Hard-constraint physics-residual networks for hydrogen crossover prediction and high-pressure extrapolation in PEM water electrolysis

Abstract

Hydrogen crossover is a critical safety and efficiency constraint in high-pressure polymer electrolyte membrane water electrolysis (PEMWE), but accurate prediction remains difficult because data are limited, transport physics are strongly coupled, and industrial operation requires reliable extrapolation beyond observed conditions. This study develops a hard-constraint physics-residual network (PR-Net) for hydrogen crossover prediction in PEMWE and compares it with a purely data-driven neural network (NN) and a soft-constraint physics-informed neural network (PINN). PR-Net embeds Henry&#39;s, Fick&#39;s, and Faraday&#39;s laws as a deterministic backbone and learns only a residual correction for unmodelled nonlinear effects. The benchmark includes 184 observations from eight peer-reviewed sources across six membrane types, covering 1-200 bar, $25-85°C$, and $0.05-5.0 A cm^{-2}$. PR-Net achieves $R^2 = 99.57 \pm 0.16%$, with 9-fold lower prediction variability than NN and PINN. In pressure-axis extrapolation, PR-Net attains $R^2 = 94.02 \pm 0.92%$ at 200 bar, 2.5 times beyond the training pressure range, compared with $68.06 \pm 5.52%$ for PINN and $58.00 \pm 8.60%$ for NN (p < 0.001). Residual analysis indicates that the learned correction captures part of the high-pressure gas-phase non-ideality and recovers a transport-regime transition near $0.23 A cm^{-2}$ between Fickian diffusion-dominated and Faradaic production-dominated transport. With a computation time of $1.08 \pm 0.34 ms$ on low-power embedded hardware, PR-Net provides a practical framework for real-time crossover monitoring, adaptive process control, and safer high-pressure green-hydrogen operation.