LiClO_(4)预氧化Ni_(0.8)Co_(0.17)Al_(0.03)(OH)_(2)提升锂离子电池的循环稳定性  

Preoxidation of Ni_(0.8)Co_(0.17)Al_(0.03)(OH)_(2)with LiClO_(4)to improve cycle stability of lithium-ion batteries

作　　者：赖福林 王玉琴 马全新 周翎飞 杨梦倩 钟盛文[1,2] Sydorov Dmytro LAI Fulin;WANG Yuqin;MA Quanxin;ZHOU Lingfei;YANG Mengqian;ZHONG Shengwen;Sydorov DMYTRO(Faculty of Materials Metallurgy and Chemistry,Jiangxi University of Science and Technology,Ganzhou 341000,Jiangxi,China;Jiangxi Key Laboratory of Power Battery and Materials,Jiangxi University of Science and Technology,Ganzhou 341000,Jiangxi,China;Far East Battery,FEB Research Institute,Yichun 336000,Jiangxi,China;Institute of Bioorganic Chemistry and Petrochemistry,National Academy of Sciences of Ukraine,Kyiv 01030,Ukraine)

机构地区：[1]江西理工大学材料冶金化学学部,江西赣州341000 [2]江西理工大学江西省动力电池及材料重点实验室,江西赣州341000 [3]江西理工大学宜春锂电新能源产业研究院,江西宜春336000 [4]乌克兰国家科学院生物有机化学与岩石化学研究所,基辅01030

出　　处：《有色金属科学与工程》2023年第1期57-66,共10页Nonferrous Metals Science and Engineering

基　　金：国家自然科学基金资助项目(51964017)。

摘　　要：层状高镍正极材料(LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2))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LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2)的进一步商业化使用。其中,Li+/Ni^(2+)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LiClO_(4)对Ni_(0.8)Co_(0.17)Al_(0.03)(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,LiClO_(4)处理后的LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2)(LiClO4-NCA)样品有着更低的Li+/Ni^(2+)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Ni^(2+)/Ni^(3+)结果相一致。电化学测试结果显示,LiClO_(4)-NCA相比于原始样品LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2)(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%)。LiClO_(4)-NCA优异的电化学性能归因于LiClO_(4)促进了材料中的Ni^(2+)转化为Ni^(3+),减少了阳离子混排现象,保持了更完整的层状结构。因此,LiClO_(4)对Ni_(0.8)Co_(0.17)Al_(0.03)(OH)_(2)前驱体进行预氧化处理可以改善材料中的Li+/Ni^(2+)混排现象,优化层状高镍正极材料的循环稳定性。Layered Ni-rich anode material(LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2))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 LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2).Among them,the mixing of Li+/Ni^(2+)in Ni-rich anode materials is one of the main reasons for the poor cycle performance of materials.In this paper,LiNi0.8Co0.17Al0.03O2precursor was preoxidized with highly oxidized LiClO4.The X-ray diffraction(XRD)and Rietveld refinement results show that the LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2)(LiClO_(4)-NCA)sample after LiClO4treatment has a lower Li+/Ni^(2+)mixing degree,which is consistent with the results of Ni^(2+)/Ni^(3+)in the anode material tested by X-ray photoelectron spectroscopy(XPS).The electrochemical test results show that LiClO_(4)-NCA has better cycling performance than the original sample LiNi_(0.8)Co_(0.17)Al_(0.03)O_(2)(NCA).The capacity retention rate of LiClO_(4)-NCA(94.3%)is significantly higher than that of NCA(82.4%)after 100 cycles of 1 C.The excellent electrochemical performance of LiClO_(4)-NCA is attributed to the fact that LiClO_(4)promotes the conversion of Ni^(2+)into Ni^(3+)in the material,reducing cation mixing phenomenon and maintaining a more complete layered structure.Therefore,LiClO_(4)preoxidation of LiNi_(0.8)Co0.17Al0.03O2precursor can improve the mixing phenomenon of Li+/Ni^(2+)in the material and optimize the cycle stability of layered Ni-rich anode material.

关 键 词：层状高镍正极材料 预氧化改性 Li+/Ni2+混排 循环稳定性 

分 类 号：TM912.6[电气工程—电力电子与电力传动] TQ152[化学工程—电化学工业]