LAUSR

Significance The high-impedance non-Faraday electric field restricts rapid ion transfer at the interface, resulting in solid-state batteries (SSBs) exhibiting limited C rates (<1 C). Most research on the non-Faradaic electric field of SSBs faces challenges of relaxation-induced ion distribution self-equilibration and perspective limitations. Here, we developed an operando Cryo-transmission X-ray microscopy (Cryo-TXM) technique that facilitates the segmented dissection of the non-Faradaic electric field generation and elimination processes, elucidating that the irreversible local electric field is the main cause of high polarization during late charging. This approach advances the capture and resolution of transient opacity signals inside SSBs and provides theoretical guidance for the design of fast-charging SSBs.