Nonlinear Quantum Effects Drive Grotthuss Proton Conduction in Structured Electrolytes Based on Deep Eutectic Solvents

ABSTRACT Structured electrolytes based on deep eutectic solvents (DESs) face electrochemical limitations of vehicular diffusion due to high viscosities often leading to low conductivities. Here, we demonstrate that the inverse relationship between viscosity and conductivity in DESs can be circumvented by leveraging their hydrogen bonding networks for Grotthuss proton transport. Using DESs comprising imidazole and levulinic acid, we show that the existence of extended hydrogen‐bonded chains coupled with rapid reorientation of protonated imidazoles result in enhanced Grotthuss proton diffusion in these concentrated hydrogen‐bonded electrolyte systems. Key machine‐learning driven simulations – crucially incorporating nuclear quantum effects (NQEs) – validate our experimental findings, which classical simulations fail to capture. This study demonstrates that NQEs promote imidazole protonation, catalyze the hydrogen‐bonded chain formation, and influence chain reorientation, resulting in enhanced dynamics surpassing classical predictions in structured electrolytes. While the conclusions are drawn here for a particular imidazole/acid system, they are expected to apply broadly to protic DESs that support chain‐like structures and exploit Grotthuss diffusion as the primary charge‐transport mechanism.