The space-charge layer (SCL) phenomenon in Li⁺-ion-conducting solid-state electrolytes (SSEs) is gaining much interest in different fields of solid-state ionics. Not only do SCLs influence charge-transfer resistance in all-solid-state batteries but also are analogous to their electronic counterpart in semiconductors; they could be used for Li⁺-ionic devices. However, the rather “elusive” nature of these layers, which occur on the nanometer scale and with only small changes in concentrations, makes them hard to fully characterize experimentally. Theoretical considerations based on either electrochemical or thermodynamic models are limited due to missing physical, chemical, and electrochemical parameters. In this work, we use kinetic Monte Carlo (kMC) simulations with a small set of input parameters to model the spatial extent of the SCLs. The predictive power of the kMC model is demonstrated by finding a critical range for each parameter in which the space-charge layer growth is significant and must be considered in electrochemical and ionic devices. The time evolution of the charge redistribution is investigated, showing that the SCLs form within 500 ms after applying a bias potential.

中文翻译：

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固态电解质中空间电荷层的建模：动力学蒙特卡罗方法及其验证

^{Li +}离子导电固态电解质 (SSE) 中的空间电荷层 (SCL) 现象在固态离子的不同领域引起了广泛关注。SCL 不仅影响全固态电池中的电荷转移电阻，而且类似于半导体中的电子对应物。它们可以用于 Li ⁺-离子设备。然而，这些层相当“难以捉摸”的性质，发生在纳米尺度上，浓度变化很小，这使得它们很难在实验上完全表征。由于缺少物理、化学和电化学参数，基于电化学或热力学模型的理论考虑受到限制。在这项工作中，我们使用具有一小组输入参数的动力学蒙特卡罗 (kMC) 模拟来模拟 SCL 的空间范围。kMC 模型的预测能力通过为每个参数找到一个临界范围来证明，在该范围内空间电荷层生长是显着的，并且在电化学和离子设备中必须考虑。研究了电荷再分布的时间演化，表明 SCL 在施加偏置电位后 500 ms 内形成。