西北工业大学王俊杰团队近日研究了用于无枝晶锌阳极的具有双功能亲锌和疏水特性的杂阴离子卤化TiBTx-MBene保护层。这一研究成果于2025年5月13日发表在《德国应用化学》杂志上。

二维（2D）六方过渡金属硼化物（h-MBenes）是2D材料的新兴成员，显示出作为金属阳极保护层的巨大潜力。然而，通过湿法蚀刻合成的传统MBenes在化学合成过程中引入了大量含氧的末端，具有疏锌性和亲水性，导致严重的枝晶生长动力学并损害电极性能。 

研究组报告了一种新型的杂卤素TiBTX（TX=Cl和I）h-MBenes，通过卤素半径异构化策略，实现了精确的混合卤素官能化，从而创造了一个超高亲锌和疏水的微环境。与单I端接相比，混合卤素TiBTX表现出显著增强的亲锌性，并具有有序的Zn²⁺吸附，这归因于较大半径I离子的不对称诱导效应。同时，-Cl部分起到保护屏障的作用，减轻了水性电解质中锌阳极的水腐蚀。 

值得注意的是，双功能TiBTx-31层（TiBI_0.32Cl_0.13）展现出卓越的电化学性能，其循环寿命超过2000小时，平均库仑效率达到99.86%。此外TiBTx-31@Zn||NVO全袋电池在100次循环中保持95.3%的容量保持率。这项工作通过定制卤素端接，突出了界面工程中创新的卤素半径异构化方法，为高性能h-MBenes基储能器件的开发提供了新的见解。

附：英文原文

Title: Heteroanionic Halogenated TiBTx MBene Protective Layer with Dual-Functional Zincophilic and Hydrophobic Characteristics for Dendrite-Free Zinc Anode

Author: Qing Shen, Jinming Wang, Zhouru He, Wangqin Fu, Edison Huixiang Ang, Junjie Wang

Issue&Volume: 2025-05-13

Abstract: Two-dimensional (2D) hexagonal transition metal borides (h-MBenes), emerging members of 2D materials, demonstrate significant potential as protective layers for metal anodes. However, conventional MBenes synthesized by wet etching have massive oxygen-containing terminations imported during chemical synthesis process, with zincophobic and hydrophilic, resulting severe dendrite growth kinetics and compromising electrode performance. In this study, we report a novel hetero-halogen TiBTX (TX = Cl and I) h-MBenes through a halogen-radius-isomerization strategy, enabling precise mixed-halogen functionalization to create an ultrahigh zincophilic and hydrophobic microenvironment. Compared to single -I terminations, the mixed-halogen TiBTX exhibits significantly enhanced zincophilicity with ordered Zn2+ adsorption, attributed to the asymmetry-inductive effect of the larger-radius -I ions. Simultaneously, the -Cl moieties serve as a protective barrier, mitigating water-induced corrosion of the Zn anode in aqueous electrolytes. Notably, the dual-functional TiBTx-31 layer (TiBI0.32Cl0.13) demonstrates exceptional electrochemical performance, achieving a prolonged cycling life exceeding 2000 hours an impressive average coulombic efficiency of 99.86%. Furthermore, the TiBTx-31@Zn||NVO full pouch cell maintains 95.3% capacity retention over 100 cycles. This work highlights the innovative halogen-radius-isomerization approach for interfacial engineering by tailoring halogen terminations, offering new insights for the development of high-performance h-MBenes-based energy storage devices.

DOI: 10.1002/anie.202507504

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202507504