A Unified Multiscale Framework for Simulating Electrochemical Gas Evolving Reactions

Abstract

The presence of gas bubbles in electrochemical systems, such as water-splitting, significantly increases overpotential and diminishes energy efficiency. High-fidelity simulation holds significant promise to gain mechanistic understanding of bubble dynamics and guide high-performance electrolytic cell design. However, the extreme length scales involved into electrochemical gas evolving systems, from sub-nanometer dictated by the electrical double layer (EDL) to a few centimeters featured by the electrolytic cell, have posed a huge challenge to enable sufficient numerical accuracy and superior computational efficiency. As a result, state-of-the-art numerical approaches either can only simulate a nanoscale computational domain or neglect the electrochemical kinetics within the EDL, impeding an in-depth understanding of how bubbles could intervene with the electrochemical process.In this work, we demonstrate a full-field simulation approach of electrochemical gas evolving reactions that can capture the electrochemical kinetics of the EDL in a centimeter-scale electrolytical cell with the presence of micro-to-millimeter scale bubbles. To resolve all characteristic length scales, the EDL is geometrically decoupled from the electrolytical cell but physically coupled with the bulk electrolyte and gas bubble through a quasi-1D treatment. As a result, the Nernst-Planck-Poisson-Boltzmann model can be rigorously solved in both the EDL and the rest of the electrolytical cell with highly affordable computational cost. Taking hydrogen evolution reaction as an example, we validated our approach by comparing with a variety of existing numerical and experimental results. For the first time, the impact of bubbles on the increase of overpotential observed in experiments can be quantitatively confirmed through numerical simulation. More notably, compared to state-of-the-art high-fidelity simulations, our approach exhibits a remarkable computational efficiency, which reduced the computational time by a factor of 100,000. This work provides a viable solution to simulate electrochemical gas evolving reactions with highly desirable numerical accuracy and unprecedented computational efficiency, which can serve as an effective tool to understand bubble dynamics and guide the design of next-generation electrolytical cells.