Halide perovskites, known for their tunable and exceptional optoelectronic properties, have been extensively explored for photovoltaics, light-emitting diodes, photodetectors, and memristors. With solar cell efficiencies closing on theoretical limits, stabilization of perovskite devices—especially via control of the ionic activity within the device—is a research gap that needs to be addressed before its commercialization. Solar cell stability is directly linked to ionic defects, and their effective passivation is essential for curbing ionic migration and associated deleterious effects. However, techniques to quantify and directly observe ionic migration are limited by the soft ionic lattice nature of the perovskite as well as its mixed ionic-electronic conductivity. This review examines both theoretical and experimental approaches to understand intrinsic and extrinsic ionic motion in halide perovskites at the material and device level. In addition to elemental and molecular analysis techniques that directly identify the ion in motion, spectroscopy techniques that measure properties associated with local stoichiometry changes have also been deployed. Measurement artifacts, strategies to mitigate their occurrence, as well as ways to differentiate electronic and ionic components related to specific techniques, are evaluated. Strict environmental control during measurement is highlighted due to perovskite’s sensitivity to external factors such as humidity, light, electric field, and heat.

卤化物钙钛矿以其可调谐和卓越的光电特性而闻名，已在光伏、发光二极管、光电探测器和忆阻器中得到广泛探索。随着太阳能电池效率接近理论极限，钙钛矿器件的稳定性——特别是通过控制器件内的离子活性——是一个在商业化之前需要解决的研究空白。太阳能电池的稳定性与离子缺陷直接相关，其有效钝化对于抑制离子迁移和相关的有害影响至关重要。然而，量化和直接观察离子迁移的技术受到钙钛矿的软离子晶格性质及其混合离子电子电导率的限制。本综述研究了理论和实验方法，以了解卤化物钙钛矿在材料和器件水平上的内在和外在离子运动。除了直接识别运动离子的元素和分子分析技术之外，还部署了测量与局部化学计量变化相关的特性的光谱技术。对测量伪影、减轻其发生的策略以及区分与特定技术相关的电子和离子组件的方法进行了评估。由于钙钛矿对湿度、光、电场和热等外部因素的敏感性，测量过程中严格的环境控制尤为突出。