Steady-state modeling on hydrogen production by anion exchange membrane water electrolysis

doi:10.11949/0438-1157.20240915

Abstract

Abstract:

In recent years, the implementation of the “dual carbon” policy and advancements in related technologies has led to a significant increase in the proportion of wind and solar power generation in China. However, the intermittent and unstable nature of these renewable energy sources often results in the phenomenon of “curtailment” of wind and solar power. Hydrogen production through water electrolysis offers a solution by utilizing excess electricity and providing the advantage of zero emissions, thereby holding greater strategic significance compared to traditional hydrogen production methods. Anion exchange membrane water electrolysis (AEMWE), a technology developed over the past decade, integrates the benefits of alkaline water electrolysis (AWE) and proton exchange membrane water electrolysis (PEMWE), offering both high performance and economic advantages. Current domestic research on AEMWE predominantly focuses on the design and improvement of electrodes and membrane materials, with relatively limited studies on system simulation. Moreover, existing models often oversimplify the calculation of crucial parameters such as exchange current density and electrode resistance. To address these gaps, this paper integrates methodologies from other established electrochemical technologies (including AWE, PEMWE, and fuel cells) and relevant electrochemical principles. It introduces correction factors for effective exchange current density and bubble coverage, thereby enhancing the calculation methods for exchange current density. Additionally, a resistance network construction approach is employed to accurately represent electrode resistance. Building upon these methodologies, a more precise and broadly applicable semi-theoretical and semi-empirical steady-state electrochemical model for AEMWE is developed. The model's accuracy is validated using experimental data from existing literature. Finally, a sensitivity analysis is conducted to identify the key variables influencing the hydrogen production efficiency of AEMWE. The results show that membrane thickness, temperature and exchange current density are the main factors affecting the performance of the electrolyzer. Thinner membranes, higher operating temperatures and electrode materials with higher exchange current density are the development trends of electrolyzers.

Key words: simulation, renewable energy, hydrogen production, anion exchange membrane, water electrolysis

摘要：

阴离子交换膜电解水（AEMWE）作为一项新技术，融合了碱性电解水（AWE）和质子交换膜电解水（PEMWE）的优点，兼具高性能和经济效益。基于国内相关研究较少及现有模型存在不足的现状，结合其他成熟的电化学模型（如AWE、PEMWE和燃料电池）和电化学原理，引入有效交换电流密度、气泡覆盖率以及电阻网络构建的修正因素改进交换电流密度和电极电阻的计算方法，由此建立一个精确且适用性强的半理论半经验AEMWE模型，并利用文献实验数据验证模型的准确性，最后使用模型对制氢重要变量进行灵敏性分析。结果表明，膜厚度、温度和交换电流密度是影响电解槽性能的主要因素，更薄的膜、更高的工作温度以及更高交换电流密度的电极材料是电解槽的发展趋势。

关键词: 模拟, 再生能源, 制氢, 阴离子交换膜, 电解水

CLC Number:

TQ 151.1

Zhineng TAO, Tong QIU, Baoguo WANG. Steady-state modeling on hydrogen production by anion exchange membrane water electrolysis[J]. CIESC Journal, 2025, 76(4): 1711-1721.

陶智能, 邱彤, 王保国. 阴离子交换膜电解水制氢稳态建模[J]. 化工学报, 2025, 76(4): 1711-1721.

Figures/Tables 8

Table 1 Performance comparison of low-temperature water electrolysis hydrogen production technology

比较项目	碱性电解水 (AWE)	质子交换膜电解水（PEMWE）	阴离子交换膜电解水（AEMWE）	AEMWE阳极加入 20%（质量）碱性离聚物
温度/℃	70~90	65~85	65~85
电流密度/( $A / c m^{2}$ )	0.2~0.5	1.5~2.5	0.8~2.1
电解液	30%(质量) KOH	纯水	1 mol/L KOH/纯水
隔膜	石棉布、PPS	质子交换膜（PEM）	阴离子交换膜（AEM）
响应范围	40%~100%	20%~120%	20%~120%
启动速度	慢	快	快
动力学性能	++	+++	++	+++
导电性能	+	++	++	+++
扩散性能	+	+++	+++	++
经济效益	+++	+	+++
技术成熟度	9	7	4
电解槽规模/MW	5	1	0.05
产业化程度	商业化应用	工程示范	工程示范，被称为“下一代绿色制氢技术”

Table 1 Performance comparison of low-temperature water electrolysis hydrogen production technology

比较项目	碱性电解水 (AWE)	质子交换膜电解水（PEMWE）	阴离子交换膜电解水（AEMWE）	AEMWE阳极加入 20%（质量）碱性离聚物
温度/℃	70~90	65~85	65~85
电流密度/( $A / c m^{2}$ )	0.2~0.5	1.5~2.5	0.8~2.1
电解液	30%(质量) KOH	纯水	1 mol/L KOH/纯水
隔膜	石棉布、PPS	质子交换膜（PEM）	阴离子交换膜（AEM）
响应范围	40%~100%	20%~120%	20%~120%
启动速度	慢	快	快
动力学性能	++	+++	++	+++
导电性能	+	++	++	+++
扩散性能	+	+++	+++	++
经济效益	+++	+	+++
技术成熟度	9	7	4
电解槽规模/MW	5	1	0.05
产业化程度	商业化应用	工程示范	工程示范，被称为“下一代绿色制氢技术”

Fig.1 Anion exchange membrane electrolyzer structure

Fig.2 Schematic diagram of electrode resistance network construction

Table 2 Four types of resistors in electrode resistance networks

电阻类型	说明	计算公式
通道支撑电阻 $R_{E S} / R_{P S}$	电极催化层和极板处通道支撑的电阻	$R_{E S} = \frac{ρ_{e} δ_{e}}{L W_{s} / 2}$ $R_{P S} = \frac{ρ_{p} h_{c}}{L W_{s} / 2}$
通道电阻 $R_{E C}$	电子不能通过气液传质通道迁移，通道前处迁移的电子需要绕过通道	$R_{E C} = \frac{ρ_{e} δ_{e}}{W_{c} L}$
补偿电阻 $R_{E D}$	绕过通道迁移至通道支撑处的过程中遇到的阻力	$R_{E D} = \frac{ρ_{e} \frac{W_{c}}{4}}{δ_{e} L}$
极板电阻 $R_{P R}$	从通道或通道支撑处通过的电子最终均要穿过极板至外接导线处，剩余极板可以当作整体考虑	$R_{P R} = \frac{ρ_{p} h_{p}}{W L}$

Table 2 Four types of resistors in electrode resistance networks

电阻类型	说明	计算公式
通道支撑电阻 $R_{E S} / R_{P S}$	电极催化层和极板处通道支撑的电阻	$R_{E S} = \frac{ρ_{e} δ_{e}}{L W_{s} / 2}$ $R_{P S} = \frac{ρ_{p} h_{c}}{L W_{s} / 2}$
通道电阻 $R_{E C}$	电子不能通过气液传质通道迁移，通道前处迁移的电子需要绕过通道	$R_{E C} = \frac{ρ_{e} δ_{e}}{W_{c} L}$
补偿电阻 $R_{E D}$	绕过通道迁移至通道支撑处的过程中遇到的阻力	$R_{E D} = \frac{ρ_{e} \frac{W_{c}}{4}}{δ_{e} L}$
极板电阻 $R_{P R}$	从通道或通道支撑处通过的电子最终均要穿过极板至外接导线处，剩余极板可以当作整体考虑	$R_{P R} = \frac{ρ_{p} h_{p}}{W L}$

Fig.3 Schematic diagram of water molecule migration in AEMWE

Table 3 Some parameters of electrochemical model settings［23-24，37］

主要参数设置	数值
操作温度 $T$	70℃
阴极压力 $p_{c}$	1 bar
膜厚度 $δ_{m e m}$	50 $μ m$
膜水合程度 $λ$	18
电渗阻力系数 $n_{d}$	3
阳极参考交换电流密度 $i_{0, a n, r e f}$	$1 \times 10^{- 7} A / m^{2}$
阴极参考交换电流密度 $i_{0, c a t, r e f}$	$10.0 A / m^{2}$
参考温度 $T_{r e f}$	298.15 K
阳极反应活化自由能 $Δ G_{c, a n}$	80.456 kJ/mol
阴极反应活化自由能 $Δ G_{c, c a t}$	52.145 kJ/mol
气泡覆盖率为100%时极限电流密度 $i_{l i m - Θ}$	300 $A / m^{2}$
电极粗糙度 $γ_{M}$	1
阳极电荷转移系数 $α_{a n}$	1.65
阴极电荷转移系数 $α_{c a t}$	0.73

Table 3 Some parameters of electrochemical model settings［23-24，37］

主要参数设置	数值
操作温度 $T$	70℃
阴极压力 $p_{c}$	1 bar
膜厚度 $δ_{m e m}$	50 $μ m$
膜水合程度 $λ$	18
电渗阻力系数 $n_{d}$	3
阳极参考交换电流密度 $i_{0, a n, r e f}$	$1 \times 10^{- 7} A / m^{2}$
阴极参考交换电流密度 $i_{0, c a t, r e f}$	$10.0 A / m^{2}$
参考温度 $T_{r e f}$	298.15 K
阳极反应活化自由能 $Δ G_{c, a n}$	80.456 kJ/mol
阴极反应活化自由能 $Δ G_{c, c a t}$	52.145 kJ/mol
气泡覆盖率为100%时极限电流密度 $i_{l i m - Θ}$	300 $A / m^{2}$
电极粗糙度 $γ_{M}$	1
阳极电荷转移系数 $α_{a n}$	1.65
阴极电荷转移系数 $α_{c a t}$	0.73

Fig.4 Comparison of simulation and experimental results

Fig.5 Sensitivity analysis results of important parameters

References 37

1	International Energy Agency. World Energy Statistics 2023 [EB/OL]. 2023. .
2	王培灿, 万磊, 徐子昂, 等. 碱性膜电解水制氢技术现状与展望[J]. 化工学报, 2021, 72(12): 6161-6175.
	Wang P C, Wan L, Xu Z A, et al. Hydrogen production based-on anion exchange membrane water electrolysis: a critical review and perspective[J]. CIESC Journal, 2021, 72(12): 6161-6175.
3	Liu L, Ma H Y, Khan M, et al. Recent advances and challenges in anion exchange membranes development/application for water electrolysis: a review[J]. Membranes, 2024, 14(4): 85.
4	Park J E, Park S, Kim M J, et al. Three-dimensional unified electrode design using a NiFeOOH catalyst for superior performance and durable anion-exchange membrane water electrolyzers[J]. ACS Catalysis, 2022, 12(1): 135-145.
5	Lin N, Feng S H, Wang J G. Multiphysics modeling of proton exchange membrane water electrolysis: from steady to dynamic behavior[J]. AIChE Journal, 2022, 68(8): e17742.
6	Biswas S, Kaur G, Paul G, et al. A critical review on cathode materials for steam electrolysis in solid oxide electrolysis[J]. International Journal of Hydrogen Energy, 2023, 48(34): 12541-12570.
7	Ryoo G W, Park S H, Kwon K C, et al. Towards high-performance and robust anion exchange membranes (AEMs) for water electrolysis: super-acid-catalyzed synthesis of AEMs[J]. Journal of Energy Chemistry, 2024, 93: 478-510.
8	Pavel C C, Cecconi F, Emiliani C, et al. Highly efficient platinum group metal free based membrane-electrode assembly for anion exchange membrane water electrolysis[J]. Angewandte Chemie International Edition, 2014, 53(5): 1378-1381.
9	Vincent I, Kruger A, Bessarabov D. Development of efficient membrane electrode assembly for low cost hydrogen production by anion exchange membrane electrolysis[J]. International Journal of Hydrogen Energy, 2017, 42(16): 10752-10761.
10	高渊, 张议洁, 赵强, 等. 阴离子交换膜电解水技术及其析氧催化剂的研究进展与展望[J]. 中国科学: 化学, 2024, 54(10): 1837-1847.
	Gao Y, Zhang Y J, Zhao Q, et al. Research progress and prospect of anionic exchange membrane electrolyzer and OER electrocatalysts[J]. Scientia Sinica (Chimica), 2024, 54(10): 1837-1847.
11	马颖, 丁睿, 刘岩岩, 等. 阴离子交换膜电解水制氢关键技术研究[J]. 今日制造与升级, 2022(9): 131-133.
	Ma Y, Ding R, Liu Y Y, et al. Study on key technology of hydrogen production by electrolysis of water with anion exchange membrane[J]. Manufacture & Upgrading Today, 2022(9): 131-133.
12	钱圣涛, 何勇, 翁武斌, 等. 阴离子交换膜电解水制氢技术的研究进展[J]. 新能源进展, 2024, 12(1): 1-14.
	Qian S T, He Y, Weng W B, et al. Research progress of anion exchange membrane water electrolysis technology for hydrogen production[J]. Advances in New and Renewable Energy, 2024, 12(1): 1-14.
13	邢学奇, 宋鹏翔, 申爱景,等. 电解水制氢用阴离子交换膜研究进展[J]. 储能科学与技术, 2024, 13(11): 3856-3870.
	Xing X Q, Song P X, Shen A J, et al. Research progress of anion exchange membranes for hydrogen production by water electrolysis [J]. Energy Storage Science and Technology, 2024, 13(11): 3856-3870.
14	白佳凯, 张安然, 李朋喜, 等. 阴离子交换膜在电解水制氢领域的研究进展[J]. 河南化工, 2024, 41(9): 36-39.
	Bai J K, Zhang A R, Li P X, et al. Research progress of anion exchange membrane in the field of electrolysis water hydrogen production[J]. Henan Chemical Industry, 2024, 41(9): 36-39.
15	李楠楠. 阴离子交换膜电解水制氢非碳基膜电极的研究[D]. 大连: 大连理工大学, 2022.
	Li N N. Research on non-carbon-based membrane electrodes for hydrogen production by anion exchange membrane electrolysis of water[D]. Dalian: Dalian University of Technology, 2022.
16	党悦晨. 高电流密度高稳定性镍基催化电极构筑及其阴离子交换膜电解水制氢性能研究[D]. 延安: 延安大学, 2023.
	Dang Y C. Construction of high-current-density and high-stability nickel-based electrode material and exploration on hydrogen production by anion exchange membrane electrolytic water [D]. Yan'an: Yan'an University, 2023.
17	Gomez Vidales A, Millan N C, Bock C. Modeling of anion exchange membrane water electrolyzers: the influence of operating parameters[J]. Chemical Engineering Research and Design, 2023, 194: 636-648.
18	Lawand K, Nuggehalli Sampathkumar S, Mury Z, et al. Membrane electrode assembly simulation of anion exchange membrane water electrolysis[J]. Journal of Power Sources, 2024, 595: 234047.
19	Moradi Nafchi F, Afshari E, Baniasadi E. Anion exchange membrane water electrolysis: numerical modeling and electrochemical performance analysis[J]. International Journal of Hydrogen Energy, 2024, 52: 306-321.
20	万磊. 碱性电解水用有序化膜电极的结构设计及制备研究[D]. 北京: 清华大学, 2023.
	Wan L. Fabrication and study of ordered membrane electrode assembly for alkaline water electrolysis[D]. Beijing: Tsinghua University, 2023.
21	McLeod A J, Bühre L V, Bensmann B, et al. Anode and cathode overpotentials under accelerated stress testing of a PEM electrolysis cell[J]. Journal of Power Sources, 2024, 589: 233750.
22	Awasthi A, Scott K, Basu S. Dynamic modeling and simulation of a proton exchange membrane electrolyzer for hydrogen production[J]. International Journal of Hydrogen Energy, 2011, 36(22): 14779-14786.
23	Abdin Z, Webb C J, Gray E M. Modelling and simulation of an alkaline electrolyser cell[J]. Energy, 2017, 138: 316-331.
24	Abdin Z, Webb C J, Gray E M. Modelling and simulation of a proton exchange membrane (PEM) electrolyser cell[J]. International Journal of Hydrogen Energy, 2015, 40(39): 13243-13257.
25	Balej J. Water vapour partial pressures and water activities in potassium and sodium hydroxide solutions over wide concentration and temperature ranges[J]. International Journal of Hydrogen Energy, 1985, 10(4): 233-243.
26	Caprì A, Gatto I, Lo Vecchio C, et al. Anion exchange membrane water electrolysis based on nickel ferrite catalysts[J]. ChemElectroChem, 2023, 10(1): e202201056.
27	Marangio F, Santarelli M, Calì M. Theoretical model and experimental analysis of a high pressure PEM water electrolyser for hydrogen production[J]. International Journal of Hydrogen Energy, 2009, 34(3): 1143-1158.
28	Marr C, Li X. An engineering model of proton exchange membrane fuel cell performance[J]. ARI — an International Journal for Physical and Engineering Sciences, 1997, 50(4): 190-200.
29	Fei D X, Fan W W, Dou Z L, et al. Mathematical model and dynamic Simulink simulation of PEM electrolyzer system[J]. E3S Web of Conferences, 2023, 441: 02012.
30	Ni M, Leung M, Leung Y. Electrochemistry modeling of proton exchange membrane (PEM) water electrolysis for hydrogen production[C]//WHEC 2006. 2006: 33-39.
31	Springer T E, Zawodzinski T A, Gottesfeld S. Polymer electrolyte fuel cell model[J]. Journal of the Electrochemical Society, 1991, 138(8): 2334-2342.
32	Shen M Z, Bennett N, Ding Y L, et al. A concise model for evaluating water electrolysis[J]. International Journal of Hydrogen Energy, 2011, 36(22): 14335-14341.
33	Colbertaldo P, Gómez Aláez S L, Campanari S. Zero-dimensional dynamic modeling of PEM electrolyzers[J]. Energy Procedia, 2017, 142: 1468-1473.
34	Han B, Steen S M, Mo J K, et al. Electrochemical performance modeling of a proton exchange membrane electrolyzer cell for hydrogen energy[J]. International Journal of Hydrogen Energy, 2015, 40(22): 7006-7016.
35	Hernández-Pacheco E, Singh D, Hutton P N, et al. A macro-level model for determining the performance characteristics of solid oxide fuel cells[J]. Journal of Power Sources, 2004, 138(1/2): 174-186.
36	Xiao L, Zhang S, Pan J, et al. First implementation of alkaline polymer electrolyte water electrolysis working only with pure water[J]. Energy & Environmental Science, 2012, 5(7): 7869-7871.
37	Thampan T, Malhotra S, Zhang J X, et al. PEM fuel cell as a membrane reactor[J]. Catalysis Today, 2001, 67(1/2/3): 15-32.

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