Probing Kinetics of Water-in-Salt Aqueous Batteries with Thick Porous Electrodes

Aqueous electrochemical systems suffer from a low energy density due to a small voltage window of water (1.23 V). Using thicker electrodes to increase the energy density and highly concentrated "water-in-salt" (WIS) electrolytes to extend the voltage range can be a promising solution. However, thicker electrodes produce longer diffusion pathways across the electrode. The highly concentrated salts in WIS electrolytes alter the physicochemical properties which determine the transport behaviors of electrolytes. Understanding how these factors interplay to drive complex transport phenomena in WIS batteries with thick electrodes via deterministic analysis on the rate-limiting factors and kinetics is critical to enhance the rate-performance in these batteries. In this work, a multimodal approach-Raman tomography, operando X-ray diffraction refinement, and synchrotron X-ray 3D spectroscopic imaging-was used to investigate the chemical heterogeneity in LiV3O8-LiMn2O4 WIS batteries with thick porous electrodes cycled under different rates. The multimodal results indicate that the ionic diffusion in the electrolyte is the primary rate-limiting factor. This study highlights the importance of fundamentally understanding the electrochemically coupled transport phenomena in determining the rate-limiting factor of thick porous WIS batteries, thus leading to a design strategy for 3D morphology of thick electrodes for high-rate-performance aqueous batteries.