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

doi:10.6023/A26050161

摘要/Abstract

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 [P_x(Co_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)_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

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 [P_x(Co_0.2Fe_0.2Mn_0.2Ni_0.2Zn_0.2)_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

引用此文

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, doi: 10.6023/A26050161.

Xu Shibiao, Pan Meiyi, Wei Zhengbing, Yin Feilong, bao Mengfan, Hu Qianqian, Sun Junhao, Lin Na, Mao Aiqin. Metalloid phosphorus doping-regulated intrinsic defect engineering in high-entropy oxides: synergistically enhanced structural stability and reaction kinetics[J]. Acta Chimica Sinica, doi: 10.6023/A26050161.

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