To explore the complex correlation between local structure and properties in the alkali chlorides ternary system, simulations were systematically conducted for 11 different (Li, Na, K) Cl compositions from 900 K to 1200 K as the fundamental study of magnesium chloride electrolysis. For the ternary system, the density was calculated across the full composition and database was established. Furthermore, the structure simulation results revealed that the coordination of Li-Cl pair tended to be a distorted tetrahedron and the Na-Cl and K-Cl pairs tended to be an octahedron. The prediction of the properties was compared with available experiments and extrapolated analytical data, the deviations are acceptable. The temperature had no significant effects on the local structure and thermal conductivity. The results also showed that the Tosi−Fumi potential predicted positive temperature dependence of self-diffusion coefficients and ionic conductivity, and negative temperature dependence of the viscosity. In addition, the correlation between the local structure and transport properties was explored. The hydrodynamic radius of Li⁺ and K⁺ is similar in the ternary system, it can be found that whilst the K⁺ ion diffuses as an atomic species, the Li⁺ ion carries at least some of its coordinating Cl⁻ ions in the diffusion process, giving the diffusing species a larger effective size than the bare ion.

为了探索碱金属氯化物三元系统中局部结构与性能之间的复杂关系，系统地模拟了900 K至1200 K的11种不同的（Li，Na，K）Cl组成，以此作为氯化镁电解的基础研究。对于三元系统，计算整个组合物的密度并建立数据库。此外，结构模拟结果表明，Li-Cl对的配位倾向于为扭曲的四面体，而Na-Cl和K-Cl对的配位倾向于为八面体。将性能的预测与可用的实验和推断的分析数据进行比较，偏差是可以接受的。温度对局部结构和热导率没有显着影响。结果还表明，Tosi-Fumi电势预测了自扩散系数和离子电导率的正温度依赖性，以及粘度的负温度依赖性。此外，还探讨了局部结构与运输性质之间的相关性。锂的流体力学半径⁺和K ⁺中的三元体系相似，可以发现，当K个⁺离子扩散作为原子种，栗⁺离子携带至少某些其协调的Cl ^-离子中的扩散过程，使扩散物质比裸离子更大的有效尺寸。