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Double-confined nanoheterostructure Sb/Sb2S3@Ti3C2Tx@C toward ultra-stable Li-/Na-ion batteries

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Abstract

Antimony-based materials with high capacities and moderate potentials are promising anodes for lithium-/sodium-ion batteries. However, their tremendous volume expansion and inferior conductivity lead to poor structural stability and sluggish reaction kinetics. Herein, a double-confined nanoheterostructure Sb/Sb2S3@Ti3C2Tx@C has been fabricated through a solvothermal method followed by low-temperature heat treatment. The dual protection of “MXene” and “carbon” can better accommodate the volume expansion of Sb/Sb2S3. The strong covalent bond (Ti–S, Ti–O–Sb, C–O–Sb) can firmly integrate Sb-based material with Ti3C2Tx and carbon, which significantly improves the structure stability. In addition, the carbon layer can restrain the oxidation of MXenes, and the nano-Sb/Sb2S3 can facilitate electron/ion transport and suppress the restacking of MXenes. The heterogeneous interface between Sb and Sb2S3 can further promote interfacial charge transfer. The MXene-Sb/Sb2S3@C-1 with the optimal Sb content shows high specific capacities, comparable rate properties and ultra-stable cycling performances (250 mAh·g−1 after 2500 cycles at 1 A·g−1 for sodium-ion batteries). Ex situ X-ray diffractometer (XRD) test reveals the storage mechanism including the conversion and alloying process of MXene-Sb/Sb2S3@C-1. Cyclic voltammetry (CV) test results demonstrate that the pseudocapacitance behavior is dominant in MXene-Sb/Sb2S3@C-1, especially at large current. This design paves the way for exploring high-performance alloy-based/conversion-type anode for energy storage devices.

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摘要

高容量, 电位适中的锑基材料是极具发展前景的锂/钠离子电池负极材料。但由于其体积膨胀大、导电性差，导致结构稳定性差、反应动力学迟钝。本文采用溶剂热结合低温热处理法制备了双限域纳米异质结构Sb/Sb2S3@Ti3C2Tx@C。“MXene”和“碳”的双重保护可以更好地容纳Sb/Sb2S3的体积膨胀。强共价键(Ti–S, Ti–O–Sb, C–O–Sb)能将Sb基材料与Ti3C2Tx和碳紧密结合，显著提高了结构稳定性。此外，碳层可以抑制MXenes的氧化，纳米Sb/Sb2S3可以促进电子/离子的传递，抑制MXenes的重堆积。Sb与Sb2S3之间的非均相界面进一步促进了界面电荷的转移。具有最佳Sb含量的MXene-Sb/Sb2S3@C-1具有较高的比容量、优异的倍率性能和超稳定的循环性能(钠离子电池在1 A·g-1下循环2500次后可达到250 mAh·g−1)。非原位XRD测试揭示了MXene-Sb/Sb2S3@C-1的储能机理，包括转化和合金化过程。循环伏安测试结果表, MXene-Sb/Sb2S3@C-1的赝电容行为占主导地位，特别是在大电流条件下。本研究为开发高性能合金/转换型负极材料提供了一定的理论指导和技术支持。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 52071073, 52177208, 52171202 and 51971055), Hebei Province “333 talent project” (No. C20221012), the Natural Science Foundation of Hebei Province (No. E2020501004), the Fundamental Research Funds for the Central Universities (No. N2123032) and the Science and Technology Project of Hebei Education Department (No. BJK2023005).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Northeastern University, Shenyang, 110819, China

    Dan Wang, Qun Ma, Huan He, Zhi-Yuan Wang, Run-Guo Zheng & Yan-Guo Liu

  2. School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao, 066004, China

    Dan Wang, Qun Ma, Huan He, Zhi-Yuan Wang, Run-Guo Zheng, Hong-Yu Sun & Yan-Guo Liu

  3. Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province, Qinhuangdao, 066004, China

    Dan Wang, Zhi-Yuan Wang, Run-Guo Zheng & Yan-Guo Liu

  4. Department of Physics and Oxide Research Center, Hankuk University of Foreign Studies, Yongin, 17035, Korea

    Chun-Li Liu

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  1. Dan Wang
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Wang, D., Ma, Q., He, H. et al. Double-confined nanoheterostructure Sb/Sb2S3@Ti3C2Tx@C toward ultra-stable Li-/Na-ion batteries. Rare Met. 43, 2067–2079 (2024). https://doi.org/10.1007/s12598-023-02550-3

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