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Title: High resolution neutron imaging of water in the polymer electrolyte membrane

Abstract

To achieve a deeper understanding of water transport and performance issues associated with water management, we have conducted in situ water examinations to help understand the effects of components and operation. High Frequency Resistance (HFR), AC Impedance and neutron radiography were used to measure water content in operating fuel cells under various operating conditions. Variables examined include: sub-freezing conditions, inlet relative humidities, cell temperature, current density and response transients, different flow field orientations and different component materials (membranes, GDLs and MEAs). Quantification of the water within the membrane was made by neutron radiography after equilibration to different humidified gases, during fuel cell operation and in hydrogen pump mode. The water content was evaluated in bare Nafion{reg_sign} membranes as well as in MEAs operated in both fuel cell and H{sub 2} pump mode. These in situ imaging results allow measurement of the water content and gradients in the PEFC membrane and relate the membrane water transport characteristics to the fuel cell operation and performance under disparate materials and operational combinations. Flow geometry makes a large impact on MEA water content. Higher membrane water with counter flow was measured compared with co-flow for sub-saturated inlet RH's. This correlates to lower HFR andmore » higher performance compared with co-flow. Higher anode stoichiometry helps remove water which accumulates in the anode channels and GDL material. Cell orientation was measured to affect both the water content and cell performance. While membrane water content was measured to be similar regardless of orientation, cells with the cathode on top show flooding and loss of performance compared with similarly operated cells with the anode on top. Transient fuel cell current measurements show a large degree of hysteresis in terms of membrane hydration as measured by HFR. Current step transients from 0.01 A cm{sup -2} to 0.68 A cm{sup -2} consistently show PEM wetting occurring within 5 to 20 sec. Whereas the PEM drying response to the reverse step transient of 0.68 A cm{sup -2} to 0.01 A cm{sup -2}, takes several minutes. The observed faster wetting response is due to reaction water being produced in the cathode and back diffusing into the membrane. The slower PEM drying is due to the water slowly being removed out of the wetted GDLs. This rate of removal of water and hence the PEM hydration level was found to be influenced strongly by the PTFE loadings in the GDL substrate and Microporous layer (MPL). The drying of the membrane is influenced by both the anode and cathode GDL PTFE loadings. Lower PTFE loading in the anode GDL leads to better membrane hydration probably due to the easier incorporation of water from the anode GDL into the membrane. Similarly a lower PTFE loading in the cathode GDL also results in better membrane hydration probably due to the better water retention properties (less hydrophobic) of this GDL. Fuel cells operated isothermal at sub-freezing temperatures show gradual cell performance decay over time and eventually drops to zero. AC impedance analysis indicates that losses are initially due to increasing charge transfer resistance. After time, the rate of decay accelerates rapidly due to mass transport limitations. High frequency resistance also increases over time and is a function of the initial membrane water content. These results indicate that catalyst layer ice formation is influenced strongly by the MEA and is responsible for the long-term degradation of fuel cells operated at sub-freezing temperatures. Water distribution measurements indicate that ice may be fonning mainly in the GDLs at -10 C but are concentrated in the catalyst layer at -20 C.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2]
  1. Los Alamos National Laboratory
  2. ORNL
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1026828
Report Number(s):
LA-UR-10-05379; LA-UR-10-5379
TRN: US201121%%126
DOE Contract Number:
AC52-06NA25396
Resource Type:
Conference
Resource Relation:
Conference: Gordon Research Conference ; August 1, 2010 ; Smithfield, RI
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 30 DIRECT ENERGY CONVERSION; ANODES; CATALYSTS; CATHODES; CURRENT DENSITY; DECAY; DRYING; ELECTROLYTES; FUEL CELLS; HYDRATION; HYDROGEN; IMPEDANCE; MEMBRANES; NEUTRON RADIOGRAPHY; NEUTRONS; POLYMERS; RESOLUTION; RETENTION; STOICHIOMETRY; SUBSTRATES; TRANSIENTS

Citation Formats

Spernjak, Dusan, Mukundan, Rangachary, Borup, Rodney L, Spendelow, Jacob S, Davey, John, Fairweather, Joseph, and Mukherjee, Partha. High resolution neutron imaging of water in the polymer electrolyte membrane. United States: N. p., 2010. Web.
Spernjak, Dusan, Mukundan, Rangachary, Borup, Rodney L, Spendelow, Jacob S, Davey, John, Fairweather, Joseph, & Mukherjee, Partha. High resolution neutron imaging of water in the polymer electrolyte membrane. United States.
Spernjak, Dusan, Mukundan, Rangachary, Borup, Rodney L, Spendelow, Jacob S, Davey, John, Fairweather, Joseph, and Mukherjee, Partha. 2010. "High resolution neutron imaging of water in the polymer electrolyte membrane". United States. doi:. https://www.osti.gov/servlets/purl/1026828.
@article{osti_1026828,
title = {High resolution neutron imaging of water in the polymer electrolyte membrane},
author = {Spernjak, Dusan and Mukundan, Rangachary and Borup, Rodney L and Spendelow, Jacob S and Davey, John and Fairweather, Joseph and Mukherjee, Partha},
abstractNote = {To achieve a deeper understanding of water transport and performance issues associated with water management, we have conducted in situ water examinations to help understand the effects of components and operation. High Frequency Resistance (HFR), AC Impedance and neutron radiography were used to measure water content in operating fuel cells under various operating conditions. Variables examined include: sub-freezing conditions, inlet relative humidities, cell temperature, current density and response transients, different flow field orientations and different component materials (membranes, GDLs and MEAs). Quantification of the water within the membrane was made by neutron radiography after equilibration to different humidified gases, during fuel cell operation and in hydrogen pump mode. The water content was evaluated in bare Nafion{reg_sign} membranes as well as in MEAs operated in both fuel cell and H{sub 2} pump mode. These in situ imaging results allow measurement of the water content and gradients in the PEFC membrane and relate the membrane water transport characteristics to the fuel cell operation and performance under disparate materials and operational combinations. Flow geometry makes a large impact on MEA water content. Higher membrane water with counter flow was measured compared with co-flow for sub-saturated inlet RH's. This correlates to lower HFR and higher performance compared with co-flow. Higher anode stoichiometry helps remove water which accumulates in the anode channels and GDL material. Cell orientation was measured to affect both the water content and cell performance. While membrane water content was measured to be similar regardless of orientation, cells with the cathode on top show flooding and loss of performance compared with similarly operated cells with the anode on top. Transient fuel cell current measurements show a large degree of hysteresis in terms of membrane hydration as measured by HFR. Current step transients from 0.01 A cm{sup -2} to 0.68 A cm{sup -2} consistently show PEM wetting occurring within 5 to 20 sec. Whereas the PEM drying response to the reverse step transient of 0.68 A cm{sup -2} to 0.01 A cm{sup -2}, takes several minutes. The observed faster wetting response is due to reaction water being produced in the cathode and back diffusing into the membrane. The slower PEM drying is due to the water slowly being removed out of the wetted GDLs. This rate of removal of water and hence the PEM hydration level was found to be influenced strongly by the PTFE loadings in the GDL substrate and Microporous layer (MPL). The drying of the membrane is influenced by both the anode and cathode GDL PTFE loadings. Lower PTFE loading in the anode GDL leads to better membrane hydration probably due to the easier incorporation of water from the anode GDL into the membrane. Similarly a lower PTFE loading in the cathode GDL also results in better membrane hydration probably due to the better water retention properties (less hydrophobic) of this GDL. Fuel cells operated isothermal at sub-freezing temperatures show gradual cell performance decay over time and eventually drops to zero. AC impedance analysis indicates that losses are initially due to increasing charge transfer resistance. After time, the rate of decay accelerates rapidly due to mass transport limitations. High frequency resistance also increases over time and is a function of the initial membrane water content. These results indicate that catalyst layer ice formation is influenced strongly by the MEA and is responsible for the long-term degradation of fuel cells operated at sub-freezing temperatures. Water distribution measurements indicate that ice may be fonning mainly in the GDLs at -10 C but are concentrated in the catalyst layer at -20 C.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2010,
month = 1
}

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  • Water transport in the ionomeric membrane, typically Nafion{reg_sign}, has profound influence on the performance of the polymer electrolyte fuel cell, in terms of internal resistance and overall water balance. In this work, high resolution neutron imaging of the Nafion{reg_sign} membrane is presented in order to measure water content and through-plane gradients in situ under disparate temperature and humidification conditions.
  • Sufficient water content within a polymer electrolyte membrane (PEM) is necessary for adequate ionic conductivity. Membrane hydration is therefore a fundamental requirement for fuel cell operation. The hydration state of the membrane affects the water transport within, as both the diffusion coefficient and electroosmotic drag depend on the water content. Membrane s water uptake is conventionally measured ex situ by weighing freeswelling samples equilibrated at controlled water activity. In the present study, water profiles in Nafion membranes were measured using high-resolution neutron imaging. The state-of-theart, 13 m resolution neutron detector is capable of resolving water distributions across N1120, N1110 andmore » N117 membranes. It provides a means to measure the water uptake and transport properties of fuel cell membranes in situ.« less
  • Sufficient water content within a polymer electrolyte membrane (PEM) is necessary for adequate ionic conductivity. Membrane hydration is therefore a fundamental requirement for fuel cell operation. The hydration state of the membrane affects the water transport within, as both the diffusion coefficient and electro-osmotic drag depend on the water content. Membrane's water uptake is conventionally measured ex situ by weighing free-swelling samples equilibrated at controlled water activity. In the present study, water profiles in Nafion{reg_sign} membranes were measured using the high-resolution neutron imaging. The state-of-the-art, 10 {micro}m resolution neutron detector is capable of resolving water distributions across N1120, N1110 andmore » N117 membranes. It provides a means to measure the water uptake and transport properties of fuel cell membranes in situ.« less
  • Water-content profiles across the membrane electrode assembly of a polymer-electrolyte fuel cell were measured using high-resolution neutron imaging and compared to mathematical-modeling predictions. It was found that the membrane held considerably more water than the other membrane-electrode constituents (catalyst layers, microporous layers, and macroporous gas-diffusion layers) at low temperatures, 40 and 60 C. The water content in the membrane and the assembly decreased drastically at 80 C where vapor transport and a heat-pipe effect began to dominate the water removal from the membrane-electrode assembly. In the regimes where vapor transport was significant, the through-plane water-content profile skewed towards the cathode.more » Similar trends were observed as the relative humidity of the inlet gases was lowered. This combined experimental and modeling approach has been beneficial in rationalizing the results of each and given insight into future directions for new experimental work and refinements to currently available models.« less
  • In this work, we investigated the dominating properties of the porous materials that impact water dynamics in a polymer electrolyte membrane fuel cell (PEMFC). Visualizations of liquid water in an operating PEMFC were performed at the Canadian Light Source. A miniature fuel cell was specifically designed for X-ray imaging investigations, and an in-house image processing algorithm based on the Beer-Lambert law was developed to extract quantities of liquid water thicknesses (cm) from raw X-ray radiographs. The X-ray attenuation coefficient of water at 24 keV was measured with a calibration device to ensure accurate measurements of the liquid water thicknesses. Frommore » this experiment, the through plane distribution of the liquid water in the fuel cell was obtained.« less