35 MPa 高压直产氢 PEM 水电解压力对开路电压的影响机理与建模研究

Mechanism and Modeling of Pressure Effects on the Open-circuit Voltage of 35 MPa High-pressure PEM Water Electrolysis for Direct Hydrogen Production

  • 摘要: 针对超高压运行下电压变化机理尚不清晰的问题,探讨了压力对PEM电解槽开路电压的影响。首先,基于能斯特方程推导了开路电压 (Open-circuit voltage, OCV) 与压力的关系;然后,在不同温度 (40 ℃、60 ℃、80 ℃) 和阴阳两极反应压力 (0.1 MPa、3.5 MPa、35 MPa)下开展极化曲线测试,分析电解压力对电压变化的规律;最后,对比实验得到的平均电压增量与理论电压增量,提出了与温度有关的经验修正系数\gamma ,并建立二次多项式经验模型。结果表明,压力升高使极化曲线整体上移,且电压增量与压力比呈对数关系;此外,温度升高会使电压水平整体降低。修正模型有效弥合了实验与理论的偏差,拟合优度R2=0.93195。在35 MPa下进行的200 h 恒电流运行实验表明高压下电解槽运行稳定,平均产氢电耗为4.04 (kW·h)/Nm3;同时,高压运行还能显著降低接触电阻老化率。研究结果揭示了超高压运行对开路电压的作用机制,为高压直产氢系统的工况设计与能效提升提供了参考依据。

     

    Abstract: To address the unclear mechanism of voltage variation under ultra-high-pressure operation, this study investigates the effect of pressure on the open-circuit voltage(OCV) of PEM electrolyzers. First, the relationship between OCV and pressure is derived based on the Nernst equation. Then, polarization curve tests are conducted at different temperatures(40 ℃, 60 ℃, 80 ℃) and anodic/cathodic pressures(0.1 MPa, 3.5 MPa, 35 MPa) to analyze the effect of electrolysis pressure on voltage variation. Finally, by comparing the experimental average voltage increment with the theoretical prediction, a temperature-dependent empirical correction coefficient (γ) is proposed, and a quadratic polynomial empirical model is established. The results show that increasing pressure shifts the polarization curve upward, and the voltage increment exhibits a logarithmic relationship with the pressure ratio; in contrast, increasing temperature lowers the overall voltage level. The correction model effectively reduced the deviation between experiment and theory, achieving a goodness of fit of R2=0.93195. A 200 hours constant-current operation at 35 MPa demonstrated stable electrolyzer performance, with an average hydrogen production energy consumption of 4.04 (kW·h)/Nm3; moreover, high-pressure operation significantly reduced the degradation rate of contact resistance. These findings elucidate the mechanism of OCV response under ultra-high-pressure operation and provide theoretical and experimental reference for the operating condition design and efficiency improvement of high-pressure direct hydrogen production systems.

     

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