Lithium halide-based solid electrolytes have high Li⁺ conductivity and can be synthesized through low-temperature aqueous solution routes. While Li₃InCl₆ can be readily synthesized through dehydration, other analogous materials, such as Li₃YCl₆, cannot. This difference may be due to differences in H₂O coordination strength, which leads to partial hydrolysis to form YOCl. In this work, we followed and compared Li₃YCl₆ synthesis using three different methods using in situ neutron diffraction. The data revealed that forming an ammonium halide complex intermediate is essential in synthesizing Li₃YCl₆ from an aqueous solution. In carefully examining the Li₃YCl₆ products, we found that changes in local structure follow on to drive significant differences in ionic transport and Li⁺ diffusivity as determined through diffusion NMR measurements. These changes were ascribed to the change in the correlative transport of Li⁺. This work provides insight into the reaction mechanisms involved in synthesizing halide solid electrolytes and highlights the importance of considering their synthetic and processing conditions to optimize their performance in all-solid-state batteries.

中文翻译：

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通过合成过程中的配位控制和混合来调节氯化锂钇局部结构

卤化锂基固体电解质具有高Li ⁺电导率，可以通过低温水溶液路线合成。虽然Li ₃ InCl ₆可以通过脱水容易地合成，但其他类似材料，例如Li ₃ YCl ₆则不能。这种差异可能是由于H ₂ O配位强度的差异导致部分水解形成YOCl。在这项工作中，我们使用原位中子衍射跟踪并比较了使用三种不同方法的Li ₃ YCl ₆合成。数据表明，形成卤化铵络合物中间体对于从水溶液合成Li ₃ YCl ₆至关重要。在仔细检查 Li ₃ YCl ₆产品时，我们发现局部结构的变化会导致离子传输和 Li ⁺扩散率的显着差异（通过扩散 NMR 测量确定）。这些变化归因于Li ⁺相关传输的变化。这项工作提供了对合成卤化物固体电解质所涉及的反应机制的深入了解，并强调了考虑其合成和加工条件以优化其在全固态电池中的性能的重要性。