Article(id=1236321543517696466, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236321537146540956, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202501035, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1736524800000, receivedDateStr=2025-01-11, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772691625717, onlineDateStr=2026-03-05, pubDate=1761321600000, pubDateStr=2025-10-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772691625717, onlineIssueDateStr=2026-03-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772691625717, creator=13701087609, updateTime=1772691625717, updator=13701087609, issue=Issue{id=1236321537146540956, tenantId=1146029695717560320, journalId=1210938733613449225, year='2025', volume='54', issue='10', pageStart='1', pageEnd='174', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1772691624199, creator=13701087609, updateTime=1772691865526, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236322549404070348, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236321537146540956, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236322549408264653, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236321537146540956, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=133, endPage=142, ext={EN=ArticleExt(id=1236321543861629410, articleId=1236321543517696466, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Performance analysis and optimization of proton exchange membrane electrolyzer with waveform channels, columnId=1211002409397129992, journalTitle=Thermal Power Generation, columnName=Power generation technology forum, runingTitle=null, highlight=null, articleAbstract=

Proton exchange membrane (PEM) electrolysis for hydrogen production has broad application prospects, but it still has disadvantages such as high equipment cost and insufficient durability. Optimizing the flow channel can improve the uniformity of water and heat distribution in PEM and extend the service life of the electrolyzer. To enhance the performance of PEM, a three-dimensional wavy flow channel model was designed and simulated using COMSOL simulation software. The polarization curves, distribution of reactants and products, and temperature distribution of electrolyzers with different frequency wavy structures were studied, and the influence of flow rate changes due to the addition of wavy structures on the performance of the electrolyzer was explored. The results show that, compared with the conventional rectangular flow channel, the electrolyzer with wavy flow channels has significantly enhanced the heat and mass transfer effects and got better polarization performance. When the wavy frequency is 1.0, the current density of the electrolyzer increases by 2.1%, and the average gas volume fraction in the anode catalyst layer decreases by 3.7%, achieving the best overall performance. This study can provide certain references for the flow channel design of PEM electrolyzers.

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质子交换膜(proton exchange membrane,PEM)电解制氢具有广阔的应用前景,但仍存在设备成本高、耐久性不足等缺点。优化流道可以提高PEM的水热分布均匀性,延长电解槽的寿命。为了提高PEM电解槽性能,利用COMSOL仿真软件设计并模拟了三维波形流道模型,研究不同频率波形结构电解槽的极化曲线、反应物与生成物分布以及温度分布,并探究增加波形结构后流速改变对电解槽性能的影响。结果表明,与传统的矩形流道相比,波形流道电解槽传热传质效果明显增强,具有更好的极化性能,当波形频率为1.0时,电解槽的电流密度提高了2.1%,阳极催化层平均气体体积分数降低了3.7%,综合性能最优。该结论可为PEM电解槽的流道设计提供一定参考。

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黄吉光(1995),男,博士后,主要研究方向为太阳能和氢能高效利用,
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李瑞莹(2001),女,硕士研究生,主要研究方向为质子交换膜电解水制氢,

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Geometric parameters of the model[26-27]

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项目数值项目数值
流道高度2.00阴阳极扩散层厚度0.38
流道宽度2.00流场板厚度1.00
质子交换膜厚度0.125流场板宽度4.00
阴阳极催化层厚度0.05流道长度50.00
), ArticleFig(id=1236321560768868495, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321543517696466, language=CN, label=表1, caption=

模型几何参数[26-27]

, figureFileSmall=null, figureFileBig=null, tableContent=
项目数值项目数值
流道高度2.00阴阳极扩散层厚度0.38
流道宽度2.00流场板厚度1.00
质子交换膜厚度0.125流场板宽度4.00
阴阳极催化层厚度0.05流道长度50.00
), ArticleFig(id=1236321560903086226, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321543517696466, language=EN, label=Tab.2, caption=

Physical parameters of the model[14,17,28-29]

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项目数值项目数值
入口温度T0/K353.15阴阳极传递系数αc、αa0.5
参考压力Pref/kPa101.325氧气导热率K(O2)/(W·(m·K)–1)0.204
扩散层电导率σgdl/(S·m–1)1 000氢气导热率K(H2)/(W·(m·K)–1)0.029 6
极板电导率σbp/(S·m–1)2 000质子交换膜导热率Kmem/(W·(m·K)–1)0.67
扩散层孔隙率εgdl0.4液态水动力黏度μ(H2O)/(Pa·s)3.55×10–14
催化层孔隙率εcl0.3氧气的动力黏度μ(O2)/(Pa·s)2.34×10–5
催化层、扩散层渗透率κclκgdl1×10–12氢气的动力黏度μ(H2)/(Pa·s)8.92×10–6
), ArticleFig(id=1236321561016332440, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321543517696466, language=CN, label=表2, caption=

模型物理参数[14,17,28-29]

, figureFileSmall=null, figureFileBig=null, tableContent=
项目数值项目数值
入口温度T0/K353.15阴阳极传递系数αc、αa0.5
参考压力Pref/kPa101.325氧气导热率K(O2)/(W·(m·K)–1)0.204
扩散层电导率σgdl/(S·m–1)1 000氢气导热率K(H2)/(W·(m·K)–1)0.029 6
极板电导率σbp/(S·m–1)2 000质子交换膜导热率Kmem/(W·(m·K)–1)0.67
扩散层孔隙率εgdl0.4液态水动力黏度μ(H2O)/(Pa·s)3.55×10–14
催化层孔隙率εcl0.3氧气的动力黏度μ(O2)/(Pa·s)2.34×10–5
催化层、扩散层渗透率κclκgdl1×10–12氢气的动力黏度μ(H2)/(Pa·s)8.92×10–6
), ArticleFig(id=1236321561129578650, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321543517696466, language=EN, label=Tab.3, caption=

Average effective mass transfer coefficient of each channel structure

, figureFileSmall=null, figureFileBig=null, tableContent=
流道结构平均EMTC
M11.68
M22.16
M32.19
M42.20
M52.16
), ArticleFig(id=1236321561226047645, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236321543517696466, language=CN, label=表3, caption=

各流道结构的平均有效传质系数

, figureFileSmall=null, figureFileBig=null, tableContent=
流道结构平均EMTC
M11.68
M22.16
M32.19
M42.20
M52.16
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波形流道质子交换膜电解槽性能分析与优化
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李瑞莹 1 , 王剑峰 2 , 黄吉光 1 , 张衡 1, 3 , 王异林 1 , 米翠丽 4 , 陈海平 1, 3
热力发电 | 发电技术论坛 2025,54(10): 133-142
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热力发电 | 发电技术论坛 2025, 54(10): 133-142
波形流道质子交换膜电解槽性能分析与优化
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李瑞莹1 , 王剑峰2, 黄吉光1 , 张衡1, 3, 王异林1, 米翠丽4, 陈海平1, 3
作者信息
  • 1.华北电力大学能源动力与机械工程学院,北京 102206
  • 2.河北建设投资集团有限责任公司,河北 石家庄 050001
  • 3.华北电力大学热电生产过程污染物监测与控制北京市重点实验室,北京 102206
  • 4.河北省热电清洁高效热电联产技术创新中心,河北 石家庄 050001
  • 李瑞莹(2001),女,硕士研究生,主要研究方向为质子交换膜电解水制氢,

通讯作者:

黄吉光(1995),男,博士后,主要研究方向为太阳能和氢能高效利用,
Performance analysis and optimization of proton exchange membrane electrolyzer with waveform channels
Ruiying LI1 , Jianfeng WANG2, Jiguang HUANG1 , Heng ZHANG1, 3, Yilin WANG1, Cuili MI4, Haiping CHEN1, 3
Affiliations
  • 1.School of Energy, Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China
  • 2.Hebei Construction & Investment Group Co., Ltd., Shijiazhuang 050001, China
  • 3.Beijing Key Laboratory of Pollutant Monitoring and Control in Thermoelectric Production Process, North China Electric Power University, Beijing 102206, China
  • 4.Hebei Technology Innovation Center for Thermal Power Clean and Efficient Cogeneration, Shijiazhuang 050001, China
出版时间: 2025-10-25 doi: 10.19666/j.rlfd.202501035
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质子交换膜(proton exchange membrane,PEM)电解制氢具有广阔的应用前景,但仍存在设备成本高、耐久性不足等缺点。优化流道可以提高PEM的水热分布均匀性,延长电解槽的寿命。为了提高PEM电解槽性能,利用COMSOL仿真软件设计并模拟了三维波形流道模型,研究不同频率波形结构电解槽的极化曲线、反应物与生成物分布以及温度分布,并探究增加波形结构后流速改变对电解槽性能的影响。结果表明,与传统的矩形流道相比,波形流道电解槽传热传质效果明显增强,具有更好的极化性能,当波形频率为1.0时,电解槽的电流密度提高了2.1%,阳极催化层平均气体体积分数降低了3.7%,综合性能最优。该结论可为PEM电解槽的流道设计提供一定参考。

质子交换膜  /  电解水制氢  /  模拟研究  /  流道设计

Proton exchange membrane (PEM) electrolysis for hydrogen production has broad application prospects, but it still has disadvantages such as high equipment cost and insufficient durability. Optimizing the flow channel can improve the uniformity of water and heat distribution in PEM and extend the service life of the electrolyzer. To enhance the performance of PEM, a three-dimensional wavy flow channel model was designed and simulated using COMSOL simulation software. The polarization curves, distribution of reactants and products, and temperature distribution of electrolyzers with different frequency wavy structures were studied, and the influence of flow rate changes due to the addition of wavy structures on the performance of the electrolyzer was explored. The results show that, compared with the conventional rectangular flow channel, the electrolyzer with wavy flow channels has significantly enhanced the heat and mass transfer effects and got better polarization performance. When the wavy frequency is 1.0, the current density of the electrolyzer increases by 2.1%, and the average gas volume fraction in the anode catalyst layer decreases by 3.7%, achieving the best overall performance. This study can provide certain references for the flow channel design of PEM electrolyzers.

proton exchange membrane  /  hydrogen production by electrolysis of water  /  simulation study  /  channel design
李瑞莹, 王剑峰, 黄吉光, 张衡, 王异林, 米翠丽, 陈海平. 波形流道质子交换膜电解槽性能分析与优化. 热力发电, 2025 , 54 (10) : 133 -142 . DOI: 10.19666/j.rlfd.202501035
Ruiying LI, Jianfeng WANG, Jiguang HUANG, Heng ZHANG, Yilin WANG, Cuili MI, Haiping CHEN. Performance analysis and optimization of proton exchange membrane electrolyzer with waveform channels[J]. Thermal Power Generation, 2025 , 54 (10) : 133 -142 . DOI: 10.19666/j.rlfd.202501035
氢作为一种清洁的可再生能源,具有低污染、高热值、来源多样且应用广泛等优点,应用和发展前景广阔[1-2]。在现有的众多制氢技术中,质子交换膜(proton exchange membrane,PEM)电解水制氢技术具有产氢纯度高、效率高、电流密度高、动态响应速度快、负荷范围广等众多优点[3-5],因其更安全无腐蚀性,且能承受较高的阳极、阴极侧压差,更适合消纳可再生能源发电负荷[6-7]。PEM电解水制氢技术作为当前研究的热点,目前已相对成熟,能够在未来进行产业化、规模化的发展[8-10]
目前,PEM电解槽的相关研究大多集中在催化剂、膜等材料的改进或是流场、流道形状的改变上。对于电解槽,流场的设计尤为重要,流场设计不当往往是导致其性能恶化的主要原因[11-12]。双极板是电解槽中体积和质量最大的部件,为电解槽的反应提供了重要保证[13]。双极板表面流动分布不均匀可能会导致催化剂材料的使用不均匀,降低装置的整体效率[14-15]。为使催化层上形成均匀的流场,一般会在双极板上雕刻流道。通过改变流道结构和流场设计,使反应物分布更均匀,及时排出电解过程中的气体,降低传质阻力,提高电解槽的稳定性和寿命。
对PEM电解槽双极板的研究主要集中在流场结构和单流道结构设计上,对单流道的研究主要集中在对单流道内部的水热优化管理,以及通道尺寸、断面形状和壁面结构等因素对对流换热的影响等方面[16-17]。Lickert等人[18]通过对比有无流道的PEM电解槽性能发现,当运行参数改变时,有流道的电解槽受到的影响更小,电解槽运行更稳定。Lin等人[19]模拟了流道内的流量和压力分布,发现影响电解槽性能最显著的因素是流场结构,其次是工作温度。Chen等人[20]对流道宽度和深度、大孔层粒径和小孔层粒径这4个因素进行了优化分析对比,发现流道深度对压降的影响最为显著,其他因素影响不大。王华等[21]采用COMSOL软件探究了流道高度、堵块、脊的宽度等对PEM电解槽性能的影响,从而优化了流场结构。马晓锋[22]通过比较达到相同工作电流密度所需的电解电压、阳极扩散层内的氧气质量分数分布、膜电极的平均温度等参数,分析了流道结构对电解槽性能的影响。刘瑗玥等[23]对电解池阳极通道速度、温度以及气液两相分布等方面进行分析,研究了仿生沟槽和常规沟槽对电解池热质传递以及电化学性能的影响。刘洋等[24]提出了一种新型楔形流道设计,并通过可视化实验验证了模型准确性。本文提出了一种新的波形流道,并基于COMSOL仿真软件建立了PEM电解槽单流道的三维模型,将不同频率波形流道与普通矩形流道进行了对比;通过对比得到稳定运行时的极化曲线、氧气和液态水的分布、流道内的流速分布和膜电极组件的平均温度等性能指标,分析了波形结构对PEM电解槽性能的改善提升效果。
PEM主要由阳极极板、阴极极板、阳极流道、阴极流道、阳极和阴极的气体扩散层、阳极和阴极的催化剂层和质子交换膜组成[25]。其中,膜电极由质子交换膜和阴阳极催化层组成,其结构如图1所示。建立单通道模型,设置流道总长为50 mm,流场板宽度为4 mm,流道高度和宽度均为2 mm。模型的具体参数见表1表2
利用COMSOL软件建立了三维两相非等温稳态PEM电解槽模型,对电解槽内的电化学反应和传热传质过程进行了模拟计算。为简化模型采取以下假设:1)忽略水的相变及液态水蒸发;反应气体为不可压缩理想气体;2)反应物和生成物均为不可压缩流体;3)材料设定为各向同性;4)质子交换膜仅允许氢离子通过,不考虑交叉渗透。
质子交换膜电解水制氢的电解电压Vcell是在电解过程中为了驱动化学反应而施加在电解槽两端的实际电压,由4部分组成,可表示为:
Vcell=Eocv+ηact+ηohm+ηdiff
式中:EOCV为开路电压;ηact为活化过电位;ηohm为欧姆过电位;ηdiff为扩散过电位。
考虑到温度和压力的变化对开路电压有一定影响,采用能斯特方程对开路电压进行计算:
Eocv=Eocv,ref(T)+RTzFln(p0.5(O2)p(H2)p(H2O))
Eocv,ref(T)=1.2290.9×103(T298.15)
式中:R为气体常数,8.314 J/(mol·K);F为法拉第常数,96 485 C/mol;T为电解槽的运行温度,K;pi表示各组分的平衡压力,i为O2、H2、H2O,Pa;z为电子转移摩尔数。
活化过电势可由Butler-Volmer方程表示:
ia=αVi0,a(C(O2)Cref(O2))12{exp(αaFηact,aRT)      exp((1αa)Fηact,aRT))
ic=αVi0,c(C(H2)Cref(H2))(exp(αcFηact,cRT)     exp((1αc)Fηact,cRT))
式中:αv为活性比表面积,1/m;i0,a、i0,c为阳极和阴极的交换电流密度,A/cm2αaαc为阳极和阴极的电荷转移系数;C(O2)、C(H2)为氧、氢浓度,mol/m3Cref(O2)、Cref(H2)为参考氧气和氢气浓度,mol/m3
当电子在流场板、催化层和扩散层中传递,以及质子通过PEM时,由于各部分之间存在传输电阻,会产生一定的欧姆损失。电子与质子的输运方程为:
is=(σsϕs)=Sϕs
im=(σmϕm)=Sϕm
式中:isim为固相和膜的电流密度;σsσm为固相和膜的有效电导率,S/m;ϕm为电解质电势;ϕs为电子电势;SϕsSϕm为源项,表示电子和质子在电化学反应中的得失速率。
采用经验公式计算质子交换膜的电导率:
σm=10×exp[1 268(1303.151T)]
总欧姆过电位为:
ηohm=i(ϕmσm+ϕsσs)
扩散过电位为:
ηdiff,a=RT4Fln(C(O2)Cref(O2))
ηdiff,c=RT2Fln(C(H2)Cref(H2))
电解槽内气液两相混合物的传质规律由质量守恒和动量守恒方程描述:
(ερfv)=Sm
(ερfvv)=εp+(εμv)+Sv
式中:ε为多孔介质的孔隙率;ρf为混合物的平均密度;v为混合物的平均体积速度;μ为混合物的黏度;p为分压;Sm为质量源项;Sv为动量损失。
在电解槽内,液态水通过电解槽流道进入扩散层和催化层,产生的气体则通过催化层和扩散层向外排出。因此,气液两相流在流道内的对流扩散现象通常用Maxwell-Stefan方程来描述:
(εvkCk)=(Dk,effCk)+Sk
式中:Ckk物质的浓度,mol/m3Dk,eff为物质k的有效扩散系数;vk为物质k的流速。
电解槽内部催化层和扩散层都属于多孔介质区域,其内部各组分流速采用达西定律近似计算:
vg=κκgμgpg
vl=κκlμlpl
式中:vgvl为气相和液相的流速;κ为多孔介质的渗透率;μgμl为气相和液相的黏度,Pa/s;κgκl为气相和液相的相对渗透率,用液体饱和度s计算得出。
κl=s3
κg=(1s)3
质子交换膜电解槽的热量主要来源于反应物带入的热量和发生电化学反应产生的热量,热量损失的主要方式为对流散热、辐射散热、生成物带走的热量以及未反应水带走的热量。其热平衡可以用能量方程来描述:
(ρeffcp,effvk)T=(keffT)+ST
式中:ρeff为有效密度,kg/m3cp,eff为有效比热容,J/(kg·K);keff为有效导热系数,W/(m·K);ST为热量源项,包括不可逆活化热、电化学反应产生的熵热、欧姆热和浓差热。
ρeff=(1ε)ρs+ερf
cp,eff=(1ε)cps+εcpf
keff=(1ε)ks+εkf
式中:ρsρf为固相、流体的密度,kg/m3cpscpf为固相、流体的比热容,J/(kg·K);kskf为固相、流体的有效导热系数,W/(kg·K)。
电解池输入功率为:
Pin=VcellIcell
电解池输出功率为:
Pout=f(H2)QLHV1 0003 600
式中:QLHV为氢气的低热值,取120 MJ/kg;Icell为电解电流;f(H2)为电解池的产氢率。
根据法拉第定律,理想电解槽中的氢气产生率与电流成正比。在假设流过每个电解槽的电流相同的条件下,电解池制氢率可表示为:
fH2=ηFIcellzF22.411 000×3 600
式中:ηF为法拉第效率,理论上为100%。
电解池效率为:
ηPEM=PoutPin
本文创新设计了一种三维波形流道,其结构如图2所示。与传统的矩形通道相比,新型流道在流道内引入了规律的周期性波形扰动,流道最高处达到2 mm,而最低处为1 mm。波形流道的波浪设计为余弦曲线:
y=0.5cos(ax)
为了更好地评估波形通道的效果,本文对不同频率的波形流道(M1—M5)进行对比探索。(其中,M1为矩形流道;M2为频率0.6的波形通道;M3为频率1的波形通道;M4为频率1.4的波形通道;M5为频率1.8的波形通道)。
本文利用多物理场耦合软件COMSOL对PEM电解槽内的电化学反应和传热传质过程进行了仿真模拟分析。为了提高数值模型的准确性和真实性,对模型的边界条件和初始值设置如下。
在阳极流场板边界处设置恒定的电解电压,在阴极流场板边界处设置电接地条件。通过计算不同电压下的电流密度,得到PEM电解槽的极化曲线。在阳极入口处设置速度入口边界条件,入口流速设置为20 mL/min,阴阳极进水设置为逆流条件。出口设定压力出口边界为1×105 Pa。壁面设为无滑移边界条件,电解槽通道与外界环境的换热方式为对流换热。
电解槽的膜电极是反应发生的核心区域,因此需要对其进行加密计算。由于膜电极的形状规则,可以将其划分为结构化六面体网格,如图3所示。为了保证模型计算结果的准确性,对网格数的无关性进行验证,不同数量网格数下电流密度和催化层氧气摩尔分数的变化如图4所示。可以发现,当网格数大于31 200时,电流密度和氧气摩尔分数的变化均小于0.5%,说明进一步增加网格数对计算结果影响不大,可用该数量的网格进行模拟。
为了验证模型的准确性,将所建立的单流道电解槽模型计算结果与Majasan等人[30]的实验结果进行比较。在与文献[30]相同的实验条件下进行极化曲线比较,设置模型中入口温度为80 ℃,进水流速为15 mL/min,结果如图5所示。模拟结果与实验结果变化趋势基本一致,且误差小于2%,所建模型准确性满足要求。
极化曲线是评估PEM电解槽性能和流场设计质量的关键指标。电流密度越大,产氢量越高;在恒定电流密度下,电压越低,经济性越好。由电解池的效率评价公式可得,当电解槽的电流密度相同时,电压越高,电解池的效率越低。图6给出了矩形流道和不同波形流道的极化曲线。从图6可以看出,与矩形流道相比,波形流道达到相同电流密度的电压更低,因此功耗更低。当电解槽运行在不同工作电压下,电压越低,不同流道之间的电流密度变化越小;电压越高,不同流道之间的电流密度差值越大。当电解槽在低电压条件下工作时,由于氧化还原反应速率相对较低,此时改变流道结构对电化学反应的影响不显著,因此极化反应差异不明显。但当电解槽在高电压下工作时,电化学反应明显增强,反应更加激烈,电流密度也随之增大,不同流道结构之间的差异逐渐明显。随着流道频率的增加,极化性能先增大后减小,电解池的效率同样先增大后减小。当波形频率为1.0时,即流道结构为M3时,极化性能最好,电解池效率最高。在2.5 V电压条件下,M3的电流密度比传统矩形通道M1高2.1%。
图7为阳极通道中氧气和液态水浓度分布。
图7可以清楚地看出,阳极处氧浓度的变化趋势与液态水浓度的变化趋势相反。这种趋势的产生主要是由于在阳极的催化层中水分子不断被消耗,随着化学反应的不断进行通道中产生的气体量增加,导致液态水的浓度降低。同时,这些生成的气体还会阻止液态水进一步进入催化层,从而降低化学反应的速率。液态水浓度的降低还会导致电解槽传热性能降低。因此,促进气体从流道中排出,提高液态水浓度有助于提高电解槽的化学反应速率,还能够保证电解槽保持良好的传热性能,从而提高其整体的工作效率和稳定性。波形流道液态水浓度高于矩形流道,且由于波形结构的作用,垂直方向速度增大,使得反应物能够更好地进入电极。
图8为阳极催化层内氧气体积分数沿流动方向的分布。随着反应的进行,氧气沿流动方向在出口处积聚,使液态水无法进入催化层参与反应,严重制约了电解效率。在波形结构的影响下,流量的增加不仅加速了氧气的排出,还促进了液态水在催化层内的均匀分布和及时补充,保证了反应物的持续供应和电解过程的稳定运行。在流道中的波形结构处,催化层中的氧气体积分数明显降低。
当输入电压统一为2 V时,阳极催化层内氧气体积分数平均值如图9所示。由图9可见,与普通矩形通道相比,波形通道阳极催化层气体的平均体积分数明显减小,降低了3.1%~4.2%,其中M2减小3.1%,M3、M4减小3.7%,M5减小4.2%。因此,在流道中加入波形结构,不仅可以有效改善因氧气积聚引起的电解槽反应性能恶化等问题,还可以优化液态水的分布,提高电解槽的整体反应性能,有效改善电解槽内的传热传质现象。
由于波形结构的扰动,当水通过狭窄区域时,因波形起伏引起的湍流效应使通道内的流体速度显著增加。这种加速作用可以更有效地将电解过程中产生的氧气带离反应区域,减少气泡的积聚,从而提高反应效率和气体传质性能。在涉及多孔介质的区域(如扩散层和催化层),由于持续的化学反应不断消耗反应物,导致局部浓度梯度增大,在此区域会造成一定的浓差损耗。浓差损耗是制约反应速率和效率提升的关键因素之一。波形扰动的增加改变了部分水流的流动路径和方向,促进了水向扩散层和催化层的扩散,增强了水的渗透性,有助于减少反应物浓度不均匀造成的损失,提高了整体反应效率,降低了浓度损失。
图10展示了不同流道设计下流体流速的对比。在传统矩形流道中,随着反应的进行和氧气的不断产生,流体速度沿流动方向逐渐增大,但总体增长速度相对平缓,最大流速仅为0.193 m/s,位于流道出口界面处。相比之下,由于波形结构设计紧凑,流道体积减小,流体通过时产生更显著的加速效果,特别是在靠近出口的波形区域,峰值流速达到0.298 m/s,远高于直流流道。波形频率是波形通道设计中的一个重要参数,随着波形频率的变化,流道内的最大流速和平均流速展现出特定的变化趋势。具体而言,当流道形状为M3时,流体流速在某一位置达到最大值0.298 m/s;当流道形状调整为M4时,虽然流道内流速峰值低于M3,但整个流道的平均流速达到最大值0.112 m/s,高于M3。这说明M4内的流速上升比较平均,该设计使流体传输的整体性能更为优越。
有效传质系数(effective mass transfer coeffi-cient,EMTC)可以反映反应物在电解槽内的输运能力,是电解槽内传质特性的直接体现。
EMTC=|νcy|
式中:cy为反应物的浓度梯度;ν为速度[27]
根据EMTC的计算公式可知,电解槽内反应物的传质能力与流道内各位置的反应速度成正比,而流道内反应物流速的变化对通道的传质有直接影响。不同波形流道的EMTC如图11所示。对于传统矩形流道,由于流体速度分布相对均匀,垂直于流动方向的速度分量较小,导致反应物在流道内的扩散和交换受到一定限制。由图11可见,从传统流道入口到出口的EMTC保持在一个较低且基本不变的水平,这在一定程度上限制了电解槽的整体性能。在加入波形结构的流道中,流体在波形结构处形成局部的高速流动区域,流速的增加不仅提高了沿流动方向的EMTC,更重要的是使垂直于流动方向的流体速度分量显著提高。这种速度分布极大地促进了反应物在扩散层内的渗透扩散,使得波形结构处的传质系数显著增大,并在第1个波形结构处达到峰值。表3为各流道结构的平均有效传质系数。因此,不仅可以通过增加沿流动方向的流速来提高流道内的传质效率,还可以通过引入垂直于流动方向的速度分量来改善扩散层内液态水的传质。这不仅优化了电解槽内部的流动情况,而且提高了整体反应效率和性能稳定性。
流道的压降与速度、流道结构、流道尺寸等有关。图12为不同形状通道的压降对比。如图12所示,压降随着流道结构的复杂程度逐渐增大。流道结构越复杂,气体或液体在流道内流动时需要克服的阻力越大,压降就越高。流道内流速增大也是造成压降上升的因素之一,较高的压降也伴随着较高的流动速度。在设计和优化质子交换膜电解槽时,需要通过合理的流道设计(如优化流道宽度、深度、结构),将流道内的压降控制在合适范围内,以实现高效的气液流动和良好的反应性能。适当提升流道内的压降能够使流道内的气体尽快排出,减少气泡积聚,从而减少气泡引起的流动不均匀性。
当输入电压一定时,由于流道形状不同,波形流道相比于矩形流道的反应速率增强,电流密度较大,反应放热更加剧烈,电解槽温度较高。由于电化学反应发生在阳极催化层,膜电极区成为电解槽内部的主要热源,高温区也集中在此。长期在高温下运行,PEM的结构稳定性和性能可能会因热降解而逐渐下降,甚至导致膜破裂、失效等后果,严重缩短电解槽的使用寿命。因此,有必要尽可能降低膜电极区域的温度,延长PEM寿命。不同形状通道的平均温度随电流密度变化曲线如图13所示。由图13可见,当流道结构改变时,在相同电流密度下,波形通道的温度相对于方形通道的温度更低。这是由于波形结构带来的影响:一是流体与通道壁的接触面积显著增加,促进了热量从电解槽内部向外部传递;二是波形结构加速了流道内流体的流动速度,提高了对流换热系数,增强了热量的对流扩散能力。
对比M5与矩形流道M1 PEM阳极催化层内中心温度沿流动方向的变化结果如图14所示。从图14可见,流道波形结构处的温度下降明显。这是因为流体速度的增加和局部湍流强度的增加,不仅增强了流体的对流换热能力,而且由于氧含量的相对降低,换热系数增大,从而使膜电极可以更好地传热。因此,波形结构的加入有效增强了电解槽内的换热效果。
综上所述,在电解槽中引入波形通道设计,不仅可以显著提高电解反应的效率和电流密度,还可以有效缓解高温对PEM的不利影响,延长整个系统的使用寿命。另外,波形流道与带有堵块的流道相比,工艺更为简单,适合批量生产。
本文提出了一种具有波形流道结构的电解槽。通过建立多物理场耦合的三维两相稳态模型,对波形流道和常规矩形流道的阳极流场速度、物质分布和温度进行模拟比较,对其传热传质性能进行了分析,结论如下。
1)与普通矩形流道相比,具有波形流道的电解槽在电解性能、流道内水流速度、物质分布、电解槽温度和传热传质性能等方面均有不同程度的优化。相比之下波形流道阳极催化层平均氧气体积分数降低3.1%~4.2%,流速和有效传质系数都有所提高。
2)随着流道波形频率的增加,波形流道电解槽的极化性能先增大后减小,液态水体积分数增大,氧体积分数减小,流道内最大流速和平均流速先增大后减小。
3)当流道波形频率为1.0时,电解槽的电流密度提高了2.1%,阳极催化层平均氧气体积分数降低了3.7%,传热传质性能最高,电解槽的效率最高,电解槽综合性能最好。
  • 国家资助博士后研究人员计划(GZC20240464)
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doi: 10.19666/j.rlfd.202501035
  • 接收时间:2025-01-11
  • 首发时间:2026-03-05
  • 出版时间:2025-10-25
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  • 收稿日期:2025-01-11
基金
Postdoctoral Fellowship Program of CPSF(GZC20240464)
国家资助博士后研究人员计划(GZC20240464)
作者信息
    1.华北电力大学能源动力与机械工程学院,北京 102206
    2.河北建设投资集团有限责任公司,河北 石家庄 050001
    3.华北电力大学热电生产过程污染物监测与控制北京市重点实验室,北京 102206
    4.河北省热电清洁高效热电联产技术创新中心,河北 石家庄 050001

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黄吉光(1995),男,博士后,主要研究方向为太阳能和氢能高效利用,
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