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National Science Foundation Workshop

on

Engineering Fundamentals
of
Low Temperature (PEM) Fuel Cells

November 14-15, 2001

ORGANIZERS
Professor Robert Savinell rfs2@po.cwru.edu
Professor Joe Payer jhp@po.cwru.edu

Yeager Center for Electrochemical Sciences
Case Western Reserve University

SPONSORS
Dr. Thomas Chapman-Acting Division Director
Dr. Robert Wellek-Deputy Division Director
Dr. Geoffrey Prentice, Program Director-Chemical Reaction Processes

National Science Foundation
Directorate of Engineering
Division of Chemical and Transport Systems (ENG/CTS).

NSF Headquarters
Arlington, VA

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NSF Workshop on Engineering Fundamentals of
Low Temperature (PEM) Fuel Cells

OBJECTIVES

The purpose of this workshop was to bring together a group of fuel cell technologists with a
cadre of engineering and scientific experts in the interdisciplinary fields that directly relate to this
technology. The focus of the workshop is on low-temperature (PEM) fuel cells. The workshop
objectives were:

Define fundamental issues and challenges affecting fuel cell and fuel cell system performance
• Identify the research needs for improved understanding of fuel cell and fuel cell system
performance
• Describe technical approaches to meet the research needs
• Establish an agenda for basic engineering research that will address these needs

In addition to this report, the workshop presentations and outcomes are available on the NSF
website and the Yeager Center for Electrochemical Sciences website.
See http://electrochem.cwru.edu.

ORGANIZERS

The Fuel Cell workshop was organized and directed by:

Professor Robert Savinell rfs2@po.cwru.edu
Professor Joe Payer jhp@po.cwru.edu

Yeager Center for Electrochemical Sciences
Case Western Reserve University
Cleveland, Ohio

SPONSORS

NSF sponsored the Fuel Cell workshop and Geoffrey Prentice was the Program Director.

Thomas Chapman-Acting Division Director
Robert Wellek-Deputy Division Director
Geoffrey Prentice, Program Director-Chemical Reaction Processes

National Science Foundation
Directorate of Engineering
Division of Chemical and Transport Systems (ENG/CTS)

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DESCRIPTION OF THE WORKSHOP

The workshop brought a group of fuel cell technologists together with a cadre of engineering and
scientific experts in the interdisciplinary fields that directly relate to this technology. There were
39 workshop participants from academia, industry and government. In addition, approximately
20 Federal participants from NSF, DOE, NASA, NIST, ONR and NSWCCD joined portions of
the proceedings. See the attached list of participants. Plenary sessions of the participants and
breakout sessions with 8-10 participants were convened on four topics: Electrodes; Membranes;
Fuel Processing; and Diagnostics and Modeling.

The approach to the organization of this workshop was to invite key technologists/scientists to
address technical issues and challenges of the fuel cell components. These engineers/scientists
have expertise and know the state-of-the-art on these components. In addition, engineering and
scientific experts from relevant engineering disciplines were also invited in order to bring the
most advanced thinking in these fields. By bringing together these two groups and sharing
information and insight, the goal was to develop a suggested research agenda for NSF that will
address the needs of the fuel cell community.

The plenary speakers are listed in the attached table. Copies of their presentations are available
on the workshop website. An informal poster session was held on the evening of the first day,
and several participants posted descriptions of relevant fuel cell research. Copies of the poster
presentations are also available on the workshop website.

The workshop was held at NSF Headquarters in Arlington, VA on November 14 and 15, 2001.
In addition to this report, the workshop presentations and outcomes are available on the NSF
website and the Yeager Center for Electrochemical Sciences website.
See (http://electrochem.cwru.edu).

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SUMMARY OF THE MAJOR FINDINGS

OVERARCHING ISSUES AND RESEARCH NEEDS

Advanced Materials
• Materials and manufacturing processes to lower costs
• Development, characterization and performance of advanced materials
• Reduced platinum group metal content in catalysts for improved cost and availability

Fundamental Understanding
• Discernment of fundamental mechanisms for electrochemical processes, conduction and
transport
• Essential to build bridges between experimentalists, spectroscopists, modelers and
theorists

Performance and Durability
• Determination of performance, reliability and durability
• Deal with complete functioning systems, in addition to single components; for example,
full membrane electrode assemblies and functioning catalyst-coated membranes

Models and Diagnostics
• Modeling and determination of performance, reliability and durability
• Theory to identify systems displaying most promising characteristics
• Model systems to assess the degree of validity of theoretical predictions

Process Control and Sensors
• Improved sensors with minimal drift, rapid response time, and high selectivity to
impurities are needed
• Improved process control for complex systems

EDUCATION AND TRAINING NEEDS
Implementation of these research initiatives will require participation of scientists across many
disciplines in coordinated efforts. Multi investigator award programs, following, for example, the
MURI model, should encourage such activities. In addition, the funding of graduate assistantship
in interdisciplinary areas as illustrated by the GOALI program is recommended.

Education is required for fuel cells to achieve public acceptance and significant market
penetration. A qualified work force and a general public awareness of fuel cells need to be
developed. The challenge was perceived to be the development of a consistent set of fuel cell
related materials suitable for education and training at all levels; K-12, undergraduate and adults
(including the general public, practicing engineers and technicians).

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MEMBRANES: SUMMARY OF ISSUES AND RESEARCH NEEDS
General requirements of membranes for fuel cells:
• Low resistance under cell operating conditions.
• Long-term chemical and mechanical stability at various operating temperatures in
oxidizing and reducing environments.
• Good mechanical strength, preferably with resistance to swelling.
• Low gas crossover and pinhole free.
• Interfacial compatibility with catalyst layers.
• Low cost.

At present, Nafion-type membranes dominate the commercial market. These membranes meet
many of the needs described above yet have perceived or real shortcomings. These
shortcomings include high cost, unacceptable methanol cross-over and water transport
rates and completely inadequate properties above 100 oC, an important emerging
condition for which membranes will be used. In an attempt to fill these gaps, several new
materials have emerged; however each of these also has significant real or perceived
shortcomings.

Recommended research thrusts:
• Fundamental research on proton conduction and solvent transport in polymer systems
• Synthetic efforts devoted to both model systems (for aiding understanding) and the
development of new polymers and/or conducting media
• Characterization of new polymers and model systems
• Development of functioning catalyst-coated membranes from new polymers
• Assessment of performance of the functioning catalyst-coated membranes in fuel cells

Fundamental research on proton conduction and solvent transport in polymer and related
systems: Fundamental studies of polymers, conducting solutions or gels and model
systems are required. Understanding fundamental steps in proton and solvent transport is
critical. Experimental studies are needed on a range of well-characterized new materials
and model systems. Research is needed on new conducting media. Developing an
understanding of factors affecting methanol uptake and transport is essential for Direct
Methanol Fuel Cells.

Development of new polymeric fuel cell membranes requires significant input from the polymer
chemistry arena with others. Research needs to address a number of facets of the
membrane such as (1) Polymer Scaffold – Polymer backbone, (2) Morphology, and (3)
Conducting Medium.

Characterization of new polymers and model systems: Research needs to be carried out in
developing and applying characterization methods. Reliable structure determination,
using techniques such as NMR, XRD (SAXS, WAXS), Microscopy (AFM, TEM, SEM)
and Neutron Studies needs to be addressed. Furthermore such techniques will allow

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identification of structure development as a function of time and processing effects.
Detailed studies of transport processes are also desirable.

Development of Catalyst-Coated Membranes from new polymers: Research is needed to
understand (1) adhesion (2) the ill-defined nature of the interfaces (3) specifics on how
the polymers interact with the electrode and (4) Molecular Level Contact between
polymer and electrode-access through polymer to electrode surface. The cathode
performance is highly sensitive to the acid used in the electrode. Also, any use of solid
acids or other transport media requires that a means be found to use these materials in
electrodes.

Assessment of performance and durability: Fuel cell testing is the ultimate probe of the adequacy
of alternative electrolytes. The effect of aging of the fuel cell must be addressed. Two
main types of aging processes that require investigation: chemical degradation of the
membrane and mechanical degradation. The degradation modes include delamination,
swelling, and membrane thinning.

ELECTRODES: SUMMARY OF ISSUES AND RESEARCH NEEDS
Recommended research thrusts:
• Development of new electrocatalysts,
• Fundamental studies on model systems,
• Fundamental understanding the mechanism of environmental/process poisons
• Catalyst dispersions

From an overall perspective, there is a need for computational studies in electrochemical systems
to be brought together including quantum and other theoretical modeling to transport
phenomenon and electrocatalysis. Essential to these activities is the building of bridges between
spectroscopists and theorists.

Approaches to new electrocatalysts for reactions of relevance to fuel cells:
Combinatorial Methods-with parallel development of preparation and performance
techniques and with strong theoretical rationale for design and evaluation of ensembles;
Surface Modification-with theory to help identify systems displaying the most promising
characteristics and accompanying development of model systems to assess the degree of
validity of theoretical predictions; and Metal Support Interactions-to modify the
electrocatalytic activity of traditional and novel materials; with priority to studies in the
area of oxygen reduction, followed by direct methanol oxidation, CO tolerant catalysts,
and next catalyst interactions with membrane and ionomer including the role of reaction
intermediates.
Fundamental studies for detailed mechanistic pathways of heterogeneous electron transfer
reactions to gain a better understanding of water activation, breaking of bonds, and co-
adsorption with water. Use of bimetallic and trimetallic surfaces with well defined single
crystals both in electrochemical and ultrahigh vacuum environments are recommended.
Also to be emphasized is the preparation and characterization of well-defined
nanocrystals. Priority should be given to studies of oxygen reduction followed by direct

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methanol oxidation and CO tolerant anodes. Particle Size Effects-Determine
unambiguously whether these effects are indeed real for particles on the order of nm and
below. Key to the success of these studies is the development and implementation of
methods for the preparation of monodispersed catalysts, which may include, among
others, template-, and micellar-based synthesis

Understanding The Role Of Environmental/Process Poisons: The presence of sulfur and nitrogen
oxides, as well as CO, sulfur oxides and aromatic species in the gas feed of cathodes and
anodes, respectively, can impair the performance of fuel cells by blocking active sites for
electron transfer. Although aspects of all such impurities, and especially their adverse
impact in performance, should be carefully investigated, carbon monoxide is perceived to
be by far the most damaging, and, as such, should receive the most immediate attention.

Catalyst Dispersion: The long-term activity and stability of fuel cell electrodes relies, among
other factors, on maintaining a stable, highly dispersed array of often supported particles
of nm dimensions. It is therefore essential to examine both experimental and theoretical
aspects of sintering.

Alkaline fuel cells: Determine whether this alternate technology may provide niche advantages
in terms of kinetics and cost considerations over the more widely developed acid
counterpart.

DIAGNOSTICS/MODELING: SUMMARY OF ISSUES AND RESEARCH NEEDS
Five main areas of research were deemed to have high priority:
• Understanding Electrode Structures
• Cell and Stack Diagnostics with an emphasis on development of non-intrusive
sensing capabilities
• Cell and Stack Models with detailed two-phase flow and thermal capabilities
• Material Properties Determination, focusing on properties of porous materials
• Education

Three other areas of research were deemed important but not as high priority:
• Diagnostic tools and sensors for manufacturing,
• Diagnostic sensors for durability/failure sensing,
• System level models, integrating detailed fuel cell models with balance of plant
component models (compressors, fuel processors) and models of the electrical
load to be powered.

Understanding Electrode Structures: The current methods for developing electrode structures are
almost purely empirical. This leads to a long, inefficient development cycle. First, there is
need for tools to probe the structures currently used. Secondly, an understanding is
needed of interactions between the components in a catalyst ink and electrode structure
formed when the solvent is removed. Similarly, the processing conditions affect the final
structure and performance. The final challenge is that given the tools to determine the

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structure and properties of these electrodes, sufficiently detailed models need to be
developed to predict effective structures and processes for forming those structures.

Cell and Stack Diagnostics: The clear issue is that very little data is available for temperature,
composition, flow and current distributions within operating cells or stacks. As a result,
existing models cannot be verified, nor can their limitations be assessed to direct the
development of advanced models. The challenge is to develop non-intrusive sensors that
can be inserted into stack components. A second challenge is to develop better
diagnostics based on time and frequency domain methodologies, based on first principles
as opposed to the common equivalent circuit approach.

Cell and Stack Models: The most important issue was the need to accurately deal with two-phase
(liquid and vapor phase) flow characteristics. Other issues include the need to account for
non-uniform properties that may result from compressive stresses or manufacturing
variations, and to integrate mechanical models with fluid flow models. A very significant
practical benefit could be realized if the phenomena of flooding could be understood and
predicted, and means to mitigate flooding could be developed.

Materials Properties: The clear issue in this area is that very little data exists for many of the
material properties of interest. The challenge is to develop methods to measure the
appropriate properties under realistic operating conditions of temperature, humidity, and
the presence of compressive forces. The properties of greatest interest are those relating
to the gas diffusion layer, its electrical conductivity and contact resistance with the
electrode and the bipolar plate, the thermal conductivity (and thermal contact resistances)
and liquid and vapor permeabilities.

FUEL PROCESSING: SUMMARY OF ISSUES AND RESEARCH NEEDS
The issues here deal with engineering design, operation, catalysts, and cost. Key issues:
• Simplify the system while improving the cost/performance,
• Elimination of reactors and reducing or eliminating precious metal catalysts,
• Improved life and impurity tolerance of the catalysts,
• Control and/or removal of impurities with sulfur and carbon monoxide being key,
• Operational control for rapid start-up, operation at different temperatures and the
transient temperature,
• Reduced cost by increased catalyst activity and stability, increased availability and
recycle ability

The focus in the fuel processing area is better methods to treat impurities and better catalysts to
generate hydrogen at lower temperatures with high yield and high through-put. Improved control
systems are required. Effort is recommended to improve the existing reprocessing approach
through improved lifetime and cost of catalysts used in the autothermal reactors (ATR), water
gas shift (WCR) reactors, and preferential oxidation (PrOx) units. In addition, work is needed for
improved PEM catalysts. Operation of integrated systems should be a high priority to optimize
the operation and efficiency of the process including the control systems. Another approach is to
focus on alternative methods to provide anode fuel; particularly membrane reactors to

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concentrate hydrogen and direct methanol fed anodes. As with all catalyst systems, reducing the
platinum group metal (PGM) content is necessary from both a cost and availability standpoint.

For autothermal reactors (ATR): Catalysts are needed with higher selectivity, reduced pyrophoric
nature and low temperature activity. Fundamental understanding of the chemistry would
help in the design of the catalyst. Lower temperature operation is desired as well as
improved hydrogen yield. Reduction in coking is also desirable.

Removal of sulfur impurities: Pursue fuel desulfurization upstream of the ATR reactor or post
ATR gas desulfurization. For onboard use, gas phase desulfurization on zinc oxide may
be preferable. For breakthrough technology, development of a hydrogen permeable
membrane reactor that uses little or no palladium would be exciting. Alternatively, the
reduction of non-reactive gases would also improve the performance and cost of the
system by reducing its size and concentrating the primary reactants.

Removal of carbon monoxide impurity: Highly active, non-noble metal shift catalysts are needed
along with operation at lower temperatures and reduced oxygen/condensate sensitivity.
Improved catalysts are also needed in the preferential oxidation unit (PrOx).
Combinations of shift catalysts with membrane reactors could yield greatly improved
performance and eliminate the PrOx reactor.

Improvement of the hydrogen anode catalyst in the PEM fuel cell in regard to poisoning by
sulfur and carbon monoxide would allow the constraints currently placed on the fuel-
processing unit to be relaxed.

Improved process control: There is a need to minimize excursions in this complex system.
Improved sensors with minimal drift, rapid response time, and high selectivity to
impurities are needed. A reliable mass flow sensor is the highest priority, followed by
high temperature CO and sulfur sensors. A dynamic model is needed to capture these
parameters and to optimize the operation of the fuel-processing unit.

New concepts include: oxygen enrichment to reduce the amount of carriers gases, plasma
generation of hydrogen, use of micro-channel reactors for reforming, thermally integrated
multi-functional reactors, and solid electrolyte membrane partial oxidation.

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PLENARY SPEAKERS, TOPICS AND CATEGORY OF PRESENTATIONS

The following is a list of speakers at the plenary sessions of the NSF Workshop on Engineering
Fundamentals of Low Temperature (PEM) Fuel Cells

Speaker Affiliation Topic Category
Hubert Gasteiger Global Alternative Electrocatalyst and electrode ELECTRODES
Propulsion Center structure
Thomas Los Alamos Nat. Lab. Membrane performance and MEMBRANES
Zawodzinski evaluation
Mark G. Roelofs DuPont CR&D Membrane performance and MEMBRANES
evaluation
Mark Mathias Global Alternative Design, engineering, modeling DIAGNOSTICS/MODELING
Propulsion Center and diagnostics
Frano Barbir Proton Power Systems Design, engineering, modeling DIAGNOSTICS/MODELING
and diagnostics
Richard Bellows IFC/Hydrogen Source Fuel processing performance FUEL PROCESSING
and evaluation
Charles K. Lavan Lockheed Martin FUEL PROCESSING
Jr. Corporation Regenerative Power Systems

BACKGROUND

Fuel cells were invented more than 150 years ago but have only emerged in the last decade as
one of the most promising new technologies for meeting worldwide energy needs in the 21st
century. The fuel cell industry will have a significant impact on the consumer market in the
future, playing a major role wherever power is needed. Potential markets include stationary
power sources for household and industrial use (heating and electricity); transportation power
(moving vehicles on land and in air or space); and portable power (battery power for cell
phones, laptop computers, power tools, etc.).

The fuel cell is a device that converts the chemical energy of a fuel into usable electricity and
heat without combustion as an intermediate step. Fuel cells are similar to batteries in that both
produce a DC current by means of an electrochemical process. As an energy source, fuel cells
produce almost none of the sulfur and nitrogen compounds released by conventional generating
methods, and are capable of using a variety of fuels including hydrogen, natural gas, coal-
derived gas, landfill gas, biogas, refined and reformed liquid fuels, or alcohols. Liquid fuels are
processed to hydrogen for feeding the fuel cell stack, heat and mass must be balanced, and the
power often needs to be conditioned. Thus the basic sciences that support fuel cell development
are varied, and require interdisciplinary approaches.

Since the early 1990's the U.S. government through major fuel cell research and development
programs sponsored by the Departments of Defense, Energy, and Transportation have
recognized the potential of fuel cell applications. All of the major automotive manufacturing
companies have recognized the need for fuel cell development as power sources for motive

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products. According to the National Fuel Cell Research Center, Daimler-Benz and Ford Motor
Companies have each invested over a half-billion dollars into Ballard Power Systems to develop
a clean vehicle engine comparable to conventional ones; and all the major automotive companies
are developing and exhibiting prototype automobiles relying on fuel-cell power. A market for
stationary distributed power generation also has been a driver for fuel cell development. This
market segment is a direct result of utility deregulation, and the need for power at new living,
shopping, and commercial complexes. There is increasing concern as to reliability of electric
energy, and this has created increased demand for emergency power for hospitals and major
computational and computer data storage resources. During the past several years, the demand
for high energy density portable power has grown. This demand is driven by the proliferation of
portable electronic and computer devices and the desire for longer operational times. All of
these factors together are the cause for an unprecedented resurgence of interest in fuel cells and
their development.

However, with all this interest in fuel cells, there are still formidable technical challenges.
Although theoretically capable of high efficiency, the catalyst and transport processes limit
actual performance. Engineering challenges of integrating and controlling the fuel cell system
(fuel processor, fuel cell, and power conditioning) must be overcome, especially for transient
operation. In the case of portable power, miniaturization requires advanced material properties
since these devices need to be passive without mechanical pumps, compressors, humidifiers, or
complex flow systems. In addition, fuel cells overall are material intensive and cost of materials
and fabrication is a significant challenge. Although the driving forces for commercializing fuel
cells are strong, significant use and market penetration will require advances and in some cases,
breakthroughs in materials and designs. Thus, fundamental research that provides the technical
basis for fuel cell advances will be essential. This workshop brought together technical experts
in order to define an appropriate research agenda.

MEMBRANES WORKGROUP REPORT

See plenary presentations: “Membrane performance and evaluation” by Thomas Zawodzinski;
“Membrane performance and evaluation” by Mark G. Roelofs

I. STATE OF THE ART AND EXISTING GAPS: FUNDAMENTAL ISSUES AND
CHALLENGES
This committee considered opportunities in the understanding and development of proton–
conducting membranes for Polymer Electrolyte Fuel Cells. In this report, we describe the state
of the art and nature of the requirements for new materials, likely components of a
comprehensive research program in polymer electrolytes and, finally, a suggested agenda to
realize the scientific and technical objectives.

A. Desired Membrane Properties

We first describe the attributes of a proton conducting membrane in the fuel cell. After
describing general aspects, we also consider a few application-specific membrane needs. These
represent the targets for membrane development.

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General Required Attributes of Membranes for Fuel Cells
• Low resistance under cell operating conditions.
• Long-term chemical and mechanical stability at various operating temperatures in
oxidizing and reducing environments.
• Good mechanical strength, preferably with resistance to swelling.
• Low gas cross-over and pinhole free.
• Interfacial compatibility with catalyst layers.
• Low cost.

Attributes of Membranes for Specific Fuel Cell Applications
Direct Methanol Fuel Cells
• Minimized cross-over of methanol through membrane combined with high
membrane conductivity
• Lowered electro-osmotic transport of water for some applications

Fuel Cells Operating in Ambient Conditions on Hydrogen
• High conductivity under conditions of widely variable humidity

Fuel Cells in Automotive Applications
o
• Operation at temperature in excess of 120 C.
• Minimal or zero dependence on external hydration at elevated temperature
o
• Conduction at very low temperature (-40 C), allowing cold starting of cells

Thus, there exist needs for a wide range of membrane types, with cost a very significant market
driver in every case.

B. State of Art and Gaps

At present, Nafion-type membranes dominate the commercial market. These membranes meet
many of the needs described above yet have perceived or real shortcomings. These shortcomings
include high cost, unacceptable methanol cross-over and water transport rates and completely
inadequate properties above 100 oC, an important emerging condition for which membranes will
be used.

In an attempt to fill these gaps, several new materials have emerged, each with significant
shortcomings. Membranes prepared from PBI/phosphoric acid and sulfonated aromatics are
currently being developed, while water ‘replacement’ systems that contain imidazole units and
inorganic acids are also under investigation. For methanol applications, some advances have
been made, notably with the sulfonated poly(sulfones). Low cost membranes such as sulfonated
Kraton have also been prepared. However, none of these materials are completely adequate for
their intended tasks.

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II. APPROACHES TO IMPROVED UNDERSTANDING AND NEW MEMBRANE
MATERIALS
The approach used to date in developing new materials has been, generically speaking,
fairly random. There has been a tendency to focus on polymer properties and/or the mere ability
to prepare a conducting system rather than on fully integrating what is known concerning proton
conduction in such systems, or vice versa. For example, in developing new polymers for
operation at elevated temperature, some workers have focused on developing thermally stable
systems with scant real consideration for requirements related to proton conduction. Others have
attempted to develop conducting systems based on polymers known to have thermal stability
limitations. Finally, the necessary transition of new polymer systems into functioning catalyst-
coated membranes (CCMs) has been problematic.

Clearly, this work calls for a coordinated effort including elements of:
• fundamental research on proton conduction in polymer systems
• synthetic efforts devoted to both model systems (for aiding understanding) and the
development of new polymers and/or conducting media
• characterization of new polymers and model systems
• development of functioning catalyst-coated membranes from new polymers
• assessment of performance in fuel cells
Generally speaking, a robust program in this area will consist of teams covering the bases
described above. More specific details will be provided in the following section.

III. AGENDA FOR ENGINEERING RESEARCH
Based on the general agenda presented above, we now suggest some more concrete research
activities. The work should be highly coordinated, with successive generations of synthesis
driven by new understanding.

Fundamental research on proton conduction and solvent transport in polymer and related
systems

There is an overarching need for fundamental studies of polymers, conducting solutions or gels
and model systems to advance this field. Understanding fundamental steps in proton and solvent
transport with the twist that such transport takes place in confined media (e.g. the pore of a
polymer membrane) is critical. This research should consider the difficult problem of connecting
the scale of ab initio computations to longer range modeling, especially since this conduction
problem is likely to involved cooperative effects. Further experimental studies are needed on a
range of well-characterized new materials and model systems. This will extend the range of our
understanding, leading too new synthetic approaches. Also, research is needed on new
conducting media. Using cues from our understanding of aqueous systems, it is of great interest
to develop solid or low volatility proton conducting phases operating at T > 150oC. Finally,
developing an understanding of factors affecting methanol uptake and transport is essential for
DMFC applications.

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Synthetic efforts devoted to both model systems (for aiding understanding) and the
development of new polymers and/or conducting media

The development of new polymeric fuel cell membranes requires significant input from the
polymer chemistry arena. Targeted funding to this area is necessary to encourage participation
from scientists in this field. More specifically this research needs to address a number of facets
of the membrane such as (1) Polymer Scaffold – Polymer backbone etc., which will influence
properties such as degradation and high temperature stability (2) Morphology – what is the
polymer morphology and can self-assembled polymers with specific morphological architectures
be used to control transport through the membrane? (3) Conducting Medium – Can current
systems e.g. Aromatic Sulfonate/water, PFSI/water, Sulfonimide/water, Imidazole and
Phosphoric Acid, be used more efficiently and can new systems be developed e.g. blended
polymer/oligomer above Tg, solid acids (inorganic phosphonates, phosphates, sulfonates,
sulfates), anion assisted transport, surface transport, multilayer or functionally “graded”
structures.

Characterization of new polymers and model systems

In order to properly implement the above, research needs to be carried out in developing and
applying characterization methods. Reliable structure determination, using techniques such as
NMR, XRD (SAXS, WAXS), Microscopy (AFM, TEM, SEM) and Neutron Studies needs to be
addressed. Such techniques will help to characterize the morphology of the polymer and allow
further nvestigation and understanding of how the functional groups interact (-SO3-, H2O,
MeOH). Furthermore such techniques will allow identification of structure development as a
function of time and processing effects.

Detailed studies of transport processes are also desirable. Much work has been done already in
developing such methods and lessons learned from that work should be applied.

Development of Catalyst-Coated Membranes (CCMs) from new polymers

The interface between the electrode and polymer electrolyte is an important area that is poorly
understood. Significant research needs to be undertaken to understand phenomena such as (1)
adhesion (2) the ill-defined nature of the interfaces (3) specifics on how the polymers interact
with the Electrode and (4) Molecular Level Contact between polymer and electrode-access
through polymer to electrode surface. It is a truism to point out that polymer electrolyte
development is useless without the ability to form high performance, multi-layer systems for the
fuel cell. A key question is ‘can we use the same polymer electrolyte in the electrode as use in
the polymer?’ To date, attempts to do just that have yielded poor performance in fuel cells. The
cathode performance is highly sensitive to the acid used in the electrode. Also, any use of solid
acids or other transport media requires that a means be found to use these materials in electrodes.
This is often difficult: compounds such as imidazoles adsorb strongly on Pt surfaces, while it is
difficult to introduce solid acids into intimate contact with the electro-active catalyst surface.

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Assessment of performance in fuel cells

Fuel cell testing is the ultimate probe of the adequacy of alternative electrolytes. Obviously, we
need to maintain the overall cell performance. The effect of aging of the fuel cell is another key
aspect that must be addressed. Detailed investigations of what happens to the membrane under
operating conditions are required. There are two main types of aging processes that require
investigation. The first is Chemical Degradation of the membrane. For example, studies on the
theoretical aspects of this type of degradation (Peroxide?), as well as detailed ex-situ testing is
desirable. There is a strong need for creative thinking concerning relevant probes of polymer
lifetime, both in situ and ex situ. The second type of degradation is Mechanical. Thus studies
examining processes such as delamination, swelling effects and changes in physical properties
under FC conditions are required. Membrane thinning phenomena are needed. Extensive
materials modeling could be applied. One useful end result would be development of
accelerated aging protocols for both membranes and derived CCMs.

ELECTRODES WORKGROUP REPORT

See plenary presentation: “Electrocatalyst and electrode structure”, Hubert Gasteiger

This panel identified four areas as being key to the further development of electrodes displaying
optimum properties for fuel cell applications:

• Search for New Electrocatalysts
• Fundamental Studies on Model Systems
• Understanding the role of Environmental/Process Poisons
• Catalyst Dispersions

I. SEARCH FOR NEW ELECTROCATALYSTS
Several novel approaches toward the search of new electrocatalysts for reactions of relevance to
fuel cells were regarded as the most viable.

Combinatorial Methods - Despite their increased popularity, implementation of combinatorial
methods for the discovery of new materials with optimized characteristics requires parallel
development of techniques for the preparation and testing of combinatorial electrodes, as well as
strong theoretical rationale for selection of components in the mixtures. Advances in this area
will require strong collaborations to be established between researchers across many different
disciplines. However, only those initiatives that demonstrate novelty and potential technological
value should be considered for funding.

Surface Modification - Research in an increasing number of laboratories has provided
unambiguous evidence for marked changes in the electrocatalytic properties of metal surfaces
induced by the presence of atomic and molecular adsorbates. Although various procedures have
been described in the literature for producing such modified surfaces, strategies based on
spontaneous deposition appear to offer unique advantages. Owing to the large number of
possible modified surfaces, it is essential for theory to help identify systems displaying most

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promising characteristics, especially those involving two or more coadsorbates. Efforts should
also focus on the development of model systems to assess the degree of validity of theoretical
predictions.

Metal Support Interactions – Attention should also be focused on metal support interactions as
means of modifying the electrocatalytic activity of traditional, as well as yet to be discovered
materials.

Given the current state of development, priority should be given to studies in the area of oxygen
reduction followed by direct methanol oxidation, CO tolerant (1000-10000 ppm) catalysts and,
lastly, catalyst interactions with membrane and ionomer including the role of reaction
intermediates such as H2O2.

II. FUNDAMENTAL STUDIES ON MODEL SYSTEMS
Experimental and theoretical efforts should be directed toward identifying detailed mechanistic
pathways of heterogeneous electron transfer reactions involved in fuel cells and, in particular,
those aimed at gaining a better understanding of water activation, breaking of bonds, such as, O2,
C-C, C-H, and co-adsorption and CO and O2 with water. Considerable gains may be derived
from studies involving bimetallic and trimetallic surfaces using well defined single crystals both
in electrochemical and ultrahigh vacuum environments and thus exploit the sensitivity and
specificity of a vast array of electron-based methods for preparation and characterization of
surfaces. Also to be emphasized is the preparation and characterization of well-defined
nanocrystals, either bare, or modified by spontaneous adsorption or other means. Priority should
be given to studies in the area of oxygen reduction followed by direct methanol oxidation and
CO tolerant anodes.

Particle Size Effects - Although reports in the literature suggest particle size effects do play a
role in electrocatalytic processes, new methods should be devised to determine unambiguously
whether these effects are indeed real for particles on the order of nm and below, especially in the
absence of species in solution capable of adsorbing specifically on metal surfaces. Key to the
success of these studies is the development and implementation of methods for the preparation of
monodispersed catalysts, which may include, among others, template-, and micellar-based
synthesis.

III. UNDERSTANDING THE ROLE OF ENVIRONMENTAL/PROCESS POISONS
The presence of sulfur and nitrogen oxides, as well as CO, sulfur oxides and aromatic species in
the gas feed of cathodes and anodes, respectively, can impair the performance of fuel cells by
blocking active sites for electron transfer. It is therefore necessary to identify the microscopic
basis for this phenomenon to develop means of offseting such undesirable effects. Of special
importance is to define, based on sound scientific arguments, tolerances that will serve to guide
the engineering design of processes aimed at the removal of such contaminants. Although
aspects of all such impurities, and especially their adverse impact in performance, should be
carefully investigated, carbon monoxide is perceived to be by far the most damaging, and, as
such, should receive the most immediate attention.

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IV. CATALYST DISPERSION
The long-term activity and stability of fuel cell electrodes relies, among other factors, on
maintaining a stable, highly dispersed array of often supported particles of nm dimensions. It is
therefore essential to examine both experimental and theoretical aspects of sintering. Efforts
should concentrate on the identification of new supports including interaction with the catalytic
particles and on achieving a better understanding of their impact on electrode architecture.

V. OTHER RELEVANT ISSUES
The panel also recommends the issue of alkaline fuel cells to be reexamined to determine
whether this alternate technology may provide niche advantages in terms of kinetics and cost
considerations over the more widely developed acid counterpart.

From an overall perspective, meeting the challenges posed by the issues described above,
requires for new methodologies for computational studies in electrochemical systems to be
brought together including quantum and other theoretical modeling to transport phenomenon and
electrocatalysis. Essential to these activities is the building of bridges between spectroscopists
and theorists who in addition to exploiting existing techniques should help design and develop
new generations of in situ spectroscopic and structural methods with improved sensitivity and
specificity, including synchrotron radiation techniques, nuclear magnetic resonance and a vast
array of photon-based methodologies for probing electronic and vibrational aspects of
electrochemical interfaces.

VI. EDUCATION AND TRAINING
Implementation of these research initiatives will require participation of scientists across many
disciplines in coordinated efforts. Such activities should be encouraged by multi investigator
award programs, following, for example, the MURI model, and also the funding of graduate
assistantship in interdisciplinary areas as illustrated by the GOALI program.

DIAGNOSTICS/MODELING WORKGROUP REPORT

See plenary presentations: “Design, engineering, modeling and diagnostics” by Mark Mathias; and
“Design, engineering, modeling and diagnostics” by Frano Barbir.

The workgroup concluded that the overall goal should be to develop design tools, which we
defined as “validated models with predictive capabilities for both components and integrated
devices”. In order to reach this goal, five main areas of research were deemed to have priority.
These areas were:
• Understanding Electrode Structures
• Cell and Stack Diagnostics with an emphasis on development of non-intrusive
sensing capabilities
• Cell and Stack Models with detailed two-phase flow and thermal capabilities
• Material Properties Determination, focusing on properties of porous materials
• Education

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ISSUES AND CHALLENGES
Understanding Electrode Structures

The primary issue here is that the current method for developing electrode structures is almost
purely empirical. This leads to a long, inefficient development cycle. This cycle is exacerbated
whenever novel materials are introduced. For example, there have numerous cases where new
polymer electrolytes have been developed with promising properties, but the development of
these materials has stalled when they could not be successfully incorporated into electrode
structures. Similarly, alternative catalyst supports have been proposed and favorably tested using
liquid electrolytes, but the promise of these materials has not been realized in fuel cell
performance due to an inadequate understanding of electrode structures. Several challenges
were identified in this area. First was the need for tools to probe the structures currently used.
Structural details such as porosity, extent of catalyst agglomeration/dispersion, uniformity of
electrolyte dispersion, and properties such as the in-plane and through-plane conductivities (both
protonic and electronic) and gas/liquid permeability need to be determined to understand what
structures are being formed, and how that structure relates to the performance observed. The
second challenge identified was to develop an understanding of how the interactions between the
various components in a catalyst ink (a dispersion of catalyst and ionomer, typically in an
organic solvent) are reflected in the final electrode structure formed when the solvent is
removed. Similarly, the processing conditions – how the ink is printed or cast, the substrate on
which the ink is deposited (membrane, or inert decal, or gas diffusion layer) and the manner in
which the solvent is removed may all affect the final structure and the performance. The final
challenge is that given the tools to determine the structure and properties of these electrodes,
sufficiently detailed models need to be developed to predict effective structures and processes for
forming those structures. These models will be crucial if new materials are to be rapidly
introduced into fuel cells. There was consensus within the group that the macrohomogeneous
models currently used are insufficient for this challenge, given the inherently non-homogeneous
nature of the electrode structure.

Cell and Stack Diagnostics

In this area, the clear issue is that very little data is available about the temperature, composition,
flow and current distributions within operating cells or stacks. As a result, existing models
cannot be verified, nor can their limitations be assessed to direct the development of advanced
models. Model prediction of polarization curves is not an adequate test, widely varying models
and parameters may predict similar polarization curves within the limited data set available. The
challenge is to develop non-intrusive sensors that can be inserted into stack components. The
non-intrusive nature must be stressed, as shown by the various attempts that have been reported
in the area of ‘segmented’ fuel cells, where the total electrode area is broken into segments so
that local current densities can be monitored. Without exception, it was felt that these segmented
cells were, as a result of their construction, not representative of typical fuel cell behavior. A
second challenge is to develop better diagnostics based on time and frequency domain
methodologies, based on first principles as opposed to the common equivalent circuit approach.

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Cell and Stack Models

As expected, several issues were raised with respect to cell and stack models. The most
important issue was the need to accurately deal with two-phase (liquid and vapor phase) flow
characteristics. For example, current models deal very poorly or not at all with entrained liquid
in a gas stream, or prediction of condensation/evaporation phenomena. Other issues include the
need to account for non-uniform properties that may result from compressive stresses or
manufacturing variations, and to integrate mechanical models with fluid flow models. The
challenges are several, particularly with two-phase flow in narrow channels and across
interfaces. A very significant practical benefit could be realized if the phenomena of flooding
could be understood and predicted, and means to mitigate flooding could be developed.

Materials Properties

As with the cell and stack diagnostics, the clear issue in this area is that very little data exists for
many of the material properties of interest. The challenge is to develop methods to measure the
appropriate properties under realistic operating conditions. Examples of the conditions that need
to considered include; temperature, humidity, and the presence of compressive forces. The
properties of greatest interest are those relating to the gas diffusion layer, its electrical
conductivity and contact resistance with the electrode and the bipolar plate, the thermal
conductivity (and thermal contact resistances) and liquid and vapor permeabilities. It is also
important to realize that these properties need to be measured both in-plane and through-plane.

Education

The issue in the area of education was that for fuel cells to achieve public acceptance and
significant market penetration, a qualified work force and a general public awareness of fuel
cells need to be developed. The challenge was perceived to be the development of a consistent
set of fuel cell related materials suitable for education and training at all levels; K-12,
undergraduate and adults (including the general public, practicing engineers and technicians).
The group felt that is was very important for these materials to be developed not by any one
university or research group, but by a consortium of university researchers and educators.

RESEARCH APPROACHES
In the area of modeling, there was a consensus that the desired approach would be to develop
solution algorithms that take advantage of the inherently parallel nature of many of the
components in a fuel cell (single cell or stack). For example, within a single cell, every
land/channel pair in a flow field is similar to any other pair. Within a stack, each cell is in
parallel, and there are a large number of cell-to-cell similarities that should be exploited in order
to allow larger, more complex models to be developed.

RESEARCH PRIORITIES
As mentioned above, five main areas were deemed to have priority. These areas were:
• Understanding Electrode Structures

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• Cell and Stack Diagnostics with an emphasis on development of non-intrusive
sensing capabilities
• Cell and Stack Models with detailed two-phase flow and thermal capabilities
• Material Properties Determination, focusing on properties of porous materials
• Education

Three other areas of research were discussed, but were not deemed to have as high priority, these
were 1) diagnostic tools and sensors for manufacturing, 2) diagnostic sensors for
durability/failure sensing and 3) system level models, integrating detailed fuel cell models with
balance of plant component models (compressors, fuel processors) and models of the electrical
load to be powered.

FUEL PROCESSING WORKGROUP REPORT

See plenary presentations: “Fuel processing performance and evaluation” by Richard Bellows;
“Regenerative Power Systems” by Charles K. Lavan Jr.

The fuel processing area is a very complex and challenging part of the fuel cell system. It must
be customized depending on the fuel used, which can run from natural gas to diesel with widely
varying levels of sulfur. The challenges are greatest for proton exchange membrane (PEM) fuel
cells used in transportation due to their intolerance of impurities. The typical fuel processing
section will have an initial autothermal reactor, which converts the fuel and water in the presence
of catalyst and heat to hydrogen, carbon dioxide, carbon monoxide and impurities. The sulfur is
removed, followed by a high temperature and low temperature water gas shift reactors to
increase the conversion to hydrogen and reduce the amount of carbon monoxide. The resultant
stream is then fed to a selective oxidation reactor to remove the last of the carbon monoxide.
This is necessary in PEMs to ensure long anode catalyst life.

ISSUES AND CHALLENGES:
There are a number of issues for improving the fuel-processing unit. They fall into several
categories: engineering design, operation, catalysts, and cost. The objective is to simplify the
system while improving the cost/performance. Elimination of reactors and reducing or
eliminating precious metal catalysts are major targets. Improved life and impurity tolerance of
the catalysts is essential. The control and/or removal of impurities is also key with sulfur and
carbon monoxide being key for PEMs. Rapid start-up, operation at different temperatures and the
transient temperature behavior make operational control a challenge. Better algorithms and
sensors are needed for this complex system. From a cost standpoint, catalyst activity and
stability as well as availability and recycleability are important issues.

RESEARCH NEEDS
The focus for autothermal reactors (ATR) is on improved catalysts with higher selectivity, with
reduced pyrophoric nature and with low temperature activity. It is here that the variety of fuel
feeds must be dealt with. A fundamental understanding of the chemistry would help in the design
of the catalyst. Lower temperature operation, dependent on improved catalysts, is desired as

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well as improved hydrogen yield. This allows more efficient operation and downsizing of
subsequent reactors. Reduction in coking is also desirable. As with all catalyst systems, reducing
the platinum group metal (PGM) content is necessary from both a cost and availability
standpoint. For operation in a transient mode, start-up is another consideration. This applies to
all the reactors.

Following the reforming, it is necessary to remove the impurities particularly sulfur. Options are
fuel desulfurization upstream of the ATR reactor or post ATR gas desulfurization by adsorption
on zinc oxide or other sorbent. Choice will be dependent on application. For onboard use, gas
phase desulfurization on zinc oxide may be preferable.

For breakthrough technology, development of a hydrogen permeable membrane reactor that uses
little or no palladium would be exciting. If this could operate at a high hydrogen flux, low
temperature and reduced pressure, then this would be a major step forward in reducing system
complexity and cost. Alternatively, the reduction of non-reactive gases would also improve the
performance and cost of the system by reducing its size and concentrating the primary reactants.
Subsequent purification steps would be eliminated and improved anode life would be assured.

The other major impurity is carbon monoxide. Carbon monoxide is first reduced by going
through a high temperature and then a low temperature water gas shift (WGS) reactor. Highly
active non-noble metal shift catalysts are needed. Operation at lower temperatures and reduced
oxygen/condensate sensitivity would also be beneficial and require catalyst development. After
these two steps, which also increase the hydrogen content of the gas, the gas stream is fed to a
preferential oxidation unit (PrOx), where the residual carbon monoxide is selectively oxidized to
carbon dioxide in the presence of excess hydrogen. This too could use improved catalysts.
Combinations of shift catalysts with membrane reactors could yield greatly improved
performance and eliminate the PrOx reactor.

Improvement of the hydrogen anode catalyst in the PEM fuel cell in regard to poisoning by
sulfur and carbon monoxide would allow the constraints currently placed on the fuel-processing
unit to be relaxed.

The size of the fuel processing unit is critical for transportation use, but less so for stationary use.
The throughput and selectivity determine the size of the reactor. The operating conditions will
set the materials of construction. Any reduction in the operating temperatures will assist in the
use of less expensive materials of construction. Currently stainless steel is the preferred material.
Because of the variety of operating temperatures, heat exchangers that are smaller and more
efficient are needed.

The reduction in use and the recycle of catalysts, particularly PGMs, is necessary to hold the
price in a reasonable range and provide sufficient material. Even a small penetration of fuel cells
at today’s PGM loadings could exhaust the current annual supplies.

Because of the complexity of the process, it is felt that good process control is necessary. One
needs to minimize excursions. This will require improved sensors with minimal drift, rapid
response time, and high selectivity to impurities. A reliable mass flow sensor is the highest

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priority, followed by high temperature CO and sulfur sensors. A dynamic model, capturing all
these parameters, will be able to optimize the operation of the fuel-processing unit.

A number of new concepts were also enumerated: oxygen enrichment to reduce the amount of
carriers gases, plasma generation of hydrogen, use of micro-channel reactors for reforming,
thermally integrated multi-functional reactors (TIMFR), and solid electrolyte membrane partial
oxidation (SEMPOR). Novel concepts, which have potential for high efficiency operation,
should be explored.

APPROACHES AND PRIORITIES
In summary, focus in the fuel processing area revolves around better methods to treat impurities
and better catalysts to generate hydrogen at lower temperatures with high yield and high through-
put. Control systems will round out the package.

A two-pronged approach is recommended. First, extensive effort should be applied to improving
the components of the existing approach, particularly the lifetime and cost of catalysts used in
the ATR, WSG and PrOx units. This work should be coupled with the work on PEM catalysts.
Operation of integrated systems should be a priority to optimize the operation and efficiency of
the process including the control systems.

Another approach would focus on alternative methods to provide anode fuel particularly
membrane reactors to concentrate hydrogen and direct methanol fed anodes.

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