高等学校化学学报

高等学校化学学报

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K/Mg/Al掺杂尖晶石型高熵氧化物负极的制备及储锂性能研究

尹飞龙1，潘美伊1，韦正兵1，徐世彪1，邵霞1，檀杰1,2，冒爱琴1,2   

  1. 1. 安徽工业大学材料科学与工程学院先进陶瓷研究中心 2. 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
  • 收稿日期:2026-05-13 修回日期:2026-07-08 网络首发:2026-07-12 发布日期:2026-07-12
  • 通讯作者: 冒爱琴 E-mail:maoaiqinmaq@163.com
  • 基金资助:
    安徽省高校自然科学研究重点项目(批准号: 2023AH051104)、氢电高效转化与固态存储安徽省重点实验室开放基金(批准号: ECSSHE2024KF05) 资助

K/Mg/Al-Doped Spinel High-Entropy Oxide Anodes: Preparation and Lithium Storage Performance

YIN Feilong1, PAN Meiyi1, WEI Zhengbing1, XU Shibiao1, SHAO Xia1, TAN Jie1,2, MAO Aiqin1,2*   

  1. 1.School of Materials Science and Engineering, Anhui University of Technology 2. Anhui Province Key Laboratory of Efficient Conversion and Solid-State Storage of Hydrogen & Electricity, Anhui University of Technology
  • Received:2026-05-13 Revised:2026-07-08 Online First:2026-07-12 Published:2026-07-12
  • Contact: MAO Ai-Qin E-mail:maoaiqinmaq@163.com
  • Supported by:
    Supported by the  University Natural Science Research Project of Anhui Province, China(No.2023AH051104) and the Open Fund of Anhui Province Key Laboratory of High-efficiency Hydrogen-electricity Conversion and Solid-state Storage, China(No.ECSSHE2024KF05)

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摘要： 通过溶液燃烧法及不同价态的非活性阳离子(K+、Mg2+和Al3+)掺杂策略，以无钴尖晶石型(Cr0.2Fe0.2Mn0.2Ni0.2Zn0.2)3O4 HEO为模型材料，成功制备了三种尖晶石型(KCrFeMnNiZn)3/6O4、(KMgCrFeMnNiZn)3/7O4和(KMgAlCrFeMnNiZn)3/8O4 HEO负极材料。测试结果表明，优化后的(KMgAlCrFeMnNiZn)3/8O4负极材料虽然理论比容量相较未掺杂的降低了17.3%，却有效遏制了循环前期的容量衰减并提高了长循环后的可逆比容量。在200 mA·g-1下可逆比容量逐步增加，第50圈可逆比容量较初始增长15%，较未掺杂样品提升51.3%；同时其长循环稳定性显著增强，300圈后比容量增至1300 mAh·g-1，较未掺杂样品提升19.5%。此外，该电极在3000 mA·g-1下的容量保持率(相对于100 mA·g-1)为33.2%。循环稳定性的提升归因于多元非活性阳离子掺杂产生的“旁观者效应”、晶胞收缩以及氧空位浓度降低；而倍率性能的增强得益于比表面积的增大、最可几孔径的优化以及适量的氧空位浓度，协同提高了赝电容贡献率和电子/Li+传输动力学。

关键词: 尖晶石型高熵氧化物, 负极材料, K/Mg/Al掺杂, 氧空位, 结构稳定性, 储锂性能

Abstract: By employing a solution combustion method and a doping strategy involving inactive cations with different valence states (K+, Mg2+, and Al3+), three spinel-type high-entropy oxide (HEO) anode materials, namely (KCrFeMnNiZn)3/6O4, (KMgCrFeMnNiZn)3/7O4, and (KMgAlCrFeMnNiZn)3/8O4, were successfully synthesized using a cobalt-free spinel (Cr0.2Fe0.2Mn0.2Ni0.2Zn0.2)3O4 HEO as a model material.Testing results demonstrate that although the optimized (KMgAlCrFeMnNiZn)3/8O4 anode material exhibits a 17.3% reduction in theoretical specific capacity compared to the undoped counterpart, it effectively suppresses the initial capacity fading during early cycles and improves the reversible specific capacity after long-term cycling. At 200 mA·g-1, the reversible specific capacity gradually increases, reaching a 15% enhancement at the 50th cycle relative to the initial value, and a 51.3% improvement compared to the undoped sample. Meanwhile, its long-term cycling stability is significantly enhanced, with the specific capacity increasing to 1300 mAh·g-1 after 300 cycles, representing a 19.5% improvement over the undoped material. In addition, the capacity retention of this electrode at 3000 mA·g-1(relative to that at 100 mA·g-1) is 33.2%.The enhanced cycling stability is attributed to the “spectator effect” induced by the multicomponent inactive cation doping, lattice contraction, and reduced oxygen vacancy concentration; while the enhanced rate performance benefits from the increased specific surface area, optimization of the most probable pore size, and an appropriate oxygen vacancy concentration, which synergistically improve the pseudocapacitive contribution and electron Li+ transport kinetics.

Key words: Spinel-type high-entropy oxide, Anode materials; K/Mg/Al doping, Oxygen vacancies, Structural stability, Lithium storage performance

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