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- deployment still exist, such as the need for an economical
ity today because of public-private investment in fuel hydrogen infrastructure.
cell technology over the past few decades. Noah Meeks and Steve Baxley (pp. 34–37) envision
I became a proponent of fuel cells when my lab, Savan- a future in which an established hydrogen infrastructure
nah River National Laboratory, participated in a road test supports a hydrogen economy, “where energy needs would
of the 2009 Toyota Highlander fuel cell electric vehicle be met by oxidizing hydrogen in a fuel cell, rather than
(FCEV). As an owner of a gasoline-powered Toyota combusting a carbon-based fuel.” They explain that, “the
Highlander, I was particularly interested in this test. The hydrogen economy may emerge because of the need for
new fuel cell powertrain’s performance was equivalent to energy efficiency improvements within fossil fuel combus-
my Highlander’s, but with a fuel economy of greater than tion processes, energy storage, or carbon-free energy.” And
68 miles per gallon of gasoline equivalent. This full-scale although they acknowledge that these needs could be met by
pilot test proved that FCEVs could compete with more tradi- other technologies, they are also confident that fuel cells are
tional gasoline-powered vehicles on performance. the best solution to these challenges.
FCEVs are attractive because they offer competitive A hydrogen infrastructure is only necessary for fuel
performance while also cutting greenhouse gas (GHG) emis- cells that require pure hydrogen as a fuel, but some fuel
sions. In their article (pp. 50–54), Krishna Reddi, Amgad cells operate at high enough temperatures to reform hydro­
Elgowainy, and Michael Wang explain that FCEVs only carbon fuels internally. Kyle Brinkman and Kevin Huang
emit water vapor (although the methods used to produce (pp. 44–49) explain how solid oxide fuel cells (SOFCs)
hydrogen to fuel the vehicles, including steam methane reform fuels like natural gas and produce excess heat that
reforming (SMR), electrolysis, and gasification, have associ- can be used for combined heat and power (CHP) applica-
ated emissions). In a well-to-wheels analysis, they compare tions, which improves the overall efficiency of the fuel cell.
the emissions from FCEVs to gasoline-powered internal This makes SOFCs particularly well-suited to large-scale
combustion engine vehicles (ICEVs). industrial processes that require both heat and power.
Environmental targets are just one of the motivations Although stationary fuel cells like SOFCs are currently
behind government involvement in fuel cell technologies. deployed in industrial applications and FCEVs are available
Sunita Satyapal and Shailesh Vora describe (pp. 38–43) the for consumers to purchase, more developments in technol-
extent to which government has had a hand in promoting ogy and infrastructure are necessary to meet cost targets and
fuel cells, and how government involvement has helped to encourage widespread user acceptance.
foster user acceptance and encourage unsubsidized pur-
chases of fuel cells for stationary and mobile applications. — Bond Calloway
However, the authors concede that barriers to wide-scale Savannah River National Laboratory

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

 Meet the Authors

STEVE BAXLEY, P.E., is manager of research and economy, advanced nuclear systems, and advanced
development efforts related to renewable, storage, fossil fuels. He has also worked on environmental
and distributed generation technologies at Southern separations for fluegas treatment, particulate matter
Company (Email: [email protected]). Previ- control, and pollutant monitoring. Meeks received his
ously, he was a senior engineering manager at Applied BS in chemistry from Northern Kentucky Univ. and PhD
Research Associates, Inc., where he directed RD&D in in chemical engineering from the Univ. of Kentucky. He
support of the U.S. Dept. of Defense. He holds patents has co-authored six peer-reviewed journal publica-
for technologies related to energy and water, and he tions and numerous industry conference publications.
has received a national award from the Society of
American Military Engineers for the development of a KRISHNA REDDI, PhD, is a systems modeling and
novel renewable jet fuel production process. Baxley analysis engineer at the Argonne National Laboratory.
earned a BS in chemistry and MS in civil and environ- KYLE BRINKMAN KRISHNA REDDI He contributes to the techno-economic analysis of the
mental engineering from Florida State Univ. hydrogen delivery infrastructure and environmental
analysis of hydrogen fuel cell vehicles. He helped to
KYLE BRINKMAN, PhD, has been an associate profes- add new features and update the Hydrogen Delivery
sor in the Dept. of Materials Science and Engineering Scenario Analysis (HDSAM) model. His research inter-
at Clemson Univ since 2014 (161 Sirrine Hall, Clemson, ests include sustainable engineering, energy systems,
SC 29634; Phone: (864) 656-1405; Email: ksbrink@ sustainable energy systems, and life cycle analysis.
clemson.edu). He previously worked for the U.S. Dept. Reddi obtained his PhD in mechanical and aerospace
of Energy’s (DOE’s) Savannah River National Labora- engineering from Syracuse Univ.
tory (SRNL) and was a fellow of the Japanese Society
for the Promotion of Science. Brinkman has received SUNITA SATYAPAL, PhD, is the Director of the U.S.
the Minerals, Metals, and Materials Society (TMS) Dept. of Energy’s (DOE) Fuel Cell Technologies Office
Young Leaders International Scholar Award (2015); (1000 Independence Ave., SW, Washington, DC 20585;
the American Ceramics Society (ACERS) Professional AMGAD ELGOWAINY SUNITA SATYAPAL Phone: (202) 586-2336; Email: sunita.satyapal@
Achievement in Ceramic Engineering (PACE) Award ee.doe.gov), where she oversees $100 million per
(2015); the Clemson Univ. College of Engineering and year in research, development, demonstration, and
Science Outstanding Young Alumni Award (2015); the deployment activities related to hydrogen and fuel
DOE-Nuclear Energy (NE) Fuel Cycle R&D Early Career cells. She has experience in academia, industry, and
Researcher Award (2013); and the SRNL Laboratory government, including at United Technologies, as a
Director’s Early Career Exceptional Achievement Award visiting professor at Vassar College, and as a visiting
(2011). He received a BS in chemical engineering and scientist at Hokkaido Univ. in Japan. Satyapal received
an MS in materials science and engineering from her PhD from Columbia Univ. in physical chemistry,
Clemson Univ., and a PhD in materials science and and conducted her postdoctoral research in applied
engineering from the Swiss Federal Institute of Laus- and engineering physics at Cornell Univ. She holds 10
anne in Switzerland (EPFL). patents.

AMGAD ELGOWAINY, PhD, is a principal energy KEVIN HUANG SHAILESH D. VORA SHAILESH D. VORA, PhD, is the Fuel Cells R&D
systems analyst and the Life-Cycle Analysis Team Portfolio Manager at the National Energy Technology
Lead at the Argonne National Laboratory. He conducts Laboratory, U.S. Dept. of Energy (DOE) (626 Cochrans
techno-economic and environmental analysis of Mill Rd., Pittsburgh, PA 15236; Phone: (412) 386-7515;
alternative transportation fuels and advanced vehicle Email: [email protected]). He provides
technologies. He contributed to the development of technology leadership related to fuel cell-based power
the GREET (Greenhouse Gases, Regulated Emissions, generation in the DOE’s Office of Fossil Energy. Prior
and Energy Use in Transportation) suite of models to joining the DOE, he worked at Westinghouse and
for life cycle accounting of energy and emissions of Siemens, conducting work related to stationary fuel
alternative fuel/vehicle systems. His research, model- cells. Vora received his MS and PhD, both in materials
ing, and analysis cover petroleum and natural gas science and engineering, from the Univ. of Florida, and
vehicles, plug-in hybrid and battery electric vehicles, MBA from the Univ. of Pittsburgh.
and hydrogen fuel cell vehicles. Elgowainy holds a
PhD in mechanical engineering from the State Univ. of NOAH D. MEEKS MICHAEL WANG MICHAEL WANG, PhD, is the manager of the Systems
New York at Buffalo. He has authored and coauthored Assessment Group of the Energy Systems Div. at the
over 60 papers and technical publications. Conversion and Storage, and holds 10 U.S. patents. Argonne National Laboratory (Email: mqwang@anl.
He was recognized with the 2015 USC’s College of gov). He leads the development and application of
KEVIN HUANG, PhD, is a professor in the Dept. of Engineering and Computing Research Achievement GREET (Greenhouse Gases, Regulated Emissions,
Mechanical Engineering and SmartState Center for Award, 2014 USC Breakthrough Stars Award, and 2007 and Energy Use in Transportation) model for life cycle
Solid Oxide Fuel Cells (SOFCs) at the Univ. of South Siemens Special Employee Recognition Award, among analysis of advanced vehicle technologies, trans-
Carolina (USC) (541 Main St., Columbia, SC 29208; others. Huang received his PhD in physical chemistry portation fuels, and other energy systems. He is an
Phone: (803) 777-0204; Email: [email protected]). from the Univ. of Science and Technology Beijing. associate editor of Biotechnology for Biofuels and on
He previously worked at Siemens-Westinghouse, the editorial board of Frontiers of Energy and Power
where he was involved in the development of NOAH D. MEEKS, PhD, is a research engineer at Engineering in China. Wang received his BS in agricul-
cathode-supported tubular SOFC technology. He is the Southern Company (Email: ndmeeks@southernco. tural meteorology from China Agricultural Univ., and
associate editor of Royal Society of Chemistry (RSC) com), where he conducts advanced energy systems PhD and MS in environmental science from the Univ. of
Advances and the Journal of Electrochemical Energy research. His current research includes the hydrogen 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 how it is converted to power in a fuel cell, the various types
be met by oxidizing hydrogen in a fuel cell, rather than of fuel cells, and the obstacles that need to be overcome for a
combusting a carbon-based fuel. Since hydrogen is hydrogen economy to become a reality.
not available freely in nature, it must be produced from an
energy source, and it can be carbon-intensive or carbon-free, Hydrogen production
depending on the energy source employed. Hydrogen for fuel cells can be produced commercially
Fuel cells are central to a hydrogen economy. They con- by reforming hydrocarbons, gasification, or electrolysis of
vert the chemical energy in a fuel directly into electricity that water. Investigations continue into other methods, such as
can be used for stationary, mobile, or transportation applica- thermochemical or photochemical water-splitting and ther-
tions (Figure 1). Energy is created via two half reactions. molysis of methane.
At the anode, a stream of hydrogen is split into protons and Reforming. Most hydrogen is currently produced by
electrons. The electrons are forced through a circuit, produc- steam methane reforming (SMR). At high temperatures
ing energy: (700–1,100°C) and in the presence of a metal-based catalyst,
steam reacts with methane to form carbon monoxide and
2H2 → 4H+ + 4e– hydrogen. Additional hydrogen is recovered via a water-
gas shift reaction (WGS) that also yields CO2. Together the
At the cathode, the protons react with oxygen to produce overall reaction is:
water as a byproduct.
CH4 + 2H2O → → CO2 + 4H2
4H+ + 4e– + O2 → 2H2O
This reaction converts methane (which has a mass
Unlike fossil fuel combustion, hydrogen fuel cells energy density of 21,500 Btu/lb) to hydrogen (mass energy
produce power with no emissions of nitrogen oxides (NOx), density = 51,500 Btu/lb), which can then be used in a fuel
sulfur oxides (SOx), particulates, or carbon dioxide (CO2). cell (1). Natural gas is typically the methane source, but other
(The production of hydrogen, however, does produce emis- sources, such as landfill gas or biogas, can be used as well.
sions.) Low emissions are just one driver behind fuel cells Gasification. Synthesis gas (or syngas, a mixture of CO,
and the hydrogen economy; efficient power production, reli- CO2, and H2) can be produced by the gasification of solid
ability, and energy storage capabilities are also steering this fossil fuels, such as lignite coal, or other solid hydrocarbons,
technology toward commercialization. such as biomass or municipal solid waste (MSW). The
This article describes how hydrogen is produced and syngas can be converted into hydrocarbons (via the Fischer-

34  www.aiche.org/cep  July 2016  CEP

Tropsch process) or combusted to produce heat and power cells are highly reliable, their use as stand-alone power for
(such as in integrated gasification combined-cycle [IGCC] data centers and industries with critical reliability needs
plants), or the hydrogen can be separated for use in a fuel is being explored. Fuel cells are generally not suitable as
cell. backup power, because startup times are often too long.
Electrolysis. Hydrogen can also be produced by elec- Low emissions. Fuel cells have low emission profiles
trolysis of water — a process that is essentially a fuel cell — zero if they utilize pure hydrogen as a fuel. (This does
in reverse. Similar to fuel cells, electrolyzers can operate at not account for the emissions generated in the production of
low, intermediate, or high temperatures, with various solid hydrogen, which would be considered in a life cycle analy-
or fluid electrolytes. By coupling electrolyzer and fuel cell sis.) Hydrogen fuel cells emit only water, while other types
unit operations, hydrogen can serve as electricity storage: of fuel cells produce emissions related to the electrochemical
the electrolyzer uses electricity to convert water to hydrogen, reaction(s) they employ (e.g., CO2, CH4, CH3OH). High-
then the fuel cell uses hydrogen to produce electricity. The temperature fuel cells may produce NOx emissions from
energy can be stored for stationary applications or for use as the nitrogen in air; however, they do not emit particulates
a transportation fuel. or other criteria pollutants. In addition, fuel cells operate
Thermochemical hydrogen. High temperatures (at silently and do not contribute to noise pollution.
least 600°C) can be used to drive coupled redox reactions Heat. High-temperature fuel cells are capable of produc-
toward the net decomposition of water. Possible sources ing heat (as well as electricity) that can be used for combined
of the required heat input are advanced nuclear reactors, heat and power (CHP) applications, which increases their
concentrating solar heat, industrial boilers, and repurposed overall energy efficiency. However, properly balancing the
utility boilers. The coupled redox reactions occur in a heat and power outputs can be a challenge. The high effi-
cycle, so the net energy input is only heat and the output is ciency of CHP applications makes fuel cells attractive to
hydrogen. Many coupled redox reactions, including sulfur- facilities that utilize a lot of heat and power, and the ability to
iodine, metal-metal oxide, and uranium carbonate, are being use fuel cells for CHP is driving early adoption of fuel cells.
explored for the production of hydrogen. The hybrid sulfur Energy storage. Hydrogen could enable large-scale
process is another thermochemical cycle, but it differs from energy storage — it could be created by the utility at times
the other reactions in that it requires both heat and electricity of low electrical demand and then converted back to electric-
inputs. ity during periods of high electrical demand. This scheme
could be leveraged to smooth electrical generation and
Motivations
Several factors are driving the emergence of fuel cells,
including abundant fuel sources, efficiency, reliability, low e–
emissions, heat production, and energy storage.
Fuel In Air In
Abundant fuel. Plentiful natural gas resources provide a e– e–
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 e– H+
of natural gas by mid-2017 (3). Some fuel cells can use natu-
ral gas directly as fuel, without its conversion to hydrogen; H2 O2
however, this process still produces CO2 emissions.
H+
Efficiency. The efficiency of a fuel cell can exceed that
of standard methods of power production, because the fuel’s H 2O Air, Water,
chemical energy is converted directly to electrical energy Heat, etc.
Excess Fuel
without intermediate conversion to mechanical energy. How- Out Out
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 Cathode
Anode
60%, which limits the electrical efficiency of a hydrogen Electrolyte
fuel cell to about 40–60%.
p Figure 1. Hydrogen enters the fuel cell and is oxidized at the anode
Reliability. While utility-scale fuel cells offer potential
to form protons. The electrolyte material conducts ions, but not electrons,
efficiency gains, small fuel cells are more reliable than other so electrons are forced into the external circuit. At the cathode, oxygen is
small power sources, such as diesel engines. Because fuel reduced to water.

CEP  July 2016  www.aiche.org/cep  35

SPECIAL SECTION: ENERGY

improve power plant performance by allowing the genera- presence of water. They operate at lower temperatures
tion unit to operate closer to steady state. (80°C), and therefore have a longer operating life. PEM
Other energy storage strategies utilize the same fuel cells require pure hydrogen as a feedstock, which must
approach, but they suffer from issues related to scale. As be produced, transported, and stored. The reactant gases
more nondispatchable generation assets (particularly wind (hydrogen and oxygen) are saturated with water to prevent
and photovoltaic solar) are added to the grid, the load profile the membrane from drying, and reacted at elevated pressure
will become more variable, and larger storage mechanisms (2–5 bar) to maintain proton conductivity.
will be needed. However, batteries do not easily scale to PEM fuel cells have the potential to compete with grid-
meet this need. Therefore, large-scale storage options that supplied electricity, particularly for automotive fuel cell
scale volumetrically, such as pumped hydroelectric and applications. Although PEM fuel cells cannot be used for
compressed air storage, would need to be deployed. Hydro- CHP applications because their operating temperature is too
gen also scales volumetrically for energy storage, and scales low, their high power density still generates heat that must
according to surface area for power delivery. be dissipated through cooling water or other coolants.
Phosphoric acid fuel cells. PAFCs (Figure 2) operate
Types of fuel cells at medium temperatures (150–200°C), and are suitable for
Fuel cells that are appropriate for stationary power pro- commercial building applications. This operating temperature
duction, either onsite or through an electrical grid, include range enables these cells to be used for CHP applications,
polymer electrolyte membrane (PEM) fuel cells, phos- which increases the efficiency of the PAFC, but the corrosive
phoric acid fuel cells (PAFCs), molten carbonate fuel cells nature of phosphoric acid can shorten the fuel cell’s life.
(MCFC), and solid oxide fuel cells (SOFCs). The suitability PAFCs typically have higher power output than PEM
of a type of fuel cell for a particular application depends fuel cells, which makes them useful to electric utilities for
on its size and temperature. The temperature affects the supplemental grid generation. Some PAFC fuel cells include
lifetime of the fuel cell, and may create additional heat for a module, separate from the fuel cell stack, that reforms
CHP applications, with the amount of heat available directly natural gas into hydrogen. This additional unit operation
related to the voltage produced. provides onsite hydrogen and creates excess heat that can aid
Polymer electrolyte membrane fuel cells. PEM fuel cells CHP operations and improve overall efficiency.
contain a solid electrolytic material, such as perf­luorinated Molten carbonate and solid oxide fuel cells. MCFCs
sulfuric acid polymer (e.g., Nafion), which swells in the (Figure 3) and SOFCs operate at high temperatures

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

(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. p Figure 3. These 15-MW molten carbonate fuel cells (MCFCs) began
operation in Bridgeport, CT, in 2013. Photo courtesy of Fuel Cell Energy.
The hydrogen economy may emerge because of the
need for energy efficiency improvements within fossil these disadvantages, and it could be employed to produce
fuel combustion processes, energy storage, or carbon-free both electricity and hydrogen for fuel cells.
energy. These objectives, however, may be also achieved Utilities are exploring the advantages that fuel cells
in other ways. Energy efficiency can be improved with and hydrogen can bring to customers that value efficiency
deeper penetration of combined-cycle natural gas power and reliability. Federal government facilities and military
plants, advanced ultrasupercritical coal-fired power plants, installations now insist on energy efficiency and low-carbon
demand-side management, renewables, and/or advanced footprints for technologies they adopt. Customers requiring
nuclear reactors. Energy can be stored in batteries and by high reliability, such as data centers and remote locations
mechanical means. Carbon-free electricity can be gener- with limited or no grid service, will benefit from fuel cell
ated by nuclear power, by hydropower, and from renewable and hydrogen technology. Southern Company, for example,
sources such as solar and wind; advancements in battery is exploring ways to meet the energy needs of these facili-
electric vehicles (BEVs) can enable carbon-free transporta- ties by owning and/or operating fuel cells and managing this
tion energy. resource along with grid power.
Hydrogen and fuel cells, however, offer advantages over While the need for energy storage is widely acknowl-
those alternative scenarios: edged, the business model to monetize storage is still being
• Batteries are not a readily scalable energy storage tech- developed. Renewables could contribute more consistently
nology and have thermodynamic power limits. Fuel cells to the grid when combined with energy storage, but the cost
scale volumetrically for energy storage and by surface area of deploying renewables and hydrogen energy storage is
for power delivery. higher than the cost of renewables with backup generation.
• The low mass energy density of BEVs limits their use Even if energy storage is monetized, competitive technolo-
for long-distance or heavy-haul transportation; hydrogen gies such as pumped hydro or compressed air may capture a
has a mass energy density of 51,500 Btu/lb compared to large part of the market. Transportation applications (which
341 Btu/lb for commercial lithium-ion batteries (such as the need mobile energy storage) are emerging but require sup-
90-kWh, approximately 900-lb Tesla Model S). Accounting port from customers — and that has yet to materialize given
for the weight of the hydrogen storage tank and the fuel cell, the current low cost of conventional onboard energy. CEP
the overall mass energy density of a hydrogen-powered car
is 1,200 Btu/lb (Toyota Mirai). With a 50% conversion to
Literature Cited
electrical energy (approximately 600 Btu/lb), this is still more
1. Lanz, A., “Hydrogen Fuel Cell Engines and Related Tech­
energy-dense than the most advanced commercial BEV. nologies,” College of the Desert Energy Technology Training
• Even if hydrogen is produced from carbon-intensive Center, Palm Desert, CA (2001).
sources, hydrogen and fuel cells produce the same or less 2. U.S. Energy Information Administration, “Natural Gas
CO2 than the most efficient fossil-fuel combustion processes. Weekly Update,” EIA, www.eia.gov/naturalgas/weekly/
• The deployment of renewables to reduce carbon emis- archive/2016/01_14/index.cfm (Jan. 2016).
3. U.S. Energy Information Administration, “U.S. Natural Gas
sions from the overall energy system is limited by geography
Wellhead Value and Marketed Production,” EIA, www.eia.gov/
and low energy return on investment. Nuclear power is the dnav/ng/ng_prod_whv_dcu_nus_a.htm (May 2016).
only scalable carbon-free energy source that could overcome

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

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 hydrogen at refueling stations (which includes the costs of
Production. Hydrogen has the highest energy content on production, delivery, storage, and dispensing).
a per-mass basis of any fuel — nearly three times more than Electrolysis is a simple and clean method for generating
gasoline. Because it is a light, low-density gas, however, hydrogen from water. Electrolyzers split water to produce
its energy density is very low — roughly one-fourth that of hydrogen and oxygen at efficiencies as high as 70%. An
gasoline. The energy content in one kilogram of hydrogen independent assessment of leading electrolyzer developers
is about the same as in one gallon of gasoline; thus, the unit estimated that the cost of hydrogen from electrolysis could
kilogram is often used interchangeably with gallon gaso- be as low as about $5/gge if it is produced at high volumes.
line equivalent (gge) to compare hydrogen and gasoline. Because electricity is the main contributor to cost, cheap or
Because FCEVs can get twice the fuel economy of conven- free electricity would reduce the cost considerably. If solar,
tional gasoline vehicles (e.g., 66 miles per kg for one FCEV wind, or other zero-emission sources are employed, low
commercially available today), half as much fuel is needed costs rather than high efficiencies could become the key
onboard. driver for fuel cell technology.
Although hydrogen is the most abundant element in Hydrogen can also be produced by other methods,
the universe, it is not found freely on Earth, and instead, including high-temperature thermochemical reactions (e.g.,
must be produced. Roughly 10 million m.t. of hydrogen are solar, nuclear), biomass gasification, coal gasification,
produced annually in the U.S., mostly via steam methane biological processes (e.g., fermentation, photobiological
reforming (SMR) of natural gas. Most of that hydrogen is systems), reforming of various fuels, and direct photo­
used for petroleum refining and ammonia production. (If all electrochemical conversion (PEC) of water.
of that hydrogen were available to power FCEVs, it could The DOE has recently focused on PEC through the Joint
fuel nearly 50 million cars.) Hydrogen production must be Center for Artificial Photosynthesis (JCAP), also known as
increased to meet the needs of the transportation sector, and the Solar to Fuels Hub. JCAP first set its sights on the pro-
to meet environmental goals, it ultimately must be gener- duction of hydrogen via PEC, and the key outcome was the
ated from renewable or low-carbon sources. To be competi- development of high-throughput tools for the rapid develop-
tive with gasoline, the DOE is targeting a cost of $4/gge for 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. ally reducing the amount of platinum group metal (PGM)
Delivery. Once the hydrogen is produced, it must be catalyst by two orders of magnitude. Los Alamos scien-
delivered to the fueling station, stored onsite, compressed, tists taught researchers worldwide how to fabricate these
and dispensed. While costs can be as low as $5/kg for high- improved MEAs, and General Motors temporarily relocated
volume onsite production from natural gas, at low volumes its fuel cell group to Los Alamos, near Albuquerque, NM, to
the estimated cost of hydrogen is $13–$16/kg (produced, focus on the technology.
delivered, and dispensed, but untaxed) (2). In parallel to the PEM efforts, the DOE launched major
Storage. Car makers are using 700-bar (70-MPa) initiatives in phosphoric acid fuel cells (PAFCs), molten
hydrogen storage tanks as the primary means of onboard carbonate fuel cells (MCFCs), and solid oxide fuel cells
vehicular storage. The majority of these tanks are made (SOFCs).
of high-strength carbon fiber composites, and more work The DOE’s early support of SOFCs began with technol-
is required to reduce their cost — from a modeled cost of ogy developed by Westinghouse. At the time, Westinghouse
$15/kWh (based on high-volume projections) to DOE’s tar- was the only company in the U.S. developing SOFCs, and
get of $10/kWh in 2020 and ultimately to $8/kWh (Figure 2). it had made significant progress with a tubular design. After
Efforts are also underway to identify low-cost materials- Siemens acquired Westinghouse in the 1990s, it placed more
based technologies that can store hydrogen onboard vehicles emphasis on SOFC commercialization. With the launch
at low pressures, circumventing the need for widespread of the Solid State Energy Conversion Alliance (SECA)
infrastructure tailored to high-pressure dispensing. program in fiscal year 2000, the DOE’s Office of Fossil
Energy (FE) ramped up funding and paved the way for
Early development planar designs as well as the involvement of more develop-
The DOE efforts that created the multibillion dollar ers. Although Siemens Westinghouse exited the fuel cell
program we know today began in the 1970s. Spurred by business in 2010, the FE’s current SOFC program continues
the oil embargo, a group of national laboratory research- to make progress, and many companies are still heavily
ers, managers, and DOE officials gathered at Los Alamos involved in SOFC commercialization.
National Laboratory to develop a breakthrough to eliminate
U.S. dependence on foreign oil. The Clean Air Act of 1970 Public-private partnerships
and the corporate average fuel economy (CAFE) standards Public-private partnerships have been instrumental in
of 1975 stimulated efforts related to fuel cells. In 1977, a growing PEM and SOFC technology.
diverse group of stakeholders from federal agencies, national The DOE and automakers partnered in the 1990s to
labs, research institutions, and industry convened at Los Ala- create the Partnership for the Next Generation of Vehicles
mos to evaluate the challenges and opportunities presented (PNGV), which established hydrogen, instead of reformed
by fuel cells for transportation. gasoline, as the PEM fuel of choice.
Subsequently, researchers developed methods to opti- In the early 2000s, the DOE again partnered with
mize the heart of the polymer electrolyte membrane (PEM) automakers as well as the U.S. Council for Auto Research
fuel cell’s membrane electrode assembly (MEA), eventu- (USCAR) to form the FreedomCAR partnership. In 2003,
five major oil companies joined the partnership;
Fuel Cell Systems 2
H Production, Delivery, Onboard H Storage
2 renamed the FreedomCar and Fuel Partnership, it
$280/kW and Dispensing (700-bar Compressed System)
focused on hydrogen and FCEVs. Now dubbed
U.S. DRIVE, utility companies have joined the
$16/gge
$33/kWh partnership, which currently emphasizes battery
to electric vehicles. The active participation of tech-
$60/kW
100k/yr
$13/gge nical experts from industry, the DOE, and national
$17/kWh
100k/yr laboratories over the decades has helped drive
$53/kW
500k/yr
$7.5/gge
$15/kWh
precompetitive research, and these participants
to
$5/gge 500k/yr helped to develop a sound basis for system-driven
$40/kW <$4/gge $10/kWh targets to guide the entire research community.
2020 Targets High-Volume Production Low-Volume Production Organizations such as the Gas Research Insti-
tute (GRI), the Electric Power Research Institute
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
among others, have helped to promote stationary
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 power development. In 1967, 28 U.S., Japanese,
500,000 units per year and low-volume production (or actual industry estimates). and Canadian utilities initiated a large-scale PAFC

40  www.aiche.org/cep  July 2016  CEP

program called the Team to Advance Research for Gas tions. For example, the DOE shared the cost to deploy 1,600
Energy Transformation, Inc. (TARGET). fuel cell systems for forklifts and backup-power units for
The DOE and industry have helped to guide and cellphone towers, after which companies purchased over
formulate rigorous technical and cost targets for fuel 13,500 systems without DOE funding. Additional applica-
cell technologies that aim to compete with incumbent tions like fuel cells for airport ground support equipment,
or other advanced technologies. The DOE updates these parcel delivery vans, and truck refrigeration — all currently
costs periodically to reflect the rapid pace of technology funded by the DOE — will open new markets, increase
development. demand for hydrogen, and reduce emissions. These deploy-
ments will help to establish infrastructure, foster user accep-
Low-temperature and tance, and enable the development of a supply chain for
mid-temperature PEM fuel cells hydrogen and fuel cell technologies. In addition to fostering
PEM fuel cells have undergone a transformation in the early market deployment, the DOE also tracks the number of
past decade — costs have been cut in half (Figure 3), and the patents issued and technologies commercialized as indica-
amount of PGM catalyst reduced by a factor of five. Figure 4 tors of the impact of its funding (Figure 5).
shows that even with the latest technology modeled at high- Although significant progress is being made, hydrogen
volume manufacturing rates, the catalyst accounts for nearly and fuel cell technologies still require additional advance-
half the cost of PEM automotive fuel cells. ments for widespread successful commercialization.
Work is underway to further reduce or eliminate the need
for PGM catalysts. Argonne National Laboratory has devel- High-temperature solid oxide fuel cells
oped nanoframe catalysts that have 30 times higher activity SOFC power systems have the potential to achieve
than conventional PGM catalysts and MEAs that perform greater than 60% efficiency and more than 97% carbon
three times better than conventional MEAs. However, in capture at a cost-of-electricity (COE) that is projected to be
general, when PGM loading is lower, durability suffers. approximately 40% lower than that of integrated gasifica-
Performance and durability need to be addressed simulta- 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 ment and manufacturing, scaleup of cells and stacks for
Number of Patents Number of DOE Funding Impact on aggregation into modules, hardware, manufacturing pro-
Commercial Additional Fuel Cell
Technologies Purchases cesses, and strategies for commercialization and market
14k penetration.
>13,500
12k
units Lift
Fuel cell stack testing. Although performance and
10k
8k Trucks degradation in a single fuel cell is acceptable, stack and
6k system performance, reliability, and endurance have yet to
46 4k ~1,600
589 units
Backup be demonstrated. Industry teams are validating cell perfor-
2k Power
249 17 0 mance in a stack through a series of progressively larger
With DOE No DOE Funding stack tests. The tests are intended to evaluate power output
By 2007 By 2015 By 2007 By 2015 Funding (additional
purchases) and voltage degradation rate at steady-state conditions and
to enable commercial module capital cost projections to be
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.
made. In more than 3,000 hours of testing, 25-kWe-rated
modules experienced voltage degradation of approximately
tion combined cycle (IGCC) systems with carbon capture 1% per 1,000 hr.
and storage (CCS). Figure 6 compares utility-scale SOFC The SOFC program is funding two 50-kWe-class stack
power systems — advanced integrated coal gasification solid tests and two proof-of-concept tests of a 125-kWe-class
oxide fuel cells (IGFC) and advanced natural gas solid oxide module. The 50-kWe-class stack tests demonstrate ther-
fuel cells (NGFC) — to state-of-the-art (SOTA) IGCC and mally self-sustaining stack technology and in-stack fuel
pulverized coal (PC), advanced IGCC, SOTA natural gas reformation. The test cells are expected to operate for more
combined cycle (NGCC), and advanced NGCC power gen- than 1,000 hr with a degradation rate of less than 0.5% per
eration systems. All of the systems are equipped with carbon 1,000 hr of operation. The module test cells operate on
capture and storage (CCS). pipeline natural gas and export A.C. power to the grid. These
The SOFC program. The DOE’s Office of Fossil Energy tests integrate a test module with commercial-scale sub­
is charged with developing ultraclean (near-zero emissions), systems and are expected to operate for 2,500 hr.
low-cost energy from fossil fuels to encourage economic A 400-kWe prototype SOFC field test is being planned
prosperity, strengthen energy independence, and improve for 2017. This project will test a SOFC power system fueled
environmental quality. A component of that effort, imple- by natural gas. The system will be thermally self-sustaining
mented by the National Energy Technology Laboratory and is expected to operate for more than 5,000 hr with a
(NETL), is the SOFC program that is developing low-cost, stack degradation rate of less than 1.5% per 1,000 hr. Upon
highly efficient SOFC systems that produce electric power successful demonstration of these targets, the DOE plans to
from natural gas or coal and have intrinsic CCS capabilities. fund the demonstration of a MWe-class natural-gas-fueled
The SOFC program coordinates efforts by core technol- distributed-generation (DG) system.
ogy R&D teams from national labs, academia, and industry The market. Distributed generation is a suitable applica-
and system development teams from industry. The core tion for utility-scale SOFC power systems. The DG market
technology effort consists of applied R&D on critical issues consists of a variety of electric power and CHP applications.
related to the commercialization of SOFCs. The coopera- Electric power applications include natural gas compressor
tion of national laboratories, academia, small business, and stations, grid strengthening, prime power for data centers,
industry has advanced SOFCs toward commercialization by and online backup power for office buildings and large-
improving performance, durability, and reliability, as well scale commercial facilities. Commercial, institutional, and
as reducing cost. The SOFC program has developed the municipal facilities can utilize CHP onsite to satisfy power
planar anode-supported cell; increased the cell active area and heat needs. In the 2020 timeframe, SOFCs could serve
by a factor of five; increased cell power by a factor of ten; the electric power and CHP segments, which collectively
created better materials for higher performance; reduced cell represent a large amount of capacity.
operating temperature by approximately 100°C; and reduced Currently, SOFC systems can be purchased for approxi-
cell power degradation to less than 0.5% per 1,000 hr, with mately $10,000 per kWe. R&D into improving cell perfor-
lifetimes routinely exceeding 10,000 hr. mance, reliability, and durability coupled with advanced,
Industry teams are independently developing unique and automated manufacturing processes and mass manufacturing
proprietary SOFCs suitable for use with natural gas or syn- are expected to reduce the cost of the first large-scale (MWe)
gas derived from coal. They have validated equipment that SOFC DG system to about $6,000 per kWe by 2020. Assum-
has been developed by the core technology R&D teams, ing SOFC systems capture 25 MW of the anticipated DG
as well as achieved breakthroughs related to cell develop- market between 2020 and 2025, the installed cost of a large-

42  www.aiche.org/cep  July 2016  CEP

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, pressure. References 1–3 provide a more detailed review of
efficient, and affordable energy technologies to SOFC technology.
address the world’s growing demand for energy. Fuel Like the components of a battery, each SOFC component
cells, which convert chemical energy to electrical energy, exhibits an internal resistance to either electronic or ionic
have been widely regarded as a promising alternative to current flow, often expressed as voltage loss. The terminal
conventional internal combustion engines for clean and effi- cell voltage is, therefore, the open circuit voltage (or electro-
cient power generation. Membranes are another important, motive force, EMF, if no fuel is lost by any means) reduced
closely related technology for utilizing fossil fuel resources by the individual voltage loss of each cell component.
to produce clean energy and value-added chemicals through The maximum cell voltage of a typical single SOFC with
process intensification. air as the oxidant is generally 1.2 V, depending on tempera-
This article briefly reviews the basic working principles, ture, system pressure, and fuel composition. This voltage is
system components, and applications of solid oxide fuel obviously inadequate for any type of practical application.
cells for clean power generation and membrane reactors for To obtain a sufficiently high voltage and power, multiple
value-added chemical production. single cells are connected in series and/or in parallel by
interconnects and/or cell-to-cell connectors that are elec-
Solid oxide fuel cells tronic conductors and oxide-ion insulators.
A solid oxide fuel cell (SOFC) directly converts the
chemical energy in fossil fuels into electrical power via an Hydrocarbon Fuel
electrochemical reaction. A SOFC (Figure 1) has three basic Load
functional elements: cathode, electrolyte, and anode. The
H2 + O2– = H2O + 2e–
cathode reduces oxygen (in the form of O2) in the air sup- CO + O2– = CO2 + 2e– –
e–
plied to it into O2–. The electrolyte transports oxygen con- Anode (Fuel Electrode)
tinuously, in the form of O2–, from the cathode to the anode
Solid
under a gradient of oxygen chemical potential. At the anode, I O2– Electrolyte V
or fuel supply electrode, the O2– delivered by the electrolyte +
e– 0.5O2 + 2e– = O2–
reacts with hydrogen or a hydrocarbon fuel to produce H2O,
Cathode (Air Electrode)
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 Air
driving force for a SOFC is the gradient of oxygen chemical p Figure 1. In a solid oxide fuel cell, the cathode reduces oxygen (from
potential that exists between the cathode with a high oxygen air) to O2–, which the electrolyte transports from the cathode to the anode,
partial pressure and the anode with a low oxygen partial where it reacts with a fuel to produce H2O, CO2, and electrons.

44  www.aiche.org/cep  July 2016  CEP 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 steam reforming reaction that occurs simultaneously, which
temperatures. And, a desulfurizer subsystem can be incorpo- makes internal on-cell reformation possible. Integration
rated into a SOFC generator to reduce sulfur oxide emissions further increases the overall system efficiency.
(collectively known as SOx) to virtually zero. In addition, • Co-production of heat and power, known as combined
SOFC power generators are much quieter and produce less heat and power (CHP), is also possible. The recovery of
vibration than a conventional engine during operation. waste heat to produce electricity enables CHP systems to
SOFCs operated at high temperatures have additional achieve a total energy efficiency in the range of 85–90%.
advantages. High-temperature operation, typically in the • Another way to recover waste heat is to combine a
range of 600–1,000°C, provides high-quality waste heat. micro gas-turbine with a SOFC stack to form a hybrid
It also effectively activates the processes of reforming and system. To maximize the electrical efficiency, a hybrid is
electrochemical oxidation of hydrocarbon fuels in the pres- often operated under pressurization, which boosts both the
ence of non-noble catalysts, which is technically important performance of the SOFC stack and the effectiveness of the
for several reasons: turbine. A bottom cycle steam turbine can be added to the
• It allows SOFCs to use most hydrocarbon fuels, either hybrid system to increase efficiency even further. This hybrid
in the gaseous or liquid state, provided that they are prop- system is particularly beneficial for generators over 100
erly cleaned and reformed into simple fuels such as H2 and MWe. Siemens/Westinghouse has demonstrated a 220-kWe
CO. This is in contrast to low-temperature fuel cells, such class hybrid SOFC generator system that achieved a net
as proton exchange membrane (PEM) fuel cells, where CO alternating-current electrical efficiency of 53% (Figure 3a).
poisons the anode. The all-solid-state components of a SOFC system can
• The excess heat produced by the electrochemical avoid the corrosion issues caused by the liquid electrolyte
oxidation of fuels can be utilized by the highly endothermic 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
p Figure 3. (a) Siemens/Westinghouse has demonstrated a 220-kWe cathode. Thus, researchers are pursuing the development of
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 advanced, catalytically active cathode materials with new
than 35,000 hours of operation, making it the longest-running SOFC ever crystal structures and morphological nanostructures.
demonstrated. Source: Photos courtesy of Siemens/Westinghouse. Another recent development is the use of a SOFC as a

46  www.aiche.org/cep  July 2016  CEP Copyright © 2016 American Institute of Chemical Engineers (AIChE)
membrane reactor (electrolyzer) that uses electricity as the reactions on the surface of the membrane.
energy input to make value-added chemicals. An example Mixed ionic-electronic conduction can be achieved in
of this application is the co-electrolysis of CO2 + H2O by a two ways, by selecting a material that either:
SOFC electrolyzer to make syngas (primarily H2 and CO). • supports both ionic and electronic conduction, or
When combined with renewable energy, these reversible • forms a two-phase composite of an ionic conductor and
SOFCs can also be viewed as electricity storage, where the an electronic conductor.
energy is stored in chemical bonds. Materials of construction for equipment used for oxy-
fuel combustion, production of synthesis gases, or CO2
Membranes separation typically require mixed oxygen ion and electronic
To electrochemically convert fuels to electricity, solid conduction.
oxide fuel cells rely on materials that transport ions and The overall process of oxygen transport (permeation) in
electrons. A closely related technology that is also electro­ an MIEC membrane is divided into three steps:
chemical in nature and that employs similar classes of mate- 1. Reduction of O2 to O2– at one surface (the feed side)
rials, including ion conductors and mixed ionic-electronic by the reaction:
conductors (MIECs), is high-temperature membranes.
Ceramic membranes that transport ions, including 0.5O2(g) + 2e– → O2–
permeation membranes and membrane reactors, play an
essential role in several energy conversion systems (4). 2. Coupled transport of O2– and two electrons in opposite
Similar to SOFC electrolytes, membranes fabricated from directions through the bulk membrane.
materials that are oxygen-ion conductors and have a low 3. Oxidation of O2– to O2 and 2e– at the other surface
electron conductivity can be used to separate oxygen from (the permeate side) by the reaction:
air upon application of an external voltage. This is analogous
to what occurs in a fuel-cell-based electrolyzer used to split O2– → 0.5O2(g) + 2e–
water and generate hydrogen.
MIECs function similar to SOFC electrode materials. In The driving force for oxygen transport is the difference
oxygen-ion-conducting materials, the oxygen concentration in chemical potential between the feed and permeate sides of
gradients drive oxygen ions from the high-partial-pressure the membrane. Figure 4 (next page) illustrates this principle
side of the membrane to the low-partial-pressure side, while for a dual-phase material consisting of an electronic conduc-
electrons are transported through the bulk of the material tor and an ionic conductor.
to participate in electrochemical surface reactions. MIEC In addition to the bulk transport of oxygen ions and
membranes can be viewed as a short-circuit fuel cell, with electrons, MIEC membranes are also subject to surface
electron transport occurring within the material instead of effects that impact performance. A common principle of
through an external circuit. In addition, the driving force for mass transport across a membrane is that flux is inversely
oxygen transport can be tailored by carrying out chemical proportional to the membrane thickness. However, the actual

Table 1. Solid-oxide fuel cell systems can be used for power generation at different scales.
Size Class Rating Efficiency Fuel Type Applications
(Net Alternating
Current, LHV)
Small-Scale <10 kWe <35% Pipeline natural gas Residential (electricity, heating, cooling)
Coal gas Auxiliary power unit (APU) on heavy-duty
Gasoline trucks
Cellular phone transmission towers
Battery chargers
Medium-Scale Industrial 100–1,000 kWe >45% Pipeline natural gas Credit-card data processing centers
Hospitals (which cannot tolerate a power
outage)
Large-Scale Dispersed 2–10 MWe >48% Pipeline natural gas Larger industrial units
Coal gas Small communities
Ultralarge-Scale Central 100 MWe >60% Pipeline natural gas Baseload power generation
Coal gas

Copyright © 2016 American Institute of Chemical Engineers (AIChE) CEP  July 2016  www.aiche.org/cep  47
SPECIAL SECTION: ENERGY

flux is also a function of the kinetics of any reactions occur- (11), methanol (12), and ethylene (13). Achieving cost-
ring on the membrane surface. As membrane thickness is effective and large-scale hydrogen production has sig-
reduced to achieve a higher gas flux, surface and interfacial nificant economic benefits and contributes to a cleaner
effects become more important and can dramatically impact environment (14).
membrane performance (6). Catalytic steam reforming of natural gas:
A critical thickness exists at which further reduction
in thickness does not increase transport. In typical oxygen CH4 + H2O → CO + 3H2
separation membranes fabricated by conventional ceramic
processing techniques, this critical thickness is on the order has been the major route for syngas production. The reac-
of 80–100 μm. Surface exchange or catalyst layers are often tion is strongly endothermic and requires high temperatures
applied to membrane surfaces to enhance the performance. (~700–900oC) and pressures (~20–40 bar) to achieve the
Membranes can be fabricated in a planar or tubular maximum conversion of CH4 to H2 and CO (15). Further-
geometry by physical vapor or chemical deposition methods more, the product stream has a H2/CO ratio of 3:1, making it
that create thin, dense layers on porous supports. Systems unsuitable for production of liquid fuels via Fischer-Tropsch
can be made of materials that conduct a variety of ionic spe- synthesis.
cies. For example, ceramic-based proton-conducting materi- An alternative is the catalytic partial oxidation of natu-
als enable H2 separation (7), while carbonate ion conductors ral gas:
enable CO2 separation (8).
CH4 + 0.5O2 → CO + 2H2
Applications of membranes
Membranes meet the critical need for highly efficient and This weakly exothermic reaction produces syngas with a
environmentally friendly utilization of existing fossil fuel H2/CO ratio of 2:1, which is an ideal feed for making metha-
resources during the transition to sustainable (e.g., renew- nol or liquid fuels by Fischer-Tropsch synthesis.
able, nuclear) energy production. Applications currently being However, if air is used as the oxidant, the syngas product
explored range from CO2 separation to combustion in oxygen- becomes highly diluted with nitrogen. Ideally, pure oxygen
rich environments, including partial oxidation of natural gas, would be used, but state-of-the-art pressure-swing adsorp-
oxy-combustion of coal, and oxidative coupling of natural gas tion (PSA) and cryogenic processes are highly energy-
upgrading to the production of higher hydrocarbons. intensive and expensive. Membranes could perform both
MIEC-based CO2 separation membranes are composites oxygen separation and catalytic partial oxidation of natural
consisting of two phases, a carbonate ion conductor and an gas in a single process, at a cost that is as much as 30%
electronic conductor. Typical configurations use a K2CO3 or lower than that of combining separate cryogenic air separa-
Li2CO3 salt as the carbonate ion conductor within a porous tion and autothermal reforming units (16).
metal support such as stainless steel or silver, which serves Large-scale membrane separation units have been aimed
as the electronic conductor (9). mainly at supplying oxygen for oxy-combustion of coal and
Fossil fuels such as natural gas are strategically production of syngas. Praxair developed an oxygen transport
important raw materials for the synthesis of important membrane system for coal-fired power plants that would
value-added materials such as syngas (10), liquid fuels 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;
p Figure 4. A mixed ionic-electronic conductor (MIEC) membrane can
be thought of as a short-circuit fuel cell, with electron transport occurring materials that are stable at high temperatures and high oxy-
within the material rather than through an external circuit. Source: Adapted gen partial-pressure gradients over long periods of time and
from (5). in the presence of contaminants, such as sulfur in fluegas

48  www.aiche.org/cep  July 2016  CEP Copyright © 2016 American Institute of Chemical Engineers (AIChE)
from coal gasification; surface exchange (reaction) layers up to 3 × 106 Pa and temperatures up to 1,323 K.
that can improve O2 flux through thin membranes; and cost- Another application for membranes in the production of
efficient manufacturing techniques. value-added chemicals is the oxidative coupling of methane
Air Products has partnered with Ceramatec to develop for ethylene production.
oxygen separation membranes for the production of syngas The electrochemically controlled delivery of oxygen, in
by partial oxidization as an alternative to autothermal reform- the form of oxygen ions, into the reaction zone minimizes the
ing. The membranes combine air separation and steam creation of byproducts, increasing selectivity and yield (18).
reforming in a single unit, significantly reducing costs (16). Membrane reactors are increasingly being considered
An additional advantage is that the use of high-pressure as a means to couple endothermic and exothermic reactions
natural gas as the feedstock allows production of syngas with in thermoneutral, and thus more energy efficient, processes.
a high pressure that matches the requirements of downstream Examples are the combination of partial oxidization of meth-
processes without additional compression. Air Products has ane (exothermic) with steam reforming or with the thermal
built commercial-scale planar membranes (Figure 5) and decomposition of CO2 to CO and O2 (endothermic).
tested them at a 27-Nm3/hr pilot plant at syngas pressures
Membranes: Challenges and opportunities
Porous Research topics under investigation include membrane
High-Pressure
Support
Syngas (External) design; efficient, low-cost manufacturing strategies; and
Thin Active a variety of material science issues related to membrane
Membrane
Internal Low-Pressure stability under the required temperature, pressure, and gas-
Flow Air (Internal) phase composition conditions. Chemical and mechanical
Channels
stability in harsh environments, including ways to mini-
High-Pressure mize surface poisoning and the demonstration of long-term
Syngas (External)
membrane performance, are among the challenges that
p Figure 5. An oxygen separation membrane can be used for syngas need to be addressed in order to move this technology into
production. Source: Adapted from (16). the marketplace. CEP

Literature Cited
1. Huang, K., and J. B. Goodenough, “Solid Oxide Fuel Cell 10. Wang, H., et al., “Partial Oxidaiton of Methane to Syngas in a
Technology: Principles, Performance, and Operations,” Woodhead Perovskite Hollow Fiber Membrane Reactor,” Catalysis Communi-
Publishing, Ltd., Cambridge, U.K. (2009). cations, 7 (11), pp. 907–912 (Nov. 2006).
2. Huang, K., “Solid Oxide Fuel Cells,” Chapter 8 in “Materials for 11. Wilhelm, D. J., et al., “Syngas Production for Gas-to-Liquids
Fuel Cells,” Woodhead Publishing, Ltd., Cambridge, U.K. (2008). Applications: Technologies, Issues, and Outlook,” Fuel Processing
3. Huang, K., and S. C. Singhal, “Cathode-Supported Tubular Solid Technology, 71 (1–3), pp. 139–148 (June 2001).
Oxide Fuel Cells Technology — A Critical Review,” 12. Taylor, S. H., et al., “The Partial Oxidation of Methane to Metha-
Journal of Power Sources, 237, pp. 84–97 (Sept. 2013). nol: An Approach to Catalyst Design,” Catalysis Today, 42 (3),
4. Sunarso, J., et al., “Mixed Ionic-Electronic Conducting (MIEC) pp. 217–224 (July 1998).
Ceramic-Based Membranes for Oxygen Separation,” Journal of 13. Lunsford, J. H., “Catalytic Conversion of Methane to More Useful
Membrane Science, 320 (1–2), pp. 13–41 (July 2008). Chemicals and Fuels: A Challenge for the 21st Century,” Catalysis
5. Reifsnider, K. L., et al., “Multiphysics Design and Development Today, 63 (2–4), pp. 165–174 (Dec. 2000).
of Heterogeneous Functional Materials for Renewable Energy 14. Jacobson, M. Z., et al., “Cleaning the Air and Improving
Devices: The HeteroFoaM Story,” Journal of The Electrochem­ical Health with Hydrogen Fuel-Cell Vehicles,” Science, 308 (5730),
Society, 160 (4), pp. F470–F481 (Mar. 2013). pp. 1901–1905 (June 2005).
6. Lane, J. A., and J. A. Kilner, “Measuring Oxygen Diffusion and 15. Twigg, M. V., “Catalyst Handbook,” 2nd ed., Wolfe Publishing
Oxygen Surface Exchange by Conductivity Relaxation,” Solid State Ltd., London, U.K. (1997).
Ionics, 136–137, pp. 997–1001 (Nov. 2000). 16. Miller, C. F., et al., “Advances in Ion Transport Membrane
7. Phair, J. W., and S. P. S. Badwal, “Review of Proton Conductors Techonology for Syngas Production,” Catalysis Today, 228 (1),
for Hydrogen Separation,” Ionics, 12 (2), pp. 103–115 (July 2006). pp. 152–157 (June 2014).
8. Chuang, S. J., et al., “Dual-Phase Metal-Carbonate Membrane for 17. Christie, M., et al. “Advanced Oxyfuel Boilers and Process Heaters
High-Temperature Carbon Dioxide Separation,” Industrial and Engi- for Cost-Effective CO2 Capture and Sequestration,” Final Technical
neering Chemistry Research, 44 (21), pp. 7999–8006 (Sept. 2005). Report for DOE Award No. DE-FC26-01NT41147 (2007).
9. Xu, N. S., et al., “Silver-Molten Carbonate Composite as a New 18. Zeng, Y., et al., “Perovskite-Type Ceramic Membrane: Synthesis,
High-Flux Membrane for Electrochemical Separation of CO2 from Oxygen Permeation, and Membrane Reactor Performance for
Flue Gas,” Journal of Membrane Science, 401–402, pp. 190–194 Oxidative Coupling of Methane,” Journal of Membrane Science,
(May 2012). 150 (1), pp. 87–98 (Nov. 1998).

Copyright © 2016 American Institute of Chemical Engineers (AIChE) 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 have shorter fueling times and longer driving ranges than
more energy efficient than conventional gasoline many of the alternative zero-emission vehicle technologies,
internal combustion engine vehicles (ICEVs), which they produce tailpipe emissions, such as greenhouse gases
are limited by the Carnot thermal engine efficiency, and (GHGs). HFCEVs can achieve fueling times and driving
they produce no tailpipe emissions other than water vapor. ranges similar to those of gasoline ICEVs while eliminat-
Hydrogen fuel can be produced from a variety of non-fossil ing tailpipe emissions and reducing the well-to-wheels
and renewable feedstocks that are widely available, and (WTW) GHG emissions (2). HFCEVs are able to provide
could help to reduce the transportation sector’s dependence a consumer experience similar to that of gasoline-powered
on petroleum-based fuels and increase the security of the vehicles, while reducing the environmental impacts of the
energy supply. transportation sector.
One drawback of hydrogen as a fuel is that because it has
Hydrogen fuel cell electric vehicles a low molecular weight and low density, it must be stored
A HFCEV consists of six major components: a hydrogen at high pressures onboard the vehicle to enable a driving
storage tank, air intake system, fuel cell stack, power control range comparable to that of gasoline-powered vehicles.
unit, battery, and electric motor. The HFCEV uses proton Various technologies have been explored to store hydro-
exchange membrane (PEM) fuel cell technology to convert gen at various states, including cryo-compressed hydrogen
the chemical energy of hydrogen into electricity. Hydrogen (CcH2) at 350 bar, gaseous hydrogen at 350 bar, and gaseous
from the onboard storage tank reacts with oxygen pulled in hydrogen at 700 bar. Hydrogen storage tanks have evolved
through the air intake system to generate electricity via an from all-metal tanks (Type I), metal hoop-wrapped composite
electrochemical process that occurs in the fuel cell stack. tanks (Type II), and metal-lined composite tanks (Type III)
The only byproduct of the process is water vapor, which to plastic-lined composite tanks (Type IV). The 700-bar
exits the fuel cell stack into the atmosphere. Type IV tank for onboard storage is the only option currently
The electricity the fuel cell generates is managed by the certified for use by all HFCEV manufacturing companies (3).
power control unit, which conditions the electricity and either
charges the battery, powers the motor, or both. Although the Fueling
battery is not a major source of power for the HFCEV, it is The Society of Automotive Engineers (SAE) has
used to store excess electricity, allows the fuel cell to operate developed protocols to control the fueling process (4), and
near its peak efficiency, and supports other functions of the fuel station developers are building facilities to fuel 700-bar
vehicle. The electric motor converts the electric energy into HFCEVs using those standardized fueling protocols. The
mechanical energy, propelling the vehicle (1). fueling protocol, SAE J2601, establishes a set of performance
Although current gasoline-powered vehicle technologies 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 Alternatively, hydrogen production may be co-located

compression or liquefaction, transmission, with the distribution terminal, where it can be further pack-
aged for transmission and distribution. Hydrogen can also
distribution, and refueling. be produced at the refueling station from natural gas using
a small-scale steam methane reforming (SMR); the gaseous
dispense the necessary amount of hydrogen in the shortest hydrogen is compressed and precooled, and then dispensed
possible time while ensuring the safety of the filling process. into a HFCEV’s onboard storage system.
The thermal diffusivity of a Type IV tank is very low, Compression and storage as well as transportation (e.g.,
enabling a near-adiabatic fueling process. The increase in pipelines, trucks, etc.) are necessary and important compo-
pressure during the short fueling event raises the tempera- nents of a complete hydrogen delivery system.
ture of hydrogen within the tank considerably (5). Type IV,
700-bar tanks have a maximum operating temperature Hydrogen production
of 85°C. At that temperature, the corresponding fill pres- Most hydrogen is produced from natural gas by SMR.
sure can be as high as 875 bar at the end of a fill. To keep The methane in the natural gas reacts with steam at high
the temperature in the vehicle’s tank below 85°C and also temperatures (700–1,000°C) and pressures (3–25 bar) in
enable fast fueling within 3 to 5 min, hydrogen is precooled the presence of a catalyst to produce hydrogen, carbon
to –40°C before it is dispensed. The SAE J2601 protocol monoxide, and a relatively small amount of carbon dioxide.
considers the tank characteristics, station precooling capa- Next, in the water-gas shift reaction, the carbon monoxide
bilities, and ambient temperature in determining the pressure and steam react in the presence of a catalyst to produce
ramp rate for vehicle fueling and thus how long it takes to carbon dioxide and additional hydrogen. In the third step,
fuel the vehicle. pressure-swing adsorption, carbon dioxide and other
Although HFCEV operation is considered clean with no impurities are removed, leaving high-purity (> 99.999%)
associated tailpipe emissions beyond water, the production of hydrogen. The well-to-production-gate GHG emissions
hydrogen fuel can create emissions. These emissions come of SMR plants with a process energy efficiency (based on
primarily from the technologies used to produce and deliver the lower heating value [LHV]) of 65–75% varies from
hydrogen, including liquefaction or compression and precool- 12.3 to 10.6 kg CO2 per kg H2 (7).
ing at refueling stations. A WTW analysis can estimate the Hydrogen can also be produced by biomass gasification,
emissions associated with the hydrogen production and using heat, steam, and oxygen to convert biomass into hydro-
delivery/dispensing pathway. gen and other products without combustion. Biomass, includ-
The WTW analysis can be broken down into well-to- ing woody and other cellulosic feedstocks, is considered a
pump (WTP) and pump-to-wheels (PTW) stages. The WTP renewable resource for hydrogen production. The gasification
stage includes fuel production from the primary source of process converts organic matter at high temperatures, in the
energy (feedstock) to its delivery to the vehicle’s energy presence of a controlled amount of oxygen and steam, into
storage system (fuel tank). The PTW stage includes fuel carbon monoxide, hydrogen, and carbon dioxide. Similar to
consumption during operation of the vehicle to power the the SMR process, the carbon monoxide reacts further with
vehicle’s wheels. The results from WTP and PTW analyses steam to form carbon dioxide and additional hydrogen.
are summed to give the WTW energy use and emissions Hydrogen can be produced by electrolysis, which
associated with various vehicle-fuel technologies. uses electricity to split water molecules into hydrogen
The large-scale deployment or adoption of HFCEVs and oxygen, as well. Producing hydrogen by electrolysis
will require a refueling infrastructure network to provide a using electricity from the grid (at its current mix) may not
consumer experience comparable to that of gasoline ICEVs. reduce the WTW GHG emissions compared to the emis-
A hydrogen pathway (6) is comprised of three components: sions associated with gasoline ICEVs, because most of the
producing the hydrogen, delivering the hydrogen to a refuel- electricity in the grid is generated from fossil fuels like coal
ing station, and dispensing the hydrogen via a series of and natural gas. The carbon intensity of the average U.S.
compression and precooling processes. grid mix, including transmission and distribution losses,
Hydrogen is usually produced at low pressure (~20 bar) is 0.54 kg CO2 e/kWh (7).
and can be compressed for transmission from the production Electrolysis is expected to be a viable option for the
plant to the distribution terminal. At the distribution termi- production of hydrogen in the future because renewable
nal, the hydrogen is further compressed or liquefied so that power generation is expected to increase, thereby reducing
it can be delivered economically to the refueling stations. the GHG emissions released per unit of electricity available
The delivery modes of gaseous and liquid hydrogen include through the grid. Because the electricity generated from
pipelines, gaseous tube trailers, and liquid tankers. renewable sources like solar and wind is intermittent, elec-

52  www.aiche.org/cep  July 2016  CEP

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 pathways compared in Figure 2 include central SMR (with
they reduce GHG emissions compared to gasoline-fueled and without carbon capture and storage [CCS]), distributed
ICEVs, they must be evaluated on a life cycle basis. SMR (with and without CCS), gasification via central-
Compression for the gaseous delivery pathway and ized biomass, and electrolysis via centralized wind. The
liquefaction for the liquid delivery pathway are the main liquid delivery pathway has the advantage of higher energy
sources of GHG emissions associated with HFCEVs. If the density and more favorable economics, but that comes at the
hydrogen is produced from fossil fuels, that also contributes expense of higher GHG emissions than the gaseous pathway,
to the emissions profile. Compression and liquefaction con- primarily from the energy-intensive liquefaction process.
sume a large amount of electricity, which contributes to the The biomass pathway has lower GHG emissions because
average GHG emissions of the U.S. grid. of CO2 uptake from the atmosphere during the biomass
Compression increases the temperature of hydrogen, growth process, which offsets the CO2 released during the
which in turn impacts the thermal durability of some com- production of hydrogen by gasification. The WTW GHG
pressor components. The hydrogen temperature increase can emissions are 88% lower than those from gasoline ICEVs
be managed by incorporating intercooling between the com- when hydrogen is produced by an electrolysis process
pression stages, reducing the amount of power consumed. powered by wind and delivered as a gas. These renewable
Liquefaction increases the density of hydrogen consider- technologies have the potential to reduce GHG emissions
ably, which makes storage and transportation more economi- associated with HFCEVs, but they require further research
cal. However, hydrogen liquefaction requires the hydrogen and development to be economically competitive with the
to be cooled to below –253°C at near-atmospheric pressure. current SMR technology. CEP

This requires a significant amount of electrical energy —

about 11–13 kWh per kg H2 — which amounts to about
Acknowledgments
one-third of the chemical energy of hydrogen (7). Advanced
The work on which this article is based was supported by the Fuel Cell Tech-
liquefaction technologies that reduce the energy require- nologies Office of the U.S. Dept. of Energy’s (DOE) Office of Energy Efficiency
ments of liquefaction plants to about 8 kWh per kg H2 (8) and Renewable Energy under Contract No. DE-AC02-06CH11357.
are under development.
Literature Cited
Well-to-wheels analysis 1. Wind, J., “Hydrogen-Fueled Road Automobiles — Passenger
Figure 2 compares the WTW GHG emissions of several Cars and Buses,” in “Compendium of Hydrogen Energy Vol. 4,”
HFCEV pathways to those of conventional gasoline-­powered Ball, M., et al., eds., Woodhead Publishing, Sawston, Cambridge,
U.K., p. 3 (2016).
ICEVs. The overall WTW GHG emission profile is the sum
2. Elgowainy, A., and M. Wang, “Sustainable Vehicle Fuels Sus-
of the emissions from the well to the pump and from the tainability/Sustainable Vehicle Fuels, Well-to-Wheel Analysis,”
pump to the wheels. Because HFCEVs do not have any tail- in “Encyclopedia of Sustainability Science and Technology,”
pipe GHG emissions, their GHG PTW contributions are zero. Meyers, R. A., ed., Springer, New York, NY, pp. 10502–10529
The liquefied (Liq H2) and gaseous (Gas H2) hydrogen (2012).
3. U.S. Dept. of Energy, Office of Energy Efficiency and
PTW WTP Production WTP Transportation Renewable Energy, “Amped Up Newsletter,” DOE, 1 (4), http://
WTP Storage and Refueling WTP Liquefaction energy.gov/sites/prod/files/2015/11/f27/AmpedUp4-final.pdf
(July–Aug. 2015).
11% 36% 39% 73% 79% 88%
400 4. Society of Automotive Engineers, “Fueling Protocols for
GHG Emissions, gCO2e/mile

Light-Duty Gaseous Hydrogen Surface Vehicles,” Standard

300 J2601_201407, SAE International, Warrendale, PA, http://
standards.sae.org/j2601_201407/ (2014).
200 5. Reddi, K., et al., “Hydrogen Refueling Station Compression and
Storage Optimization with Tube-Trailer Deliveries,” Interna-
100
tional Journal of Hydrogen Energy, 39 (33), pp. 19169–19181
(2014).
6. Reddi, K., et al., “Building a Hydrogen Infrastructure in the
0
Gasoline
Liq H2, Gas H2, Gas H2, Gas H2, Gas H2, Gas H2, United States,” in “Compendium of Hydrogen Energy, Vol. 4,”
ICEV
Central Distributed Central Central Central Central Ball, M., et al., eds., Woodhead Publishing, Sawston, Cambridge,
SMR SMR SMR SMR, Biomass Wind U.K., p. 293 (2016).
with CCS
7. Argonne National Laboratory, “GREET Model,” https://greet.
PTW = Pump to wheels
WTP = Well to pump SMR = Steam methane reforming es.anl.gov/index.php (2015).
ICEV = Internal combustion engine vehicle CCS = Carbon capture and storage 8. U.S. Dept. of Energy, “Hydrogen Delivery Scenario Analysis
Model (HDSAM 3.0),” DOE, https://www.hydrogen.energy.gov/
p Figure 2. Hydrogen fuel cell electric vehicles (HFCEVs) have lower overall h2a_delivery.html (2015).
emissions than gasoline-powered internal combustion engine vehicles (ICEVs).

54  www.aiche.org/cep  July 2016  CEP

 Register for the 2nd RCN Conference on Pan American
Biofuels & Bioenergy Sustainability
Location: Buenos Aires, Argentina Dates: September 13-16, 2016

The PanAm RCN will hold its 2nd RCN Conference on Pan American Biofuels
& Bioenergy Sustainability in September 2016 in Buenos Aires, Argentina
in collaboration with AAIQ, AIChE® and IfS. The conference will be
chaired by David Shonnard, Michigan Technological University, USA, and
co-chaired by Jorge Antonio Hilbert, Instituto Nacional de Tecnología
Agropecuaria and Universidad Tecnologica Nacional, Argentina.
Keynote Speakers
• Bruce E. Dale, Chemical Engineering and Materials Sciences, Michigan State University
• Glaucia Souza, Institute of Chemistry, University of Sao Paulo

For more information and to register go to - www.aiche.org/2rcn

Get the best rates when you register by August 1, 2016.
The conference is co-organized by the PanAm RCN, with AAIQ, AIChE and IfS.

© 2016 AIChE 0100-16 07.16

n

Save the Date for the ICOSSE ‘16 Key Themes:

5th International 1. Sustainable Technologies in
Processing Industries
Congress on 2. Sustainable Manufacturing
Sustainability 3. Nanotechnology Sustainability
4. Energy for Sustainability
Science &
5. Environmental Sustainability &
Engineering Industrial Ecology
6. Sustainability Education

Location: the Jinji Lake Shilla For more information go to

http://icosse.org
Hotel in Suzhou, China
Dates: October 24-27, 2016

ICOSSE International Congress on

Sustainability Science & Engineering

© 2016 AIChE 0129-16 07.16

n

CEP  June 2016  www.aiche.org/cep  55