Vertical Diffusion of Ions within Single Particles during Electrochemical Charging

Determining the trajectory of ionic transport and diffusion within single electroactive nanomaterials is critical for understanding the charging kinetics and capacity fading associated with ion batteries, with implications for rational design of excellent-performance electrode materials. While the horizontal pathway of mass transport has been feasibly investigated by optical superlocalization methods and electron microscopes, determination on the vertical trajectory has proven a more challenging task. Herein, we developed dual-angle total internal reflection microscopy by simultaneously introducing different angle-dependent illumination depths to trace the optical centroid shifts of nano-objects in the vertical dimension. We first demonstrated the proof of concept by resolving the vertical moving trails of a nanosphere doing Brownian motion and subsequently explored the picture of mass transport in the interior of single Prussian blue (PB) particles during electrochemical cycling. The results indicated that the vertical centroids of single PB particles remained unchanged when ions were inserted or extracted, suggesting an outside-in ionic transport pathway instead of bottom-up trajectory that one would intuitively expect.