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Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials

机译:含铁层状电池电极材料中可逆的从平坦到波纹的相变

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摘要

Layered sodium transition metal oxides of NaTMO2 (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO2. Here, a novel spontaneous TM layer rippling in the sodium ion battery cathode materials is reported, revealed by in situ X-ray diffraction, Cs-corrected scanning transmission electron microscopy, and density functional theory simulation, where the softening and distortion of FeO6 octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.
机译:NaTMO2的层状钠过渡金属氧化物(TM = 3d过渡金属)显示出将不同成分的Fe混合到TM层的独特能力,这在LiTMO2中不存在。在此,通过原位X射线衍射,Cs校正的扫描透射电子显微镜和密度泛函理论模拟(其中FeO6八面体共同软化和变形)揭示了钠离子电池正极材料中起伏的新型自发TM层。在高压下将平坦的TM平面驱动成波纹状,且层间距离不均匀。在这样的起伏阶段,Na离子的充电和放电采用不同的演化路径,从而导致异常的磁滞电压环路。重要的是,当放电超过一定的Na含量时,波纹的TM层将恢复平整,从而在随后的循环中具有这种结构演变的可逆性。

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