56 Energy & Fuels 1998, 12, 56-71

Regenerative Fuel Cell Systems

Fred Mitlitsky,* Blake Myers, and Andrew H. Weisberg
Lawrence Livermore National Laboratory, 7000 East Avenue, L-045,
Livermore, California 94551

Received August 22, 1997. Revised Manuscript Received October 2, 1997X

Regenerative fuel cell (RFC) systems produce power and electrolytically regenerate their
reactants using stacks of electrochemical cells. Energy storage systems with extremely high
specific energy (>400 Wh/kg) have been designed that use lightweight pressure vessels to contain
the gases generated by reversible (unitized) regenerative fuel cells (URFCs). Progress is reported
on the development, integration, and operation of rechargeable energy storage systems with such
high specific energy. A primary fuel cell test rig with a single cell (46 cm2 active area) has been
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modified and operated reversibly as a URFC (for up to 2010 cycles on a single cell). This URFC
uses bifunctional electrodes (oxidation and reduction electrodes reverse roles when switching
from charge to discharge, as with a rechargeable battery) and cathode feed electrolysis (water is
fed from the hydrogen side of the cell). Lightweight pressure vessels with performance factors
(burst pressure × internal volume/tank weight) > 50 km (2.0 million in.) have been designed,
and a vessel with performance factor of 40 km (1.6 million in.) was fabricated. These vessels use
lightweight bladder liners that act as inflatable mandrels for composite overwrap and provide
the permeation barrier for gas storage. Bladders are fabricated using materials that are
compatible with humidified, electrolyzed gases and are designed to be compatible with elevated
temperatures that occur during fast fills or epoxy curing cycles. RFC systems are considered
that use hydrogen/oxygen, hydrogen/air, or hydrogen/halogen chemistries. Hydrogen/halogen
URFCs are capable of higher round-trip efficiency than hydrogen/oxygen URFCs but are
significantly heavier. Therefore, hydrogen/halogen URFCs are advantageous for stationary
applications, whereas hydrogen/oxygen URFCs are advantageous for mobile applications. Safety
aspects of halogens may prohibit their use in densely populated areas and some commercial
applications, so these niches can also benefit from hydrogen/oxygen URFCs.

Introduction their preliminary testing already demonstrates the

NASA Dryden Flight Research Center is supporting
research and development on regenerative fuel cells
(RFCs) as an enabling technology for high-altitude long
endurance (HALE) solar rechargeable aircraft (SRA),
under its Environmental Research Aircraft and Sensors
Technology (ERAST) program. This research is being
leveraged by the U.S. Department of Energy to develop
similar systems for ground transportation and utility
applications. A significant advance in energy storage
is being developed to address a range of applications
including HALE SRA, zero emission vehicles (ZEVs),
hybrid energy storage/propulsion systems for spacecraft,
energy storage for remote (off-grid) power sources, and
peak shaving for on-grid applications.1-5 Innovative
energy storage designs are being implemented, and
* Corresponding author. Phone: (510) 423-4852. Fax: (510) 423-
9178. E-mail fm@llnl.gov.
X Abstract published in Advance ACS Abstracts, December 1, 1997.
capability to significantly outperform foreseeable bat-
tery technologies. One performance measure these
developments are designed to excel at is specific energy,
which describes how much energy can be stored per unit
mass (Wh/kg or J/kg).
Designs capable of delivering a significant advance
in specific energy must openly assume innovations in
key components, and integration experience with ad-
vanced technologies that have yet to be operated in
combination. Investigation of the performance and
operating characteristics of the two classes of critical
components, electrochemical power converters (RFCs)
and vessels capable of containing pressurized reactants,
is proceeding independently toward implementations
likely to minimize system mass. Lightweight pressure
vessels with high cycle life and low permeability to
stored reactants are the other class of critical compo-
nents that call for innovative development to enable

(1) de Groot, W. A.; Arrington, L. A.; McElroy, J. F.; Mitlitsky, F.;

Weisberg, A. H.; Carter II, P. H.; Myers, B.; Reed, B. D. 33rd AIAA/
ASME/SAE/ASEE Joint Propulsion Conf., July 6-9, 1997 1997, AIAA
97-2948.
(2) Mitlitsky, F.; Myers, B.; Weisberg, A. H. 1996 Fuel Cell Seminar
1996, UCRL-JC-125220, 743-746.
(3) Mitlitsky, F.; de Groot, W.; Butler, L.; McElroy, J. F. AIAA Small
Satellite Conf., Sept 16-20, 1996 1996, UCRL-JC-125242.
(4) Mitlitsky, F.; Colella, N. J.; Myers, B. 1994 Fuel Cell Seminar
1994, UCRL-JC-117130, 624-627.
RFC systems that excel at lightweight energy storage.
Encouraging test results reported herein demonstrate
that both classes of innovative components can already
provide the performance levels necessary to realize
unprecedented specific energy storage levels (above 400
(5) Mitlitsky, F.; Colella, N. J.; Myers, B.; Anderson, C. J. 28th
IECEC 1993, 1, 1.1255-1.1262; UCRL-JC-113485.

S0887-0624(97)00151-5 CCC: $15.00 © 1998 American Chemical Society

Published on Web 01/12/1998
Regenerative Fuel Cell Systems Energy & Fuels, Vol. 12, No. 1, 1998 57

Figure 1. Water rocket block diagram.

Wh/kg) in the near term. Further integration testing

is planned to prove the performance of entire energy
storage systems over the next few years. Preliminary
integration results emerging from component tests are
also reported that prove the most mass-conserving
electrochemical power converters, reversible (unitized)
regenerative fuel cells (URFCs), have adequate cycle life
to build useful energy storage systems.
Limitations of Batteries. The search for a near-
term, flightweight solution to propelling a solar-powered
aircraft at night on stored solar energy created the
original rationale for this cluster of innovations. Re-
chargeable batteries provide the proven route to electri-
cal energy storage, but even the projected types are far
too heavy for acceptable HALE SRA designs. Consider-
able spreadsheet analysis of aircraft system require-
ments endorsed the development of URFCs, coupled Figure 2. Pathfinder solar-powered aircraft.
with novel lightweight pressure vessels that are inte-
grated into the structure of the aircraft. Such systems coupling URFCs with lightweight pressure vessels that
were designed to have exceedingly high specific energies are integrated into the vehicle’s structure. Hydrogen
(energy/weight) of >400 Wh/kg.4 Related terrestrial and oxygen that are made by the solar-powered elec-
applications including portable power supplies, auto- trolysis of water can be used for energy storage, or as
mobiles, and remote power sources were investigated propellants for a high specific impulse, high thrust-to-
with similar top-down design tools, and were found to weight ratio rocket propulsion system. The nontoxic
require less demanding subsets of the same develop- nature of water, and the ability to convert it into rocket
ment plan. propellants on the fly, may provide the strongest incen-
Integrating the best components of the SRA energy tives to develop spaceborne applications, which also pose
storage technology with nontoxic propulsion, and shar- the toughest development challenges.
ing function with structure mass already required in HALE SRA requirements demand specific energy
spacecraft, are expected to offer an extremely attractive levels that are within the capabilities of URFC and
approach for spacecraft applications.1,3 Figure 1 shows pressure vessel components. The Pathfinder solar-
a schematic of the components interconnected in such powered aircraft is a flying wing that was designed and
a spacecraft. All of the applications discussed herein manufactured, and is operated, by AeroVironment, Inc.,
can be visualized as subsets of the Figure 1 schematic, of Simi Valley, CA. Pathfinder measures 99 ft (30 m)
although real implementations will also include various wingspan and 8 ft (2.4 m) chord. The total weight for
ancillary components (valves, pumps, regulators, tubing, this ∼800 ft2 (74 m2) aircraft is ∼500 lb (230 kg).
cabling, insulation, connectors, and controllers). For Pathfinder set a solar-powered altitude record of 50 500
spaceborne applications, as well as for HALE aircraft, ft (15.4 km) on September 11, 1995 (see Figure 2). The
lightweight energy storage would best be achieved by plane took off and landed at the NASA Dryden Research
58 Energy & Fuels, Vol. 12, No. 1, 1998 Mitlitsky et al.

Table 1. Specific Energy of URFC and Rechargeable Batteries

theoretical specific packaged specific
battery system energy (Wh/kg) energy (Wh/kg) comments
H2/O2 URFC 3660 400-1000 URFC with lightweight pressure vessels
Li-SPE/MOx 735 220 Li-solid polymer electrolyte/ metal oxide, novel packaging
Ag/Zn 450 200 excess Zn required for high cycle life, low charge rate
Li/LiCoO2 735 150 poor cycle life, high capacity fade
Li/AlFeS2 515 150 g400 °C thermal management
Na/S 1180 150 ∼350 °C thermal management
Li/TiS2 470 130 ∼50% DOD for high cycle life (900 cycles)
Li/ion 700 100 (135a) projection revised Nov 1996
Ni/Zn 305 90 excess Zn required, low specific energy
Ni/MHx 470 70 (85a) MHx is metal hydride, projection revised Nov 1996
Ni/H2 470 60 low specific energy
Ni/Cd 240 60 low specific energy
Pb/acid 170 50 low specific energy
a Projections revised in November 1996 by private communications with B. M. Barnett (A. D. Little, Inc.).

Center, in Edwards, CA, and was solar powered during

take off, climb, and most of the descent. Primary
lithium batteries were used to maneuver and control-
lably land the plane at night. During the latest series
of flight tests (which are ongoing during the writing of
this paper) at the Pacific Missile Range Facility, Kauai,
Hawaii, Pathfinder set a new world record of 71 500 ft
(21.8 km) on July 7, 1997. In addition to exceeding the Figure 3. Theoretical vs packaged specific energy.
solar-powered altitude record, this recent flight set the
record for the highest altitude ever attained by any
complete cells, which add the weight of electrolyte,
propeller-driven aircraft. The previous record of 67 028
separators, and current collectors required to draw
ft (20.43 km) was held by the experimental Boeing
current from the cell. Functional cells add the weight
Condor, which was powered by a multistage turbo-
of nonstoichiometric reactants necessary to achieve the
charged engine burning fossil fuel.6 Photographs of
application’s required cycle life. Packaged cells add the
Pathfinder are available on the World Wide Web site
weight of packaging required for safe containment,
set up by NASA Dryden at http://www.dfrc.nasa.gov/
shipping, handling, and use in real systems. The
PhotoServer/Pathfinder/index.html.
packaged specific energy is based on packaged cells and
One of the goals of the NASA ERAST program is to
typically does not achieve better than ∼30% of the
design and build a plane that has sufficient energy
theoretical specific energy, especially when high cycle
storage on board to enable level flight at high altitudes
life is required.
for multiple days or weeks. A particular design to
Estimates for the packaged specific energies of bat-
accomplish this would have ∼220 ft (67 m) wingspan
teries in Table 1 were performed by A. D. Little, Inc.
and assumes the use of RFCs with lightweight tanks
under contract to Lawrence Livermore National Labo-
integrated into the main structural wingspar. The
ratory (LLNL) in 1993, and assume novel packaging for
conceptual arrangement for such a system is a subset
large systems.5 Since then, there have been some
of the spacecraft schematic shown in Figure 1, without
advances in packaged specific energies projected for
the thrusters. An airborne system can make even better
lithium ion (∼135 Wh/kg) and nickel metal hydride (∼85
use of the integration of pressure vessels for reactant
Wh/kg). These improvements do not change the conclu-
gas storage with a vehicle’s structure, especially in a
sion that rechargeable batteries are not capable of
flying wing configuration, where almost all of the
achieving the required >400 Wh/kg. The estimate for
vehicle’s structure mass resides in the wingspar. Be-
URFCs and lightweight tankage assumes several com-
cause that wingspar must be designed to withstand high
ponent and integration innovations that are currently
bending loads, much of the structure mass requirements
being investigated.
that would make pressure vessels burdensome are
Energy Storage Designs. RFC-based energy stor-
already supplied by the spar’s structure.
age alternatives free the vehicle designer from many of
Energy storage requirements were investigated for
the hidden compromises that accompany battery tech-
the design of the next-generation HALE SRA. Specific
nologies. RFC energy storage is uncoupled from power
energy >400 Wh/kg and efficiency ∼43-50% will be
generation or consumption, because reactants are stored
required for many desired missions. Rechargeable
outside any electrochemical cells, in reactant tanks that
batteries (see Table 1) and flywheels are projected to
can be sized independently. Power ratings determine
have insufficient packaged specific energy to achieve
the cell stack size, but not the sizing of the containers
this goal. The difference between “theoretical” and
that hold reactants. Energy storage requirements size
“packaged” specific energies of battery technologies is
the capacity of reactant containers independently of the
highlighted in Figure 3. Theoretical specific energy uses
RFC stack(s). More tank capacity can be added to store
the weight of stoichiometric reactants only. Optimum
more energy, without redesigning electrodes. Since
specific energy could be achieved with stoichiometric
reactants are actively transported to/from the RFC cell
(6) NASA Headquarters Press Release 97-153, July 14, 1997; http: stack, depth of discharge does not reduce available
//www.dfrc.nasa.gov/PAO/PressReleases/1997/97-153.html. power. Many RFC applications require tanks that are
Regenerative Fuel Cell Systems Energy & Fuels, Vol. 12, No. 1, 1998 59

Table 2. Specific Energy of RFC Designs

stack ancillary tank fuel layout penalty system specific energy
stack type wt (kg) wt (kg) wt (kg) wt (kg) wt (kg) wt (kg) (Wh/kg) comments
1 URFC 41.8 16.4 26.8 32.3 12.7 130 431 not redundant lightweight
2 URFCs 49.6 26.4 26.8 32.3 0.0 135 415 redundant, favored
3 URFCs 55.0 36.4 26.8 32.3 0.9 151 370 redundant, heavy
1 FC/1 EC 63.2 28.6 26.8 32.3 38.6 190 295 not redundant, heavy
2 FCs/1 EC 79.1 38.6 26.8 32.3 44.1 221 253 partly redundant, heavy
3 FCs/3 ECs 73.2 73.2 26.8 32.3 17.7 258 217 redundant, heavy

heavier than their cell stacks, so that their system mass
may be dominated by tankage mass for even the lightest
weight tank designs discussed below. Applications
where energy storage times (useful energy capacity/
rated power; or specific energy/specific power; or typical
discharge times) are longer than ∼1 h will generally
lead to the case where tankage dominates energy
storage mass. If heavy tanks are used, this energy
storage time can be as short as several minutes.
RFC system designs require lightweight gas storage
to achieve the 400 Wh/kg levels necessary for HALE
SRA missions. A lightweight gas storage system was
designed and prototyped at LLNL that uses bladders
integrated into the wingspar to minimize tank mass.
This bladder design is ∼100 lb (45 kg) lighter (∼500 kg
gross weight) than similar tanks with other liners.
Hydrogen permeation losses should be adequately low
(<1/4% per year) to give the aircraft capability for long
missions. Detailed analyses performed in 1994 deter-
mined that URFCs are lighter and less complex (re-
duced parts count) than RFCs using separate (discrete)
stacks. Fully packaged URFC systems for HALE SRA
applications in this study exceeded 400 Wh/kg, as shown
in Table 2.4
These studies assumed 4.5 kW nominal fuel cell (FC)
output, 5.8 kW peak FC output, 19 kW peak electrolyzer
(EC) input, and 56 kWh useful capacity, for a 220 ft (67
m) wingspan HALE SRA with 1080 lb (491 kg) gross
weight. The layout penalty weight in this table is the
additional structural, wiring, and plumbing weights due
to system layout choices compared to a reference case
(two URFCs). Fuel weight is the total weight of
hydrogen, oxygen, and water. These results indicate the
possibility of achieving >400 Wh/kg for a fully packaged
energy storage system (based on one or two URFCs)
depending upon lightweight pressure vessels that are
integrated into the wingspar, to form a structural tank.
Structural Tanks. The integration of structure and
tankage requirements is particularly promising for
spaceborne energy storage applications, where mass and
volume are most severely constrained. Structural tanks
can range from applications which are predominantly
structure (e.g., the wingspar of HALE SRA) to applica-
tions which are predominantly tankage (e.g., tankage
for gaseous fueled automobiles). The importance of
lightweight pressurized gas containment for other types
of vehicles, and many alternative energy technologies
that employ hydrogen, have prompted a more broadly
applicable development of extremely lightweight pres-
sure vessel technology at LLNL that will be discussed
below.
The strength per weight of a tubular spar (assuming
constant mass per unit length of a given material)
increases linearly with tube diameter and is not sensi-
tive to wall thickness. Buckling resistance per weight
of a tubular spar (assuming constant mass per unit
Table 3. Wingspar Loading Conditions
loading condition maximum value
+5g flight shear 14500 lb (64500 N)
+5g flight moment 29000 ft‚lb (39300 N‚m)
+5g flight torsion 240 ft‚lb (325 N‚m)
control deflection torsion 760 ft‚lb (1030 N‚m)
landing shear 10000 lb (44000 N)
landing moment 12200 ft‚lb (16500 N‚m)
landing torsion 280 ft‚lb (380 N‚m)
gas storage pressure 300 psia (2.1 MPa)
length of a given material) increases linearly with wall
thickness and is not directly dependent on tube diam-
eter. The strength per weight and buckling resistance
per weight criteria lead to an optimum tube diameter
and wall thickness for fabricating a lightweight struc-
ture using a given material. For HALE SRA designs,
tube diameter is constrained by airfoil geometry. A
tubular spar can provide a large volume for storing
gaseous reactants if it is transformed into a structural
tank by adding some additional composite overwrap,
bulkheads, and a permeation barrier. Larger diameter
tubes increase the volume available for reactant storage
and will reduce the peak pressure required for fixed
capacity. Reducing the peak pressure requirements
results in improved electrolyzer efficiency (and round-
trip efficiency), but can make the tubes buckling-critical
rather than strength-critical.
Table 3 summarizes preliminary wingspar structural
requirements and system tankage requirements assum-
ing that tankage is integrated into a tubular wingspar
for most of an aircraft’s wingspan.5 The stresses
induced by the large flight moment in this design are
significantly larger than the stresses induced by the
relatively low pressure loads. As a result, the tank mass
can represent a relatively small fraction of the composite
material required for structure, and its presence will
thicken the spar wall and help improve buckling resis-
tance of the large diameter structure. This design
requires a lightweight permeation barrier to enable gas
storage within the volume of the composite wingspar.
Permeation Barriers. Various materials were in-
vestigated for their potential to serve as hydrogen
permeation barriers inside composite pressure vessels.
Table 4 is an excerpt of the best barrier candidates from
a tabulation of the hydrogen permeabilities (K) for thick
samples of various materials.7 Hydrogen permeability
for a given temperature can be calculated from the table
by using the following formulas:
K ) K0 exp(-θK/T) for metals
K ) K0T exp(-θK/T) for glasses
The table entries are ranked in terms of extrapolated
permeabilities at room temperature, with the best
(7) Souers, P. C. Hydrogen Properties for Fusion Energy; University
of California Press: Berkeley, CA, 1986; pp 370-373.
60 Energy & Fuels, Vol. 12, No. 1, 1998 Mitlitsky et al.

Table 4. Hydrogen Permeability of Various Materials

material hydrogen K0 (mol/(m‚s‚Pa0.5) or extrapolated K at 300 K, measured temp
permeated isotope mol/(m‚s‚Pa)) θK (K) 1 Pa (mol/(m‚s)) range (K)
Fe H2 4.1 E-8b 4200 3 E-14 375-850
stainless, 304S H2 2.0 E-6 8660 6 E-19 370-570
Ag H2 3.4 E-8 7350 8 E-19 730-980
Cu H2 8.4 E-7 9320 3 E-20 470-700
silica glass H2 3.4 E-17‚T 3600 6 E-20 300-1000
stainless, 309S D2 1.5 E-7 8500 7 E-20 520-720
M ) 15a glass H2 6.1 E-17‚T 6080 3 E-23 550-720
Al T2 5.8 E-5 14800 2 E-26 420-520
M ) 30a glass H2 2.5 E-16‚T 8550 3 E-26 550-720
Au D2 3.1 E-6 14800 1 E-27 500-900
Si H2 1.4 E-5 27000 1 E-44 1240-1485
β-SiC T2 1.8 E-10 55600 6 E-91 700-1570
a M is the percent of non-network formers (e.g., Na O, CaO, K O, and Al O ) which break up the network formers (e.g., SiO , B O , and
2 2 2 3 2 2 3
P2O5) that hold the glass together. b E-n ≡ × 10-n.

materials (having the largest negative exponent) ap-

pearing at the bottom of the table. Permeability is listed
in mol/(m2‚s‚Pa0.5) for metals and mol/(m2‚s‚Pa) for
glasses. The different pressure dependencies of these
two classes of materials are due to the assumption that
hydrogen will dissociate and diffuse through metals as
atoms, whereas hydrogen diffuses through glasses as
molecules. The table lists the hydrogen isotope that was
used for measurements in each of the materials. A
correction should be applied to estimate permeability
for a desired isotope, since permeability increases as
molecular weight to the -0.5 power. However, this
correction is negligible compared to the error of extra-
polating elevated temperature measurements to room
temperature.7
From this table, one can deduce that the permeability
of gold (or aluminum) is such that even a few contiguous
monolayers could result in an acceptable hydrogen
permeation barrier at room temperature, provided that
such layers lacked imperfections (pinholes or cracks).
Silicon or beta silicon carbide should be many orders of
magnitude better. Copper or silver would be adequate
if thin films are considered, instead of monolayers.
Several rounds of American Society for Testing and
Materials (ASTM) permeation barrier tests (described
below) were used to test various metal layers deposited
onto thin plastic substrates for use in fabricating
lightweight bladders. These tests showed that defects
such as pinholes and cracks can be more important than
bulk properties when choosing a permeation barrier.
In order to use thin films as permeation barriers in
pressure vessels, other properties of the layer must be
considered. The layers need to be formed or deposited
into contoured liners with plumbing attachments (bosses),
and they must be compatible with the range of temper-
atures, pressures, shock loads, strains, and chemicals
that may be experienced from fabrication through the
entire lifecycle of the pressure vessel. The liner may
need additional properties to enable it to serve as a
mandrel for composite overwrap.
Pressure Vessels. The burst pressure (P) multiplied
by internal volume (V) is a measure of the ultimate gas
capacity of a pressure vessel. Dividing this product by
tank weight (W) gives the performance factor (PV/W,
usually measured in inches) for the pressure vessel.
PV/W is a function of the properties of the materials
used for the vessel’s fabrication. Lightweight pressure
vessels with large PV/W will require considerable de-
Figure 4. PV/W for high cycle life pressure cylinders.17
velopment for URFC-powered vehicles, since hydrogen
is not easily contained by composites or many other
materials. Larger volume tanks, with higher burst
pressures, and relatively small gas ports (bosses) will
tend to have the highest ratio of high strength composite
to relatively low strength liner materials (sufficient to
limit hydrogen permeation), and so they achieve the
highest performance factors. Aerospace tanks built with
composite overwrapping on thin aluminum or titanium
liners can be lightweight, but the highest performance
factor designs are achievable only with relatively large
capacity tanks, with low cycle life requirements. Metal
liners will yield before their high-strength composite
overwrap fails, causing cycle life to be limited by fatigue
of the thin metal liner. For higher cycle life, thicker
metal liners are required (at the expense of weight).
Figure 4 shows how the use of laminated metallized
bladder liners (to replace thick plastic or metal liners
in graphite composite cylinders) can increase specific
energy by ∼30% over comparable composite tanks
designed for high cycle life. Bladder-lined composite
pressure vessels can be an order-of-magnitude lighter
weight compared to steel tanks for a similar capacity.
These innovative tanks can be enabling to weight
critical applications, such as HALE aircraft, pressure-
fed rocket propulsion, and other mobile or portable
systems requiring tankage.
Several thermal issues must be considered to design
pressure vessels capable of fast filling with hydrogen.
Regenerative Fuel Cell Systems Energy & Fuels, Vol. 12, No. 1, 1998 61

Gas compression during pressure vessel filling results

in gas heating which can result in underfilling and/or
overpressurization. The temperature rise associated
with filling a pressure vessel is related to the pressure
ratio, fill rate, properties of the gas, thermal mass of
the vessel and plumbing, and heat transfer coefficients.
Large pressure ratios, rapid fill rates, hydrogen gas, and
lightweight pressure vessels with poor heat transfer
coefficient can result in large temperature rises. Ne-
glecting heat transfer and the thermal mass of the
vessel and plumbing, a study8 shows that for an infinite
pressure ratio of an ideal gas, the temperature ratio for
a fast fill is equal to the ratio of specific heats (which is Figure 5. URFC electrochemical cycles.
1.41 for hydrogen). By this criterion, a vessel with 300
K (27 °C ) 81 °F) initial gas temperature would achieve
ion, the active area for the URFC stack is equivalent to
a final gas temperature of up to 420 K (147 °C ) 297
the sum of the active areas for the dedicated FC and
°F). Such worst case temperature rise would result in
EC stacks combined. In such a comparison, a given
filling the tank to only 71.4% of rated capacity at the
power setting (either input or output) will result in less
maximum operating pressure. The final gas tempera-
power per unit active area for the URFC by virtue of
ture peaks can be worsened by high ambient tempera-
the larger active area utilized in each mode of operation.
ture or gas lines that are already warm.
The operational current densities in the URFC will be
Temperature rise (underfilling) for natural gas vessels
below the corresponding current densities in the dedi-
is less than for hydrogen due to lower ratio of specific
cated FC/EC stacks, resulting in an improved voltage
heats (∼1.32). Even so, by the criterion above, a fast
efficiency for the URFC system. This efficiency im-
fill from 300 K would yield a temperature of 396 K (253
provement may even overwhelm the efficiency reduction
°F). A typical temperature rise to ∼140 °F (333 K), from
caused by using compromise catalysts.
an initial temperature of 70 °F, for fast fills of com-
The electrochemical reactions for FC and EC opera-
pressed natural gas (CNG) into a vessel with an
tions for hydrogen/oxygen based systems are depicted
adiabatic inner wall has been reported.9 One of the
in Figure 5. The URFC can be designed for electrolysis
main reasons for the discrepancy is due to the heat
with water fed from either the anode (oxygen side) or
capacity of the pressure vessel, as will be discussed in
the cathode (hydrogen side). For cathode feed electroly-
a fast fill experiment described below.
sis, a single phase separator is used in the hydrogen/
URFCs. URFCs should be capable of higher specific
water recirculation loop. Water must then diffuse
energy and less complexity (due to reduced parts count)
through the cell to the oxygen side in order to be split.
compared with RFCs using separate (dedicated) fuel cell
This necessary flow is decreased by an opposing flow of
and electrolyzer stacks. However, there is an erroneous
water caused by proton pumping, whereby each proton
presumption that URFCs are not capable of high cycle
migrating through the membrane toward the cathode
life, due to the lack of well-publicized data showing tests
must be accompanied by at least four water molecules.10
lasting more than ∼25 cycles. Results from tests
This creates a situation where cell drying at the anode
reported herein are an existence proof that URFC cells
may result, especially at high current densities. Anode
can be cycled repeatedly (>2000 cycles) without signifi-
feed electrolysis provides excess water at the anode,
cant degradation (less than a few percent). These tests
avoiding the drying (at high current densities) that may
are also an existence proof that bifunctional catalysts
be caused by proton pumping. For anode feed, phase
can operate reversibly without significant degradation.
separators are required in both the anode/water and the
Even though bifunctional catalysts will not be simul-
cathode/water recirculation loops, which add complexity
taneously optimized for both oxidation and reduction
and weight to the system.
reactions, URFC systems will not necessarily be less
Other URFC chemistries are possible, such as
efficient than RFC systems using dedicated stacks.
hydrogen/halogen.11-14 These are of interest because
Although it is true that bifunctional catalysts may have
they are capable of higher round-trip electrical efficien-
slightly reduced performance in either the oxidation or
cies. Since they may be more than an order of magni-
reduction reaction (depending on catalyst composition,
tude heavier for comparable energy content, they are
which may be optimized for a given system application),
not of interest for mobile applications but are considered
this will result in a modest round-trip efficiency de-
for stationary applications. Since halogens and their
crease per unit of active area for the URFC stack, and
acids are corrosive and toxic, safety considerations may
not necessarily an efficiency decrease for the entire
limit the use of hydrogen/halogen URFCs to specific
URFC system. It should be realized that the efficiency
niches where the improved efficiency is an overriding
of a dedicated fuel cell during the charge cycle is zero,
and likewise, the efficiency of a dedicated electrolyzer (10) Appleby, A. J.; Yeager, E. B. Energy 1986, 11, 137.
during the discharge cycle is also zero. Therefore, it is (11) McElroy, J.; Patwa, G. G. Proc. 72nd AICHE Nov. 25-29 1979.
more reasonable to compare the efficiency of RFC (12) McElroy, J. Proceedings of the DOE Chemical Energy Storage
and Hydrogen Energy Systems Contract Review; JPL Publication 78-
systems which use similar active areas. By this criter- 1, November 16-17, 1977, 27-33.
(13) Beaufrere, A.; Yeo, R. S.; Srinivasan, S.; McElroy, J.; Hart, G.
(8) Daney, D. E.; Edeskuty, F. J.; Daugherty, M. A.; Prenger, F. C.; 12th IECEC 1977, 959-963.
Hill, D. D. Cryogenic Eng. Conf., July 17-21, 1995. (14) Nutall, L. J. “Development progress on solid polymer electrolyte
(9) Kountz, K. J. Proc. 207th ACSsDivision of Fuel Chemistry, fuel cells with various reactant sources”; General Electric, Electro-
March 13-17, 1994. chemical Energy Conversion Programs, Report, 1982.
62 Energy & Fuels, Vol. 12, No. 1, 1998
Figure 6. Representative URFC polarization curves for
various HBr concentrations.11
Figure 7. HBr URFC polarization curves demonstrated and
projected.11
consideration. The H2O cycle, HCl cycle, and HBr cycle
URFCs are shown schematically in Figure 5. Efficiency
of hydrogen/halogen URFC systems is a function of acid
concentration and current density, as illustrated by the
representative polarization curves shown in Figure 6.11
This figure shows that unlike for water cycle URFCs,
hydrogen/halogen stacks can be nearly 100% efficient,
if operation is restricted to very low current densities,
where FC and EC polarization curves approach one
another. Figure 711 shows results from the late 1970s,
where >90% electric-to-electric (ETE) voltage efficiency
was achieved at low current density (108 mA/cm2). It
was estimated that system-level parasitics would reduce
the actual round-trip energy storage efficiency by ∼10%
due to pumping power, current inefficiencies, and power
conditioning inefficiencies.
Electric utilities are interested in peak shaving energy
storage systems to maximize utilization of existing base
load electric generators and to postpone the installation
of new generating equipment. Lead acid batteries are
a preferred utility energy storage technology. Unlike
the lead acid battery, RFCs uncouple power and energy
ratings. This allows the RFC to accommodate weekly
and even seasonal cycles. The H2/bromine URFC has
been demonstrated in single cells for up to 4000 h with
80% round-trip energy storage efficiency, and showed
Mitlitsky et al.
stable cyclic performance in the early 1980s for a Boeing
MX missile program.14 Scale-up of cells from 0.23 m2
(2.5 ft2) and minimization of corrosion currents have yet
to be demonstrated.
Less conventional stationary applications currently
use lead acid batteries to store electric energy for remote
off-grid applications. Primary electricity for these ap-
plications can come from solar, wind, or diesel genera-
tors. Up to ∼3 days of energy capacity are typically
stored in the lead acid systems. H2/O2 or H2/air URFC
systems will have longer life, and could have lower
lifecycle cost, as well as allowing weekly and seasonal
energy storage capabilities. The selection of H2/O2
versus H2/air URFCs depends on a number of consid-
erations. URFC systems based on H2/O2 have higher
performance per unit area of membrane, do not need
oxidant compressors, can operate completely closed cycle
with little maintenance, are capable of slightly higher
efficiency, but require ∼50% more tankage to store
oxygen. H2/O2 systems are generally preferred in cases
where the compressed oxygen storage does not pose a
significant safety hazard.
Daytime shortages of electrical power (brown-outs or
black-outs) are becoming more frequent in industrial
countries. Total energy supplies are adequate on aver-
age, but daytime peaks cannot be sustained. A small
H2/air URFC could provide the utility customer with
energy during peak power periods. With sufficient
numbers of individual homeowner units in place, this
significant pressure on electric utilities would be re-
duced. Hydrogen/halogen URFC systems with an at-
tractive mix of high efficiency and low capital cost for
utility load leveling are being investigated enroute to a
demonstration facility.
URFC systems with lightweight pressure vessels have
been designed for automobiles and are expected to be
cost competitive with primary FC powered vehicles that
operate on hydrogen/air with capacitors or batteries for
power peaking and regenerative braking. URFC-
powered vehicles can be safely and rapidly (<5 min)
refueled from high-pressure hydrogen sources, when
available, to achieve driving ranges in excess of 360
miles (600 km). The employment of URFCs would save
the consumer the entire capital cost of a home hydrogen
generation unit. That consumer would now be able to
electrically recharge at any available electrical source,
instead of being tethered to a single home electrolysis
unit. URFC-powered automobiles would still be able
to rapidly refuel by direct hydrogen transfer when a
hydrogen infrastructure becomes available.
Experiments and Results
Permeation Barriers. In order to investigate the
possibility of very thin liners, laminated metal coated
polyester films were fabricated using sputtered silver
films (Southwall Technologies) and evaporated alumi-
num films (National Metallizing). Lightweight bladder
development work for hybrid wingspar/pressure vessels
has been reported previously.5 Some of the data re-
ported previously, and more recent data presented here,
were measured using a Dow gas transmission cell at
LLNL, conforming to the procedures described in ASTM
Designation: D 1434-82, section 9.1, 1982, Philadelphia,
PA. The Dow gas transmission cell used was Model CS-
Regenerative Fuel Cell Systems
Figure 8. Permeability patch sample for testing seams.
89, manufactured by Custom Scientific Instruments,
Inc. NIST 1470 standard polyester film was used to
calibrate the Dow gas transmission cell with oxygen gas
following the ASTM procedure. Pressure transducers
were similarly calibrated following the ASTM procedure.
Hydrogen permeation measurements of laminate
material (designated P-03) were performed at room
temperature to replicate data from 1993. The P-03
material was fabricated with ∼100 nm of Ag sputter-
deposited onto 1 mil (25 micron) thick poly(ethylene
terephthalate) (PET) and laminated on both sides with
a an extruded copolymer of ethylene and acrylic acid
(EAA). A hydrogen permeance of (4.5-5.2) × 10-15 mol/
(m2‚s‚Pa) was measured for the P-03 material at room
temperature (294-295 K) and differential pressure of
0.24-0.28 MPa. This measurement is consistent with
the measured range of (3.4-7.2) × 10-15 mol/(m2‚s‚Pa)
found for similar Ag-coated PET material laminated
using a different copolymer.5 Specimens were also
created to test the permeation of hydrogen gas through
bladder seams using the P-03 material (see Figure 8).
For a circumferential seam that was ∼1 cm wide, the
permeance was measured to be (6.4-8.4) × 10-15 mol/
(m2‚s‚Pa). These measurements are ∼50% greater than
through the base P-03 material measured under similar
conditions and are consistent with patched samples
previously reported.5
Additional hydrogen permeation measurements were
performed on the P-03 material to assess the effects of
temperature and handling. Measurements were per-
formed at a temperature of 115 °F (319 K), by wrapping
the entire cell with heater tape and allowing it to
equilibrate for 24 h prior to data collecting. A hydrogen
permeance of 1.5 × 10-14 mol/(m2‚s‚Pa) was measured
for the heated P-03 material, a result approximately a
factor of 3 higher than the base case at room temper-
ature. Severe handling was simulated by folding a
laminate sample in half and rolling it several times with
a metal roller. The “handled” sample was found to have
a hydrogen permeance of 2.5 × 10-14 mol/(m2‚s‚Pa). This
result is approximately a factor of 5 higher than the
value measured at room temperature.
Many other film samples deposited onto PET were
tested prior to selecting P-03 for further evaluation.
Thicker silver films (600 nm), evaporated and sputtered
aluminum films with various thicknesses, and gold with
various thicknesses were tested. These samples gener-
ally had permeation rates that were at least 1-2 orders
of magnitude higher than that of the sputtered silver
samples, so further evaluation was not considered. A
complex laminate was formed by bonding two samples
of 15-20 nm thick evaporated aluminum on polyester,
Energy & Fuels, Vol. 12, No. 1, 1998 63
Figure 9. Photograph of bladder for use as a mandrel.
Figure 10. Inflated bladder as mandrel on winding axis.
was laminated in polyethylene and tested, and yielded
a permeation measurement of 8.5 × 10-15 mol/(m2‚s‚
Pa). Although this rate was ∼50% higher than that of
the P-03 material, it showed that multiple film layers
can significantly reduce permeation dominated by pin-
holes.
Pressure Vessels. Tooling was completed to fabri-
cate bladder-lined pressure vessels. Bladders were
designed and fabricated which held adequate pressure
for use as inflatable mandrels. Thick end domes (∼0.64
cm) with bosses molded in place were used in these
prototypes to reduce development costs. Figure 9 shows
a picture of one such bladder, where the longitudinal
(laminate to laminate) and circumferential (laminate to
thick end dome) seams are visible. Bladders with
lightweight ends have been designed but have not yet
been fabricated. Bladders similar to the one shown in
Figure 9 were used to fabricate prototype composite
pressure vessels. Figures 10-12 show the tank fabrica-
tion sequence. Figure 10 shows a bladder inflated on a
winding axis prior to application of composite overwrap.
Figure 11 shows application of the first composite layer.
Figure 12 shows application of the final composite layer.
Prototype vessels with estimated performance factors
of 40 km (1.6 million in.) were built and tested in
collaboration with various aerospace and industrial
(bladder and pressure vessel) contractors. Fabricating
vessels with proposed design changes (higher aspect
ratio, lightweighted bosses, and thin end domes) should
yield vessels with performance factors of 51 km (2.0
million in.). Preliminary experiments using polymers
with high-temperature capability (>250 °F ) 120 °C)
suggest that bladder liners can be compatible with fast
64 Energy & Fuels, Vol. 12, No. 1, 1998
Figure 11. Inflated bladder with first composite wrap.
Figure 12. Inflated bladder with last composite wrap.
Figure 13. Fast fill experimental schematic.
fills and high-temperature curing cycles. Some of these
materials are also compatible with cryogenic operation.
A fast fill experiment at LLNL used a hydrogen source
(deuterium) at 15 150 psi (104.5 MPa) to fill a 1.5 ft3
(0.0425 m3) stainless steel vessel (with maximum al-
lowable working pressure of 6000 psi ) 41.4 MPa). The
initial pressure for the steel vessel was atmospheric 15
psi (0.103 MPa) and it was filled to 3500 psi (24.1 MPa)
in 5 min using a 2 stage cascade (Figure 13). After ∼20
h the pressure was 3226 psi and temperature was 293
K (20 °C ) 68 °F). The implied increase in absolute
temperature (overpressurizing or underfilling) during
the fill cycle was ∼8.5%, compared to the adiabatic limit
of ∼41%.
Structural Tanks. Representative sections of hy-
brid wingspar/tanks for a ∼200 ft (61 m) wingspan SRA
were designed, fabricated, and load tested to failure in
bending. The first series of experiments were performed
on the apparatus shown in Figure 14, and shown
functionally in the top rig sketched in Figure 15 (EDO
Test Rig). Failure was due to subarea buckling in all
cases. The first buckling failure was associated with
the discontinuity conditions at the reinforcing plugs
used to couple the test section to the load frame. In
subsequent tests, this transition region was reinforced.
Although the applied bending moment was correct, the
equivalent tensile force on axis reduced the compression
by ∼30%. Second and third generation test rigs (shown
Mitlitsky et al.
Figure 14. Wingspar load test photograph at EDO.
Figure 15. Wingspar test rig sketches.
as BYU Rig #1 and #2 in Figure 15) were constructed
to correctly represent the wingspar loading conditions.
The BYU Rig #1 failed in the support structure when a
test article exceeded the 58 000 ft‚lb bending moment
requirement by ∼5%. The BYU Rig #2 was reinforced
to enable the structure to withstand >100 000 ft‚lb.
Several design/fabricate/test iterations were required
to exceed the safety factor of 2 requirement applied to
the +5g flight moments (29 000 ft‚lb × 2 ) 58 000 ft‚lb
or 79 000 N‚m), as presented in Table 3. The first
successful composite prototype wingspar section weighs
less than 55% of estimates for a similar section fabri-
cated from high-strength aluminum capable of with-
standing the same loads. Note that the +5g flight
moment dominates the structural design and that this
specification implies an order of magnitude higher
moment than the spar designs being used on the current
Pathfinder aircraft.
URFCs. A photograph of part of the URFC test rig
used at General Electric (GE) in 1972 is shown in Figure
16.15 The URFC cell tested in this rig was a prototype
for use in zero gravity. In order to feed water to the
cell for this design, wicking cloths were used and had
not been optimized. Initially hydrophilic wicks became
hydrophobic, so the sparse data recorded on this cell
may be inconclusive. Figure 1715 shows the extent of
(15) Chludzinski, P. J.; Danzig, I. F.; Fickett, A. P.; Craft, D. W.
General Electric Company Technical Report AFAPL-TR-73-34, June
1973.
Regenerative Fuel Cell Systems Energy & Fuels, Vol. 12, No. 1, 1998 65

Figure 16. URFC cycle test at GE in 1972.15

Figure 17. URFC cycle test data from 1972.15

Figure 18. LLNL URFC test rig photograph.
the data that had been reported about this experiment.
These data show that less than 40 mV degradation in
both fuel cell and electrolyzer operation was observed
when a single URFC cell was cycled ∼700 times at low
current density (108 mA/cm2).
A new URFC test facility has been built at LLNL. A
primary fuel cell test rig with a single cell (46 cm2 active
area) was modified for use as a URFC test rig. A
photograph of the URFC test rig is shown in Figure 18
and is presented schematically in Figure 19. Hydrogen
and oxygen are supplied by source bottles, or by recycle
bottles that can be filled by electrolysis. A phase
separator is used on the hydrogen side of the cell to
separate hydrogen gas from a hydrogen/water mixture
during cathode feed electrolysis. This rig was fabricated
by enhancing the functionality of a primary fuel cell test
rig. The URFC cell in this rig is located in the cabinet
at the lower right of Figure 18, and is photographed Figure 19. LLNL URFC test rig schematic.
separately in Figure 20.
Experiments with this URFC test rig were limited track small changes in performance as a function of
within a parameter space of “safe” testing that could cycle life (hundreds of microvolts to tens of millivolts).
be performed while unattended. Exact duplication of Operating temperatures and pressures were selected
the conditions in the 1972 study (108 mA/cm2 current that could be safely and consistently maintained by the
density, room temperature, 0.45-2.17 MPa) was not unattended apparatus during the protracted periods
possible because the LLNL apparatus was not certified required to accumulate many cycles, representing con-
to the same high pressure levels, and was not initially ditions that would be of interest for several applications.
approved for gas capture during electrolysis. Detailed The maximum allowable working pressure (MAWP)
studies of degradation as a function of cycles demanded of the hydrogen side of the system is 80 psig (0.653
an accelerated test procedure that allowed measure- MPa), and the MAWP for the oxygen side is 160 psig
ments to be rapidly accumulated. Accumulating experi- (1.20 MPa). For safety reasons, the oxygen pressure
ence gained in debugging the apparatus verified that was required to be slightly higher (consistently) than
data could be logged periodically in a consistent, repeat- the hydrogen pressure. Since 0.45 MPa was nearly the
able fashion with sufficient precision and accuracy to minimum pressure in the 1972 data, and just below the
66 Energy & Fuels, Vol. 12, No. 1, 1998
Figure 20. LLNL URFC cell photograph.
pressure certification limit that bounded the safe (unat-
tended) operational regime (in late 1996), 0.45 MPa was
chosen for the oxygen side (oxygen plus water vapor).
For safety purposes and unattended operational margin,
0.37 MPa was chosen for the hydrogen side (hydrogen
plus water vapor).
Various operational temperatures were considered
between ∼24 °C (matching the 1972 GE data) and ∼90
°C (the maximum temperature allowed by some of the
solenoids in the system). Unattended operation at this
early stage made it unwise to stress the upper end of
this range. An operating temperature of 82 °C was
considered to be a useful temperature for some aircraft
and automotive applications. High overall round-trip
efficiency for closed systems is a strong function of
diffusion losses, which increase exponentially with
temperature. Therefore, relatively low operating tem-
peratures, such as 49 °C (or less) may have merit.
Cycling at 49 °C was specified anticipating efficiency
measurements, as well as a desire to test temperature
control.
The H2 and O2 gas flows in the test rig are plumbed
for flow through (rather than dead-ended) FC operation.
High flow rates can cause some gas to flow past the
membrane and electrode assembly (M&E) without
reacting. Flow and pressure settings in the test rig were
initially somewhat variable due to lack of feedback
control. Data logging accuracy can be improved by
measuring under conditions of high gas flow, in order
to make measurements insensitive to slight flow varia-
tions.
Initially, current density during cycling was investi-
gated at 100 ASF (108 mA/cm2) to be consistent with
1972 GE data. However, electrolyzer current density
for some RFC designs often optimizes at values higher
than fuel cell current density. During some initial rapid
cycle testing, it was determined that at least 200-240
ASF (215-258 mA/cm2) was required to quickly pres-
surize the system during electrolysis, to consistently
maintain control of the positive pressure differential
required on the oxygen during unattended operation,
and to rapidly dry the hydrogen input side of the cell
when switching from electrolysis to fuel cell operation.
This short drying cycle may be required to remove
the small amount of water that has been trapped in the
“dead space” of the cell after water supply has been
Mitlitsky et al.
Figure 21. URFC cycle test at LLNL for 2010 cycles.
turned off. For cells requiring very rapid switching
times, this dead space should be minimized to reduce
drying time. For the cell configuration being tested
(which was a designed initially for dedicated fuel cell
operation and converted to a URFC without considering
this design parameter), it was determined that 2.0-2.5
min at 240 ASF (250 mA/cm2) were required for drying.
Various cycle times were considered. Lunar rovers
have cycle times of ∼28 days. HALE SRA have cycle
times of ∼24 h. Low earth orbit satellites (and the 1972
GE experiment) have one cycle per ∼90 min. Automo-
biles using electrolytic regenerative braking may un-
dergo charge cycles as short as 10-15 s. A 2.5 min
electrolytic drying time was chosen and was set as half
of the electrolysis (charge) cycle. A 5 min fuel cell
(discharge) time and a 2.5 min cathode feed electrolysis
time were chosen for a total cycle time of 10 min.
Cycling of the URFC (cell LLNL01) was stopped
periodically to acquire data for polarization curves. The
data for these polarization curves were measured after
allowing the system to stabilize for 30 min with high
gas flow rates at 100 ASF (108 mA/cm2) fuel cell or 240
ASF (258 mA/cm2) electrolyzer. After 30 min, the
system was quickly ramped to the highest current
density to be recorded and allowed to stabilize for 2 min,
and the voltage was recorded. The current density was
then reduced by 20 ASF for fuel cell or 40 ASF for
electrolyzer, followed by a 2 min stabilization period and
data were again recorded. This was repeated until 0
ASF was recorded. The system was then rapidly
ramped back to 100 ASF fuel cell or 240 ASF electro-
lyzer and another set of measurements was made to
check drift. After fuel cell and electrolyzer polarization
data were recorded, cycle testing was resumed.
Cycle testing of a single-cell URFC was started in
November 1996 at LLNL. The test results for a single
cell cycled 2010 times are presented in Figure 21 at four
different current densities for both fuel cell (FC) and
electrolyzer (EC) modes (eight curves total). This
experiment accurately measured the cell voltage under
repeatable conditions to determine the extent of cell
degradation. Zero degradation would be reflected in
horizontal curves (no change in voltage as a function of
cycle life). If there was significant degradation due to
cycling, the FC curves would display larger negative
slopes and the EC curves would display larger positive
slopes. The plot in Figure 21 shows negligible degrada-
tion in both FC and EC performance, over a range of
current densities.
Six of the eight curves from Figure 21 are magnified
in Figures 22-27. The plot limits for these expanded
Regenerative Fuel Cell Systems
Figure 22. URFC cycle test for FC at 43 mA/cm2.
Figure 23. URFC cycle test for FC at 108 mA/cm2.
Figure 24. URFC cycle test for FC at 172 mA/cm2.
Figure 25. URFC cycle test for EC at 86 mA/cm2.
curves were chosen to show up to 50 mV of degradation
and up to 30 mV of performance improvement compared
to the cycle 1 measurement (80 mV full scale). A large
fraction of remaining uncertainty about performance
degradation is due to experimental error, which can be
reduced with an upgraded apparatus. These figures
show that performance has degraded by less than a few
Energy & Fuels, Vol. 12, No. 1, 1998 67
Figure 26. URFC cycle test for EC at 172 mA/cm2.
Figure 27. URFC cycle test for EC at 258 mA/cm2.
Figure 28. URFC polarization curves after 750 cycles.
percent during cycling. Figure 28 shows polarization
curves measured for this cell after 750 cycles at two
different temperatures for fuel cell and electrolyzer.
Performance of this cell was limited by a large internal
resistance (12 mohm/46 cm2 active area at 297 K), which
dropped slightly to 11.4 mohm at 297 K by the end of
the test.
A new URFC membrane and electrode assembly
(M&E) was installed and tested (cell 9734A). This cell
had an internal resistance of 6.3 mohm/46 cm2 active
area at 297 K, a value much closer to the expected value
for a good cell. Internal resistance was measured to be
3.8 mohm/46 cm2 at 188 °F inlet temperature (360 K).
A polarization curve for this cell is shown in Figure 29
at conditions which are very close to the highest
temperatures and pressures allowable for the test rig
in its present configuration. This figure proves that
URFC cells can be cycled at >1 A/cm2 in both fuel cell
and electrolyzer modes using Nafion 117 membrane.
The polarization curves of Figure 28 and Figure 29 are
plotted on the same graph in Figure 30 to show the
68 Energy & Fuels, Vol. 12, No. 1, 1998
Figure 29. High-performance URFC polarization curves.
Figure 30. URFC polarization curve comparison.
performance improvement achieved. Cell 9734A has
been operated as a fuel cell at current densities in excess
of 1000 ASF (1.08 A/cm2, a factor of 3 higher than cell
LLNL01). Cell 9734A was also operated to perform
electrolysis at the same high power density, regenerat-
ing reactant gases for extended periods, despite the
concern that cathode feed designs may be prone to
membrane dry-out at high current density.
These results are an important milestone and a
significant improvement over what has previously been
demonstrated. Both of the cells (9734A and LLNL01)
tested used Nafion 117 membrane and Hamilton Stan-
dard’s E-5 catalyst, which is a proprietary mixture of
platinum, platinum group metals, and their oxides.
Catalyst loading was 4 mg/cm2 per electrode in both
cells. The reduced internal resistance of cell 9734A and
its corresponding performance improvement is attrib-
uted to the use of a new porous plate.
The drying procedure required to cycle into FC
operation has been accomplished in 25-30 s using a
current density of 1.08 A/cm2. The drying procedure has
also been accomplished in ∼15 s using a current density
of 1.5 A/cm2. It is expected that redesign of the cell,
catalyst, and drying procedure could reduce this drying
time to a fraction of a second.
Preliminary experiments also demonstrated that
rapid cycling (with round-trip cycle times of less than
60 s) at current densities in excess of 1000 ASF is
feasible. Two new URFC M&Es using Nafion 115 have
been received by LLNL from Hamilton Standard. These
cells have internal resistances of 5.7-5.8 mohm at room
temperature and are expected to outperform the Nafion
117 cells, but have yet to be tested.
Mitlitsky et al.
Discussion
Permeation Barriers. ASTM hydrogen gas trans-
mission tests were performed on laminates using gold,
aluminum, and silver as the barrier layers. Although
gold and aluminum have room temperature permeabili-
ties that are 7-8 orders of magnitude lower than silver,7
measurements on laminates at room temperature showed
that silver is a better choice as a barrier material.
Permeation rates for silver laminates were consistent
(within an order of magnitude) with the extrapolated
room temperature permeability of silver, whereas per-
meation rates for gold and aluminum were >9 orders
of magnitude worse than their respective extrapolated
room temperature permeabilities. Hydrogen perme-
ation in the gold and aluminum laminates was domi-
nated by pinholes (or cracks for thicker aluminum
films). A complex laminate with two thin aluminum
layers in series had permeation that was 1-2 orders of
magnitude lower than a single aluminum layer. Al-
though this permeation rate is ∼50% higher than that
of the silver laminate, it proves the utility of multiple
film layers in reducing permeation dominated by pin-
holes. Such complex laminates may pose thermo-
mechanical challenges to seam formation, since inter-
laminate bonds must be at least as strong as the seams
in order to avoid failures due to delamination.
The P-03 bladder material was developed for applica-
tions which had peak service temperatures of ∼140 °F
(60 °C). One of the layers in the P-03 bladder has a
peak temperature capability of ∼195 °F (90 °C). To
better tolerate the heating that occurs during fast fills,
and/or to incorporate some epoxy curing processes which
may require temperatures to 250 °F (120 °C), a search
for new bladder materials with higher temperature
capability is underway. Bladder materials with upper
service temperature >120 °C must be tested in prepara-
tion for forming into laminates. The exponential de-
pendence of permeation on temperature requires a
careful consideration of the highest temperatures ex-
pected during normal operation, including fast fills.
Fully integrated bladder-lined pressure vessels have yet
to be manufactured and tested in conformance with the
standards required for their intended use.
Hydrogen permeance is estimated to be less than
0.25%/year (∼8 g/yr out of ∼3.5 kg/aircraft) for a high-
altitude aircraft point design using P-03 laminate for
bladder liners.5 Scaling these room temperature results
for automotive applications, which may have ∼20 times
higher pressure (a square root dependence) and ∼10
times lower surface area (a linear dependence), suggests
permeance comparable to high-altitude aircraft. The
“handling” test provided early warning of the risk posed
by wrinkles that might be captured in the liner during
either the fiber winding or curing process steps. Al-
though severe handling was shown to increase perme-
ation locally by a factor of approximately 5, such
degradation is not catastrophic for many applications
and can be avoided by appropriate quality control during
fabrication.
Pressure Vessels. Prototype pressure vessels with
PV/W of 40 km (1.6 million inches) were fabricated.2
Performance factors were calculated for automotive
applications, investigating the tankage mass advan-
tages of higher aspect ratio pressure vessels using
Regenerative Fuel Cell Systems
Table 5. PV/W for Bladder-Lined Hydrogen Storage Cylinders
end dome boss wt per
fiber type thickness (in.) vessel (lb)
T1000G 1/8 (0.317 cm) 3.04 (1.38 kg)
T1000G 1/4 (0.635 cm) 3.04 (1.38 kg)
T1000G 3/8 (0.952 cm) 3.04 (1.38 kg)
T1000G 1/2 (1.27 cm) 3.04 (1.38 kg)
T700S 1/8 (0.317 cm) 3.04 (1.38 kg)
T700S 1/4 (0.635 cm) 3.04 (1.38 kg)
T700S 3/8 (0.952 cm) 3.04 (1.38 kg)
T700S 1/2 (1.27 cm) 3.04 (1.38 kg)
T1000G 1/16 (0.159 cm) 2.75 (1.25 kg)
T1000G 1/8 (0.317 cm) 2.00 (0.909 kg)
T1000G 3/16 (0.476 cm) 1.25 (0.568 kg)
T1000G 1/4 (0.635 cm) 0.52 (0.236 kg)
a En ≡ × 10n.
various fiber types, end domes, and bosses (see Table
5). The calculations are presented to three significant
figures to show small variations in different designs.
Actual performance factors are expected to be within a
few percent of these values but require testing for
validation. The last column of this table shows the %
hydrogen storage by weight that is calculated by con-
sidering hydrogen weight/(vessel weight + hydrogen
weight). The calculations assume three vessels per
vehicle, 13.6 lb (6.18 kg) hydrogen per vehicle, 5 ksi (34.5
MPa) maximum operating pressure, 300 K operating
temperature, 12.0 in. (30.5 cm) i.d., 51.0 in. (130 cm)
overall length excluding boss protrusions, 2.25 safety
factor, 924 ksi ultimate tensile strength of T1000G, 711
ksi ultimate tensile strength of T700S, ultimate tensile
strengths derated to 81% of these values (accounting
for variability in fibers and manufacturing), 1.80 g/cm3
fiber density, 1.20 g/cm3 resin density, 58% volume
fraction of fibers, and 1.5:1 oblate spheroid approximate
end dome shape.
The last four entries in Table 5 show possible com-
binations of lightweighting the end domes and bosses
that would yield a calculated PV/W ) 2.00 million in.
(50.8 km) under the abovementioned assumptions.
These tanks, when filled with hydrogen to their maxi-
mum operating pressure, would have a specific energy
of 4260 Wh/kg based on 100% efficient utilization of the
contained hydrogen’s lower heating value.
The implied increase in absolute temperature (over-
pressurizing or underfilling) during the fill experiment
(Figure 13) was ∼8.5%, compared to the adiabatic limit
of ∼41%.8 This discrepancy is likely due to the assump-
tions made in calculating the adiabatic limit, which
neglects heat flow into the pressure vessel wall (and the
environment) during the filling process. The thermal
mass of the 312 lb (142 kg) stainless steel test vessel
was estimated to be 31 BTU/°F (59 kJ/K), whereas the
thermal mass of the ∼3 lb (1.4 kg) of deuterium was
estimated to be 5.2 BTU/°F (9.9 kJ/K). Although heat
transfer to the environment during the fill process was
probably small, the heat transfer into the wall of the
cylinder was fast enough to substantially reduce tem-
perature rise. High-strength composite pressure vessels
with thin walls will provide thermal masses that are
comparable to that of the hydrogen gas they contain,
instead of being roughly 6-fold larger than hydrogen as
in the experimental case. Therefore, temperature rises
during fast fills of these lightweight pressure vessels
will be accentuated, but still less than the adiabatic
limit.
Energy & Fuels, Vol. 12, No. 1, 1998 69
performance factor H2 wt/(H2 + tank)
P(burst)V/W (in.) wt (%)
1.93 E6 (49.0 km)a 12.4
1.85 E6 (47.0 km) 12.0
1.77 E6 (45.0 km) 11.5
1.69 E6 (42.9 km) 11.1
1.54 E6 (39.1 km) 10.2
1.48 E6 (37.6 km) 9.8
1.43 E6 (36.3 km) 9.5
1.38 E6 (35.1 km) 9.2
2.00 E6 (50.8 km) 12.8
2.00 E6 (50.8 km) 12.8
2.00 E6 (50.8 km) 12.8
2.00 E6 (50.8 km) 12.8
A number of strategies may be employed to compen-
sate for heating during fast filling of pressure vessels.
One study suggests precooling hydrogen gas to ∼214
K, to avoid underfilling, overpressurization, or high final
gas temperatures.8 Precooling may be advantageous if
liquid hydrogen is available at the filling station but
could represent a large parasitic energy loss otherwise.
Another study considers the use of phase change plugs
in order to reduce temperature rise during fast fills.16
The materials used as the plugs would introduce
significant weight and volume penalties. Active cooling
with microchannels can solve heating problems but may
be expensive and would add complexity to filling sta-
tions. Overpressurizing the vessel can be considered if
tank materials are compatible with the worst case
possible temperature rise. Safety factor would then be
reduced for the time it takes to cool back to ambient
temperature, which can be several hours for vessels with
poor heat transfer. Heat transfer from the gas can be
improved by using heat pipes, conducting foams, or
other heat exchangers.
The highest performance, lightest weight composite
pressure vessels are currently available for large diam-
eter, high pressure, low cycle life space applications. For
applications requiring smaller diameter, lower pressure,
and/or much higher cycle life, the performance factors
will be significantly reduced. This performance factor
reduction results from an increase in the ratio of
parasitic masses (liners and bosses) in comparison to
the mass of high-strength composite wall. In some
cases, the liner weight dominates to the point where
there is little merit in applying composite (as opposed
to thickening the liner a little further and considering
it a metallic pressure vessel). The use of thin bladder
liners improves performance and enables composites to
be competitive in relatively small diameter applications.
For applications where weight and cost are paramount
concerns, the weight decrease associated with the use
of bladder liners can be traded for a weight gain accrued
by using a lower strength fiber that is less expensive
(e.g., using T700S or Panex 33 instead of T1000G).
Structural Tanks. For some applications, the com-
posite wall thickness required for pressure alone (or
structure alone) can be less than the minimum gauge
that is manufacturable and/or handleable. In such
(16) Jasionowski, W.; Kountz, K. J.; Blazek, C. F. Gas Research
Institute Report #GRI-92/0350, July 1992.
(17) Arthur D. Little, Inc. “Multi-fuel reformers for fuel cells used
in transportation: Assessment of hydrogen storage technologies”,
Report Number DOE/CE/50343-1, March 1994.
70 Energy & Fuels, Vol. 12, No. 1, 1998
cases, combining the functionality of pressure contain-
ment and structure into a single unit will enable a more
efficient use of composite, with an associated weight
savings. The HALE SRA design is an example of a
pressure vessel with the desired shape designed to
contain gas at the optimal pressure that would have
specified a minimum gauge composite wall, causing
difficulties with manufacturing and handling, were it
not for the neighboring mass of structural composite.
Combining the pressure containment requirements with
the structural requirements of the wingspar results in
a design which avoids the inefficiencies associated with
minimum gauge fabrication and handling issues, while
also providing additional structural integrity. The
presence of internal pressure in a spar has the positive
effect of increasing the buckling-critical moment. This
improved structural performance cannot be considered
an advantage in the design of the wingspar/tanks
because of a global design requirement demanding that
the structure remain intact even if there is a loss of
internal pressure.
In many cases, a tank designed for pressure loads
may already be stiff enough to act as a structural
member for the vehicle. In these cases there may be
little or no additional composite required to act as a
structural member, with the exception of designing
nodes at the ends to couple the structural loads into the
tank. For cases where structure requires slightly higher
stiffness than is provided by the tank, alternate fibers
with higher modulus and lower strength than T1000G
(e.g., M40J) can be considered to help customize designs
for minimum weight of the structural tank.
The first successful composite prototype wingspar
section weighs less than 55% of estimates for a similar
section fabricated from high-strength aluminum capable
of withstanding the same loads. Additional testing of
wingspar/tanks under pressure and mixed loading
conditions should be performed before integrating this
design into a vehicle.
URFCs. The plot in Figure 21 shows that negligible
degradation occurred as a result of operating a URFC
for 2010 cycles. The extent of degradation (if any) is
less than 30 mV for all current densities reported and
is dominated by experimental error in many cases.
Ignoring the experimental error, the electrolyzer opera-
tion actually improved by a few millivolts over the
course of cycling at all current densities reported. An
upper limit for degradation can be calculated from
Figures 22-27, by evaluating the difference between the
most pessimistic extreme of the error bar on the final
measurement (cycle 2010) and the most optimistic
extreme of the error bars on the first measurement.
Using this worst-case calculation, the upper limits for
degradation were <19 mV for FC operation at 43 mA/
cm2, <28 mV for FC operation at 108 mA/cm2, <30 mV
for FC operation at 172 mA/cm2, <15 mV for EC at 86
mA/cm2, <19 mV for EC at 172 mA/cm2, and <14 mV
for EC at 258 mA/cm2.
Results from the cycle test presented herein are an
existence proof that URFC cells can be cycled repeatedly
without significant degradation (less than a few per-
cent). These results are also an existence proof that
bifunctional catalysts can operate reversibly without
significant degradation. Similar experiments should be
Mitlitsky et al.
performed with lower catalyst loadings, since the M&Es
used in the experiments reported above employed high
catalyst loadings (4 mg/cm2 per electrode) that may be
more than an order of magnitude too high for the
economic rigors of some nonaerospace applications. The
performance of the first cell in the cycle test was lower
than expected at high current densities, due to higher
than expected internal resistance. However, internal
resistance actually dropped slightly (from 12 to 11.4
mohm at room temperature) over the course of the cycle
test. This suggests that URFC cell manufacture had
not been optimized and additional development and
testing is recommended.
The performance of cell 9734A is much closer to the
performance expected for a dedicated fuel cell. This
URFC cell was cycled several hundred times reversibly
at current densities in excess of 1000 ASF (1.08 A/cm2)
in both fuel cell and cathode feed electrolysis modes.
This high-power, reversible operation is an important
milestone and a significant improvement over what has
previously been demonstrated. It also furnishes an
existence proof that cathode feed electrolysis can take
place at relatively high current density, without sig-
nificant cell drying. Preliminary experiments also
demonstrated that rapid cycling (with round-trip cycle
times less than 60 s) at current densities in excess of
1000 ASF is feasible. URFC cells using Nafion 115 (and
other high-performance membranes) are expected to
outperform the Nafion 117 cells reported herein.
URFCs in vehicular applications are projected to have
performance, weight, volume, and cost comparable to
primary FCs which use capacitors for power boost and
regenerative braking. Rapid switching from FC to
electrolyzer (EC) enables regenerative braking and
power boosting via low pressure oxygen supercharge.
URFC cells for most vehicular applications would use
bifunctional electrodes which employ a catalyst that is
optimized for FC performance. Electrolysis capability
of URFCs enables efficient recharge from electrical
sources at home, at work, or at the highest power
electric vehicle charging stations under consideration.
Vehicles powered by URFCs can rapidly refuel from
high-pressure hydrogen sources as they become avail-
able, but avoid a requirement for a hydrogen infrastruc-
ture in the near term. URFC-powered automobiles
effectively carry their infrastructure on-board, so they
save the consumer from procurement of a home EC unit.
Electric utilities are interested in peak-shaving en-
ergy storage systems in order to better utilize existing
base load electric generators and to postpone the instal-
lation of new generating equipment. Lead acid batteries
are a preferred utility energy storage technology. Un-
like the lead acid battery, the H2/halogen URFC un-
couples power and energy. This allows the URFC to
accommodate weekly and even seasonal cycles. The H2/
halogen URFC has been demonstrated in single cells
for up to 4000 h with 80% round-trip energy storage
efficiency and stable cyclic performance. Scale-up of
cells to >2.5 ft2 and minimization of corrosion currents
are the next development hurdles for hydrogen/halogen
URFC utility systems. Fabrication and test of hydrogen/
halogen cells using higher performance membranes
should demonstrate significant improvements compared
to work reported from the 1970s and early 1980s.
Regenerative Fuel Cell Systems
Acknowledgment. This work was performed under
the auspices of the U.S. Department of Energy by
Lawrence Livermore National Laboratory under Con-
tract W-7405-Eng-48. This work was funded in part by
Ballistic Missile Defense Organization, Ford Motor Co.,
LLNL Laboratory Discretionary Research Funds, NASA,
and U.S. Department of Energy. This work was per-
formed in conjunction with various organizations, in-
cluding Aero Tec Laboratories (Ramsey, NJ), AeroVi-
Energy & Fuels, Vol. 12, No. 1, 1998 71
ronment (Monrovia, CA), Brigham Young University
(Provo, UT), Composite Solutions (Salt Lake City, UT),
Directed Technologies Inc. (Arlington, VA), EDO Fiber
Science Division (Salt Lake City, UT), Proton Energy
Systems (Rocky Hill, CT), Thiokol Corporation (Brigham
City, UT), and United Technologies, Hamilton Standard
Division (Windsor Locks, CT).
EF970151W