SPECIAL SECTION: ENERGY

Fuel Cells

32 Tomorrow’s Technology is a Reality Today

33 Meet the Authors
34 The Hydrogen Economy
38 Establishing the Fuel Cell Industry
44 Solid Oxide Fuel Cells and Membranes
50 Fuel Cells for Mobile Applications
SPECIAL SECTION: ENERGY
Tomorrow’s Technology
is a Reality Today
C
lean and efficient transportation and power are a real-
ity today because of public-private investment in fuel
cell technology over the past few decades.
I became a proponent of fuel cells when my lab, Savan-
nah River National Laboratory, participated in a road test
of the 2009 Toyota Highlander fuel cell electric vehicle
(FCEV). As an owner of a gasoline-powered Toyota
Highlander, I was particularly interested in this test. The
new fuel cell powertrain’s performance was equivalent to
my Highlander’s, but with a fuel economy of greater than
68 miles per gallon of gasoline equivalent. This full-scale
pilot test proved that FCEVs could compete with more tradi-
tional gasoline-powered vehicles on performance.
FCEVs are attractive because they offer competitive
performance while also cutting greenhouse gas (GHG) emis-
sions. In their article (pp. 50–54), Krishna Reddi, Amgad
Elgowainy, and Michael Wang explain that FCEVs only
emit water vapor (although the methods used to produce
hydrogen to fuel the vehicles, including steam methane
reforming (SMR), electrolysis, and gasification, have associ-
ated emissions). In a well-to-wheels analysis, they compare
the emissions from FCEVs to gasoline-powered internal
combustion engine vehicles (ICEVs).
Environmental targets are just one of the motivations
behind government involvement in fuel cell technologies.
Sunita Satyapal and Shailesh Vora describe (pp. 38–43) the
extent to which government has had a hand in promoting
fuel cells, and how government involvement has helped to
foster user acceptance and encourage unsubsidized pur-
chases of fuel cells for stationary and mobile applications.
However, the authors concede that barriers to wide-scale
CEP extends a special thanks to Bond Calloway for serving as guest editor of this special section.
32  www.aiche.org/cep  July 2016  CEP
deployment still exist, such as the need for an economical
hydrogen infrastructure.
Noah Meeks and Steve Baxley (pp. 34–37) envision
a future in which an established hydrogen infrastructure
supports a hydrogen economy, “where energy needs would
be met by oxidizing hydrogen in a fuel cell, rather than
combusting a carbon-based fuel.” They explain that, “the
hydrogen economy may emerge because of the need for
energy efficiency improvements within fossil fuel combus-
tion processes, energy storage, or carbon-free energy.” And
although they acknowledge that these needs could be met by
other technologies, they are also confident that fuel cells are
the best solution to these challenges.
A hydrogen infrastructure is only necessary for fuel
cells that require pure hydrogen as a fuel, but some fuel
cells operate at high enough temperatures to reform hydro­
carbon fuels internally. Kyle Brinkman and Kevin Huang
(pp. 44–49) explain how solid oxide fuel cells (SOFCs)
reform fuels like natural gas and produce excess heat that
can be used for combined heat and power (CHP) applica-
tions, which improves the overall efficiency of the fuel cell.
This makes SOFCs particularly well-suited to large-scale
industrial processes that require both heat and power.
Although stationary fuel cells like SOFCs are currently
deployed in industrial applications and FCEVs are available
for consumers to purchase, more developments in technol-
ogy and infrastructure are necessary to meet cost targets and
encourage widespread user acceptance.
— Bond Calloway
Savannah River National Laboratory

STEVE BAXLEY, P.E., is manager of research and
development efforts related to renewable, storage,
and distributed generation technologies at Southern
Company (Email: jsbaxley@southernco.com). Previ-
ously, he was a senior engineering manager at Applied
Research Associates, Inc., where he directed RD&D in
support of the U.S. Dept. of Defense. He holds patents
for technologies related to energy and water, and he
has received a national award from the Society of
American Military Engineers for the development of a
novel renewable jet fuel production process. Baxley
earned a BS in chemistry and MS in civil and environ-
mental engineering from Florida State Univ.
KYLE BRINKMAN, PhD, has been an associate profes-
sor in the Dept. of Materials Science and Engineering
at Clemson Univ since 2014 (161 Sirrine Hall, Clemson,
SC 29634; Phone: (864) 656-1405; Email: ksbrink@
clemson.edu). He previously worked for the U.S. Dept.
of Energy’s (DOE’s) Savannah River National Labora-
tory (SRNL) and was a fellow of the Japanese Society
for the Promotion of Science. Brinkman has received
the Minerals, Metals, and Materials Society (TMS)
Young Leaders International Scholar Award (2015);
the American Ceramics Society (ACERS) Professional
Achievement in Ceramic Engineering (PACE) Award
(2015); the Clemson Univ. College of Engineering and
Science Outstanding Young Alumni Award (2015); the
DOE-Nuclear Energy (NE) Fuel Cycle R&D Early Career
Researcher Award (2013); and the SRNL Laboratory
Director’s Early Career Exceptional Achievement Award
(2011). He received a BS in chemical engineering and
an MS in materials science and engineering from
Clemson Univ., and a PhD in materials science and
engineering from the Swiss Federal Institute of Laus-
anne in Switzerland (EPFL).
AMGAD ELGOWAINY, PhD, is a principal energy
systems analyst and the Life-Cycle Analysis Team
Lead at the Argonne National Laboratory. He conducts
techno-economic and environmental analysis of
alternative transportation fuels and advanced vehicle
technologies. He contributed to the development of
the GREET (Greenhouse Gases, Regulated Emissions,
and Energy Use in Transportation) suite of models
for life cycle accounting of energy and emissions of
alternative fuel/vehicle systems. His research, model-
ing, and analysis cover petroleum and natural gas
vehicles, plug-in hybrid and battery electric vehicles,
and hydrogen fuel cell vehicles. Elgowainy holds a
PhD in mechanical engineering from the State Univ. of
New York at Buffalo. He has authored and coauthored
over 60 papers and technical publications.
KEVIN HUANG, PhD, is a professor in the Dept. of
Mechanical Engineering and SmartState Center for
Solid Oxide Fuel Cells (SOFCs) at the Univ. of South
Carolina (USC) (541 Main St., Columbia, SC 29208;
Phone: (803) 777-0204; Email: huang46@cec.sc.edu).
He previously worked at Siemens-Westinghouse,
where he was involved in the development of
cathode-supported tubular SOFC technology. He is the
associate editor of Royal Society of Chemistry (RSC)
Advances and the Journal of Electrochemical Energy
Meet the Authors
KYLE BRINKMAN KRISHNA REDDI
AMGAD ELGOWAINY SUNITA SATYAPAL
KEVIN HUANG SHAILESH D. VORA
NOAH D. MEEKS MICHAEL WANG
Conversion and Storage, and holds 10 U.S. patents.
He was recognized with the 2015 USC’s College of
Engineering and Computing Research Achievement
Award, 2014 USC Breakthrough Stars Award, and 2007
Siemens Special Employee Recognition Award, among
others. Huang received his PhD in physical chemistry
from the Univ. of Science and Technology Beijing.
NOAH D. MEEKS, PhD, is a research engineer at
Southern Company (Email: ndmeeks@southernco.
com), where he conducts advanced energy systems
research. His current research includes the hydrogen
economy, advanced nuclear systems, and advanced
fossil fuels. He has also worked on environmental
separations for fluegas treatment, particulate matter
control, and pollutant monitoring. Meeks received his
BS in chemistry from Northern Kentucky Univ. and PhD
in chemical engineering from the Univ. of Kentucky. He
has co-authored six peer-reviewed journal publica-
tions and numerous industry conference publications.
KRISHNA REDDI, PhD, is a systems modeling and
analysis engineer at the Argonne National Laboratory.
He contributes to the techno-economic analysis of the
hydrogen delivery infrastructure and environmental
analysis of hydrogen fuel cell vehicles. He helped to
add new features and update the Hydrogen Delivery
Scenario Analysis (HDSAM) model. His research inter-
ests include sustainable engineering, energy systems,
sustainable energy systems, and life cycle analysis.
Reddi obtained his PhD in mechanical and aerospace
engineering from Syracuse Univ.
SUNITA SATYAPAL, PhD, is the Director of the U.S.
Dept. of Energy’s (DOE) Fuel Cell Technologies Office
(1000 Independence Ave., SW, Washington, DC 20585;
Phone: (202) 586-2336; Email: sunita.satyapal@
ee.doe.gov), where she oversees $100 million per
year in research, development, demonstration, and
deployment activities related to hydrogen and fuel
cells. She has experience in academia, industry, and
government, including at United Technologies, as a
visiting professor at Vassar College, and as a visiting
scientist at Hokkaido Univ. in Japan. Satyapal received
her PhD from Columbia Univ. in physical chemistry,
and conducted her postdoctoral research in applied
and engineering physics at Cornell Univ. She holds 10
patents.
SHAILESH D. VORA, PhD, is the Fuel Cells R&D
Portfolio Manager at the National Energy Technology
Laboratory, U.S. Dept. of Energy (DOE) (626 Cochrans
Mill Rd., Pittsburgh, PA 15236; Phone: (412) 386-7515;
Email: shailesh.vora@netl.doe.gov). He provides
technology leadership related to fuel cell-based power
generation in the DOE’s Office of Fossil Energy. Prior
to joining the DOE, he worked at Westinghouse and
Siemens, conducting work related to stationary fuel
cells. Vora received his MS and PhD, both in materials
science and engineering, from the Univ. of Florida, and
MBA from the Univ. of Pittsburgh.
MICHAEL WANG, PhD, is the manager of the Systems
Assessment Group of the Energy Systems Div. at the
Argonne National Laboratory (Email: mqwang@anl.
gov). He leads the development and application of
GREET (Greenhouse Gases, Regulated Emissions,
and Energy Use in Transportation) model for life cycle
analysis of advanced vehicle technologies, trans-
portation fuels, and other energy systems. He is an
associate editor of Biotechnology for Biofuels and on
the editorial board of Frontiers of Energy and Power
Engineering in China. Wang received his BS in agricul-
tural meteorology from China Agricultural Univ., and
PhD and MS in environmental science from the Univ. of
California at Davis.
CEP  July 2016  www.aiche.org/cep  33
SPECIAL SECTION: ENERGY
Fuel Cells and
the Hydrogen Economy
Noah D. Meeks Hydrogen fuel cells are already a reality,
Steve Baxley, P.E.
Southern Company but obstacles must be overcome before
a hydrogen economy can be realized.
I
n a future hydrogen-based economy, energy needs would
be met by oxidizing hydrogen in a fuel cell, rather than
combusting a carbon-based fuel. Since hydrogen is
not available freely in nature, it must be produced from an
energy source, and it can be carbon-intensive or carbon-free,
depending on the energy source employed.
Fuel cells are central to a hydrogen economy. They con-
vert the chemical energy in a fuel directly into electricity that
can be used for stationary, mobile, or transportation applica-
tions (Figure 1). Energy is created via two half reactions.
At the anode, a stream of hydrogen is split into protons and
electrons. The electrons are forced through a circuit, produc-
ing energy:
2H2 → 4H+ + 4e–
At the cathode, the protons react with oxygen to produce
water as a byproduct.
4H+ + 4e– + O2 → 2H2O
Unlike fossil fuel combustion, hydrogen fuel cells
produce power with no emissions of nitrogen oxides (NOx),
sulfur oxides (SOx), particulates, or carbon dioxide (CO2).
(The production of hydrogen, however, does produce emis-
sions.) Low emissions are just one driver behind fuel cells
and the hydrogen economy; efficient power production, reli-
ability, and energy storage capabilities are also steering this
technology toward commercialization.
This article describes how hydrogen is produced and
34  www.aiche.org/cep  July 2016  CEP
how it is converted to power in a fuel cell, the various types
of fuel cells, and the obstacles that need to be overcome for a
hydrogen economy to become a reality.
Hydrogen production
Hydrogen for fuel cells can be produced commercially
by reforming hydrocarbons, gasification, or electrolysis of
water. Investigations continue into other methods, such as
thermochemical or photochemical water-splitting and ther-
molysis of methane.
Reforming. Most hydrogen is currently produced by
steam methane reforming (SMR). At high temperatures
(700–1,100°C) and in the presence of a metal-based catalyst,
steam reacts with methane to form carbon monoxide and
hydrogen. Additional hydrogen is recovered via a water-
gas shift reaction (WGS) that also yields CO2. Together the
overall reaction is:
CH4 + 2H2O → → CO2 + 4H2
This reaction converts methane (which has a mass
energy density of 21,500 Btu/lb) to hydrogen (mass energy
density = 51,500 Btu/lb), which can then be used in a fuel
cell (1). Natural gas is typically the methane source, but other
sources, such as landfill gas or biogas, can be used as well.
Gasification. Synthesis gas (or syngas, a mixture of CO,
CO2, and H2) can be produced by the gasification of solid
fossil fuels, such as lignite coal, or other solid hydrocarbons,
such as biomass or municipal solid waste (MSW). The
syngas can be converted into hydrocarbons (via the Fischer-
Tropsch process) or combusted to produce heat and power
(such as in integrated gasification combined-cycle [IGCC]
plants), or the hydrogen can be separated for use in a fuel
cell.
Electrolysis. Hydrogen can also be produced by elec-
trolysis of water — a process that is essentially a fuel cell
in reverse. Similar to fuel cells, electrolyzers can operate at
low, intermediate, or high temperatures, with various solid
or fluid electrolytes. By coupling electrolyzer and fuel cell
unit operations, hydrogen can serve as electricity storage:
the electrolyzer uses electricity to convert water to hydrogen,
then the fuel cell uses hydrogen to produce electricity. The
energy can be stored for stationary applications or for use as
a transportation fuel.
Thermochemical hydrogen. High temperatures (at
least 600°C) can be used to drive coupled redox reactions
toward the net decomposition of water. Possible sources
of the required heat input are advanced nuclear reactors,
concentrating solar heat, industrial boilers, and repurposed
utility boilers. The coupled redox reactions occur in a
cycle, so the net energy input is only heat and the output is
hydrogen. Many coupled redox reactions, including sulfur-
iodine, metal-metal oxide, and uranium carbonate, are being
explored for the production of hydrogen. The hybrid sulfur
process is another thermochemical cycle, but it differs from
the other reactions in that it requires both heat and electricity
inputs.
Motivations
Several factors are driving the emergence of fuel cells,
including abundant fuel sources, efficiency, reliability, low
emissions, heat production, and energy storage.
Abundant fuel. Plentiful natural gas resources provide a
ready source of hydrogen for utility-scale fuel cells. In 2015,
78.8 billion ft3 (bcf) per day of natural gas was marketed in
the U.S. (2). Growth is expected to continue well into the
next decade, with the U.S. poised to become a net exporter
of natural gas by mid-2017 (3). Some fuel cells can use natu-
ral gas directly as fuel, without its conversion to hydrogen;
however, this process still produces CO2 emissions.
Efficiency. The efficiency of a fuel cell can exceed that
of standard methods of power production, because the fuel’s
chemical energy is converted directly to electrical energy
without intermediate conversion to mechanical energy. How-
ever, hydrogen is not readily available in nature; therefore,
the overall process efficiency must include hydrogen genera-
tion. SMR, for example, has a thermal efficiency of about
60%, which limits the electrical efficiency of a hydrogen
fuel cell to about 40–60%.
Reliability. While utility-scale fuel cells offer potential
efficiency gains, small fuel cells are more reliable than other
small power sources, such as diesel engines. Because fuel
cells are highly reliable, their use as stand-alone power for
data centers and industries with critical reliability needs
is being explored. Fuel cells are generally not suitable as
backup power, because startup times are often too long.
Low emissions. Fuel cells have low emission profiles
— zero if they utilize pure hydrogen as a fuel. (This does
not account for the emissions generated in the production of
hydrogen, which would be considered in a life cycle analy-
sis.) Hydrogen fuel cells emit only water, while other types
of fuel cells produce emissions related to the electrochemical
reaction(s) they employ (e.g., CO2, CH4, CH3OH). High-
temperature fuel cells may produce NOx emissions from
the nitrogen in air; however, they do not emit particulates
or other criteria pollutants. In addition, fuel cells operate
silently and do not contribute to noise pollution.
Heat. High-temperature fuel cells are capable of produc-
ing heat (as well as electricity) that can be used for combined
heat and power (CHP) applications, which increases their
overall energy efficiency. However, properly balancing the
heat and power outputs can be a challenge. The high effi-
ciency of CHP applications makes fuel cells attractive to
facilities that utilize a lot of heat and power, and the ability to
use fuel cells for CHP is driving early adoption of fuel cells.
Energy storage. Hydrogen could enable large-scale
energy storage — it could be created by the utility at times
of low electrical demand and then converted back to electric-
ity during periods of high electrical demand. This scheme
could be leveraged to smooth electrical generation and
e–
Fuel In Air In
e– e–
e– H+
H2 O2
H+
H 2O Air, Water,
Heat, etc.
Excess Fuel
Out Out
Cathode
Anode
Electrolyte
p Figure 1. Hydrogen enters the fuel cell and is oxidized at the anode
to form protons. The electrolyte material conducts ions, but not electrons,
so electrons are forced into the external circuit. At the cathode, oxygen is
reduced to water.
CEP  July 2016  www.aiche.org/cep  35
SPECIAL SECTION: ENERGY
improve power plant performance by allowing the genera-
tion unit to operate closer to steady state.
Other energy storage strategies utilize the same
approach, but they suffer from issues related to scale. As
more nondispatchable generation assets (particularly wind
and photovoltaic solar) are added to the grid, the load profile
will become more variable, and larger storage mechanisms
will be needed. However, batteries do not easily scale to
meet this need. Therefore, large-scale storage options that
scale volumetrically, such as pumped hydroelectric and
compressed air storage, would need to be deployed. Hydro-
gen also scales volumetrically for energy storage, and scales
according to surface area for power delivery.
Types of fuel cells
Fuel cells that are appropriate for stationary power pro-
duction, either onsite or through an electrical grid, include
polymer electrolyte membrane (PEM) fuel cells, phos-
phoric acid fuel cells (PAFCs), molten carbonate fuel cells
(MCFC), and solid oxide fuel cells (SOFCs). The suitability
of a type of fuel cell for a particular application depends
on its size and temperature. The temperature affects the
lifetime of the fuel cell, and may create additional heat for
CHP applications, with the amount of heat available directly
related to the voltage produced.
Polymer electrolyte membrane fuel cells. PEM fuel cells
contain a solid electrolytic material, such as perf­luorinated
sulfuric acid polymer (e.g., Nafion), which swells in the
p Figure 2. This 400-kW phosphoric acid fuel cell (PAFC) produces hydrogen onsite. Photo courtesy of Doosan Fuel Cell.
36  www.aiche.org/cep  July 2016  CEP
presence of water. They operate at lower temperatures
(80°C), and therefore have a longer operating life. PEM
fuel cells require pure hydrogen as a feedstock, which must
be produced, transported, and stored. The reactant gases
(hydrogen and oxygen) are saturated with water to prevent
the membrane from drying, and reacted at elevated pressure
(2–5 bar) to maintain proton conductivity.
PEM fuel cells have the potential to compete with grid-
supplied electricity, particularly for automotive fuel cell
applications. Although PEM fuel cells cannot be used for
CHP applications because their operating temperature is too
low, their high power density still generates heat that must
be dissipated through cooling water or other coolants.
Phosphoric acid fuel cells. PAFCs (Figure 2) operate
at medium temperatures (150–200°C), and are suitable for
commercial building applications. This operating temperature
range enables these cells to be used for CHP applications,
which increases the efficiency of the PAFC, but the corrosive
nature of phosphoric acid can shorten the fuel cell’s life.
PAFCs typically have higher power output than PEM
fuel cells, which makes them useful to electric utilities for
supplemental grid generation. Some PAFC fuel cells include
a module, separate from the fuel cell stack, that reforms
natural gas into hydrogen. This additional unit operation
provides onsite hydrogen and creates excess heat that can aid
CHP operations and improve overall efficiency.
Molten carbonate and solid oxide fuel cells. MCFCs
(Figure 3) and SOFCs operate at high temperatures
(at least 600°C), making them best suited to industrial or
commercial applications that require heat. High-temperature
operation shortens the life of these fuel cells, but also elimi-
nates the need for fossil fuel reforming in a separate unit
operation. Natural gas is fed directly to the fuel cell, where it
is internally reformed into hydrogen that is used to generate
electricity.
The hydrogen economy
Electric utilities are at the center of an emerging
hydrogen economy. Utilities already manage many of the
resources necessary for producing hydrogen at scale, includ-
ing fossil fuels for gasification or reforming, electricity for
water electrolysis, and heat for thermochemical hydrogen-
generation technologies.
The hydrogen economy may emerge because of the
need for energy efficiency improvements within fossil
fuel combustion processes, energy storage, or carbon-free
energy. These objectives, however, may be also achieved
in other ways. Energy efficiency can be improved with
deeper penetration of combined-cycle natural gas power
plants, advanced ultrasupercritical coal-fired power plants,
demand-side management, renewables, and/or advanced
nuclear reactors. Energy can be stored in batteries and by
mechanical means. Carbon-free electricity can be gener-
ated by nuclear power, by hydropower, and from renewable
sources such as solar and wind; advancements in battery
electric vehicles (BEVs) can enable carbon-free transporta-
tion energy.
Hydrogen and fuel cells, however, offer advantages over
those alternative scenarios:
• Batteries are not a readily scalable energy storage tech-
nology and have thermodynamic power limits. Fuel cells
scale volumetrically for energy storage and by surface area
for power delivery.
• The low mass energy density of BEVs limits their use
for long-distance or heavy-haul transportation; hydrogen
has a mass energy density of 51,500 Btu/lb compared to
341 Btu/lb for commercial lithium-ion batteries (such as the
90-kWh, approximately 900-lb Tesla Model S). Accounting
for the weight of the hydrogen storage tank and the fuel cell,
the overall mass energy density of a hydrogen-powered car
is 1,200 Btu/lb (Toyota Mirai). With a 50% conversion to
electrical energy (approximately 600 Btu/lb), this is still more
energy-dense than the most advanced commercial BEV.
• Even if hydrogen is produced from carbon-intensive
sources, hydrogen and fuel cells produce the same or less
CO2 than the most efficient fossil-fuel combustion processes.
• The deployment of renewables to reduce carbon emis-
sions from the overall energy system is limited by geography
and low energy return on investment. Nuclear power is the
only scalable carbon-free energy source that could overcome
p Figure 3. These 15-MW molten carbonate fuel cells (MCFCs) began
operation in Bridgeport, CT, in 2013. Photo courtesy of Fuel Cell Energy.
these disadvantages, and it could be employed to produce
both electricity and hydrogen for fuel cells.
Utilities are exploring the advantages that fuel cells
and hydrogen can bring to customers that value efficiency
and reliability. Federal government facilities and military
installations now insist on energy efficiency and low-carbon
footprints for technologies they adopt. Customers requiring
high reliability, such as data centers and remote locations
with limited or no grid service, will benefit from fuel cell
and hydrogen technology. Southern Company, for example,
is exploring ways to meet the energy needs of these facili-
ties by owning and/or operating fuel cells and managing this
resource along with grid power.
While the need for energy storage is widely acknowl-
edged, the business model to monetize storage is still being
developed. Renewables could contribute more consistently
to the grid when combined with energy storage, but the cost
of deploying renewables and hydrogen energy storage is
higher than the cost of renewables with backup generation.
Even if energy storage is monetized, competitive technolo-
gies such as pumped hydro or compressed air may capture a
large part of the market. Transportation applications (which
need mobile energy storage) are emerging but require sup-
port from customers — and that has yet to materialize given
the current low cost of conventional onboard energy. CEP
Literature Cited
1. Lanz, A., “Hydrogen Fuel Cell Engines and Related Tech­
nologies,” College of the Desert Energy Technology Training
Center, Palm Desert, CA (2001).
2. U.S. Energy Information Administration, “Natural Gas
Weekly Update,” EIA, www.eia.gov/naturalgas/weekly/
archive/2016/01_14/index.cfm (Jan. 2016).
3. U.S. Energy Information Administration, “U.S. Natural Gas
Wellhead Value and Marketed Production,” EIA, www.eia.gov/
dnav/ng/ng_prod_whv_dcu_nus_a.htm (May 2016).
CEP  July 2016  www.aiche.org/cep  37
SPECIAL SECTION: ENERGY

Establishing
the Fuel Cell Industry
Sunita Satyapal Fuel cells are now a commercial reality.
U.S. Dept. of Energy
Shailesh Vora
Government and industry programs have been
National Energy Technology integral in encouraging technological growth
Laboratory, U.S. Dept. of Energy
and establishing the market.

A
fter decades of development, hydrogen fuel cell
technologies are becoming an established commer-
cial reality. Global fuel cell industry revenues sur-
passed $2.2 billion in 2014, with more than 50,000 fuel cell
systems shipped worldwide and consistent annual growth
in shipments of almost 30% since 2010 (Figure 1) (1). Fuel
cells for stationary power have been the pre­dominant appli-
cation to date, but now some major automakers are provid-
ing commercial fuel cell electric vehicles (FCEVs) for sale
or lease (1).
Government-funded programs worldwide, including
those through the U.S. Dept. of Energy (DOE), ramped up
their efforts in the past decade, injecting vital funds and
60,000
Portable
Transportation
50,000
Stationary
Fuel Cell Systems
encouraging initiatives to accelerate commercialization and
bridge the gaps in research and development. How did it all
begin, where are we now, and what more is required to make
hydrogen fuel cell technology part of our everyday lives?
Why fuel cells?
Fuel cells convert the chemical energy from a fuel into
electricity, without the need for combustion, thereby generat-
ing power at high efficiencies and with low or even zero
emissions (depending on the fuel). Fuel cells are character-
ized by their chemical reaction, electrolyte, and operating
temperature, among other properties (Table 1).
Fuel cells can use diverse domestic resources as fuel,
are quiet with no moving parts, and are scalable — allowing
them to provide power for applications ranging from
small-scale portable power to large-scale stationary power
plants. They can also be used in automotive applications and
to ensure grid resiliency, since they have excellent tran-

40,000
sient response and quick startup times, depending on their
30,000
operating temperature. For light-duty vehicles, fuel cells
are currently the only zero-emissions technology that meets
20,000 customer demands for long driving ranges, fast fueling,
outstanding fuel economies, and high performance. High-
10,000 temperature fuel cells are often used for combined heat and
power (CHP) applications in industrial plants and commer-
0
2008 2009 2010 2011 2012 2013 2014 cial buildings.
The need to reduce carbon emissions, pollutants, and
p Figure 1. The global fuel cell industry has experienced consistent growth
since 2010. The growth in stationary systems is due in part to thousands of
petroleum dependence, as well as the need for highly reli-
small stationary fuel cells being sold in Japan, subsidized by the Japanese able power, drive the development and deployment of fuel
government, to provide reliable power and heat for homes. cell technologies.

38  www.aiche.org/cep  July 2016  CEP

 Table 1. Fuel cells are characterized by their electrolyte and operating temperature, as well as other properties.
Fuel Cell Electrolyte* Operating Stack Size Efficiency Applications Advantages Challenges
Type Temperature
Polymer Perfluoro­ <120°C <1–100 kW 40–45% • Mobile • Solid electrolyte • Expensive catalyst
Electrolyte sulfonic acid power • Low • Sensitive to fuel
Membrane • Portable temperature impurities
(PEM) power • Quick startup • Relatively low
• Backup • Rapid load efficiency
power following
Alkaline Potassium <100°C 1–100 kW 60% • Space • Low • Extremely sensitive
(AFC) hydroxide • Military temperature to CO2 in fuel and air
• Quick startup • Electrolyte man­
agement is needed
Phosphoric Phosphoric ~200°C 5–400 kW 40% • Stationary • Combined heat • Expensive catalyst
Acid (PAFC) acid power and power (CHP) • Sensitive to sulfur
capable in fuel
• Long startup times
Molten Molten lithium, 600–700°C 300 kW 50% • Stationary • High efficiency • High-temperature
Carbonate sodium, power • Fuel flexible corrosion
(MCFC) and/or • CHP capable • Long startup times
potassium • Low power density
carbonate • Expensive
Solid Oxide Yttria- 600–850°C 1 kW–2 MW Distributed • Stationary • Solid electrolyte • High-temperature
(SOFC) stabalized generation power • High efficiency corrosion
zirconia >50% • Fuel flexible • Reliability
Central • CHP capable • Long startup times
>60% • Expensive
* Conventional electrolytes are listed. Advanced electrolytes, such as alkaline exchange membranes, are an area of active research.

Hydrogen production, delivery, and storage
Production. Hydrogen has the highest energy content on
a per-mass basis of any fuel — nearly three times more than
gasoline. Because it is a light, low-density gas, however,
its energy density is very low — roughly one-fourth that of
gasoline. The energy content in one kilogram of hydrogen
is about the same as in one gallon of gasoline; thus, the unit
kilogram is often used interchangeably with gallon gaso-
line equivalent (gge) to compare hydrogen and gasoline.
Because FCEVs can get twice the fuel economy of conven-
tional gasoline vehicles (e.g., 66 miles per kg for one FCEV
commercially available today), half as much fuel is needed
onboard.
Although hydrogen is the most abundant element in
the universe, it is not found freely on Earth, and instead,
must be produced. Roughly 10 million m.t. of hydrogen are
produced annually in the U.S., mostly via steam methane
reforming (SMR) of natural gas. Most of that hydrogen is
used for petroleum refining and ammonia production. (If all
of that hydrogen were available to power FCEVs, it could
fuel nearly 50 million cars.) Hydrogen production must be
increased to meet the needs of the transportation sector, and
to meet environmental goals, it ultimately must be gener-
ated from renewable or low-carbon sources. To be competi-
tive with gasoline, the DOE is targeting a cost of $4/gge for
hydrogen at refueling stations (which includes the costs of
production, delivery, storage, and dispensing).
Electrolysis is a simple and clean method for generating
hydrogen from water. Electrolyzers split water to produce
hydrogen and oxygen at efficiencies as high as 70%. An
independent assessment of leading electrolyzer developers
estimated that the cost of hydrogen from electrolysis could
be as low as about $5/gge if it is produced at high volumes.
Because electricity is the main contributor to cost, cheap or
free electricity would reduce the cost considerably. If solar,
wind, or other zero-emission sources are employed, low
costs rather than high efficiencies could become the key
driver for fuel cell technology.
Hydrogen can also be produced by other methods,
including high-temperature thermochemical reactions (e.g.,
solar, nuclear), biomass gasification, coal gasification,
biological processes (e.g., fermentation, photobiological
systems), reforming of various fuels, and direct photo­
electrochemical conversion (PEC) of water.
The DOE has recently focused on PEC through the Joint
Center for Artificial Photosynthesis (JCAP), also known as
the Solar to Fuels Hub. JCAP first set its sights on the pro-
duction of hydrogen via PEC, and the key outcome was the
development of high-throughput tools for the rapid develop-
ment of materials with high solar-to-hydrogen efficiencies

CEP  July 2016  www.aiche.org/cep  39

SPECIAL SECTION: ENERGY
that are stable and durable for several days.
Delivery. Once the hydrogen is produced, it must be
delivered to the fueling station, stored onsite, compressed,
and dispensed. While costs can be as low as $5/kg for high-
volume onsite production from natural gas, at low volumes
the estimated cost of hydrogen is $13–$16/kg (produced,
delivered, and dispensed, but untaxed) (2).
Storage. Car makers are using 700-bar (70-MPa)
hydrogen storage tanks as the primary means of onboard
vehicular storage. The majority of these tanks are made
of high-strength carbon fiber composites, and more work
is required to reduce their cost — from a modeled cost of
$15/kWh (based on high-volume projections) to DOE’s tar-
get of $10/kWh in 2020 and ultimately to $8/kWh (Figure 2).
Efforts are also underway to identify low-cost materials-
based technologies that can store hydrogen onboard vehicles
at low pressures, circumventing the need for widespread
infrastructure tailored to high-pressure dispensing.
Early development
The DOE efforts that created the multibillion dollar
program we know today began in the 1970s. Spurred by
the oil embargo, a group of national laboratory research-
ers, managers, and DOE officials gathered at Los Alamos
National Laboratory to develop a breakthrough to eliminate
U.S. dependence on foreign oil. The Clean Air Act of 1970
and the corporate average fuel economy (CAFE) standards
of 1975 stimulated efforts related to fuel cells. In 1977, a
diverse group of stakeholders from federal agencies, national
labs, research institutions, and industry convened at Los Ala-
mos to evaluate the challenges and opportunities presented
by fuel cells for transportation.
Subsequently, researchers developed methods to opti-
mize the heart of the polymer electrolyte membrane (PEM)
fuel cell’s membrane electrode assembly (MEA), eventu-
Fuel Cell Systems 2
H Production, Delivery,
$280/kW and Dispensing (700-bar Compressed System)
$16/gge
to
$60/kW
100k/yr
$13/gge
$53/kW
500k/yr
$7.5/gge
to
$5/gge
$40/kW <$4/gge
2020 Targets High-Volume Production
p Figure 2. Costs are estimated for low-volume (red) and high-volume (orange) production (EPRI), and the U.S. Dept. of Defense (DOD),
of automotive fuel cells, hydrogen fuel at the pump, and hydrogen storage tanks onboard
fuel-cell-powered vehicles. Because these technologies are not currently manufactured
at commercial volumes, costs are projected for high-volume production of 100,000 and
500,000 units per year and low-volume production (or actual industry estimates).
40  www.aiche.org/cep  July 2016  CEP
ally reducing the amount of platinum group metal (PGM)
catalyst by two orders of magnitude. Los Alamos scien-
tists taught researchers worldwide how to fabricate these
improved MEAs, and General Motors temporarily relocated
its fuel cell group to Los Alamos, near Albuquerque, NM, to
focus on the technology.
In parallel to the PEM efforts, the DOE launched major
initiatives in phosphoric acid fuel cells (PAFCs), molten
carbonate fuel cells (MCFCs), and solid oxide fuel cells
(SOFCs).
The DOE’s early support of SOFCs began with technol-
ogy developed by Westinghouse. At the time, Westinghouse
was the only company in the U.S. developing SOFCs, and
it had made significant progress with a tubular design. After
Siemens acquired Westinghouse in the 1990s, it placed more
emphasis on SOFC commercialization. With the launch
of the Solid State Energy Conversion Alliance (SECA)
program in fiscal year 2000, the DOE’s Office of Fossil
Energy (FE) ramped up funding and paved the way for
planar designs as well as the involvement of more develop-
ers. Although Siemens Westinghouse exited the fuel cell
business in 2010, the FE’s current SOFC program continues
to make progress, and many companies are still heavily
involved in SOFC commercialization.
Public-private partnerships
Public-private partnerships have been instrumental in
growing PEM and SOFC technology.
The DOE and automakers partnered in the 1990s to
create the Partnership for the Next Generation of Vehicles
(PNGV), which established hydrogen, instead of reformed
gasoline, as the PEM fuel of choice.
In the early 2000s, the DOE again partnered with
automakers as well as the U.S. Council for Auto Research
(USCAR) to form the FreedomCAR partnership. In 2003,
five major oil companies joined the partnership;
Onboard H Storage
2 renamed the FreedomCar and Fuel Partnership, it
focused on hydrogen and FCEVs. Now dubbed
U.S. DRIVE, utility companies have joined the
$33/kWh partnership, which currently emphasizes battery
electric vehicles. The active participation of tech-
nical experts from industry, the DOE, and national
$17/kWh
100k/yr laboratories over the decades has helped drive
$15/kWh
precompetitive research, and these participants
500k/yr helped to develop a sound basis for system-driven
$10/kWh targets to guide the entire research community.
Low-Volume Production Organizations such as the Gas Research Insti-
tute (GRI), the Electric Power Research Institute
among others, have helped to promote stationary
power development. In 1967, 28 U.S., Japanese,
and Canadian utilities initiated a large-scale PAFC
program called the Team to Advance Research for Gas
Energy Transformation, Inc. (TARGET).
The DOE and industry have helped to guide and
formulate rigorous technical and cost targets for fuel
cell technologies that aim to compete with incumbent
or other advanced technologies. The DOE updates these
costs periodically to reflect the rapid pace of technology
development.
Low-temperature and
mid-temperature PEM fuel cells
PEM fuel cells have undergone a transformation in the
past decade — costs have been cut in half (Figure 3), and the
amount of PGM catalyst reduced by a factor of five. Figure 4
shows that even with the latest technology modeled at high-
volume manufacturing rates, the catalyst accounts for nearly
half the cost of PEM automotive fuel cells.
Work is underway to further reduce or eliminate the need
for PGM catalysts. Argonne National Laboratory has devel-
oped nanoframe catalysts that have 30 times higher activity
than conventional PGM catalysts and MEAs that perform
three times better than conventional MEAs. However, in
general, when PGM loading is lower, durability suffers.
Performance and durability need to be addressed simulta-
tions. For example, the DOE shared the cost to deploy 1,600
fuel cell systems for forklifts and backup-power units for
cellphone towers, after which companies purchased over
13,500 systems without DOE funding. Additional applica-
tions like fuel cells for airport ground support equipment,
parcel delivery vans, and truck refrigeration — all currently
funded by the DOE — will open new markets, increase
demand for hydrogen, and reduce emissions. These deploy-
ments will help to establish infrastructure, foster user accep-
tance, and enable the development of a supply chain for
hydrogen and fuel cell technologies. In addition to fostering
early market deployment, the DOE also tracks the number of
patents issued and technologies commercialized as indica-
tors of the impact of its funding (Figure 5).
Although significant progress is being made, hydrogen
and fuel cell technologies still require additional advance-
ments for widespread successful commercialization.
High-temperature solid oxide fuel cells
SOFC power systems have the potential to achieve
greater than 60% efficiency and more than 97% carbon
capture at a cost-of-electricity (COE) that is projected to be
approximately 40% lower than that of integrated gasifica-
160
100,000–500,000 systems/yr, U.S.$/yr

neously, which is the focus of the DOE’s new consortium

140
project, FC-PAD (Fuel Cell Performance and Durability).
Catalysts that are totally PGM-free would be an important 120
Modeled Cost for

breakthrough, the development of which is the primary 100

goal of the ElectroCat consortium. 80
Current Status
$53/kW
Industry status. The Energy Independence and Policy Ultimate
60
Act of 2005 directed the DOE, along with industry and Target
other stakeholders, to undertake a large-scale concerted 40
R&D effort that by 2015 would allow decisions to be 20 2020
Target
made about the commercialization of FCEVs. Not only
0
did industry and the DOE meet this goal and decide to 06 007 008 009 010 011 012 013 014 015 020
20 2 2 2 2 2 2 2 2 2 2
move forward with FCEV technology, but commercial
FCEVs are on the road today. Toyota started selling p Figure 3. Modeled costs of automotive fuel cell systems have fallen since 2006,
FCEVs in 2015, Hyundai is currently leasing FCEVs, but have leveled off in the past few years — perhaps reaching an asymptote,
and Honda is selling FCEVs in Japan and has plans although that remains to be seen.
for U.S. sales in 2016. 100,000 Systems/Yr 500,000 Systems/Yr Bipolar Plates
The DOE has independently validated more than 5%
13% 8%
5% Membranes
220 FCEVs from six automakers and more than 30 13%
27%
5%
hydrogen stations over the past several years. More Catalysts
than 80,000 kg of hydrogen have been dispensed 28% Gas Diffusion Layers
and FCEV vehicles have been driven more than 20%
10% Membrane Electrode
6 million miles. The latest results from the DOE’s 45% Assembly Frame/Gaskets
independent validation show that current FCEVs 21% Stacks
boast 3,900-hr durability (equivalent to roughly
117,000 miles) (3) and driving ranges of up to p Figure 4. Modeling of costs for producing automotive fuel cell stacks at manufactur-
ing rates of 100,000 systems per year indicates that catalysts, membranes, and gas
350 miles on a single fill of hydrogen (4).
diffusion layers contribute significantly to total cost. When volumes are projected to
Early market deployments in other applications 500,000 systems per year, catalyst costs are higher than the cost of the other fuel cell
have helped pave the way for automotive applica- stack components.

CEP  July 2016  www.aiche.org/cep  41

SPECIAL SECTION: ENERGY
Innovation Commercialization Deployment
Number of Patents Number of DOE Funding Impact on
Commercial Additional Fuel Cell
Technologies Purchases
14k
>13,500
12k
units
10k
8k
6k
46 4k ~1,600
589 units
2k
249 17 0 mance in a stack through a series of progressively larger
With DOE No DOE Funding
By 2007 By 2015 By 2007 By 2015 Funding
p Figure 5. In addition to the 46 fuel cell technologies already commercialized,
another 65 are anticipated to hit the market in the next three to five years.
tion combined cycle (IGCC) systems with carbon capture
and storage (CCS). Figure 6 compares utility-scale SOFC
power systems — advanced integrated coal gasification solid
oxide fuel cells (IGFC) and advanced natural gas solid oxide
fuel cells (NGFC) — to state-of-the-art (SOTA) IGCC and
pulverized coal (PC), advanced IGCC, SOTA natural gas
combined cycle (NGCC), and advanced NGCC power gen-
eration systems. All of the systems are equipped with carbon
capture and storage (CCS).
The SOFC program. The DOE’s Office of Fossil Energy
is charged with developing ultraclean (near-zero emissions),
low-cost energy from fossil fuels to encourage economic
prosperity, strengthen energy independence, and improve
environmental quality. A component of that effort, imple-
mented by the National Energy Technology Laboratory
(NETL), is the SOFC program that is developing low-cost,
highly efficient SOFC systems that produce electric power
from natural gas or coal and have intrinsic CCS capabilities.
The SOFC program coordinates efforts by core technol-
ogy R&D teams from national labs, academia, and industry
and system development teams from industry. The core
technology effort consists of applied R&D on critical issues
related to the commercialization of SOFCs. The coopera-
tion of national laboratories, academia, small business, and
industry has advanced SOFCs toward commercialization by
improving performance, durability, and reliability, as well
as reducing cost. The SOFC program has developed the
planar anode-supported cell; increased the cell active area
by a factor of five; increased cell power by a factor of ten;
created better materials for higher performance; reduced cell
operating temperature by approximately 100°C; and reduced
cell power degradation to less than 0.5% per 1,000 hr, with
lifetimes routinely exceeding 10,000 hr.
Industry teams are independently developing unique and
proprietary SOFCs suitable for use with natural gas or syn-
gas derived from coal. They have validated equipment that
has been developed by the core technology R&D teams,
as well as achieved breakthroughs related to cell develop-
42  www.aiche.org/cep  July 2016  CEP
ment and manufacturing, scaleup of cells and stacks for
aggregation into modules, hardware, manufacturing pro-
cesses, and strategies for commercialization and market
penetration.
Lift
Fuel cell stack testing. Although performance and
Trucks degradation in a single fuel cell is acceptable, stack and
system performance, reliability, and endurance have yet to
Backup be demonstrated. Industry teams are validating cell perfor-
Power
stack tests. The tests are intended to evaluate power output
(additional
purchases) and voltage degradation rate at steady-state conditions and
to enable commercial module capital cost projections to be
made. In more than 3,000 hours of testing, 25-kWe-rated
modules experienced voltage degradation of approximately
1% per 1,000 hr.
The SOFC program is funding two 50-kWe-class stack
tests and two proof-of-concept tests of a 125-kWe-class
module. The 50-kWe-class stack tests demonstrate ther-
mally self-sustaining stack technology and in-stack fuel
reformation. The test cells are expected to operate for more
than 1,000 hr with a degradation rate of less than 0.5% per
1,000 hr of operation. The module test cells operate on
pipeline natural gas and export A.C. power to the grid. These
tests integrate a test module with commercial-scale sub­
systems and are expected to operate for 2,500 hr.
A 400-kWe prototype SOFC field test is being planned
for 2017. This project will test a SOFC power system fueled
by natural gas. The system will be thermally self-sustaining
and is expected to operate for more than 5,000 hr with a
stack degradation rate of less than 1.5% per 1,000 hr. Upon
successful demonstration of these targets, the DOE plans to
fund the demonstration of a MWe-class natural-gas-fueled
distributed-generation (DG) system.
The market. Distributed generation is a suitable applica-
tion for utility-scale SOFC power systems. The DG market
consists of a variety of electric power and CHP applications.
Electric power applications include natural gas compressor
stations, grid strengthening, prime power for data centers,
and online backup power for office buildings and large-
scale commercial facilities. Commercial, institutional, and
municipal facilities can utilize CHP onsite to satisfy power
and heat needs. In the 2020 timeframe, SOFCs could serve
the electric power and CHP segments, which collectively
represent a large amount of capacity.
Currently, SOFC systems can be purchased for approxi-
mately $10,000 per kWe. R&D into improving cell perfor-
mance, reliability, and durability coupled with advanced,
automated manufacturing processes and mass manufacturing
are expected to reduce the cost of the first large-scale (MWe)
SOFC DG system to about $6,000 per kWe by 2020. Assum-
ing SOFC systems capture 25 MW of the anticipated DG
market between 2020 and 2025, the installed cost of a large-
scale SOFC DG system is estimated to be less than 140 135.4 134.2
$2,500 per kWe — a level that is cost-competitive with
conventional fossil-fueled DG technologies. Continued 120

Cost of Electricity (COE), U.S.$/MWh

market capture of an additional 1,000 MWe from 2025
100
through 2030 would reduce the estimated cost to less 86.4
78.8 82.9
than $1,000 per kWe. 80 74.5 68.7
The manufacturing and operational experience
acquired during the deployment of DG SOFC systems 60
will benefit the development of larger systems based
40
on the same SOFC module technology, and ultimately
foster utility-scale central generating stations fueled by 20
either natural gas or coal-derived synthesis gas.
The SOFC’s ability to internally reform methane 0
SOTA SOTA Advanced Advanced SOTA Advanced Advanced
permits a common cell/stack/module design for use IGCC PC IGCC IGFC NGCC NGCC NGFC
with either syngas or natural gas. Thus, the cell, stack,
and module technology that evolved from the SOFC 70
64.7
program, and presently being developed and tested by
Higher Heating Value (HHV) Efficiency, %

60
industry teams, will likely be the basis for commercial-­ 54.1
class SOFC power systems. The fuel flexibility, 50
49.7
46.0
coupled with the SOFC’s modularity, allows for valida-
40.1
tion of standard stack and module designs at progres- 40
sively larger scales simply by aggregating modules to 32.6 32.5
the desired power level. 30

The SOFC program technology development will

20
culminate with a first-of-a-kind, 50-MWe utility-scale
demonstration, combined with either an integrated 10
gasification fuel cell or natural gas fuel cell system
and carbon capture capabilities, in the 2025 to 2030 0
SOTA SOTA Advanced Advanced SOTA Advanced Advanced
timeframe. Critical to this development timeline are the IGCC PC IGCC IGFC NGCC NGCC NGFC
ongoing stack, proof-of-concept, and prototype field IGCC = Integrated Gasification Combined Cycle
tests that will enable the commercial deployment of PC = Pulverized Coal
IGFC = Integrated Coal Gasification Solid Oxide Fuel Cell
SOFC technology by the early 2020s. NGCC = Natural Gas Combined Cycle
In parallel with these efforts, the SOFC program NGFC = Natural Gas Solid Oxide Fuel Cell
will continue transformational R&D into advanced cell
p Figure 6. The advanced natural gas solid oxide fuel cell (NGFC) power system is
technology, syngas processing, and novel stack archi-
projected to have the lowest cost-of-electricity (COE) and the highest efficiency of any
tectures, as well as conduct progressively larger stack advanced fossil fuel power generation technology, assuming cost targets are met.
tests and system demonstrations.

Looking to the future Literature Cited

As fuel cells become a commercial reality, the lack of 1. U.S. Dept. of Energy, “Fuel Cell Technologies Market Report
2014,” DOE Office of Energy Efficiency and Renewable Energy,
hydrogen infrastructure remains a challenge for fuel cell http://energy.gov/sites/prod/files/2015/10/f27/fcto_2014_
systems that rely on pure hydrogen as fuel. In 2013, the DOE market_report.pdf (Oct. 2015).
and industry launched H2USA, a partnership to address the 2. Sutherland, E., and F. Joseck, “Low Volume Production and
barriers to installing a hydrogen infrastructure. California has Delivery Cost,” DOE Hydrogen and Fuel Cells Program Record
15011, DOE, www.hydrogen.energy.gov/pdfs/15011_low_
committed $100 million to support the rollout of 100 hydro- volume_production_delivery_cost.pdf (Nov. 6, 2015).
gen stations, and other states, such as Hawaii, Connecticut, 3. Marcinkoski, J., et al., “On-Road Fuel Cell Stack Durability,”
and Massachusetts, are developing plans for station rollouts. DOE Hydrogen and Fuel Cells Program Record 15014, DOE,
Efforts are underway to reduce the cost of hydrogen www.hydrogen.energy.gov/pdfs/15014_fuel_cell_stack_
infrastructure technologies and enable the efficient, safe, durability.pdf (Oct. 22, 2015).
4. National Renewable Energy Laboratory, “Average On-Road
and timely deployment of hydrogen technologies both in
Vehicle Range,” www.nrel.gov/hydrogen/images/cdp_fcev_47.jpg
the U.S. and abroad to meet our environmental goals (Oct. 30 2015).
by 2050. CEP

CEP  July 2016  www.aiche.org/cep  43

SPECIAL SECTION: ENERGY
Solid Oxide Fuel Cells
and Membranes
Kyle Brinkman Fuel cells and membranes are similar in that they
Clemson Univ.
Kevin Huang
employ materials that transport ions and electrons.
Univ. of South Carolina Both can play important roles in
making clean energy a reality.
A
sustainable future calls for the development of clean,
efficient, and affordable energy technologies to
address the world’s growing demand for energy. Fuel
cells, which convert chemical energy to electrical energy,
have been widely regarded as a promising alternative to
conventional internal combustion engines for clean and effi-
cient power generation. Membranes are another important,
closely related technology for utilizing fossil fuel resources
to produce clean energy and value-added chemicals through
process intensification.
This article briefly reviews the basic working principles,
system components, and applications of solid oxide fuel
cells for clean power generation and membrane reactors for
value-added chemical production.
Solid oxide fuel cells
A solid oxide fuel cell (SOFC) directly converts the
chemical energy in fossil fuels into electrical power via an
electrochemical reaction. A SOFC (Figure 1) has three basic
functional elements: cathode, electrolyte, and anode. The
cathode reduces oxygen (in the form of O2) in the air sup-
plied to it into O2–. The electrolyte transports oxygen con-
tinuously, in the form of O2–, from the cathode to the anode
under a gradient of oxygen chemical potential. At the anode,
or fuel supply electrode, the O2– delivered by the electrolyte
reacts with hydrogen or a hydrocarbon fuel to produce H2O,
CO2, and electrons. The electrons required for the cathode
reaction are released by the anode and arrive at the cathode
via an external load that produces electricity. The overall
driving force for a SOFC is the gradient of oxygen chemical
potential that exists between the cathode with a high oxygen
partial pressure and the anode with a low oxygen partial
44  www.aiche.org/cep  July 2016  CEP
pressure. References 1–3 provide a more detailed review of
SOFC technology.
Like the components of a battery, each SOFC component
exhibits an internal resistance to either electronic or ionic
current flow, often expressed as voltage loss. The terminal
cell voltage is, therefore, the open circuit voltage (or electro-
motive force, EMF, if no fuel is lost by any means) reduced
by the individual voltage loss of each cell component.
The maximum cell voltage of a typical single SOFC with
air as the oxidant is generally 1.2 V, depending on tempera-
ture, system pressure, and fuel composition. This voltage is
obviously inadequate for any type of practical application.
To obtain a sufficiently high voltage and power, multiple
single cells are connected in series and/or in parallel by
interconnects and/or cell-to-cell connectors that are elec-
tronic conductors and oxide-ion insulators.
Hydrocarbon Fuel
Load
H2 + O2– = H2O + 2e–
CO + O2– = CO2 + 2e– –
e–
Anode (Fuel Electrode)
Solid
I O2– Electrolyte V
+
e– 0.5O2 + 2e– = O2–
Cathode (Air Electrode)
Air
p Figure 1. In a solid oxide fuel cell, the cathode reduces oxygen (from
air) to O2–, which the electrolyte transports from the cathode to the anode,
where it reacts with a fuel to produce H2O, CO2, and electrons.
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
SOFC stack designs Multiple cells have also been deposited in series on
To increase the reliability and reduce the cost of SOFCs, an electrochemically inactive and electrically insulating
designers strive to obtain high performance at low operating substrate. This design, termed segmented-in-series, has
temperatures. To achieve this goal, modern SOFCs typically unique advantages, including low fabrication costs. More
contain a thin electrolyte film supported on a substrate — a importantly, such a SOFC stack operates at higher voltage
porous or channeled dense layer that enables gas transport. and low current for a fixed power rating. This feature could
The porous electrode (cathode or anode), dense metal or help reduce the power losses on current connections, which
ceramic interconnect, or porous inactive insulator can serve is particularly important for large-class SOFC generators.
as the substrate. The substrate can be made into either a Figure 2c shows a segmented-in-series SOFC designed by
tubular or a planar shape (Figure 2). LG Fuel Cells.
An important requirement for a SOFC is that oxygen
must be transported across the electrolyte in the form of Advantages of SOFCs
O2–, but not as molecular O2. To achieve this, dense barri- Since a SOFC operates on electrochemical principles,
ers between air and fuel must be established. In the tubular its efficiency is unbounded by the Carnot cycle that limits
SOFC design, dense electrolyte and interconnect layers the highest achievable efficiency of conventional internal
create such a barrier, allowing air and fuel to meet only at combustion engines (ICEs). Therefore, a SOFC has an inher-
the open end and combustion to occur only after most of the ently higher electrical efficiency than ICEs, particularly in the
fuel has been consumed by the oxidation reaction over the sub-MW range. Higher electrical efficiency infers lower CO2
entire cylindrical surface. Tubular SOFCs, therefore, do not emissions per unit of electricity produced if hydrocarbons are
need a physical sealing material. Planar SOFCs, on the other used as fuels. A SOFC also produces virtually no nitrogen
hand, require sealing materials along the perimeters of the oxide emissions (collectively known as NOx) because of its
interconnect/electrode and electrolyte/electrode interfaces to low operating temperature, whereas NOx emissions are a big
prevent air from mixing with fuels, which often presents a
challenge to the reliability and stability of the planar SOFCs.
Certain substrate/geometry combinations have advan-
tages. For example, a cathode substrate paired with a tubular
stack design is an excellent marriage. Because cell-to-cell
connections in the stack take place in a reducing atmosphere,
inexpensive transition metals such as nickel and copper can
be used. Otherwise, more-expensive noble metals are needed
for connecting anode-supported cells into stacks in an
oxidizing atmosphere. Figure 2a shows a cathode-supported
tubular SOFC stack designed by Siemens/Westinghouse.
On the other hand, an anode substrate and a planar stack
is a good combination. High-power-density anode-supported
single cells can operate at a lower temperature, allowing
economic, commercially available oxidation-resistant alloys
to be used to connect single cells into a stack. The oxidation-
resistant alloys provide the mechanical support for the stack
and function as interconnects and current collectors simulta-
neously. Figure 2b shows an anode-supported planar SOFC
stack designed by FuelCell Energy.
Porous metal substrates have garnered considerable
interest in recent years. Potential advantages include robust-
ness and cost-effectiveness of cells and stacks made with
these materials. However, a major challenge is the fabrica-
tion of dense electrolyte and/or interconnect layers on the
substrate at a temperature low enough to prevent significant
oxidation and chemical reactions between underlying layers. p Figure 2. The SOFC substrate supporting the thin electrolyte film can be
made into a tubular (a) or planar (b) shape. The segment-in-series design
In addition, vaporization of chromium from the chromium- (c) is a special type of planar construction made by depositing multiple
containing metal interconnects during operation can degrade cells in series on an electrochemically inactive and electrically insulating
the cathode performance in the presence of air and moisture. substrate. Source: Adapted from (1).

Copyright © 2016 American Institute of Chemical Engineers (AIChE) CEP  July 2016  www.aiche.org/cep  45
SPECIAL SECTION: ENERGY
issue for conventional ICEs that burn fuel at much higher
temperatures. And, a desulfurizer subsystem can be incorpo-
rated into a SOFC generator to reduce sulfur oxide emissions
(collectively known as SOx) to virtually zero. In addition,
SOFC power generators are much quieter and produce less
vibration than a conventional engine during operation.
SOFCs operated at high temperatures have additional
advantages. High-temperature operation, typically in the
range of 600–1,000°C, provides high-quality waste heat.
It also effectively activates the processes of reforming and
electrochemical oxidation of hydrocarbon fuels in the pres-
ence of non-noble catalysts, which is technically important
for several reasons:
• It allows SOFCs to use most hydrocarbon fuels, either
in the gaseous or liquid state, provided that they are prop-
erly cleaned and reformed into simple fuels such as H2 and
CO. This is in contrast to low-temperature fuel cells, such
as proton exchange membrane (PEM) fuel cells, where CO
poisons the anode.
• The excess heat produced by the electrochemical
oxidation of fuels can be utilized by the highly endothermic
p Figure 3. (a) Siemens/Westinghouse has demonstrated a 220-kWe
SOFC/micro-turbine hybrid generator that achieved a net electrical effi-
ciency of 53%. (b) A different unit, a 100-kWe SOFC generator, has more
than 35,000 hours of operation, making it the longest-running SOFC ever
demonstrated. Source: Photos courtesy of Siemens/Westinghouse.
46  www.aiche.org/cep  July 2016  CEP
steam reforming reaction that occurs simultaneously, which
makes internal on-cell reformation possible. Integration
further increases the overall system efficiency.
• Co-production of heat and power, known as combined
heat and power (CHP), is also possible. The recovery of
waste heat to produce electricity enables CHP systems to
achieve a total energy efficiency in the range of 85–90%.
• Another way to recover waste heat is to combine a
micro gas-turbine with a SOFC stack to form a hybrid
system. To maximize the electrical efficiency, a hybrid is
often operated under pressurization, which boosts both the
performance of the SOFC stack and the effectiveness of the
turbine. A bottom cycle steam turbine can be added to the
hybrid system to increase efficiency even further. This hybrid
system is particularly beneficial for generators over 100
MWe. Siemens/Westinghouse has demonstrated a 220-kWe
class hybrid SOFC generator system that achieved a net
alternating-current electrical efficiency of 53% (Figure 3a).
The all-solid-state components of a SOFC system can
avoid the corrosion issues caused by the liquid electrolyte
in a molten carbonate fuel cell (MCFC) system, which pro-
longs the life of a SOFC. With over 35,000 operating hours
at an acceptable degradation rate, the Siemens/Westinghouse
100-kWe unit in Figure 3b is the longest running SOFC
generator ever demonstrated.
Applications of SOFCs
An ideal application for SOFCs is distributed station-
ary power generation. Depending on the size of the SOFC
generator, stationary power generation can be categorized
into the markets summarized in Table 1.
SOFCs: Challenges and opportunities
The two most critical challenges to the commercializa-
tion of modern SOFC technology are reliability and cost. In
order to compete with ICEs, efficient and low-emission SOFC
generators need to have a lifetime of 40,000 hr and cost less
than $500/kWe. None of today’s SOFC technologies can
achieve this level of performance. However, with advances in
materials and design, it is widely believed that SOFC cost and
durability barriers can eventually be overcome.
An important milestone will be reducing the operat-
ing temperature of a SOFC from the current 700–800°C
to below 600°C, where thermal degradation is lower and
inexpensive materials can be used but the distinct advan-
tages of a SOFC, such as hydrocarbon compatibility and
CHP capability, can be maintained. The performance of
such intermediate-temperature SOFCs is limited by the
cathode. Thus, researchers are pursuing the development of
advanced, catalytically active cathode materials with new
crystal structures and morphological nanostructures.
Another recent development is the use of a SOFC as a
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
membrane reactor (electrolyzer) that uses electricity as the
energy input to make value-added chemicals. An example
of this application is the co-electrolysis of CO2 + H2O by a
SOFC electrolyzer to make syngas (primarily H2 and CO).
When combined with renewable energy, these reversible
SOFCs can also be viewed as electricity storage, where the
energy is stored in chemical bonds.
Membranes
To electrochemically convert fuels to electricity, solid
oxide fuel cells rely on materials that transport ions and
electrons. A closely related technology that is also electro­
chemical in nature and that employs similar classes of mate-
rials, including ion conductors and mixed ionic-electronic
conductors (MIECs), is high-temperature membranes.
Ceramic membranes that transport ions, including
permeation membranes and membrane reactors, play an
essential role in several energy conversion systems (4).
Similar to SOFC electrolytes, membranes fabricated from
materials that are oxygen-ion conductors and have a low
electron conductivity can be used to separate oxygen from
air upon application of an external voltage. This is analogous
to what occurs in a fuel-cell-based electrolyzer used to split
water and generate hydrogen.
MIECs function similar to SOFC electrode materials. In
oxygen-ion-conducting materials, the oxygen concentration
gradients drive oxygen ions from the high-partial-pressure
side of the membrane to the low-partial-pressure side, while
electrons are transported through the bulk of the material
to participate in electrochemical surface reactions. MIEC
membranes can be viewed as a short-circuit fuel cell, with
electron transport occurring within the material instead of
through an external circuit. In addition, the driving force for
oxygen transport can be tailored by carrying out chemical
Table 1. Solid-oxide fuel cell systems can be used for power generation at different scales.
Size Class Rating Efficiency
(Net Alternating
Current, LHV)
Small-Scale <10 kWe <35%
Medium-Scale Industrial 100–1,000 kWe >45%
Large-Scale Dispersed 2–10 MWe >48%
Ultralarge-Scale Central 100 MWe >60%
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
reactions on the surface of the membrane.
Mixed ionic-electronic conduction can be achieved in
two ways, by selecting a material that either:
• supports both ionic and electronic conduction, or
• forms a two-phase composite of an ionic conductor and
an electronic conductor.
Materials of construction for equipment used for oxy-
fuel combustion, production of synthesis gases, or CO2
separation typically require mixed oxygen ion and electronic
conduction.
The overall process of oxygen transport (permeation) in
an MIEC membrane is divided into three steps:
1. Reduction of O2 to O2– at one surface (the feed side)
by the reaction:
0.5O2(g) + 2e– → O2–
2. Coupled transport of O2– and two electrons in opposite
directions through the bulk membrane.
3. Oxidation of O2– to O2 and 2e– at the other surface
(the permeate side) by the reaction:
O2– → 0.5O2(g) + 2e–
The driving force for oxygen transport is the difference
in chemical potential between the feed and permeate sides of
the membrane. Figure 4 (next page) illustrates this principle
for a dual-phase material consisting of an electronic conduc-
tor and an ionic conductor.
In addition to the bulk transport of oxygen ions and
electrons, MIEC membranes are also subject to surface
effects that impact performance. A common principle of
mass transport across a membrane is that flux is inversely
proportional to the membrane thickness. However, the actual
Fuel Type Applications
Pipeline natural gas Residential (electricity, heating, cooling)
Coal gas Auxiliary power unit (APU) on heavy-duty
Gasoline trucks
Cellular phone transmission towers
Battery chargers
Pipeline natural gas Credit-card data processing centers
Hospitals (which cannot tolerate a power
outage)
Pipeline natural gas Larger industrial units
Coal gas Small communities
Pipeline natural gas Baseload power generation
Coal gas
CEP  July 2016  www.aiche.org/cep  47
SPECIAL SECTION: ENERGY
flux is also a function of the kinetics of any reactions occur-
ring on the membrane surface. As membrane thickness is
reduced to achieve a higher gas flux, surface and interfacial
effects become more important and can dramatically impact
membrane performance (6).
A critical thickness exists at which further reduction
in thickness does not increase transport. In typical oxygen
separation membranes fabricated by conventional ceramic
processing techniques, this critical thickness is on the order
of 80–100 μm. Surface exchange or catalyst layers are often
applied to membrane surfaces to enhance the performance.
Membranes can be fabricated in a planar or tubular
geometry by physical vapor or chemical deposition methods
that create thin, dense layers on porous supports. Systems
can be made of materials that conduct a variety of ionic spe-
cies. For example, ceramic-based proton-conducting materi-
als enable H2 separation (7), while carbonate ion conductors
enable CO2 separation (8).
Applications of membranes
Membranes meet the critical need for highly efficient and
environmentally friendly utilization of existing fossil fuel
resources during the transition to sustainable (e.g., renew-
able, nuclear) energy production. Applications currently being
explored range from CO2 separation to combustion in oxygen-
rich environments, including partial oxidation of natural gas,
oxy-combustion of coal, and oxidative coupling of natural gas
upgrading to the production of higher hydrocarbons.
MIEC-based CO2 separation membranes are composites
consisting of two phases, a carbonate ion conductor and an
electronic conductor. Typical configurations use a K2CO3 or
Li2CO3 salt as the carbonate ion conductor within a porous
metal support such as stainless steel or silver, which serves
as the electronic conductor (9).
Fossil fuels such as natural gas are strategically
important raw materials for the synthesis of important
value-added materials such as syngas (10), liquid fuels
p Figure 4. A mixed ionic-electronic conductor (MIEC) membrane can
be thought of as a short-circuit fuel cell, with electron transport occurring
within the material rather than through an external circuit. Source: Adapted
from (5).
48  www.aiche.org/cep  July 2016  CEP
(11), methanol (12), and ethylene (13). Achieving cost-
effective and large-scale hydrogen production has sig-
nificant economic benefits and contributes to a cleaner
environment (14).
Catalytic steam reforming of natural gas:
CH4 + H2O → CO + 3H2
has been the major route for syngas production. The reac-
tion is strongly endothermic and requires high temperatures
(~700–900oC) and pressures (~20–40 bar) to achieve the
maximum conversion of CH4 to H2 and CO (15). Further-
more, the product stream has a H2/CO ratio of 3:1, making it
unsuitable for production of liquid fuels via Fischer-Tropsch
synthesis.
An alternative is the catalytic partial oxidation of natu-
ral gas:
CH4 + 0.5O2 → CO + 2H2
This weakly exothermic reaction produces syngas with a
H2/CO ratio of 2:1, which is an ideal feed for making metha-
nol or liquid fuels by Fischer-Tropsch synthesis.
However, if air is used as the oxidant, the syngas product
becomes highly diluted with nitrogen. Ideally, pure oxygen
would be used, but state-of-the-art pressure-swing adsorp-
tion (PSA) and cryogenic processes are highly energy-
intensive and expensive. Membranes could perform both
oxygen separation and catalytic partial oxidation of natural
gas in a single process, at a cost that is as much as 30%
lower than that of combining separate cryogenic air separa-
tion and autothermal reforming units (16).
Large-scale membrane separation units have been aimed
mainly at supplying oxygen for oxy-combustion of coal and
production of syngas. Praxair developed an oxygen transport
membrane system for coal-fired power plants that would
provide oxygen for oxy-combustion and enable subsequent
CO2 capture (17). Economic analysis indicated that the
membrane separation unit has a higher overall efficiency
than existing cryogenic air separation units.
Several material-related challenges remain in the devel-
opment of membrane systems that can deliver large volumes
of oxygen in harsh, real-world conditions. Since O2 flux is
inversely proportional to membrane thickness, research has
focused on thin membranes on porous support substrates.
These thin membranes are fragile and often prove difficult
and expensive to manufacture. Research and development
needs include: new materials with higher intrinsic (bulk)
ion and electron conductivity, which underlies O2 transport;
materials that are stable at high temperatures and high oxy-
gen partial-pressure gradients over long periods of time and
in the presence of contaminants, such as sulfur in fluegas
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
from coal gasification; surface exchange (reaction) layers
that can improve O2 flux through thin membranes; and cost-
efficient manufacturing techniques.
Air Products has partnered with Ceramatec to develop
oxygen separation membranes for the production of syngas
by partial oxidization as an alternative to autothermal reform-
ing. The membranes combine air separation and steam
reforming in a single unit, significantly reducing costs (16).
An additional advantage is that the use of high-pressure
natural gas as the feedstock allows production of syngas with
a high pressure that matches the requirements of downstream
processes without additional compression. Air Products has
built commercial-scale planar membranes (Figure 5) and
tested them at a 27-Nm3/hr pilot plant at syngas pressures
Porous
High-Pressure
Support
Syngas (External)
Thin Active
Membrane
Internal Low-Pressure
Flow Air (Internal)
Channels
High-Pressure
Syngas (External)
p Figure 5. An oxygen separation membrane can be used for syngas
production. Source: Adapted from (16).
Literature Cited
1. Huang, K., and J. B. Goodenough, “Solid Oxide Fuel Cell
Technology: Principles, Performance, and Operations,” Woodhead
Publishing, Ltd., Cambridge, U.K. (2009).
2. Huang, K., “Solid Oxide Fuel Cells,” Chapter 8 in “Materials for
Fuel Cells,” Woodhead Publishing, Ltd., Cambridge, U.K. (2008).
3. Huang, K., and S. C. Singhal, “Cathode-Supported Tubular Solid
Oxide Fuel Cells Technology — A Critical Review,”
Journal of Power Sources, 237, pp. 84–97 (Sept. 2013).
4. Sunarso, J., et al., “Mixed Ionic-Electronic Conducting (MIEC)
Ceramic-Based Membranes for Oxygen Separation,” Journal of
Membrane Science, 320 (1–2), pp. 13–41 (July 2008).
5. Reifsnider, K. L., et al., “Multiphysics Design and Development
of Heterogeneous Functional Materials for Renewable Energy
Devices: The HeteroFoaM Story,” Journal of The Electrochem­ical
Society, 160 (4), pp. F470–F481 (Mar. 2013).
6. Lane, J. A., and J. A. Kilner, “Measuring Oxygen Diffusion and
Oxygen Surface Exchange by Conductivity Relaxation,” Solid State
Ionics, 136–137, pp. 997–1001 (Nov. 2000).
7. Phair, J. W., and S. P. S. Badwal, “Review of Proton Conductors
for Hydrogen Separation,” Ionics, 12 (2), pp. 103–115 (July 2006).
8. Chuang, S. J., et al., “Dual-Phase Metal-Carbonate Membrane for
High-Temperature Carbon Dioxide Separation,” Industrial and Engi-
neering Chemistry Research, 44 (21), pp. 7999–8006 (Sept. 2005).
9. Xu, N. S., et al., “Silver-Molten Carbonate Composite as a New
High-Flux Membrane for Electrochemical Separation of CO2 from
Flue Gas,” Journal of Membrane Science, 401–402, pp. 190–194
(May 2012).
Copyright © 2016 American Institute of Chemical Engineers (AIChE)
up to 3 × 106 Pa and temperatures up to 1,323 K.
Another application for membranes in the production of
value-added chemicals is the oxidative coupling of methane
for ethylene production.
The electrochemically controlled delivery of oxygen, in
the form of oxygen ions, into the reaction zone minimizes the
creation of byproducts, increasing selectivity and yield (18).
Membrane reactors are increasingly being considered
as a means to couple endothermic and exothermic reactions
in thermoneutral, and thus more energy efficient, processes.
Examples are the combination of partial oxidization of meth-
ane (exothermic) with steam reforming or with the thermal
decomposition of CO2 to CO and O2 (endothermic).
Membranes: Challenges and opportunities
Research topics under investigation include membrane
design; efficient, low-cost manufacturing strategies; and
a variety of material science issues related to membrane
stability under the required temperature, pressure, and gas-
phase composition conditions. Chemical and mechanical
stability in harsh environments, including ways to mini-
mize surface poisoning and the demonstration of long-term
membrane performance, are among the challenges that
need to be addressed in order to move this technology into
the marketplace. CEP
10. Wang, H., et al., “Partial Oxidaiton of Methane to Syngas in a
Perovskite Hollow Fiber Membrane Reactor,” Catalysis Communi-
cations, 7 (11), pp. 907–912 (Nov. 2006).
11. Wilhelm, D. J., et al., “Syngas Production for Gas-to-Liquids
Applications: Technologies, Issues, and Outlook,” Fuel Processing
Technology, 71 (1–3), pp. 139–148 (June 2001).
12. Taylor, S. H., et al., “The Partial Oxidation of Methane to Metha-
nol: An Approach to Catalyst Design,” Catalysis Today, 42 (3),
pp. 217–224 (July 1998).
13. Lunsford, J. H., “Catalytic Conversion of Methane to More Useful
Chemicals and Fuels: A Challenge for the 21st Century,” Catalysis
Today, 63 (2–4), pp. 165–174 (Dec. 2000).
14. Jacobson, M. Z., et al., “Cleaning the Air and Improving
Health with Hydrogen Fuel-Cell Vehicles,” Science, 308 (5730),
pp. 1901–1905 (June 2005).
15. Twigg, M. V., “Catalyst Handbook,” 2nd ed., Wolfe Publishing
Ltd., London, U.K. (1997).
16. Miller, C. F., et al., “Advances in Ion Transport Membrane
Techonology for Syngas Production,” Catalysis Today, 228 (1),
pp. 152–157 (June 2014).
17. Christie, M., et al. “Advanced Oxyfuel Boilers and Process Heaters
for Cost-Effective CO2 Capture and Sequestration,” Final Technical
Report for DOE Award No. DE-FC26-01NT41147 (2007).
18. Zeng, Y., et al., “Perovskite-Type Ceramic Membrane: Synthesis,
Oxygen Permeation, and Membrane Reactor Performance for
Oxidative Coupling of Methane,” Journal of Membrane Science,
150 (1), pp. 87–98 (Nov. 1998).
CEP July 2016 www.aiche.org/cep 49
SPECIAL SECTION: ENERGY

The Fuel Cell Electric Vehicle (FCEV)

Hydrogen FCEV (HFCEV) Reduces Greenhouse Gas Emissions

Power 50% 90%

Control Unit
Electric Gasoline H2 from H2 from Wind
Motor natural gas

Refuels Rapidly Can Travel 300 Miles

Fuel Cell takes only a few minutes and between refills
Stack uses familiar technology
N

W E
Hydrogen
Storage Tanks
Battery
S

Emits Only Water Uses Domestic Fuel

from the tailpipe

• natural gas • water (electrolysis)

• biomass • waste products

Hydrogen Fuel Cell Operates Efficiently Runs Quietly

20–30% even at highway speeds, since
Electric Current there are no mechanical gears
Internal Combustion
or combustion
60%
FCEV
Fuel In
Hydrogen from
Natural Gas Air In Efficiency
(Methane) or
Renewables

Scales Up Easily
as fuel cells can be added to the stack to increase power
Water and
Heat Out

50  www.aiche.org/cep  July 2016  CEP

 Fuel Cells for
Mobile Applications
Krishna Reddi Clean and efficient transportation
Amgad Elgowainy
Michael Wang can become a reality for everyone with
Argonne National Laboratory hydrogen fuel cell electric vehicles.
H
ydrogen fuel cell electric vehicles (HFCEVs) are
more energy efficient than conventional gasoline
internal combustion engine vehicles (ICEVs), which
are limited by the Carnot thermal engine efficiency, and
they produce no tailpipe emissions other than water vapor.
Hydrogen fuel can be produced from a variety of non-fossil
and renewable feedstocks that are widely available, and
could help to reduce the transportation sector’s dependence
on petroleum-based fuels and increase the security of the
energy supply.
Hydrogen fuel cell electric vehicles
A HFCEV consists of six major components: a hydrogen
storage tank, air intake system, fuel cell stack, power control
unit, battery, and electric motor. The HFCEV uses proton
exchange membrane (PEM) fuel cell technology to convert
the chemical energy of hydrogen into electricity. Hydrogen
from the onboard storage tank reacts with oxygen pulled in
through the air intake system to generate electricity via an
electrochemical process that occurs in the fuel cell stack.
The only byproduct of the process is water vapor, which
exits the fuel cell stack into the atmosphere.
The electricity the fuel cell generates is managed by the
power control unit, which conditions the electricity and either
charges the battery, powers the motor, or both. Although the
battery is not a major source of power for the HFCEV, it is
used to store excess electricity, allows the fuel cell to operate
near its peak efficiency, and supports other functions of the
vehicle. The electric motor converts the electric energy into
mechanical energy, propelling the vehicle (1).
Although current gasoline-powered vehicle technologies
have shorter fueling times and longer driving ranges than
many of the alternative zero-emission vehicle technologies,
they produce tailpipe emissions, such as greenhouse gases
(GHGs). HFCEVs can achieve fueling times and driving
ranges similar to those of gasoline ICEVs while eliminat-
ing tailpipe emissions and reducing the well-to-wheels
(WTW) GHG emissions (2). HFCEVs are able to provide
a consumer experience similar to that of gasoline-powered
vehicles, while reducing the environmental impacts of the
transportation sector.
One drawback of hydrogen as a fuel is that because it has
a low molecular weight and low density, it must be stored
at high pressures onboard the vehicle to enable a driving
range comparable to that of gasoline-powered vehicles.
Various technologies have been explored to store hydro-
gen at various states, including cryo-compressed hydrogen
(CcH2) at 350 bar, gaseous hydrogen at 350 bar, and gaseous
hydrogen at 700 bar. Hydrogen storage tanks have evolved
from all-metal tanks (Type I), metal hoop-wrapped composite
tanks (Type II), and metal-lined composite tanks (Type III)
to plastic-lined composite tanks (Type IV). The 700-bar
Type IV tank for onboard storage is the only option currently
certified for use by all HFCEV manufacturing companies (3).
Fueling
The Society of Automotive Engineers (SAE) has
developed protocols to control the fueling process (4), and
fuel station developers are building facilities to fuel 700-bar
HFCEVs using those standardized fueling protocols. The
fueling protocol, SAE J2601, establishes a set of performance
parameters that need to be met and maintained in order to
CEP  July 2016  www.aiche.org/cep  51
SPECIAL SECTION: ENERGY
Hydrogen delivery includes
compression or liquefaction, transmission,
distribution, and refueling.
dispense the necessary amount of hydrogen in the shortest
possible time while ensuring the safety of the filling process.
The thermal diffusivity of a Type IV tank is very low,
enabling a near-adiabatic fueling process. The increase in
pressure during the short fueling event raises the tempera-
ture of hydrogen within the tank considerably (5). Type IV,
700-bar tanks have a maximum operating temperature
of 85°C. At that temperature, the corresponding fill pres-
sure can be as high as 875 bar at the end of a fill. To keep
the temperature in the vehicle’s tank below 85°C and also
enable fast fueling within 3 to 5 min, hydrogen is precooled
to –40°C before it is dispensed. The SAE J2601 protocol
considers the tank characteristics, station precooling capa-
bilities, and ambient temperature in determining the pressure
ramp rate for vehicle fueling and thus how long it takes to
fuel the vehicle.
Although HFCEV operation is considered clean with no
associated tailpipe emissions beyond water, the production of
hydrogen fuel can create emissions. These emissions come
primarily from the technologies used to produce and deliver
hydrogen, including liquefaction or compression and precool-
ing at refueling stations. A WTW analysis can estimate the
emissions associated with the hydrogen production and
delivery/dispensing pathway.
The WTW analysis can be broken down into well-to-
pump (WTP) and pump-to-wheels (PTW) stages. The WTP
stage includes fuel production from the primary source of
energy (feedstock) to its delivery to the vehicle’s energy
storage system (fuel tank). The PTW stage includes fuel
consumption during operation of the vehicle to power the
vehicle’s wheels. The results from WTP and PTW analyses
are summed to give the WTW energy use and emissions
associated with various vehicle-fuel technologies.
The large-scale deployment or adoption of HFCEVs
will require a refueling infrastructure network to provide a
consumer experience comparable to that of gasoline ICEVs.
A hydrogen pathway (6) is comprised of three components:
producing the hydrogen, delivering the hydrogen to a refuel-
ing station, and dispensing the hydrogen via a series of
compression and precooling processes.
Hydrogen is usually produced at low pressure (~20 bar)
and can be compressed for transmission from the production
plant to the distribution terminal. At the distribution termi-
nal, the hydrogen is further compressed or liquefied so that
it can be delivered economically to the refueling stations.
The delivery modes of gaseous and liquid hydrogen include
pipelines, gaseous tube trailers, and liquid tankers.
52  www.aiche.org/cep  July 2016  CEP
Alternatively, hydrogen production may be co-located
with the distribution terminal, where it can be further pack-
aged for transmission and distribution. Hydrogen can also
be produced at the refueling station from natural gas using
a small-scale steam methane reforming (SMR); the gaseous
hydrogen is compressed and precooled, and then dispensed
into a HFCEV’s onboard storage system.
Compression and storage as well as transportation (e.g.,
pipelines, trucks, etc.) are necessary and important compo-
nents of a complete hydrogen delivery system.
Hydrogen production
Most hydrogen is produced from natural gas by SMR.
The methane in the natural gas reacts with steam at high
temperatures (700–1,000°C) and pressures (3–25 bar) in
the presence of a catalyst to produce hydrogen, carbon
monoxide, and a relatively small amount of carbon dioxide.
Next, in the water-gas shift reaction, the carbon monoxide
and steam react in the presence of a catalyst to produce
carbon dioxide and additional hydrogen. In the third step,
pressure-swing adsorption, carbon dioxide and other
impurities are removed, leaving high-purity (> 99.999%)
hydrogen. The well-to-production-gate GHG emissions
of SMR plants with a process energy efficiency (based on
the lower heating value [LHV]) of 65–75% varies from
12.3 to 10.6 kg CO2 per kg H2 (7).
Hydrogen can also be produced by biomass gasification,
using heat, steam, and oxygen to convert biomass into hydro-
gen and other products without combustion. Biomass, includ-
ing woody and other cellulosic feedstocks, is considered a
renewable resource for hydrogen production. The gasification
process converts organic matter at high temperatures, in the
presence of a controlled amount of oxygen and steam, into
carbon monoxide, hydrogen, and carbon dioxide. Similar to
the SMR process, the carbon monoxide reacts further with
steam to form carbon dioxide and additional hydrogen.
Hydrogen can be produced by electrolysis, which
uses electricity to split water molecules into hydrogen
and oxygen, as well. Producing hydrogen by electrolysis
using electricity from the grid (at its current mix) may not
reduce the WTW GHG emissions compared to the emis-
sions associated with gasoline ICEVs, because most of the
electricity in the grid is generated from fossil fuels like coal
and natural gas. The carbon intensity of the average U.S.
grid mix, including transmission and distribution losses,
is 0.54 kg CO2 e/kWh (7).
Electrolysis is expected to be a viable option for the
production of hydrogen in the future because renewable
power generation is expected to increase, thereby reducing
the GHG emissions released per unit of electricity available
through the grid. Because the electricity generated from
renewable sources like solar and wind is intermittent, elec-
trolysis of water to produce and store hydrogen may enable plant to terminals. Geologic storage or physical storage at
high penetration of renewable electricity while balancing a distribution gas terminal serves as a buffer to mitigate
supply and demand. seasonal variations and any disparities between supply and
demand.
Delivery options The hydrogen may also be compressed to a moderate
The hydrogen delivery pathway, which includes com- pressure of about 200–500 bar and loaded onto gaseous
pression or liquefaction, transmission, distribution, and tube trailers that carry between 300 kg and 1,000 kg of fuel.
refueling, packages and transports hydrogen from the pro- The loaded tube trailer delivers the fuel to the refueling sta-
duction plant gate to the vehicle’s tank. Currently, hydrogen tion, where it is compressed to about 1,000 bar and held in a
is primarily distributed to refueling stations (Figure 1) as a high-pressure buffer storage system.
cryogenic liquid by a liquid tanker or at moderate pressures Hydrogen may also be produced onsite at the refueling
(200–500 bar) by gaseous tube trailers. station using a small-scale SMR plant or an electrolyzer,
Liquid delivery. Gaseous hydrogen produced at low pres- compressed to a high pressure, and held in buffer storage
sures (about 20 bar) is liquefied by a series of compression tanks. The high-pressure buffer storage system cascades the
and expansion processes that use liquid nitrogen. The liquid flow of hydrogen into a dispenser, where a refrigeration sys-
hydrogen is stored in large cryogenic storage tanks, and then tem precools it to –40°C for dispensing to the vehicle tank.
loaded onto liquid tankers for delivery to refueling stations. Limitations. A major benefit of HFCEVs is their poten-
The cryogenic storage tanks at
the distribution terminal satisfy
demand during production
outages and serve as a buffer
against variations between sup-
ply and demand.
A tanker carrying a payload
of 4 m.t. of liquid hydrogen
unloads at small cryogenic
tanks at one or more refueling
stations, where the hydrogen
is stored at a pressure of about
2–8 bar and supplied to the
pump. A cryogenic pump raises
the pressure of the hydrogen
above 700 bar, a heat exchanger
(vaporizer) heats the hydrogen
to –40°C, and the pump dis-
penses the fuel into the vehicle.
Alternatively, the cryogenic
pump may be used to directly
pump the cryogenic hydrogen
into a cryogenic-­compressed
vehicle tank at 350 bar and
–230°C. Cryogenic-compressed
dispensing is currently in the
demonstration phase, but it has
the potential to increase the
HFCEV onboard storage energy
density and improve the driving
range of FCEVs.
Gaseous delivery. A
transmission pipeline network
transports pressurized gaseous p Figure 1. Hydrogen can be delivered to refueling stations as a liquid or a gas. Both approaches involve
hydrogen from the production compression, which consumes a large amount of electricity.

CEP  July 2016  www.aiche.org/cep  53

SPECIAL SECTION: ENERGY
tial to reduce GHG emissions. To determine to what degree
they reduce GHG emissions compared to gasoline-fueled
ICEVs, they must be evaluated on a life cycle basis.
Compression for the gaseous delivery pathway and
liquefaction for the liquid delivery pathway are the main
sources of GHG emissions associated with HFCEVs. If the
hydrogen is produced from fossil fuels, that also contributes
to the emissions profile. Compression and liquefaction con-
sume a large amount of electricity, which contributes to the
average GHG emissions of the U.S. grid.
Compression increases the temperature of hydrogen,
which in turn impacts the thermal durability of some com-
pressor components. The hydrogen temperature increase can
be managed by incorporating intercooling between the com-
pression stages, reducing the amount of power consumed.
Liquefaction increases the density of hydrogen consider-
ably, which makes storage and transportation more economi-
cal. However, hydrogen liquefaction requires the hydrogen
to be cooled to below –253°C at near-atmospheric pressure.
This requires a significant amount of electrical energy —
about 11–13 kWh per kg H2 — which amounts to about
one-third of the chemical energy of hydrogen (7). Advanced
liquefaction technologies that reduce the energy require-
ments of liquefaction plants to about 8 kWh per kg H2 (8)
are under development.
Well-to-wheels analysis
Figure 2 compares the WTW GHG emissions of several
HFCEV pathways to those of conventional gasoline-­powered
ICEVs. The overall WTW GHG emission profile is the sum
of the emissions from the well to the pump and from the
pump to the wheels. Because HFCEVs do not have any tail-
pipe GHG emissions, their GHG PTW contributions are zero.
The liquefied (Liq H2) and gaseous (Gas H2) hydrogen
PTW WTP Production
WTP Storage and Refueling
11% 36% 39% 73%
400
GHG Emissions, gCO2e/mile
300
200
100
0
Gasoline
Liq H2, Gas H2, Gas H2, Gas H2, Gas H2, Gas H2,
ICEV
Central Distributed Central Central Central Central
SMR SMR SMR SMR, Biomass Wind
with CCS
PTW = Pump to wheels
WTP = Well to pump SMR = Steam methane reforming
ICEV = Internal combustion engine vehicle CCS = Carbon capture and storage
p Figure 2. Hydrogen fuel cell electric vehicles (HFCEVs) have lower overall
emissions than gasoline-powered internal combustion engine vehicles (ICEVs).
54  www.aiche.org/cep  July 2016  CEP
pathways compared in Figure 2 include central SMR (with
and without carbon capture and storage [CCS]), distributed
SMR (with and without CCS), gasification via central-
ized biomass, and electrolysis via centralized wind. The
liquid delivery pathway has the advantage of higher energy
density and more favorable economics, but that comes at the
expense of higher GHG emissions than the gaseous pathway,
primarily from the energy-intensive liquefaction process.
The biomass pathway has lower GHG emissions because
of CO2 uptake from the atmosphere during the biomass
growth process, which offsets the CO2 released during the
production of hydrogen by gasification. The WTW GHG
emissions are 88% lower than those from gasoline ICEVs
when hydrogen is produced by an electrolysis process
powered by wind and delivered as a gas. These renewable
technologies have the potential to reduce GHG emissions
associated with HFCEVs, but they require further research
and development to be economically competitive with the
current SMR technology. CEP
Acknowledgments
The work on which this article is based was supported by the Fuel Cell Tech-
nologies Office of the U.S. Dept. of Energy’s (DOE) Office of Energy Efficiency
and Renewable Energy under Contract No. DE-AC02-06CH11357.
Literature Cited
1. Wind, J., “Hydrogen-Fueled Road Automobiles — Passenger
Cars and Buses,” in “Compendium of Hydrogen Energy Vol. 4,”
Ball, M., et al., eds., Woodhead Publishing, Sawston, Cambridge,
U.K., p. 3 (2016).
2. Elgowainy, A., and M. Wang, “Sustainable Vehicle Fuels Sus-
tainability/Sustainable Vehicle Fuels, Well-to-Wheel Analysis,”
in “Encyclopedia of Sustainability Science and Technology,”
Meyers, R. A., ed., Springer, New York, NY, pp. 10502–10529
(2012).
3. U.S. Dept. of Energy, Office of Energy Efficiency and
WTP Transportation Renewable Energy, “Amped Up Newsletter,” DOE, 1 (4), http://
WTP Liquefaction energy.gov/sites/prod/files/2015/11/f27/AmpedUp4-final.pdf
(July–Aug. 2015).
79% 88%
4. Society of Automotive Engineers, “Fueling Protocols for
Light-Duty Gaseous Hydrogen Surface Vehicles,” Standard
J2601_201407, SAE International, Warrendale, PA, http://
standards.sae.org/j2601_201407/ (2014).
5. Reddi, K., et al., “Hydrogen Refueling Station Compression and
Storage Optimization with Tube-Trailer Deliveries,” Interna-
tional Journal of Hydrogen Energy, 39 (33), pp. 19169–19181
(2014).
6. Reddi, K., et al., “Building a Hydrogen Infrastructure in the
United States,” in “Compendium of Hydrogen Energy, Vol. 4,”
Ball, M., et al., eds., Woodhead Publishing, Sawston, Cambridge,
U.K., p. 293 (2016).
7. Argonne National Laboratory, “GREET Model,” https://greet.
es.anl.gov/index.php (2015).
8. U.S. Dept. of Energy, “Hydrogen Delivery Scenario Analysis
Model (HDSAM 3.0),” DOE, https://www.hydrogen.energy.gov/
h2a_delivery.html (2015).
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