Ma Dehua, Wang Jiawei, Wang Haifeng, Qian Guibao, Zhou Xingjie, Pei Zhengqing, Zheng Kexin, Wang Qian, Lu Ju
College of Materials and Metallurgy, Guizhou University, Guiyang 550025, China.
Guizhou Key Laboratory of Metallurgical Engineering and Process Energy Conservation, Guiyang 550025, China.
Nanomaterials (Basel). 2025 Mar 11;15(6):429. doi: 10.3390/nano15060429.
In this study, pure and Mg/Cr co-doped Ni/Mn bimetallic oxides were used as precursors to synthesize pristine and doped LNMO samples. The LNMO samples exhibited the same crystal structure as the precursors. XRD analysis confirmed the successful synthesis of LNMO cathode materials using Ni/Mn bimetallic oxides as precursors. FTIR and Raman spectroscopy reveal that Mg/Cr co-doping promotes the formation of the Fd3m disordered phase, effectively reducing electrochemical polarization and charge transfer resistance. Furthermore, co-doping significantly lowers the Mn content on the LNMO surface, thereby mitigating Mn dissolution. Significantly, Mg/Cr co-doping induces the emergence of high-surface-energy {100} crystal facets in LNMO grains, which promote lithium-ion transport and, finally, enhance rate capability and cycling performance. Electrochemical analysis indicates that the initial discharge capacities of LNMO-0, LNMO-0.005, LNMO-0.010, and LNMO-0.015 were 126.4, 125.3, 145.3, and 138.2 mAh·g, respectively, with capacity retention rates of 82.45%, 82.93%, 83.32%, and 82.08% after 100 cycles. Furthermore, the impedance of LNMO-0.010 prior to cycling was 97.38 Ω, representing a 14.35% reduction compared to the pristine sample. After 100 cycles, its impedance was only 58.61% of that of the pristine sample, highlighting its superior rate capability and cycling stability. As far as we know, studies on the synthesis of LNMO cathode materials via the design of Ni/Mn bimetallic oxides remain limited. Accordingly, this work provides an innovative approach for the preparation and modification of LNMO cathode materials. The investigation of Ni/Mn bimetallic oxides as precursors, combined with co-doping by Mg and Cr, for the synthesis of high-performance LiNiMnO (LNMO) aims to provide insights into improving rate capability, cycling stability, reducing impedance, and enhancing capacity retention.
在本研究中,纯的和Mg/Cr共掺杂的Ni/Mn双金属氧化物被用作前驱体来合成原始的和掺杂的LNMO样品。LNMO样品呈现出与前驱体相同的晶体结构。XRD分析证实了以Ni/Mn双金属氧化物为前驱体成功合成了LNMO正极材料。FTIR和拉曼光谱表明,Mg/Cr共掺杂促进了Fd3m无序相的形成,有效降低了电化学极化和电荷转移电阻。此外,共掺杂显著降低了LNMO表面的Mn含量,从而减轻了Mn的溶解。值得注意的是,Mg/Cr共掺杂在LNMO晶粒中诱导出高表面能的{100}晶面,这促进了锂离子传输,并最终提高了倍率性能和循环性能。电化学分析表明,LNMO-0、LNMO-0.005、LNMO-0.010和LNMO-0.015的初始放电容量分别为126.4、125.3、145.3和138.2 mAh·g,在100次循环后的容量保持率分别为82.45%、82.93%、83.32%和82.08%。此外,LNMO-0.010循环前的阻抗为97.38 Ω,与原始样品相比降低了14.35%。在100次循环后,其阻抗仅为原始样品的58.61%,突出了其优异的倍率性能和循环稳定性。据我们所知,通过设计Ni/Mn双金属氧化物合成LNMO正极材料的研究仍然有限。因此,这项工作为LNMO正极材料的制备和改性提供了一种创新方法。研究以Ni/Mn双金属氧化物为前驱体,并结合Mg和Cr的共掺杂来合成高性能LiNiMnO(LNMO),旨在为提高倍率性能、循环稳定性、降低阻抗和提高容量保持率提供见解。