Fe-O-Ti异质界面工程对高熵氧化物电子结构及储锂动力学的调控作用

doi:10.15541/jim20260178

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Fe-O-Ti异质界面工程对高熵氧化物电子结构及储锂动力学的调控作用

肖彬, 朱浩然, 邹鹏, 吴刚, 谢泽林, 隋艳伟

中国矿业大学材料与物理学院,徐州 221116

收稿日期:2026-04-23 修回日期:2026-07-19
作者简介:肖彬, 副教授. E-mail: binxiao@cumt.edu.cn
基金资助:
国家重点研发计划(2024YFE0108500); 国家自然科学基金(52504345); 江苏省基础研究计划(BK20251657); 教育部基础学科和交叉学科突破计划(JYB2025XDXM308); 江苏省高校“青蓝工程”

Regulating Electronic Structure and Lithium-storage Kinetics of High-entropy Oxides via Fe-O-Ti Heterointerface Engineering

XIAO Bin, ZHU Haoran, ZOU Peng, WU Gang, XIE Zelin, SUI Yanwei

School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, China

Received:2026-04-23 Revised:2026-07-19
About author:XIAO Bin, associate professor. E-mail: binxiao@cumt.edu.cn
Supported by:
National Key R&D Program of China (2024YFE0108500); National Natural Science Foundation of China (52504345); Basic Research Program of Jiangsu (BK20251657); Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM308); Jiangsu Province Qinglan Project

摘要/Abstract

摘要： 高熵氧化物(HEOs)因组分可调、多阳离子协同氧化还原及丰富的缺陷化学特征,在锂离子电池负极领域展现出重要应用潜力,但其本征导电性不足和储锂动力学缓慢限制了实际应用。本研究采用高能球磨结合高温氧化-空气淬火方法构筑了具有紧密Fe-O-Ti异质界面的(FeZnCrMn)₃O₄/TiO₂复合材料。与以尖晶石高熵氧化物相为主的Ti引入型(FeTiZnCrMn)₃O₄和机械混合(FeZnCrMn)₃O₄-TiO₂对照样品相比,该异质结构表现出更优异的倍率性能和循环稳定性,在5 A·g^-1下仍可实现512.9 mAh·g^-1的放电比容量。(FeZnCrMn)₃O₄/TiO₂表面O1s X射线光电子能谱中氧空位相关组分相对峰面积占比为45%,表明异质界面形成可以调控表面缺陷环境。第一性原理计算表明,Fe-O-Ti界面键诱导Fe/Ti相关轨道在费米能级附近重新分布,并引发界面电荷重新分配,同时提高导带底附近的低能电子态密度。上述电子结构重构和缺陷调控共同改善界面电荷转移动力学与Li⁺传输行为,从而提升高倍率储锂性能。本研究为高熵氧化物负极的异质界面工程设计提供了参考。

关键词: 高熵氧化物, 异质界面工程, Fe-O-Ti键, 储锂动力学, 锂离子电池负极

Abstract: High-entropy oxides (HEOs) show great potential as anode materials for lithium-ion batteries owing to their compositional tunability, synergistic multication redox activity, and rich defect chemistry. However, their practical application is still limited by insufficient intrinsic conductivity and sluggish lithium-storage kinetics. In this work, a (FeZnCrMn)₃O₄/TiO₂ composite with tightly coupled Fe-O-Ti heterointerfaces was constructed via high-energy ball milling followed by high-temperature oxidation and air quenching. Compared with the Ti-incorporated (FeTiZnCrMn)₃O₄ control sample dominated by a spinel high-entropy oxide phase and the mechanically mixed (FeZnCrMn)₃O₄-TiO₂ control sample, the heterostructured composite exhibits superior rate capability and cycling stability, delivering a discharge capacity of 512.9 mAh·g^-1 at 5 A·g^-1. The relative peak-area ratio of oxygen-vacancy-related components in the surface O1s X-ray photoelectron spectrum of (FeZnCrMn)₃O₄/TiO₂ reaches 45%, indicating that the formation of heterointerfaces is accompanied by modulation of the surface defect environment. First-principles calculations demonstrate that Fe-O-Ti interfacial bonds induce redistribution of Fe/Ti-related orbitals near the Fermi level and interfacial charge rearrangement, while increasing the density of low-energy electronic states near the conduction-band minimum. The electronic structure reconstruction and defect modulation jointly improve interfacial charge-transfer kinetics and Li⁺ transport behavior, thereby enhancing high-rate lithium-storage performance. This work provides a reference for the heterointerface engineering of high-entropy oxide anodes.

Key words: high-entropy oxide, heterointerface engineering, Fe-O-Ti bond, lithium-storage kinetics, lithium-ion battery anodes

中图分类号:

O646

肖彬, 朱浩然, 邹鹏, 吴刚, 谢泽林, 隋艳伟. Fe-O-Ti异质界面工程对高熵氧化物电子结构及储锂动力学的调控作用[J]. 无机材料学报, DOI: 10.15541/jim20260178.

XIAO Bin, ZHU Haoran, ZOU Peng, WU Gang, XIE Zelin, SUI Yanwei. Regulating Electronic Structure and Lithium-storage Kinetics of High-entropy Oxides via Fe-O-Ti Heterointerface Engineering[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260178.

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Fe-O-Ti异质界面工程对高熵氧化物电子结构及储锂动力学的调控作用

Regulating Electronic Structure and Lithium-storage Kinetics of High-entropy Oxides via Fe-O-Ti Heterointerface Engineering

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