Tracking Ion Transport in Nanochannels via Transient Single‐Particle Imaging

The transport behavior of ions in the nanopores has an important impact on the performance of the electrochemical devices. Although the classical Transmission‐Line (TL) model has long been used to describe ion transport in pores, the boundary conditions for the applicability of the TL model remain controversial. Here, we investigated the transport kinetics of different ions, within nanochannels of different lengths, by using transient single‐particle imaging with temporal resolution up to microseconds. We found that the ion transport kinetics within short nanochannels may deviate significantly from the TL model. The reason is that the ion transport under nanoconfinement is composed of multi basic stages, and the kinetics differ much under different stage domination. With the shortening of nanochannels, the electrical double layer (EDL) formation would become the “rate‐determining step” and dominate the apparent ion kinetics. Our results imply that using the TL model directly and treating the in‐pore mobility as an unchanged parameter to estimate the ion transport kinetics in short nanopores/nanochannels may lead to orders of magnitude bias. These findings may advance the understanding of the nanoconfined ion transport and promote the related applications. In situ tracking of ion transport kinetics under nanoconfinement was achieved by transient single‐particle imaging method. The results implied that the ion transport kinetics in long nanochannels is dominated by the in‐pore diffusion, while in short nanopores/nanochannels is governed by electrical double layer (EDL) formation. The local ion accumulation within EDL changes the ion mobility and then affects the apparent ion transport kinetics.