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Ab initio study of the stabilities of and mechanism of superionic transport in lithium-rich antiperovskites

机译：从头开始研究富含锂的钙钛矿中超离子运输的稳定性及其机理

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摘要

Recently, a family of halogen-based Li-rich antiperovskites were synthesized [J. Am. Chem. Soc. 134, 15042 (2012)], and the measured superionic conductivity makes these materials promising candidates as solid electrolytes for applications in Li-ion and Li-air batteries. This discovery raises several pressing issues on the fundamental physics concerning the thermodynamic and electrochemical stability of the synthesized materials and the mechanism of the observed superionic Li~+ transport. Here, we study the reported antiperovskites Li_3OCl, Li_3OBr, and their mixed compounds using first-principles density functional theory and molecular dynamics simulations. Our calculations show that these materials are thermodynamically metastable. Their large electronic band gaps and chemical stability against electrodes suggest the excellent electrochemical performance, which bodes well for the use in potentially harsh working conditions in practical battery applications. The calculated low activation enthalpy for Li-ion migration well below the crystal melting temperature and superionic transport near the Li sublattice melting state explain the experimentally observed phenomena. Our study identifies mobile Li vacancies and anion disorder as the primary driving mechanisms for superionic Li~+ conductivity in the antiperovskites. This work unveils essential working principles of the Li-rich antiperovskites, which are crucial to further exploration, development, and application of these and other charge-inverted materials with tailored properties.
机译：最近，合成了一系列基于卤素的富含锂的抗钙钛矿[J．上午。化学Soc。 134，15042（2012）]，并且测得的超离子电导率使这些材料有望成为用于锂离子和锂空气电池的固体电解质的候选材料。这一发现在基本物理方面引起了一些紧迫的问题，这些问题涉及合成材料的热力学和电化学稳定性以及观察到的超离子Li〜+传输的机理。在这里，我们使用第一性原理密度泛函理论和分子动力学模拟研究了报道的抗钙钛矿Li_3OCl，Li_3OBr及其混合化合物。我们的计算表明，这些材料是热力学亚稳态的。它们的大电子带隙和对电极的化学稳定性表明其优异的电化学性能，这预示着在实际电池应用中潜在的苛刻工作条件下使用。计算得出的锂离子迁移的低活化焓远低于晶体熔融温度，而超离子在Li亚晶格熔融态附近的迁移解释了实验观察到的现象。我们的研究确定了移动锂空位和阴离子障碍是抗钙钛矿中超离子Li〜+电导率的主要驱动机制。这项工作揭示了富含锂的抗钙钛矿的基本工作原理，这些原理对于进一步探索，开发和应用这些以及其他具有定制性能的电荷反转材料至关重要。

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  • 来源
    《Physical review》 |2013年第13期|134303.1-134303.8|共8页
  • 作者

    Yi Zhang; Yusheng Zhao; Changfeng Chen;

  • 作者单位

    Department of Physics and High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, USA;

    Department of Physics and High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, USA;

    Department of Physics and High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, USA;

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  • 正文语种 eng
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  • 关键词

    lithium-ion batteries; chemical thermodynamics;

    机译：锂离子电池;化学热力学;

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