脉冲电压下二维PEMWE模型的制氢特性仿真研究

doi:10.11949/0438-1157.20241433

化工学报 ›› 2025, Vol. 76 ›› Issue (7): 3521-3530.DOI: 10.11949/0438-1157.20241433

脉冲电压下二维PEMWE模型的制氢特性仿真研究

陈佳祥¹(), 周伟¹(), 张学伟¹, 王丽杰², 黄玉明¹, 于洋¹, 孙苗婷¹, 李宛静¹, 袁骏舒¹, 张宏博², 孟晓晓¹, 高继慧¹, 赵广播¹

^1.哈尔滨工业大学能源科学与工程学院，黑龙江哈尔滨 150001
^2.中国大唐集团科技创新有限公司，河北雄安 071799

收稿日期:2024-12-11 修回日期:2025-03-28 出版日期:2025-07-25 发布日期:2025-08-13
通讯作者: 周伟
作者简介:陈佳祥（2001—），男，硕士研究生，23S102147@stu.hit.edu.cn
基金资助:
国家自然科学基金项目(52476192);国家自然科学基金项目(52106237);中国大唐集团科技创新有限公司2024年第一批科技项目(DTKC-2024-20610)

Simulation study on the hydrogen production performance of a two-dimensional PEMWE model under pulsed voltage

Jiaxiang CHEN¹(), Wei ZHOU¹(), Xuewei ZHANG¹, Lijie WANG², Yuming HUANG¹, Yang YU¹, Miaoting SUN¹, Wanjing LI¹, Junshu YUAN¹, Hongbo ZHANG², Xiaoxiao MENG¹, Jihui GAO¹, Guangbo ZHAO¹

^1.School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China
^2.China Datang Technology Innovation Co. , Ltd. , Xiong’an 071799, Hebei, China

Received:2024-12-11 Revised:2025-03-28 Online:2025-07-25 Published:2025-08-13
Contact: Wei ZHOU

摘要/Abstract

摘要：

可再生能源电解水制氢是未来获取氢能的重要途径。为理解脉冲供电条件下质子交换膜电解水（PEMWE）体系的瞬态响应特性，结合电化学、气液两相流、固体和流体传热模块建立了二维PEMWE模型。数值模拟结果表明：施加脉冲方波电压可产生比恒电位更大的电流密度，在1.75 V、0.2 Hz、50%占空比条件下产氢速率为0.628 ml/（min·cm²）；增大电压到2 V、频率降低为0.025 Hz时出现最大产氢速率1.59 ml/（min·cm²）；不同电压匹配的最佳产氢频率不同。20%~90%占空比范围的仿真结果表明，50%和60%占空比的产氢速率比恒电位高，最佳占空比为50%。改变输入的脉冲电压波形，发现三角波的产氢速率最低，这可能与三角波的有效电解时间较短有关。

关键词: 制氢, 瞬态响应, 数值模拟, 产氢速率, 频率, 占空比, 波形

Abstract:

Hydrogen production from renewable energy water electrolysis is an important way to obtain hydrogen energy in the future. To investigate the transient response characteristics of proton exchange membrane water electrolysis (PEMWE) under pulsed power conditions, a two-dimensional PEMWE model was developed, incorporating electrochemical processes, gas-liquid two-phase flow, and solid-fluid heat transfer modules. Numerical simulations reveal that applying a pulsed square-wave voltage generates higher current densities compared to constant potential conditions, achieving a hydrogen production rate of 0.628 ml/(min·cm²) at 1.75 V, 0.2 Hz and a 50% duty cycle. Increasing the voltage to 2 V and reducing the frequency to 0.025 Hz yields the maximum hydrogen production rate of 1.59 ml/(min·cm²), with optimal frequencies varying for different voltage levels. Simulations across duty cycles ranging from 20% to 90% indicate that hydrogen production rates at 50% and 60% duty cycles exceed those under constant potential conditions, with 50% identified as the optimal duty cycle. By changing the input pulse voltage waveform, it is found that the triangular wave has the lowest hydrogen production rate, which may be related to the shorter effective electrolysis time of the triangular wave.

Key words: hydrogen production, transient response, numerical simulation, hydrogen evolution rate, frequency, duty cycle, waveform

中图分类号:

TQ 426

陈佳祥, 周伟, 张学伟, 王丽杰, 黄玉明, 于洋, 孙苗婷, 李宛静, 袁骏舒, 张宏博, 孟晓晓, 高继慧, 赵广播. 脉冲电压下二维PEMWE模型的制氢特性仿真研究[J]. 化工学报, 2025, 76(7): 3521-3530.

Jiaxiang CHEN, Wei ZHOU, Xuewei ZHANG, Lijie WANG, Yuming HUANG, Yang YU, Miaoting SUN, Wanjing LI, Junshu YUAN, Hongbo ZHANG, Xiaoxiao MENG, Jihui GAO, Guangbo ZHAO. Simulation study on the hydrogen production performance of a two-dimensional PEMWE model under pulsed voltage[J]. CIESC Journal, 2025, 76(7): 3521-3530.

图/表 10

图1 PEMWE的建模及网格划分

Fig.1 Modeling and meshing in PEMWE

图2 网格无关性和模型验证：(a)网格独立性检验；(b)模拟和实验结果的极化曲线

Fig.2 Grid-independence and model validation: (a) grid-independence test; (b) polarization curves for simulated and experimental results

表1 主要守恒方程的边界条件

Table 1 Boundary conditions for the main conservation equations

ACL

CCL

电势：E_cell

电接地：0 V

质量和动量守恒

ACH的入口

CCH的出口

入口速度：0.2 m/s

出口压力：1 atm

能量守恒

ACH的入口

CCH的出口

恒温入口：293 K

流出：-nq=0

相传输守恒

ACH的入口

CCH的出口

气体体积分数：0

自然对流：20℃

表2 PEMWE的模拟参数和物理参数

Table 2 Simulation and physical parameters of PEMWE

参数	数值
阳极/阴极传递系数	0.027/0.5
膜的比定压热容^[26]/(J/(kg·K))	1090
阳极/阴极反应活化能^[23]/(J/mol)	72997/16000
孔隙率（APTL/CLs/CPTL）	0.65/0.25/0.78
阳极/阴极参考交换电流密度/(A/m²)	0.227/10000
膜的导热率^[27-28]	0.21
渗透率^[28-29]（PTLs/CLs/膜）/m²	$1 × 10 - 12 / 1 × 10 - 13 /$ $2 × 10 - 20$
出口压力/Pa	$1.01 × 105$
入口速度/(m/s)	0.2
膜的密度^[30]/(kg/m³)	1980
电导率^{[16, 22, 28, 31-32]}（APTL/CPTL/ACL/CCL）/(S/m)	2000/1250/1000/1000
对流传热系数^[33]/(W/(m²·K))	25
接触角^[16]（APTL/CPTL/CL）/(°)	80/120/100
进水温度/K	293.15

表2 PEMWE的模拟参数和物理参数

Table 2 Simulation and physical parameters of PEMWE

参数	数值
阳极/阴极传递系数	0.027/0.5
膜的比定压热容^[26]/(J/(kg·K))	1090
阳极/阴极反应活化能^[23]/(J/mol)	72997/16000
孔隙率（APTL/CLs/CPTL）	0.65/0.25/0.78
阳极/阴极参考交换电流密度/(A/m²)	0.227/10000
膜的导热率^[27-28]	0.21
渗透率^[28-29]（PTLs/CLs/膜）/m²	$1 × 10 - 12 / 1 × 10 - 13 /$ $2 × 10 - 20$
出口压力/Pa	$1.01 × 105$
入口速度/(m/s)	0.2
膜的密度^[30]/(kg/m³)	1980
电导率^{[16, 22, 28, 31-32]}（APTL/CPTL/ACL/CCL）/(S/m)	2000/1250/1000/1000
对流传热系数^[33]/(W/(m²·K))	25
接触角^[16]（APTL/CPTL/CL）/(°)	80/120/100
进水温度/K	293.15

图3 (a)1.75 V、0.2 Hz、50%占空比条件下的电流密度；(b)0.2 Hz脉冲方波与恒电位的电流密度

Fig.3 (a) Current density at 1.75 V, 0.2 Hz, and 50% duty cycle; (b) Current density under a 0.2 Hz pulse square wave and constant potential

图4 不同频率（0.025、0.05、0.1、0.5 Hz）下方波脉冲与恒电位的电流密度

Fig.4 Current density under square wave pulses at different frequencies (0.025, 0.05, 0.1 and 0.5 Hz) compared to constant potential

图5 1.75 V恒电位与0.2 Hz方波脉冲的产氢速率

Fig.5 Hydrogen evolution rate at 1.75 V constant potential and 0.2 Hz square wave pulse

图6 (a)1.75 V、50%占空比时不同频率方波脉冲和恒电位的产氢速率；(b)2.0 V、50%占空比时不同频率方波脉冲和恒电位的产氢速率

Fig.6 (a) Hydrogen evolution rate at 1.75 V with 50% duty cycle for square wave pulses at different frequencies and constant potential; (b) Hydrogen evolution rate at 2.0 V with 50% duty cycle for square wave pulses at different frequencies and constant potential

图7 (a) 1.75 V、0.2 Hz时不同占空比的脉冲波形；(b) 1.75 V、0.2 Hz、20%占空比与恒电位的电流密度；(c) 1.75 V、0.2 Hz时不同占空比法拉第电流密度最小值与恒电位的电流密度；(d) 1.75 V、0.2 Hz时不同占空比与恒电位的产氢速率

Fig.7 (a) Pulse waveforms with different duty cycles at 1.75 V and 0.2 Hz; (b) Current density at 1.75 V and 0.2 Hz with 20% duty cycle pulse and constant potential; (c) Minimum current density under different duty cycles at 1.75 V and 0.2 Hz compared to the constant potential current density; (d) Hydrogen evolution rate under different duty cycles at 1.75 V and 0.2 Hz compared to constant potential

图8 (a) PEMWE中施加的电压波形和响应的电流密度曲线；(b) 1.75 V、0.2 Hz、50%占空比下不同波形的产氢速率

Fig.8 (a) Voltage waveforms applied in PEMWE and the corresponding current density responses; (b) Hydrogen evolution rate under different waveforms at 1.75 V, 0.2 Hz and 50% duty cycle

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脉冲电压下二维PEMWE模型的制氢特性仿真研究

Simulation study on the hydrogen production performance of a two-dimensional PEMWE model under pulsed voltage

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