LiClO4预氧化Ni0.8Co0.17Al0.03(OH)2提升锂离子电池的循环稳定性

Preoxidation of Ni0.8Co0.17Al0.03(OH)2 with LiClO4 to improve cycle stability of lithium-ion batteries

  • 摘要: 层状高镍正极材料(LiNi0.8Co0.17Al0.03O2)因为具有高的镍含量,相比于LiCoO2拥有更高的比容量和更低的成本,受到了大众的欢迎。然而,循环过程中容量的快速衰退阻碍了LiNi0.8Co0.17Al0.03O2的进一步商业化使用。其中,Li+/Ni2+混排现象是造成材料不良循环性能的主要原因之一。本文中,使用具有强氧化性的LiClO4对Ni0.8Co0.17Al0.03(OH)2前驱体进行预氧化处理。X射线衍射(XRD)测试和精修结果显示,LiClO4处理后的LiNi0.8Co0.17Al0.03O2(LiClO4-NCA)样品有着更低的Li+/Ni2+混排程度,这与X射线光电子能谱(XPS)测试得到的正极材料中Ni2+/Ni3+结果相一致。电化学测试结果显示,LiClO4-NCA相比于原始样品LiNi0.8Co0.17Al0.03O2(NCA)具有更优异的循环性能,1 C倍率循环100圈后,LiClO4-NCA的容量保持率(94.3%)明显高于NCA(82.4%)。LiClO4-NCA优异的电化学性能归因于LiClO4促进了材料中的Ni2+转化为Ni3+,减少了阳离子混排现象,保持了更完整的层状结构。因此,LiClO4对Ni0.8Co0.17Al0.03(OH)2前驱体进行预氧化处理可以改善材料中的Li+/Ni2+混排现象,优化层状高镍正极材料的循环稳定性。

     

    Abstract: Layered Ni-rich anode material (LiNi0.8Co0.17Al0.03O2) is welcomed by the public because of its high nickel content, higher specific capacity and lower cost than LiCoO2. However, the rapid capacity decline in the process of cycling prevents further commercial application of LiNi0.8Co0.17Al0.03O2. Among them, the mixing of Li+ /Ni2+ in Ni-rich anode materials is one of the main reasons for the poor cycle performance of materials. In this paper, LiNi0.8Co0.17Al0.03O2 precursor was preoxidized with highly oxidized LiClO4. The X-ray diffraction (XRD) and Rietveld refinement results show that the LiNi0.8Co0.17Al0.03O2 (LiClO4-NCA) sample after LiClO4 treatment has a lower Li+/Ni2+ mixing degree, which is consistent with the results of Ni2+/Ni3+ in the anode material tested by X-ray photoelectron spectroscopy (XPS). The electrochemical test results show that LiClO4-NCA has better cycling performance than the original sample LiNi0.8Co0.17Al0.03O2 (NCA). The capacity retention rate of LiClO4-NCA (94.3%) is significantly higher than that of NCA (82.4%) after 100 cycles of 1 C. The excellent electrochemical performance of LiClO4-NCA is attributed to the fact that LiClO4 promotes the conversion of Ni2+ into Ni3+ in the material, reducing cation mixing phenomenon and maintaining a more complete layered structure. Therefore, LiClO4 preoxidation of LiNi0.8Co0.17Al0.03O2 precursor can improve the mixing phenomenon of Li+/Ni2+ in the material and optimize the cycle stability of layered Ni-rich anode material.

     

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