Zr-MOF衍生ZrO2的晶相调控及其对单晶NCM的掺杂改性
Phase Control of Zr-MOF-Derived ZrO2 for Structural Modification of Single-Crystal NCM Electrodes
摘要: 为制备晶型可控、粒径分布均匀的纳米氧化锆(ZrO2)，本研究构建了一套以经典Zr-MOF——UiO-66为前驱体的二次烧结(前驱体煅烧 + 高温热处理)策略，实现了纳米ZrO2的可控制备，并初步探索了不同晶型纳米ZrO2对单晶NCM正极材料掺杂效果的影响。研究结果表明，采用UiO-66作为前驱体制备出的纳米ZrO2保留了前驱体的形貌特征，且晶体边缘清晰、平均粒径小、粒径分布均匀(Span = 0.83)。在对单晶NCM掺杂改性方面，ZrO2掺杂后材料镍锂混排加剧、层状结构有序度降低，不同晶型间的首次电化学性能未见显著差异。晶型可控且粒径分布均匀的纳米ZrO2制备方案可为推动锂离子电池三元正极材料优化改性策略提供参考。
Abstract: The performance enhancement of Li-ion battery cathodes, particularly the NCM ternary material, fundamentally relies on the stability and structural integrity of the active material. Although ZrO2 is widely recognized as a critical additive for improving cathode stability, synthesizing ZrO2 with precise crystal phase control, uniform particle size, and narrow size distribution remains a significant challenge. To address this gap, we developed a secondary sintering strategy utilizing the classic Zr-MOF precursor, UiO-66, enabling the controlled preparation of nano-ZrO2. This process involves the sequential steps of precursor calcination and high-temperature annealing, enabling the controlled preparation of nanostructured ZrO2. Characterization revealed that the resulting ZrO2 nanoparticles successfully retain the original mesoporous morphology of the MOF precursor, while simultaneously exhibiting sharp crystalline edges, ultra-small average particle size, and a remarkably narrow size distribution (Span = 0.83). Furthermore, we preliminarily explored the influence of different ZrO2 crystal phases on the doping effect of single-crystal NCM cathode materials. After ZrO2 doping, Ni/Li mixing was aggravated and the layered structural ordering decreased, while the initial electrochemical performance showed no significant difference among different crystal phases. In conclusion, the synthesis strategy for nano-ZrO2 with controllable crystal phase and uniform particle size distribution provides a reference for promoting the optimization of modification strategies for Li-ion battery ternary cathode materials.
文章引用：翟淑媛, 韩明阳, 刘昌文, 黄佳鑫, 马兆池, 廖立. Zr-MOF衍生ZrO2的晶相调控及其对单晶NCM的掺杂改性[J]. 材料科学, 2026, 16(10): 87-98. https://doi.org/10.12677/ms.2026.1610193

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