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Cage-confinement synthesis of MoC nanoclusers as efficient sulfiphilic and lithiophilic regulator for superior Li–S batteries

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Abstract

High-energy-density Li-S batteries are subjected to serious sulfur deactivation and short cycle lifetime caused by undesirable polysulfide shuttle effect and frantic lithium dendrite formation. In this work, a controllable cage-confinement strategy to fabricate molybdenum carbide (MoC) nanoclusters as a high-efficient sulfiphilic and lithiophilic regulator to mitigate the formidable issues of Li-S batteries is demonstrated. The sub-2 nm MoC nanoclusters not only guarantee robust chemisorption and fast electrocatalytic conversion of polysulfides to enhance the sulfur electrochemistry, but also homogenize Li+ flux to suppress the lithium dendrite growth. As a consequence, the MoC-modified separator endows the batteries with boosted reaction kinetics, promoted sulfur utilization, and improved cycling stability. A reversible capacity of 701 mAh·g−1 at a high rate of 5.0C and a small decay rate of 0.076% per cycle at 1.0C over 600 cycles are achieved. This study offers a rational route for design and synthesis of bifunctional nanoclusers with both sulfiphilicity and lithiophilicity for high-performance Li-S batteries.

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摘要

高比能锂硫电池因其多硫化物穿梭效应和锂枝晶的问题导致活性物质快速损失且循环稳定性差。本研究报道了一种可控的笼式限域策略来制备碳化钼（MoC）纳米团簇，并将其用作高效的亲硫性和亲锂性调节器以解决上述问题。MoC纳米团簇的尺寸在2 nm以下，对多硫化物具有较强的化学吸附以及快速的电催化转化能力，提高了硫正极的电化学性能。此外，该纳米团簇还有利于均匀Li+通量，从而抑制了锂枝晶的生长。因此，基于MoC团簇修饰的隔膜能够有效提高锂硫电池的反应动力学，显著提升了活性硫的电化学利用率及其循环稳定性。电池在5 C的高倍率下实现了701 mAh·g-1的可逆比容量，同时在1 C@600次循环过程中的衰减率低至0.076%每圈。这项研究为设计和合成用于高性能锂硫电池的亲硫/亲锂特性的双功能纳米团簇提供了新的途径。

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Acknowledgements

This study was financially supported by the research funds from the National Natural Science Foundation of China (No. 52272239), the Fundamental Research Funds for the Central Universities (Nos. D5000210894 and 3102019JC005) and the Analytical & Testing Center of Northwestern Polytechnical University for TEM analysis.

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  1. State Key Laboratory of Solidification Processing, Center for Nano Energy Materials, School of Materials Science and Engineering, Northwestern Polytechnical University and Shaanxi Joint Laboratory of Graphene (NPU), Xi’an, 710072, China

    Xing-Yuan Zhang, Mei-Na Lei, Shan Tian & Jian-Gan Wang

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Jian-Gan Wang is an editorial board member for Rare Metals and was not involved in the editorial review or the decision to publish this article. The authors declare that they have no conflict of interest.

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Zhang, XY., Lei, MN., Tian, S. et al. Cage-confinement synthesis of MoC nanoclusers as efficient sulfiphilic and lithiophilic regulator for superior Li–S batteries. Rare Met. 43, 624–634 (2024). https://doi.org/10.1007/s12598-023-02455-1

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