Wang Yanfang, Wang Hongzhi, Huang Yongcong, Li Yingzhi, Li Zongrun, Makepeace Joshua W, Liu Quanbing, Zhang Fucai, Allan Phoebe K, Lu Zhouguang
Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China.
School of Chemistry, University of Birmingham, Birmingham, B15 2TT, U.K.
J Phys Chem Lett. 2024 May 23;15(20):5359-5365. doi: 10.1021/acs.jpclett.4c00748. Epub 2024 May 10.
Lithium ruthenium oxide (LiRuO) is an archetypal lithium rich cathode material (LRCM) with both cation and anion redox reactions (ARRs). Commonly, the instability of oxygen redox activities has been regarded as the root cause of its performance degradation in long-term operation. However, we find that not triggering ARRs does not improve and even worsens its cyclability due to the detrimental strain accumulation induced by Ru redox activities. To solve this problem, we demonstrate that F-doping in LiRuO can alter its preferential orientation and buffer interlayer repulsion upon Ru redox, both of which can mitigate the strain accumulation along the -axis and improve its structural stability. This work highlights the importance of optimizing cation redox reactions in LRCMs and provides a new perspective for their rational design.
氧化钌锂(LiRuO)是一种典型的富锂正极材料(LRCM),具有阳离子和阴离子氧化还原反应(ARR)。通常,氧氧化还原活性的不稳定性被认为是其在长期运行中性能退化的根本原因。然而,我们发现不触发ARR并不会改善甚至会恶化其循环性能,这是由于Ru氧化还原活性引起的有害应变积累所致。为了解决这个问题,我们证明在LiRuO中进行F掺杂可以改变其择优取向并缓冲Ru氧化还原时的层间排斥力,这两者都可以减轻沿c轴的应变积累并提高其结构稳定性。这项工作突出了优化LRCM中阳离子氧化还原反应的重要性,并为其合理设计提供了新的视角。