Olivine-type phosphates have attracted considerable attention as cathode materials for rechargeable lithium batteries. Here, the defect and ion transport properties of the mixed-metal material LiFe_(0.5)Mn_(0.5)PO4 are investigated by atomistic modeling methods. The intrinsic defect type with the lowest energy is the cation antisite defect, in which Li and Fe/Mn ions exchange positions. As found in the LiFePO4 material, lithium ion diffusion in the mixed-metal system occurs down the i-axis channels following a curved path. Migration energies for Fe and Mn antisite cations on Li sites suggest that Mn defects would impede bulk Li mobility in LiFe_(0.5)Mn_(0.5)PO4 to a greater extent than Fe antisite defects in LiFePO4. Association or binding energies for various defect clusters comprised of lithium vacancies and/or antisite cations are examined.
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机译:橄榄石型磷酸盐作为可充电锂电池的正极材料引起了人们的广泛关注。本文采用原子建模方法研究了混合金属材料LiFe_(0.5)Mn_(0.5)PO4的缺陷和离子输运性能.能量最低的本征缺陷类型是阳离子反位缺陷,其中Li和Fe/Mn离子交换位置。正如在 LiFePO4 材料中发现的那样,混合金属系统中的锂离子扩散沿着弯曲的路径沿 i 轴通道向下发生。Li位点上Fe和Mn反位点阳离子的迁移能表明,Mn缺陷对Li在LiFe_(0.5)Mn_(0.5)PO4中的体迁移率的阻碍程度大于Li反位点缺陷在LiFePO4中的迁移率。研究了由锂空位和/或反定点阳离子组成的各种缺陷簇的缔合能或结合能。
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