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Impact of phosphorus structural position on the electrochemical enhancement of phosphorus doped LiMn2O4
Electrochimica Acta ( IF 5.5 ) Pub Date : 2020-01-17 , DOI: 10.1016/j.electacta.2020.135712
Renier Arabolla Rodríguez , Luciano A. Montoro , Manuel Ávila Santos , Nelcy Della Santina Mohallem , Yodalgis Mosqueda Laffita , Eduardo L. Pérez-Cappe

Nanostructures of phosphorus doped and undoped LiMn2O4 have been obtained through the thermal decomposition of different citrate precursors. The oxides have been characterized by XRD, XPS, 7Li-NMR-MAS, STEM and electrochemical tests in aqueous electrolyte. XPS showed that no pyrophosphate species were formed during the doping process. The position of the phosphorus in the LiMn2O4 nanostructure were elucidated on both samples through analyses of STEM images and structural refinement using the Rietveld method. These analyses allowed to set the P in a 48f position with coordinates (1/8, 1/8, 0.338) at the crystalline structure of the LiMn2O4 spinel. Electrochemical tests corroborated the improvement of electrochemical properties of the oxide when phosphorus is used as dopant. XRD measurements on cycled electrodes showed the inhibition of segregated collateral phases during the cycling process. That allows to propose an explanation of the achieved advantages of doping the lithium manganese oxide spinel structure on the ground of the phosphorous position in the LiMn2O4 crystalline cell.



中文翻译:

磷结构位置对掺磷LiMn 2 O 4电化学增强的影响

通过不同柠檬酸盐前体的热分解,获得了掺磷和不掺磷的LiMn 2 O 4的纳米结构。通过XRD,XPS,7 Li-NMR-MAS,STEM和在水性电解质中的电化学测试对氧化物进行了表征。XPS显示在掺杂过程中没有形成焦磷酸盐。通过对STEM图像的分析和使用Rietveld方法对结构进行细化,可以阐明两个样品中LiMn 2 O 4纳米结构中磷的位置。这些分析允许将Li设置在LiMn 2 O 4晶体结构的48f位置,坐标为(1/8,1/8,0.338)。尖晶石。当使用磷作为掺杂剂时,电化学测试证实了氧化物电化学性能的改善。在循环电极上的XRD测量表明,在循环过程中,偏析的副相被抑制。这允许提出对在LiMn 2 O 4晶胞中磷位置的基础上掺杂锂锰氧化物尖晶石结构的已实现优点的解释。

更新日期:2020-01-17
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