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Selectivity for intercalated ions in MXene toward a high-performance capacitive electrode

高电容性能MXene电极对插层修饰离子的选择性

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Abstract

The intercalation of foreign ions has been demonstrated to be one of the effective methods to improve the electrochemical performance of Ti3C2Tx MXene. However, whether different intercalated ions have diverse impacts on the MXene structure and electrochemical properties is not well understood. Herein, we comprehensively investigated the structural features and electrochemical performances of a series of ions, including Li+, Na+, K+, Cs+, Zn2+, Mg2+, SO42−, and OH− intercalated MXenes. Different ions are observed to exhibit variations in the intercalation effect because of the differences in their sizes, charge numbers, and chemical features. Among the investigated intercalation agents, CsOH composed of monovalent Cs+ with a large size and strong base anion OH− exhibits a superior intercalation effect, where a large interlayer space accommodating a large amount of free water, a high oxidation state of Ti and a preferred surface with more O-containing functional groups for redox reaction is created, intensifying the pseudocapacitive H+ intercalation. Therefore, CsOH-treated MXene exhibits a significant enhancement in gravimetric capacitance (i.e., approximately 725% of the original) and more than 100% capacitance retention over 20,000 cycles. This paper provides a guideline for the rational design and construction of high-capacitance MXene and MXene-based hybrid electrodes in aqueous electrolytes.

摘要

离子插层是提高Ti3C2Tx MXene电化学性能的有效方法之一. 然而, 不同的插层离子对MXene的结构和电化学性能的影响是否相同这一问题尚不清楚. 本文系统研究了Li+、Na+、K+、Cs+、Zn2+、Mg2+、SO42−和OH−等一系列离子插层后的MXene的结构特征和电化学性能. 研究结果表明, 插层离子的半径、电荷数和化学特性对插层效果都会产生影响. 在所研究的插层剂中, 由离子半径最大的一价阳离子Cs+和具有强碱性的阴离子OH−组成的插层剂CsOH对MXene具有较好的插层效果. 插层后的MXene层间距增大, 层间容纳了大量游离水, Ti的价态升高, 片层表面有利于氧化还原反应的含O官能团增多, 这都大大促进了电解液离子H+的扩散与存储. 由此制备的电极的质量比电容大幅度提高, 为原始MXene电极的7倍多, 而且经过20,000次充放电循环后电容保持率未发生下降. 本文为具有高电容性能的MXene和MXene基复合电极的合理设计和制备提供了指导.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (52072196, 52002199, 52002200, and 52102106), the Major Basic Research Program of Natural Science Foundation of Shandong Province (ZR2020ZD09), the Natural Science Foundation of Shandong Province (ZR2019BEM042 and ZR2020QE063), the Innovation and Technology Program of Shandong Province (2020KJA004), the Open Project of Chemistry Department of Qingdao University of Science and Technology (QUSTHX201813), the Postdoctoral Innovation Project of Shandong Province (202101020), and Taishan Scholars Program of Shandong Province (ts201511034).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Minmin Hu  (胡敏敏), Lihong Chen  (陈丽红), Guicun Li  (李桂村) & Zhenjiang Li  (李镇江)

  2. College of Electromechanical Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Jun Dai  (代君)

  3. State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Alan Meng  (孟阿兰) & Lei Wang  (王磊)

  4. Hangzhou Yanqu Information Technology Co., Ltd., Hangzhou, 310003, China

    Haijiao Xie  (谢海姣)

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  1. Minmin Hu  (胡敏敏)
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  2. Jun Dai  (代君)
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  3. Lihong Chen  (陈丽红)
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  6. Guicun Li  (李桂村)
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  7. Haijiao Xie  (谢海姣)
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  8. Zhenjiang Li  (李镇江)
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Contributions

Author contributions Li Z and Hu M initiated the research; Hu M, Dai J and Chen L performed the experiments; Meng A, Wang L and Li G performed the product characterizations and property tests. Xie H performed the theoretical calculation and analysis. Hu M wrote the paper with support from Li Z. All authors contributed to the general discussion.

Corresponding author

Correspondence to Zhenjiang Li  (李镇江).

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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.

Zhenjiang Li obtained his PhD degree from the Northwest Polytechnic University, China in 2003. He has been a full professor at Qingdao University of Science and Technology, China, since 2004. His current research mainly focuses on the synthesis, properties and mechanism of nanomaterial-based novel electrode materials.

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Hu, M., Dai, J., Chen, L. et al. Selectivity for intercalated ions in MXene toward a high-performance capacitive electrode. Sci. China Mater. 66, 974–981 (2023). https://doi.org/10.1007/s40843-022-2243-2

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