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"Intrinsic" strategies for manipulating the local electronic structure and coordination environment of defect-regulated materials can optimize electrochemical storage performance. Nevertheless, the structure–activity relationship between defects and charge storage is ambiguous, which may be revealed by constructing highly ordered vacancy structures. Herein, we demonstrate molybdenum carbide MXene nanosheets with customized in-plane chemical ordered vacancies (Mo1.33CTx), by utilizing selective etching strategies. Synchrotron-based X-ray characterizations reveal that Mo atoms in Mo1.33CTx show increased average valence of +4.44 compared with the control Mo2CTx. Benefited from the introduced atomic active sites and high valence of Mo, Mo1.33CTx achieves an outstanding capacity of 603 mAh·g−1 at 0.2 A·g−1, superior to most original MXenes. Li+ storage kinetics analysis and density functional theory (DFT) simulations show that this optimized performance ensues from the more charge compensation during charge–discharge process, which enhances Faraday reaction compared with pure Mo2CTx. This vacancy manipulation provides an efficient way to realize MXene's potential as promising electrodes.


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Vacancy manipulating of molybdenum carbide MXenes to enhance Faraday reaction for high performance lithium-ion batteries

Show Author's information Xin Guo1,§Changda Wang1,§( )Wenjie Wang1Quan Zhou1Wenjie Xu1Pengjun Zhang1Shiqiang Wei1Yuyang Cao1Kefu Zhu1Zhanfeng Liu1Xiya Yang1Yixiu Wang1Xiaojun Wu2Li Song1Shuangming Chen1( )Xiaosong Liu1( )
National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230029, China
School of Chemistry and Material Sciences, University of Science and Technology of China, Hefei 230029, China

§ Xin Guo and Changda Wang contributed equally to this work.

Abstract

"Intrinsic" strategies for manipulating the local electronic structure and coordination environment of defect-regulated materials can optimize electrochemical storage performance. Nevertheless, the structure–activity relationship between defects and charge storage is ambiguous, which may be revealed by constructing highly ordered vacancy structures. Herein, we demonstrate molybdenum carbide MXene nanosheets with customized in-plane chemical ordered vacancies (Mo1.33CTx), by utilizing selective etching strategies. Synchrotron-based X-ray characterizations reveal that Mo atoms in Mo1.33CTx show increased average valence of +4.44 compared with the control Mo2CTx. Benefited from the introduced atomic active sites and high valence of Mo, Mo1.33CTx achieves an outstanding capacity of 603 mAh·g−1 at 0.2 A·g−1, superior to most original MXenes. Li+ storage kinetics analysis and density functional theory (DFT) simulations show that this optimized performance ensues from the more charge compensation during charge–discharge process, which enhances Faraday reaction compared with pure Mo2CTx. This vacancy manipulation provides an efficient way to realize MXene's potential as promising electrodes.

Keywords:

ordered vacancies, MXenes, X-ray absorption fine structure (XAFS), lithium-ion storage, mechanism
Received: 24 June 2022 Revised: 18 July 2022 Accepted: 19 July 2022 Published: 31 August 2022
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Publication history

Received: 24 June 2022
Revised: 18 July 2022
Accepted: 19 July 2022
Published: 31 August 2022

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© The Author(s) 2022. Published by Tsinghua University Press.

Acknowledgements

Acknowledgements

We acknowledge financial support from the National Key Research and Development Program of China (Nos. 2020YFA0405800 and 2019YFA0405601), the National Natural Science Foundation of China (NSFC) (Nos. U1932201 and U2032113), the Youth Innovation Promotion Association of CAS (No. 2022457), USTC Research Funds of the Double First-Class Initiative (No. YD2310002003), the Fundamental Research Funds for the Central Universities (Nos. WK2060000039 and WK2310000088), Institute of Energy, Hefei Comprehensive National Science Center, University Synergy Innovation Program of Anhui Province (No. GXXT-2020-002), Collaborative Innovation Program of Hefei Science Center, CAS (No. 2021HSC-CIP016). C. D. W. (No. 202006340190) acknowledge financial support from the China Scholarship Council (CSC). L. S. acknowledges support from the Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education). We thank the Beijing Synchrotron Radiation Facility (1W1B, BSRF), Hefei Synchrotron Radiation Facility (MCD-A and MCD-B Soochow Beamline for Energy Materials at NSRL), and the USTC Center for Micro and Nanoscale Research and Fabrication for help with the characterization.

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