The influence of space-charge layers on the ionic charge transport over cathode-solid electrolyte interfaces in all-solid-state batteries remains unclear because of the difficulty to unravel it from other contributions to the ion transport over the interfaces. Here, we reveal the effect of the space-charge layers by systematically tuning the space-charge layer on and off between Li_xV₂O₅ and Li_1.5Al_0.5Ge_1.5(PO₃)₄ (LAGP), by changing the Li_xV₂O₅ potential and selectively measuring the ion transport over the interface by two-dimensional (2D) NMR exchange. The activation energy is demonstrated to be 0.315 eV for lithium-ion exchange over the space-charge-free interface, which increases dramatically to 0.515 eV for the interface with a space-charge layer. Comparison with a space-charge model indicates that the charge distribution due to the space-charge layer is responsible for the increased interface resistance. Thereby, the present work provides selective and quantitative insight into the effect of space-charge layers over electrode-electrolyte interfaces on ionic transport.

在全固态电池中，空间电荷层对离子-电荷在阴极-固体电解质界面上的迁移的影响仍然不清楚，因为很难将其从其他对离子在界面上迁移的贡献中解脱出来。在这里，我们通过改变Li来系统地调节Li _x V ₂ O ₅和Li _1.5 Al _0.5 Ge _1.5（PO ₃）₄（LAGP）之间的空间电荷层的开和关，从而揭示了空间电荷层的作用。_x V ₂ O ₅电位，并通过二维（2D）NMR交换选择性地测量离子在界面上的传输。事实证明，在无空间电荷的界面上进行锂离子交换的活化能为0.315 eV，对于与空间电荷层的界面而言，活化能急剧增加至0.515 eV。与空间电荷模型的比较表明，由于空间电荷层引起的电荷分布是导致界面电阻增加的原因。因此，本工作提供了对电极-电解质界面上的空间电荷层对离子迁移的影响的选择性和定量研究。