燃料电池薄膜在不同电流密度下的水传递规律
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摘要
为了提高燃料电池的性能而采用的质子交换膜越来越薄,但薄膜会带来水的反渗透而导致阳极水淹问题.为了研究低加湿条件下不同电流密度燃料电池薄膜的水传递规律,设计了三维简化电池模型并导入FLUENT软件,在工作温度75°C、操作压力150 kPa、阴极不加湿条件下进行了气流场及电化学模拟计算,并设计露点仪水平衡实验测试实际情况下水的传输通量,与模拟计算数值进行对比分析.研究发现使用15μm薄膜,电流密度增大到超过0.4 A/cm2以上并继续增大时,会持续发生总水量传递通量朝向阳极的现象,而当电流密度大于3.0 A/cm~2时,这一现象将减缓.同时研究还发现越薄的质子交换膜传递的总水量将越多.
Proton exchange membrane fuel cell(PEMFC) is considered to be one of the most promising technical for automotive power. Because it has high power density, low operating temperature and environmental friendliness. During the operation of the fuel cell, hydrogen protons accompanying water was transferred from the anode to the cathode by electro-osmotic drag. At the same time, the water will be produced at the cathode, and diffused from the cathode to the anode by a certain concentration difference. When the electro-osmotic drag is greater than the back diffusion, the anode needs to be continuously humidified to prevent the water loss in the membrane. When the back diffusion is greater than the electroosmotic drag, the water generated in the cathode is continuously transferred to the anode. Therefore, the law of water transfer in the membrane is an important issue in fuel cell research.In the present work, it adapted such thicker homogeneous membranes such as Nafion 117. It was found that at low current densities(0.2 A/cm~2), the anode was more likely to be flooded. While at high current densities, they believed that a higher electroosmotic drag will drag the anode water to the cathode, thereby reducing the anode water content. However,the used more and more thin membranes become a trend in fuel cell technology. For example, in the past, DuPont′s most thin membrane Nafion 211 was 25 μm, but now the 15 μm membrane represented by Gore was widely used, and Toyota has used 10 μm membrane. these thin membranes are different from the conventional thick membrane with uniform structure.Generally, the membrane was a sandwich structure with a perfluorosulfonic acid resin on both sides of the porous PTFE reinforced matrix. Therefore, the law of water transport was different from the homogeneous membrane.The water transport flux of the actual situation was tested by designing a dew point meter water balance test to analyze the water transfer law in the fuel cell. At the same time, the three-dimensional PEM fuel cell was simulated by using the fluid dynamics calculation software. The distribution of water content, anode water molar concentration and hydrogen mole fraction in the membrane was obtained. The results of experiment were compared to simulation results. The simulation results show that under the working condition of 75°C, 150 kPa, and cathode non-humidification conditions, the anode moisture of 15 μm membrane below 0.4 A/cm~2 decreases with the increase of current. In this case, electroosmosis drags counteract partial back diffusion; The anode water above 0.4 A/cm~2 increases with the increase of current, and the back diffusion played a leading role in transferring a large amount of water from cathode to the anode; the higher the current density, the more water was transferred to the anode. The actual test results showed that as the current increases, the more liquid water could be observed by the anode, which was consistent with the simulation results. When the membrane thickness was 15 μm, a thinner membrane increases the amount of water transferred from the cathode to anode. When the current was higher than 3.0 A/cm~2, the anode water volume of 25 μm membrane will decrease due to electroosmotic drag.But the anode water of 15 μm membrane will still increase, and the effect of back diffusion will increase with the decrease of membrane thickness.
Proton exchange membrane fuel cell(PEMFC) is considered to be one of the most promising technical for automotive power. Because it has high power density, low operating temperature and environmental friendliness. During the operation of the fuel cell, hydrogen protons accompanying water was transferred from the anode to the cathode by electro-osmotic drag. At the same time, the water will be produced at the cathode, and diffused from the cathode to the anode by a certain concentration difference. When the electro-osmotic drag is greater than the back diffusion, the anode needs to be continuously humidified to prevent the water loss in the membrane. When the back diffusion is greater than the electroosmotic drag, the water generated in the cathode is continuously transferred to the anode. Therefore, the law of water transfer in the membrane is an important issue in fuel cell research.In the present work, it adapted such thicker homogeneous membranes such as Nafion 117. It was found that at low current densities(0.2 A/cm~2), the anode was more likely to be flooded. While at high current densities, they believed that a higher electroosmotic drag will drag the anode water to the cathode, thereby reducing the anode water content. However,the used more and more thin membranes become a trend in fuel cell technology. For example, in the past, DuPont′s most thin membrane Nafion 211 was 25 μm, but now the 15 μm membrane represented by Gore was widely used, and Toyota has used 10 μm membrane. these thin membranes are different from the conventional thick membrane with uniform structure.Generally, the membrane was a sandwich structure with a perfluorosulfonic acid resin on both sides of the porous PTFE reinforced matrix. Therefore, the law of water transport was different from the homogeneous membrane.The water transport flux of the actual situation was tested by designing a dew point meter water balance test to analyze the water transfer law in the fuel cell. At the same time, the three-dimensional PEM fuel cell was simulated by using the fluid dynamics calculation software. The distribution of water content, anode water molar concentration and hydrogen mole fraction in the membrane was obtained. The results of experiment were compared to simulation results. The simulation results show that under the working condition of 75°C, 150 kPa, and cathode non-humidification conditions, the anode moisture of 15 μm membrane below 0.4 A/cm~2 decreases with the increase of current. In this case, electroosmosis drags counteract partial back diffusion; The anode water above 0.4 A/cm~2 increases with the increase of current, and the back diffusion played a leading role in transferring a large amount of water from cathode to the anode; the higher the current density, the more water was transferred to the anode. The actual test results showed that as the current increases, the more liquid water could be observed by the anode, which was consistent with the simulation results. When the membrane thickness was 15 μm, a thinner membrane increases the amount of water transferred from the cathode to anode. When the current was higher than 3.0 A/cm~2, the anode water volume of 25 μm membrane will decrease due to electroosmotic drag.But the anode water of 15 μm membrane will still increase, and the effect of back diffusion will increase with the decrease of membrane thickness.
引文
1 Bozorgnezhad A,Shams M,Kanani H,et al.Two-phase flow and droplet behavior in microchannels of PEM fuel cell.Int J Hydrogen Energy,2016,41:19164-19181
2 Yan Q,Toghiani H,Wu J.Investigation of water transport through membrane in a PEM fuel cell by water balance experiments.J Power Sources,2006,158:316-325
3 Nguyen T V,White R E.A water and heat management model for proton-exchange-membrane fuel cells.J Electrochem Soc,1993,140:2178-2186
4 Iranzo A,Boillat P.Liquid water distribution patterns featuring back-diffusion transport in a PEM fuel cell with neutron imaging.Int J Hydrogen Energy,2014,39:17240-17245
5 Pasaogullari U,Wang C Y.Two-phase modeling and flooding prediction of polymer electrolyte fuel cells.J Electrochem Soc,2005,152:A380
6 Ge S,Wang C Y.Liquid water formation and transport in the PEFC anode.J Electrochem Soc,2007,154:B998
7 Xing L,Mamlouk M,Kumar R,et al.Numerical investigation of the optimal Nafion?ionomer content in cathode catalyst layer:An agglomerate two-phase flow modelling.Int J Hydrogen Energy,2014,39:9087-9104
8 McKay D A,Ott W T,Stefanopoulou A.Modeling,parameter identification,and validation of reactant and water dynamics for a fuel cell stack.In:Proceedings of the ASME Dynamic Systems and Control Division 2005,Pts A and B,2005:1177-1186
9 Cai Y H.Study on water transfer phenomenon of proton exchange membrane fuel cell(in Chinese).Doctor Dissertation.Dalian:Graduate School of Chinese Academy of Sciences,2006[才英华.质子交换膜燃料电池水传递现象研究.博士学位论文.大连:中国科学院研究生院,2006]
10 Abe T,Shima H,Watanabe K,et al.Study of PEFCs by AC impedance,current interrupt,and dew point measurements.J Electrochem Soc,2004,151:A101
11 Borup R L,Mukundan R,More K,et al.PEM Fuel Cell Catalyst Layer(MEA)Architectures.Los Alamos National Lab.(LANL),Los Alamos,NM(United States),2018
12 Wilson M S,Zawodzinski T A,Gottesfeld S,et al.Advanced composite polymer electrolyte fuel cell membranes.Los Alamos National Lab.(LANL),Los Alamos,NM(United States),1995
13 Vengatesan S,Kim H J,Cho E A,et al.Operation of a proton-exchange membrane fuel cell under non-humidified conditions using thin cast Nafion membranes with different gas-diffusion media.J Power Sources,2006,156:294-299
14 Breitwieser M,Moroni R,Schock J,et al.Water management in novel direct membrane deposition fuel cells under low humidification.Int JHydrogen Energy,2016,41:11412-11417
15 Hu L.Study on water diffusion of composite proton exchange membrane for fuel cells(in Chinese).Master Dissertation.Wuhan:Wuhan University of Technology,2013[胡玲.燃料电池用复合质子交换膜水扩散的研究.硕士学位论文.武汉:武汉理工大学,2013]
16 Yuan W,Tang Y,Pan M,et al.Model prediction of effects of operating parameters on proton exchange membrane fuel cell performance.Renew Energy,2010,35:656-666
17 Dicks A,Rand D A J.Fuel Cell Systems Explained.New York:Wiley Online Library,2018
18 Wu H,Li X,Berg P.On the modeling of water transport in polymer electrolyte membrane fuel cells.Electrochim Acta,2009,54:6913-6927
19 Zhang G,Jiao K,Wang R.Three-dimensional simulation of water management for high-performance proton exchange membrane fuel cell.SAE Int J Alt Power,2018,7:233-247
20 Tao W Q,Min C H,Liu X L,et al.Parameter sensitivity examination and discussion of PEM fuel cell simulation model validation.J Power Sources,2006,160:359-373
21 Fischer A,Jindra J,Wendt H.Porosity and catalyst utilization of thin layer cathodes in air operated PEM-fuel cells.J Appl Electrochem,1998,28:277-282
22 Zhang G,Fan L,Sun J,et al.A 3D model of PEMFC considering detailed multiphase flow and anisotropic transport properties.Int J Heat Mass Transfer,2017,115:714-724
2 Yan Q,Toghiani H,Wu J.Investigation of water transport through membrane in a PEM fuel cell by water balance experiments.J Power Sources,2006,158:316-325
3 Nguyen T V,White R E.A water and heat management model for proton-exchange-membrane fuel cells.J Electrochem Soc,1993,140:2178-2186
4 Iranzo A,Boillat P.Liquid water distribution patterns featuring back-diffusion transport in a PEM fuel cell with neutron imaging.Int J Hydrogen Energy,2014,39:17240-17245
5 Pasaogullari U,Wang C Y.Two-phase modeling and flooding prediction of polymer electrolyte fuel cells.J Electrochem Soc,2005,152:A380
6 Ge S,Wang C Y.Liquid water formation and transport in the PEFC anode.J Electrochem Soc,2007,154:B998
7 Xing L,Mamlouk M,Kumar R,et al.Numerical investigation of the optimal Nafion?ionomer content in cathode catalyst layer:An agglomerate two-phase flow modelling.Int J Hydrogen Energy,2014,39:9087-9104
8 McKay D A,Ott W T,Stefanopoulou A.Modeling,parameter identification,and validation of reactant and water dynamics for a fuel cell stack.In:Proceedings of the ASME Dynamic Systems and Control Division 2005,Pts A and B,2005:1177-1186
9 Cai Y H.Study on water transfer phenomenon of proton exchange membrane fuel cell(in Chinese).Doctor Dissertation.Dalian:Graduate School of Chinese Academy of Sciences,2006[才英华.质子交换膜燃料电池水传递现象研究.博士学位论文.大连:中国科学院研究生院,2006]
10 Abe T,Shima H,Watanabe K,et al.Study of PEFCs by AC impedance,current interrupt,and dew point measurements.J Electrochem Soc,2004,151:A101
11 Borup R L,Mukundan R,More K,et al.PEM Fuel Cell Catalyst Layer(MEA)Architectures.Los Alamos National Lab.(LANL),Los Alamos,NM(United States),2018
12 Wilson M S,Zawodzinski T A,Gottesfeld S,et al.Advanced composite polymer electrolyte fuel cell membranes.Los Alamos National Lab.(LANL),Los Alamos,NM(United States),1995
13 Vengatesan S,Kim H J,Cho E A,et al.Operation of a proton-exchange membrane fuel cell under non-humidified conditions using thin cast Nafion membranes with different gas-diffusion media.J Power Sources,2006,156:294-299
14 Breitwieser M,Moroni R,Schock J,et al.Water management in novel direct membrane deposition fuel cells under low humidification.Int JHydrogen Energy,2016,41:11412-11417
15 Hu L.Study on water diffusion of composite proton exchange membrane for fuel cells(in Chinese).Master Dissertation.Wuhan:Wuhan University of Technology,2013[胡玲.燃料电池用复合质子交换膜水扩散的研究.硕士学位论文.武汉:武汉理工大学,2013]
16 Yuan W,Tang Y,Pan M,et al.Model prediction of effects of operating parameters on proton exchange membrane fuel cell performance.Renew Energy,2010,35:656-666
17 Dicks A,Rand D A J.Fuel Cell Systems Explained.New York:Wiley Online Library,2018
18 Wu H,Li X,Berg P.On the modeling of water transport in polymer electrolyte membrane fuel cells.Electrochim Acta,2009,54:6913-6927
19 Zhang G,Jiao K,Wang R.Three-dimensional simulation of water management for high-performance proton exchange membrane fuel cell.SAE Int J Alt Power,2018,7:233-247
20 Tao W Q,Min C H,Liu X L,et al.Parameter sensitivity examination and discussion of PEM fuel cell simulation model validation.J Power Sources,2006,160:359-373
21 Fischer A,Jindra J,Wendt H.Porosity and catalyst utilization of thin layer cathodes in air operated PEM-fuel cells.J Appl Electrochem,1998,28:277-282
22 Zhang G,Fan L,Sun J,et al.A 3D model of PEMFC considering detailed multiphase flow and anisotropic transport properties.Int J Heat Mass Transfer,2017,115:714-724