Identification of Local Overpotentials and Their Spatial Distributions in Polymer Electrolyte Water Electrolyzers
Authors: Roy Anirban , Roenning Frida H , Aaron Douglas S , Mench Matthew M 
Published: August 2024

Polymer electrolyte water electrolyzers (PEWEs) are pivotal in the transition to a clean energy economy, promising green and efficient hydrogen production. Understanding the complexities of overpotentials within PEWEs is crucial for optimizing their performance and efficiency1. For PEWEs to attain the highest possible system efficiency, considering a specific material set and operating parameters, meticulous design is imperative. The goal is to achieve a high reaction rate that is not only optimal but also uniform across the entire active surface area of the electrodes. This uniformity should ideally be maintained with minimal sensitivity to variations in operating conditions.
This study focuses on the contribution of different overpotential categories and reveals their spatial variations through in-situ analysis to understand and overcome the issues caused by non-uniformity in reaction. Employing a segmented cell and printed circuit board (PCB) approach2, current density distribution (CDD) and distributed area-specific resistance (DASR) measurements are obtained, enabling a detailed examination of the mass transport overpotentials (as shown in Figure 1). Typically, in the fuel cell community, modeling mass transport limitations is thought of as diffusion-limited transport3. In the anode porous transport layer (PTL), oxygen accumulation (i.e. product transport limitation) can cause membrane dry-out and an increase in ASR4. The experimental results elucidate the intricate relationship between ohmic and mass transport losses, emphasizing the deep coupling induced by the two-phase nature of the system. Figure 1 shows that, as mass transport limitation grows, the highest increase in overpotential comes from mass transport-coupled ohmic losses. Beyond conventional diffusion limited mass transport losses, bubble dynamics significantly impact local hydration and ASR, highlighting the need for a holistic approach in device optimization5.
This research contributes to the understanding of PEWE dynamics, providing a basis for informed engineering decisions. By unraveling the intricate interdependencies between overpotentials, this work empowers the efficient utilization of expensive catalyst materials. Moreover, it offers insights into mitigating the challenges associated with bubble removal, accomplishing this with lower pumping requirements that scale non-linearly. These insights enrich both theoretical understanding and are paramount for enhancing system efficiency and economic viability of PEWEs, thereby advancing the prospect of sustainable hydrogen production.

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Figure 1