Correlating Structural Disorder to Li+ Ion Transport in Li4–xGe1–xSbxS4 (0 ≤ x ≤ 0.2),Chemistry of Materials

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Correlating Structural Disorder to Li+ Ion Transport in Li4–xGe1–xSbxS4 (0 ≤ x ≤ 0.2)
Chemistry of Materials ( IF 7.2 ) Pub Date : 2022-06-09 , DOI: 10.1021/acs.chemmater.2c00608
Bianca Helm ₁ , Nicolò Minafra ₁ , Björn Wankmiller _{1,

2,

3} , Matthias T. Agne ₄ , Cheng Li ₅ , Anatoliy Senyshyn ₆ , Michael Ryan Hansen ₃ , Wolfgang G. Zeier _{1,

4}

Affiliation

Strong compositional influences are known to affect the ionic transport within the thio-LISICON family; however, a deeper understanding of the resulting structure–transport correlations has up until now been lacking. Employing a combination of high-resolution neutron diffraction, impedance spectroscopy, and nuclear magnetic resonance spectroscopy, together with bond valence site energy calculations and the maximum entropy method for determining the underlying Li⁺ scattering density distribution of a crystal structure, this work assesses the impact of the Li⁺ substructure and charge carrier density on the ionic transport within the Li_4–xGe_1–xSb_xS₄ substitution series. By incorporating Sb⁵⁺ into Li₄GeS₄, an anisometric expansion of the unit cell is observed. An additional Li⁺ position is found as soon as (SbS₄)^3– polyhedra are present, leading to a better local polyhedral connectivity and a higher disorder in the Li⁺ substructure. Here, we are able to relate structural disorder to an increase in configurational entropy, together with a 2 order-of-magnitude increase in ionic conductivity. This result reinforces the typically believed paradigm that structural disorder leads to improvements in ionic transport.

中文翻译：

将结构紊乱与 Li4–xGe1–xSbxS4 中的 Li+ 离子传输相关联 (0 ≤ x ≤ 0.2)

已知强烈的成分影响会影响硫代-LISICON 家族中的离子传输；然而，迄今为止，对由此产生的结构-运输相关性的深入了解一直缺乏。结合使用高分辨率中子衍射、阻抗谱和核磁共振谱，结合键价位能量计算和最大熵方法来确定晶体结构的潜在 Li ⁺散射密度分布，这项工作评估了影响Li ⁺子结构和电荷载流子密度对 Li _{4– x} Ge _{1– x} Sb _x S _{4内离子传输的影响}替代系列。通过将Sb ⁵⁺结合到Li ₄ GeS ₄中，观察到晶胞的不等轴膨胀。一旦存在 (SbS ₄ ) ^3-多面体，就会发现一个额外的 Li ⁺位置，从而导致更好的局部多面体连通性和更高的 Li ⁺子结构无序。在这里，我们能够将结构无序与构型熵的增加以及离子电导率的 2 个数量级增加联系起来。这一结果强化了通常认为的结构紊乱导致离子传输改善的范式。

更新日期：2022-06-09

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