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Cationic vanadium vacancy-enriched V2−xO5 on V2C MXene as superior bifunctional electrocatalysts for Li-O2 batteries

富含钒空位的V2−xO5@V2C MXene作为锂-氧气电池双功能电催化剂

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Abstract

The development of cationic vacancies has been extensively examined as an effective strategy to improve the activity of electrocatalysts. However, it is a challenge to effectively introduce cationic vacancies on the material surface. Their specific effects on the electrochemical performance of lithium-oxygen (Li-O2) batteries are rarely reported. In this work, vanadium pentoxide with abundant vanadium vacancies (V2−xO5) is in situ prepared on the V2C MXene (V2−xO5@V2C MXene) surface, and their bifunctional catalytic activity toward the oxygen electrode reaction in Li-O2 batteries is systematically examined. The results show that the V2−xO5@V2C MXene-based Li-O2 battery exhibits excellent performance. It delivers a high energy efficiency of 83.4% at 100 mA g−1 and excellent cycling performance of more than 500 cycles. Furthermore, density functional theory calculations confirm that the presence of cationic vanadium vacancies can provide abundant active sites to reduce the reaction barrier and optimize the adsorption of reactants, increasing the oxygen electrode reactions in the Li-O2 battery. This work provides a meaningful view that modulating the electronic structure by creating cationic metal vacancies can improve the electrocatalytic activity of transition metal oxides.

摘要

构造阳离子空位被认为是一种可以提高电催化剂活性的有效策略. 然而, 在材料表面高效地引入阳离子空位仍面临诸多挑战. 另外, 关于阳离子空位对锂-氧气(Li-O2)电池氧电极反应活性的影响少有报道. 本文报道了在V2C MXene表面原位构造富含钒空位的五氧化二钒(V2−xO5@V2C MXene)的方法, 并系统研究了该材料对Li-O2电池氧电极反应的双功能催化活性. 结果表明, 基于V2−xO5@V2C MXene的Li-O2电池具有良好的性能. 其在100 mA g−1电流密度下展示出高的能量效率(83.4%)和优异的循环性能(超过500次循环). 密度泛函理论计算结果表明, 阳离子钒空位的存在可以提供大量活性位点以降低Li-O2电池氧电 极反应能垒并促进反应物的吸附. 本工作表明, 通过构造阳离子金属空 位来调节材料表面电子结构是提高过渡金属氧化物电催化活性的有效路径.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21905033), the Science and Technology Department of Sichuan Province (2019YJ0503), and the State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization (2020P4FZG02A).

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Authors and Affiliations

  1. College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu, 610059, China

    Haoyang Xu  (徐浩洋), Ruixin Zheng  (郑瑞鑫), Dayue Du  (杜大越), Longfei Ren  (任龙飞), Runjing Li  (李润璟), Xiaojuan Wen  (温晓娟), Chuan Zhao  (赵川), Ting Zeng  (曾婷), Bo Zhou  (周波) & Chaozhu Shu  (舒朝著)

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  1. Haoyang Xu  (徐浩洋)
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  2. Ruixin Zheng  (郑瑞鑫)
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  3. Dayue Du  (杜大越)
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  7. Chuan Zhao  (赵川)
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  10. Chaozhu Shu  (舒朝著)
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Contributions

Author contributions Shu C conceived the project and directed the experiments. Xu H and Zheng R designed the experiments. Xu H and Zheng R carried out the material synthesis, device fabrication, and most of the measurements. Xu H wrote the manuscript. Shu C revised the manuscript. All authors contributed to the data analysis, discussed the results, and commented on the manuscript.

Corresponding author

Correspondence to Chaozhu Shu  (舒朝著).

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

Additional information

Haoyang Xu received his BSc degree from Chengdu University of Technology. He is now pursuing his Master degree under the supervision of Prof. Chaozhu Shu. His research interests mainly focus on the synthesis and characterization of nanomaterials for metal-air battery.

Ruixin Zheng received his Master degree (2021) from Chengdu University of Technology. His current research interests focus on the development of functional nanomaterials for emerging energy storage and conversion devices.

Chaozhu Shu received his BSc degree (2006) from Dalian University of Technology and PhD degree (2013) from Dalian Institute of Chemical Physics, Chinese Academy of Sciences. He is now a professor at the College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology. His research group works on materials for rechargeable batteries and electrocatalysis.

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Xu, H., Zheng, R., Du, D. et al. Cationic vanadium vacancy-enriched V2−xO5 on V2C MXene as superior bifunctional electrocatalysts for Li-O2 batteries. Sci. China Mater. 65, 1761–1770 (2022). https://doi.org/10.1007/s40843-021-1959-1

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