Academy of Sciences. He pursued his PhD degree under the supervision of Prof. Xiangfeng Liu at the University of Chinese Academy of Sciences. His research focuses on the design and fabrication of high-performance catalysts for Li-O2 batteries and in-situ analytical techniques.

Tianran Zhang received his PhD degree from Nankai University in 2014. From 2015 to 2020, he worked as a postdoctoral researcher in Prof. Jim Yang Lee’s research group at the National University of Singapore. In 2021, he joined the School of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences. He is mainly engaged in the research of controllable preparation and theoretical design of low-cost nano functional materials, and new long-life and high-specific energy batteries.

Xiangfeng Liu received his PhD degree in materials sciences from the University of Chinese Academy of Sciences in 2006. From 2006 to 2012, he worked as a postdoctoral at the National Institute of Advanced Industrial Science and Technology, University of New Brunswick and University of Missouri-St. Louis. In 2012, he set up the “Laboratory of Advanced Energy and Functional Materials” under the support of “Hundred Talents Project” and since 2012 he has been a professor at the College of Materials Science and Optoelectronics Technology, University of Chinese Academy of Sciences. His research focuses on lithium-ion battery, Li-air battery, and sodium-ion battery.

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Selectively Anchoring Pd Single Atoms on Specific Sites in Defective Cobalt Oxides for Efficient Lithium–Oxygen Batteries

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Zheng, J., Zhang, W., Li, T. et al. Selectively anchoring Pd single atoms on specific sites in defective cobalt oxides for efficient lithium-oxygen batteries. Sci. China Mater. 67, 1433–1444 (2024). https://doi.org/10.1007/s40843-023-2765-3

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