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0 26050161

DOI: https://doi.org/10.6023/A26050161

研究论文

类金属磷掺杂调控高熵氧化物本征缺陷:协同提升结构稳定性与反应动力学

  • 徐世彪 ,
  • 潘美伊 ,
  • 韦正兵 ,
  • 尹飞龙 ,
  • 鲍梦凡 ,
  • 胡倩倩 ,
  • 孙君豪 ,
  • 林娜 ,
  • 冒爱琴
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  • a安徽工业大学 先进陶瓷研究中心 马鞍山 243032;
    b安徽工业大学 氢电高效转化与固态存储安徽省重点实验室 马鞍山 243032

收稿日期: 2026-05-13

  网络出版日期: 2026-08-17

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Metalloid phosphorus doping-regulated intrinsic defect engineering in high-entropy oxides: synergistically enhanced structural stability and reaction kinetics

  • Xu Shibiao ,
  • Pan Meiyi ,
  • Wei Zhengbing ,
  • Yin Feilong ,
  • bao Mengfan ,
  • Hu Qianqian ,
  • Sun Junhao ,
  • Lin Na ,
  • Mao Aiqin
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  • aSchool of Materials Science and Engineering, Anhui University of Technology, Ma’ anshan, Anhui 243032;
    bAnhui Province Key Laboratory of Efficient Conversion and Solid-State Storage of Hydrogen & Electricity, Anhui University of Technology, Ma’ anshan, Anhui 243032

Received date: 2026-05-13

  Online published: 2026-08-17

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摘要

高熵氧化物(High-entropy oxides, HEO)因具有高熵效应、多主元协同效应和可调组成, 在锂离子电池负极材料领域展现出良好的应用前景. 然而, 尖晶石型高熵氧化物在储锂过程中仍存在电子/离子传输动力学缓慢等问题, 限制了其电化学性能的进一步提升. 本研究采用类金属P掺杂策略, 通过溶液燃烧法制备了尖晶石型HEO [Px(Co0.2Fe0.2Mn0.2Ni0.2Zn0.2)1-x]3O4 (x=0, 0.05, 0.10, 0.15, 0.2, 记为Px-HEO), 并研究了P掺杂对材料结构、缺陷特征及储锂性能的影响. 结果表明, P掺杂形成的P-O及P-O-M共价键促进了氧空位生成, 并通过电荷补偿使部分Mn3+转化为Mn4+, 有效减弱Jahn-Teller效应, 提升了结构稳定性. 其中, P0.1-HEO样品具有较高的比表面积(60.85 m2·g-1)和丰富的表面氧空位(50.1%), 显著改善了电子/离子传输动力学. P0.1-HEO电极在200 mA·g-1下循环250圈后仍保持1711 mAh·g-1的可逆容量, 在3000 mA·g-1下仍可提供385 mAh·g-1的可逆容量. 该研究为通过类金属P掺杂协同优化高熵氧化物的结构稳定性和储锂性能提供了实验基础.

关键词： 高熵氧化物; 磷掺杂; 氧空位; 结构稳定性; 反应动力学

本文引用格式

徐世彪 , 潘美伊 , 韦正兵 , 尹飞龙 , 鲍梦凡 , 胡倩倩 , 孙君豪 , 林娜 , 冒爱琴 . 类金属磷掺杂调控高熵氧化物本征缺陷:协同提升结构稳定性与反应动力学[J]. 化学学报, 0 : 26050161 . DOI: 10.6023/A26050161

Abstract

High-entropy oxides (HEOs) have attracted considerable attention as promising anode materials for lithium-ion batteries (LIBs) owing to their high-entropy effect, multicomponent synergistic effect, and highly tunable compositions. However, spinel-structured HEOs still suffer from sluggish electron/ion transport kinetics during lithiation and delithiation, which limits their further electrochemical performance enhancement. In this work, a metalloid phosphorus (P) doping strategy was employed to synthesize spinel-structured [Px(Co0.2Fe0.2Mn0.2Ni0.2Zn0.2)1-x]3O4 (x = 0, 0.05, 0.10, 0.15, 0.2, Px-HEO) via a solution combustion synthesis (SCS) method, and the effects of P doping on the crystal structure, defect characteristics, and lithium-storage properties were systematically investigated. The results demonstrate that the formation of covalent P-O and P-O-M bonds promotes the generation of oxygen vacancies and induces the partial conversion of Mn3+ to Mn4+ through charge compensation, thereby effectively suppressing the Jahn-Teller effect and enhancing the structural stability of the spinel framework. Among all samples, P0.1-HEO exhibits a relatively high specific surface area (60.85 m2·g-1) and abundant surface oxygen vacancies (50.1%), which significantly improve electron/ion transport kinetics. As a result, the P0.1-HEO electrode delivers a high reversible capacity of 1711 mAh·g-1 after 250 cycles at 200 mA·g-1 and retains a reversible capacity of 385 mAh·g-1 even at a high current density of 3000 mA·g-1. This study provides an experimental basis for synergistically optimizing the structural stability and lithium-storage performance of high-entropy oxide anodes through metalloid P doping.

Key words： High-entropy oxides; Phosphorus doping; Oxygen vacancies; Structural stability; Reaction kinetics

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