Lithium-rich manganese-based transition metal oxide LiNiMnO (LNMO) can achieve high energy density due to the interaction of anionic redox kinetics in LiMnO. However, the irreversible release of oxygen and migration of Mn ions during deep de-lithiation disrupts its layer structure, leading to a decrease in voltage and capacity. Herein, we confine oxygen anion through Zr and Al co-doping. Combined analysis of structure refinement, XPS and XAS, the co-doped strategy effectively prohibits cation disordering of Li/Ni, inhibits the Jahn-Teller effect and reduces the transition metal (TM) and oxygen hybridization. As a result, the Zr and Al co-doping LNMO sample (ZA-LNMO) possesses a capacity retention of 92% after 100 cycles and 86% after 200 long-term cycles, much higher than the value of the undoped sample (79% for 100 cycles and 58% for 200 cycles). Even at the harsh conditions such as ultra-high current rate (10 C) or high temperature (60 °C), ZA-LNMO also maintains higher 70% retention after 200 cycles. Our findings provide an insight into the synergistic effect of cation co-doping and help to design layered oxides for future applications.

中文翻译：

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Zr-Al双掺杂限制氧阴离子稳定层状氧化物Li1.2Ni0.2Mn0.6O2

由于LiMnO中阴离子氧化还原动力学的相互作用，富锂锰基过渡金属氧化物LiNiMnO（LNMO）可以实现高能量密度。然而，深度脱锂过程中氧的不可逆释放和锰离子的迁移破坏了其层结构，导致电压和容量下降。在此，我们通过Zr和Al共掺杂来限制氧阴离子。结合结构细化、XPS和XAS分析，共掺杂策略有效地抑制了Li/Ni的阳离子无序化，抑制了Jahn-Teller效应并减少了过渡金属（TM）和氧杂化。结果表明，Zr和Al共掺杂的LNMO样品（ZA-LNMO）在100次循环后的容量保持率为92%，在200次长期循环后的容量保持率为86%，远高于未掺杂样品的容量保持率（79%） 100 个周期为 58%，200 个周期为 58%）。即使在超高电流倍率（10℃）或高温（60℃）等恶劣条件下，ZA-LNMO在200次循环后也能保持较高的70%保留率。我们的研究结果提供了对阳离子共掺杂协同效应的深入了解，并有助于设计用于未来应用的层状氧化物。