反钙钛矿结构锂离子电池材料的第一性原理研究

  锂离子电池作为实现能源安全的关键环节，在可再生能源储存和电动汽车等领域中扮演着重要角色，开发更高能量密度的锂离子电池已成为科学研究的焦点。提升能量密度的主要技术路线，一是开发固态电池，二是开发高比能正极材料。作为新型的电池材料体系，具有反钙钛矿结构的电池材料包含固态电解质与正极材料，在提升电池能量密度方面，展现出较强的应用前景。探索反钙钛矿结构电池材料的电化学性质，深入理解其作用机理，构建材料结构与性能之间的关联，将极大地推动反钙钛矿结构电池材料开发进程。本文我们主要采用第一性原理计算方法，研究具有反钙钛矿结构的固态电解质与正极材料的反应机理，探索性能优化的策略，具体研究内容如下：

  设计层状反钙钛矿固态电解质，可有效的提升反钙钛矿固态电解质的锂离子电导率。然而层状反钙钛矿结构固态电解质Li₇O₂Br₃由于实验上未获得纯相，诸多性质不清晰。我们采用第一性原理计算方法系统评估了Li₇O₂Br₃的基础物理性质。计算结果表明，Li₇O₂Br₃展现出动力学稳定性，并具有5.83 eV的宽带隙，说明其具有良好的电子绝缘性。相比于立方反钙钛矿Li₃OBr，层状反钙钛矿Li₇O₂Br₃展现出更优异的力学延展性。在锂离子输运机制研究方面，我们发现在Li₇O₂Br₃的层边缘，锂的声子软化作用导致迁移势垒降低。此外，研究发现LiBr缺陷可有效促进锂离子的迁移。根据压力-温度-吉布斯（PTG）自由能相图的预测，施加高温高压条件更利于合成Li₇O₂Br₃。

  反钙钛矿正极材料Li₂FeSO具有容量高，成本低的优势，然而较低的电压平台（~2 V）限制了其应用，其锂传输性能也有待优化。针对此问题，我们系统计算了反钙钛矿正极材料的电压、电子导电性及其脱锂过程中的体积变化，梳理出了反钙钛矿正极材料电压调控的物理图像。计算结果表明，替换S元素为Se或Te会导致Li₂FeSO和Li₂MnSO的电压降低。对于Li₂TMSO（TM = Cu，Ni，Co，Fe，V，Cr，Ti），TM由Ti → Ni过程中，电压随之下降。此过程与TM-3d电子轨道能级的下移密切相关：在TM-3d的能级与S-3p轨道能级的能级差大时，电压由TM-3d轨道决定；当能级差小时，S-3p则会参与反应。此外，非活性元素Mg的掺杂能使更深能级的电子参与反应，进而提升电压。在提升锂离子输运性质方面，我们给出了掺杂优化电子导电性和锂离子传输性能的改性策略。计算结果表明，在TM（TM = Fe，Mn）位掺杂Na或K，以及在S位掺杂F或Cl，可以有效的降低锂迁移势垒，促进锂扩散。

  另一方面，理解Li₂FeSO脱嵌锂机制是提升其电化学性能的关键所在。我们构建了含有多种Li_xFe_6-xO八面体局域构型的超胞，模拟其脱锂过程，解释晶格变化的机理。结果表明，富Fe八面体中的锂会优先脱出，贫Fe八面体中的锂较后脱出。脱锂过程中Fe²⁺转变为Fe³⁺，Fe-d_xy轨道由d_xy(↑↓)占据转变为d_xy(↑)，d_xy轨道对S的排斥减小，导致Fe位置发生偏移。Fe将靠近两个S原子而远离另外两个S原子，引发S阴离子框架的局部收缩和局部扩大。在脱锂的中后期，S阴离子框架的局部扩大效应占优，导致该阶段Li_xFeSO体积扩大。为进一步优化反钙钛矿正极材料容量，我们发现LiFeSO继续脱锂时主要由S贡献反应电子。因此，我们采用Fe位掺杂Ti的方法，在LiFeSO继续脱锂过程中提供额外的电子，抑制S参与反应，提升脱锂深度，并增加能量密度。计算表明，Li₂Ti_0.25Fe_0.75SO在脱出1.25 Li情况下理论能量密度比Li₂FeSO高9%。

  综上所述，本论文通过第一性原理计算，从微观的原子和电子尺度出发，对新型反钙钛矿电池材料进行了系统的基础物理性质和反应机理研究。以上研究可为新型反钙钛矿电池材料的应用和改性提供理论基础和指导，加速高能量密度锂电池体系的开发。

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