Revealing the Impact of Space-Charge Layers on the Li-Ion Transport in All-Solid-State Batteries

Abstract

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
_xV
₂O
₅ and Li
_1.5Al
_0.5Ge
_1.5(PO
₃)
₄ (LAGP), by changing the Li
_xV
₂O
₅ 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.