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Oxygen vacancy-expedited ion diffusivity in transition-metal oxides for high-performance lithium-ion batteries

氧空位提高金属氧化物锂离子扩散动力学及储锂性能

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Abstract

Rapid capacity decay and inferior kinetics are the vital issues of anodes in the conversion reaction for lithium-ion batteries. Vacancy engineering can efficiently modulate the intrinsic properties of transition-metal oxide (TMO)-based electrode materials, but the effect of oxygen vacancies on electrode performance remains unclear. Herein, abundant oxygen vacancies are in situ introduced into the lattice of different TMOs (e.g., Co3O4, Fe2O3, and NiO) via a facile hydrothermal treatment combined with calcination. Taking Co3O4 as a typical example, results prove that the oxygen vacancies in Co3O4−x effectively accelerate charge transfer at the interface and significantly increase electrical conductivity and pseudocapacitance contribution. The Li-ion diffusion coefficient of Co3O4−x is remarkably improved by two orders of magnitude compared with that of Co3O4. Theoretical calculations reveal that Co3O4−x has a lower Li-insertion energy barrier and more density of states around the Fermi level than Co3O4, which is favorable for ion and electron transport. Therefore, TMOs with rich vacancies exhibit superior cycling performance and enhanced rate capability over their counterparts. This strategy regulating the reaction kinetics would provide inspiration for designing other TMO-based electrodes for energy applications.

摘要

转化反应过程中锂离子电池负极材料面临容量快速衰减和动力学缓慢的问题. 氧空位缺陷可以有效调节过渡金属氧化物(TMO)基电极材料的内在特性, 但是, 氧空位对电极材料性能的影响机制尚不清楚. 本研究通过简单的方法, 将丰富的氧空位原位引入到不同TMO(例如Co3O4、 Fe2O3和NiO)的晶格中. 以Co3O4为例, Co3O4−x中的氧空位能够有效加快界面处的电荷转移, 显著提高电导率和赝电容贡献. 理论计算表明, 氧空位的引入能够降低锂嵌入能垒, 且增加费米能级附近的态密度, 有利于离子和电子传输. 因此, 富含氧空位的TMO表现出更优异的循环稳定性和倍率性能. 本研究可以为设计用于能源应用的其他TMO电极材料提供参考.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (92163117 and 52072389) and the Program of Shanghai Academic Research Leader (20XD1424300).

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Authors and Affiliations

  1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 201899, China

    Xunlu Wang  (王寻路), Jie Liu  (刘婕), Yifan Hu  (胡一帆), Ruguang Ma  (马汝广) & Jiacheng Wang  (王家成)

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Xunlu Wang  (王寻路), Yifan Hu  (胡一帆) & Jiacheng Wang  (王家成)

  3. School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215011, China

    Ruguang Ma  (马汝广)

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  1. Xunlu Wang  (王寻路)
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  2. Jie Liu  (刘婕)
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  3. Yifan Hu  (胡一帆)
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  4. Ruguang Ma  (马汝广)
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Contributions

Author contributions Wang J and Ma R initiated the research. Wang X prepared the samples and conducted experimental measurements on the samples. All authors participated in the discussion of the results. Wang X, Ma R and Wang J wrote the paper.

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Correspondence to Ruguang Ma  (马汝广) or Jiacheng Wang  (王家成).

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

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Supplementary information Experimental details and supporting data are available in the online version of the paper.

Xunlu Wang is a PhD candidate in Prof. Jiacheng Wang’s group at the State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of the Ceramics, Chinese Academy of Sciences, Shanghai, China. Her current research focuses on the nanostructured electrode materials for Li ion batteries and highly efficient non-precious metal catalysts.

Ruguang Ma received his PhD degree in materials science from the City University of Hong Kong in 2013. He is currently a professor at the College of Materials Science and Engineering, Suzhou University of Science and Technology. His research interests include the design and synthesis of highly efficient non-precious metal catalysts and new nanostructured electrode materials for Li ion batteries, supercapacitors and metal-oxygen batteries.

Jiacheng Wang is a full professor and group leader of the Electrocatalytic Materials and Energy Devices Group at Shanghai Institute of Ceramics, Chinese Academy of Sciences. He was awarded several famous talent projects including Chinese Academy of Sciences Distinguished Talent, Shanghai Academic Research Leader, Alexander von Humboldt Fellow, the Japan Society for the Promotion of Science (JSPS) Postdoctoral Fellow for Foreign Researcher, and Marie Curie Intra-European Fellow. His current research interests include rational design and preparation of high-performance electrocatalysts for advanced energy storage and conversion.

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Wang, X., Liu, J., Hu, Y. et al. Oxygen vacancy-expedited ion diffusivity in transition-metal oxides for high-performance lithium-ion batteries. Sci. China Mater. 65, 1421–1430 (2022). https://doi.org/10.1007/s40843-021-1909-5

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