J Appl Electrochem (2016) 46:829–839
DOI 10.1007/s10800-016-0962-0
RESEARCH ARTICLE
Electrolyzer performance for producing hydrogen via a solar-
driven hybrid-sulfur process
John W. Weidner1
Received: 22 February 2016 / Accepted: 16 April 2016 / Published online: 29 April 2016
Ó Springer Science+Business Media Dordrecht 2016
Abstract Advances in fuel-cell technology and an
increasing demand for hydrogen are driving the need for
the development of more efficient methods to produce
hydrogen. Thermochemical cycles, which produce pure
hydrogen by splitting water through a series of chemical
reactions, are being investigated as avenues for producing
hydrogen efficiently on a large scale. Although there are
hundreds of possible thermochemical cycles, the hybrid-
sulfur process is the only practical, all-fluid, two-step
thermochemical cycle. In a solar-driven process, solar
radiation is used in a solar receiver/reactor to provide the
energy needed to vaporize and decompose sulfuric acid.
The resulting sulfur dioxide (SO2) is used in the second
step consisting of an SO2-depolarized electrolyzer (SDE)
that electrochemically oxidizes SO2 with water to form
sulfuric acid at the anode and hydrogen at the cathode. All
the sulfur species are internally recycled and the overall
reaction is the splitting of water to form hydrogen and
oxygen. We report here on our patented gas-fed SDE that
was tested over a range of operating conditions (e.g., cur-
rent, temperature) and design variations (e.g., membrane
type and thickness). A key insight from our work is that
perfluorinated sulfonic acid membranes like NafionÒ
dehydrate at high acid concentrations, leading to high
membrane resistance. Using acid-doped polybenzimida-
zole membranes represent an alternative material because
they do not rely on water for their proton conductivity, and
they can operate at temperatures above 100 °C.
& John W. Weidner
weidner@engr.sc.edu
1 The hydrogen production program at the US Department
Center for Electrochemical Engineering, Department of
Chemical Engineering, University of South Carolina,
Columbia, SC 29208, USA
Keywords Thermochemical cycles  Hydrogen
production  Electrolyzer  Polymer membranes
1 Introduction
1.1 Hydrogen production
Hydrogen is abundant in nature, but it occurs primarily in
stable compounds (e.g., water) that require significant
energy to produce for use as a fuel. As such, hydrogen is an
energy carrier, much like electricity, that requires a primary
energy source to produce. A transition to hydrogen as a
major energy carrier could fundamentally transform a
countries energy system, creating opportunities to increase
energy security through the use of a variety of domestic
energy sources for hydrogen production while reducing
environmental impacts, including global CO2 emissions
and local air quality [1, 2]. Due to advances in fuel-cell
technologies, there has been considerable research activity
over the past twenty years to expand the use of hydrogen as
an energy carrier. However, despite these compelling
benefits, realization of a hydrogen economy faces multiple
challenges in the areas of hydrogen production, storage and
delivery technologies. Although technologies in these areas
are in commercial use by the chemical and refining
industries, existing hydrogen storage and conversion tech-
nologies either rely on hydrocarbons or are too costly and
inefficient for widespread use in energy applications. In the
case of hydrogen production, there is considerable research
activities to lower the cost and improve efficiency of
hydrogen-production technologies [1–3].
of Energy is examining an array of distributed and cen-
tralized facilities, shown in Fig. 1, that could contribute to
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830
Fig. 1 This figure shows the technologies being examined by the
Hydrogen Production program at the US Department of Energy for
distributed and centralized facilities that could contribute to the
hydrogen infrastructure for the short and long term. The square
the hydrogen infrastructure for the short and long term [3].
Large centralized facilities are expected to dominate a
mature hydrogen economy because they provide econo-
mies of scale. However, distributed production systems are
coming on line first since they can be installed rapidly as
the demand for hydrogen increases, thus allowing hydro-
gen production to better match hydrogen demand. Dis-
tributed systems also have the advantage in that large-scale
pipeline systems are not required because hydrogen pro-
duction is co-located with hydrogen dispensing and/or use.
Eventually though, the efficiency and cost advantages of
large-scale, centralized facilities will probably prevail.
Currently, reforming natural gas is the most cost-effec-
tive, established industrial process for producing hydrogen,
both in small, distributed units and at large, centralized
facilities. However this process emits carbon dioxide to the
atmosphere. To produce CO2-neutral hydrogen, the tech-
nologies depicted in Fig. 1 can be placed into four general
categories: (1) electrolysis; (2) biological processes; (3)
fossil-fuel reforming with carbon capture and storage
(CCS) (i.e., carbon sequestration); (4) thermochemical
cycles.
Electrolysis, where electricity is used to split water into
hydrogen and oxygen, is used commercially to produced
ultrapure hydrogen in applications where this is critical (e.g.,
semi-conductor industry). However this approach, whether
using alkaline electrolyzers (operated at 100–150 °C) or
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J Appl Electrochem (2016) 46:829–839
(\1500 kg H2/day) and the size of the circles reflect the relative
production capacities (50,000 to over 500,000 kg H2/day) of these
various technologies [3]
polymer exchange membrane electrolyzers (operated at
70–90 °C), is currently more expensive than natural-gas
reforming. High-temperature electrolysis, which uses cera-
mic membranes operated at 700–800 °C hold promise due to
their potential for high efficiencies. Photo electrochemical
water splitting is a form of electrolysis where the solar
collection is integrated into the electrolyzer.
As the name implies, biomass gasification uses renew-
able biomass and traditional gasification technology to
produce hydrogen. Because the carbon source is renewable,
there is no net CO2 emissions to the atmosphere. Biological
processes also include photobiological hydrogen produc-
tion, which uses microorganisms and sunlight to turn water,
and sometimes organic matter, into hydrogen, and micro-
bial biomass conversion, which takes advantage of the
ability of microorganisms to consume and digest biomass
and release hydrogen [3]. These last two biological pro-
cesses suffer from low hydrogen-production rates and
hence are better suited for small-scale applications.
Linking the production of hydrogen from reforming
fossil fuels with CCS is another way of producing CO2-
neutral hydrogen [4, 5]. Here the CO2 is captured before it
can enter the atmosphere and stored underground (e.g.,
mined salt domes, depleted oil or gas reservoirs, deep
aquifers) or in the ocean. This approach, however, adds
cost and inefficiencies, and a hydrogen-production facility
needs to be co-located with an appropriate storage cite to
J Appl Electrochem (2016) 46:829–839
avoid costly transportation of CO2. There are also no
guarantees the CO2 will not find its way into the atmo-
sphere, or its storage will not have other unforeseen envi-
ronmental impacts, especially if stored in the oceans.
Finally, solar thermochemical hydrogen production is
viewed as a long-term technology pathway. Thermo-
chemical cycles involve a series of chemical reactions that
result in the splitting of water at much lower temperatures
(*500–1000 °C) than direct thermal dissociation
([2500 °C) [1]. All other chemical species in these
reactions are recycled resulting in the consumption of
only heat and water to produce hydrogen and oxygen.
Although there are hundreds of possible thermochemical
cycles that can produce hydrogen from water, there are
only a few that are considered commercially viable. An
example of a viable direct (i.e., all chemical) process is
the two step cerium oxide thermal cycle [3]. An example
of a viable hybrid (i.e., combination chemical and elec-
trochemical) process is the hybrid sulfur (HyS) cycle [6].
Typically direct cycles offer efficiency advantages, but
they require higher operating temperatures.
1.2 Hybrid-sulfur process
In the 1970s, Westinghouse Electric Corporation devel-
oped the HyS process, which is the only practical, all-fluid,
two-step thermochemical cycle [7, 8]. The high-tempera-
ture step (850–950 °C) involves the decomposition of
H2SO4 to produce oxygen and sulfur dioxide via the fol-
lowing reaction:
1 duct as an impurity that must be separated or be reduced to
H2 SO4 ! SO2 þ O2 þ H2 O
2 elemental sulfur through the following parasitic side
In the Westinghouse design, sulfur dioxide (SO2) was
separated, cooled, and bubbled through concentrated sul-
furic acid (30–60 wt %). This liquid phase was sent to the
anode and water was sent to the cathode of a low-tem-
perature (70–90 °C) SO2-depolarized electrolyzer (SDE).
The resulting reactions at the anode and cathode, respec-
tively, are:
SO2 þ 2H2 O ! H2 SO4 þ 2Hþ
þ 2e U0SO2 ¼ 0:158 V vs: SHE
2Hþ þ 2e ! H2 U0H2 = 0 V vs: SHE
Thus the overall reaction in the electrolyzer is repre-
sented as
SO2 þ 2H2 O ! H2 SO4 þ H2
Unfortunately poor performance (i.e., low efficiencies
and large, costly cells) and a significant drop in oil prices in
the 1980s caused Westinghouse to abandon the HyS pro-
cess. Breakthroughs in membrane technology renewed
interest in this technology in 2000 via the Nuclear
831
Hydrogen Initiative [1], and more recently by the US DOE
Office of Energy Efficiency and Renewable Energy. The
Savannah River National Laboratory envisions the HyS
process to be link to solar energy as shown in Fig. 2 [6, 9].
Here solar radiation (right side of figure) is used in a solar
receiver/reactor to provide the energy needed to vaporize
and decompose sulfuric acid (red reaction = Reaction 1).
The resulting SO2 is used in the second step (left side)
consisting of an SDE that electrochemically oxidizes SO2
with water to form sulfuric acid at the anode and hydrogen
at the cathode (blue reaction = Reaction 4). All sulfur
species are recycled and the overall reaction is the splitting
of water to form hydrogen and oxygen. Excess SO2 is
stored during daylight operation and used at night to permit
continuous electrolyzer operation and hydrogen produc-
tion. Electricity is supplied from a companion solar-electric
plant or obtained from the grid.
The focus of this paper is on the SO2-depolarized
electrolyzer. The general design goals to maximize energy
efficient (i.e., minimize energy input per kilogram of
hydrogen) and minimize system costs are three fold: (1)
minimize the cell voltage to minimize electrical input; (2)
maximize the cell current density to minimize stack size
and in turn stack costs; (3) maximize the concentration of
sulfuric acid exiting the SDE to minimize the energy
associated with removing water prior to the H2SO4
decomposer.
A potential issue facing this process is the diffusion of
SO2 from the anode to the cathode during operation. Upon
crossing the membrane, SO2 can either enter the H2 pro-
ð1Þ
reaction:
SO2 þ 4e þ 4H ! S þ 2H2 O ð5Þ
Although it has been demonstrated that a negligible
amount of SO2 crosses the membrane and reduces to sulfur
(i.e., 100 % columbic efficiency was measured for 2 and 3
[13]), even a small amount of sulfur deposition at the
cathode may result in significant changes in the cathode
composition [14] and may impact electrode kinetics. Thus,
ð2Þ controlling the SO2 crossover is essential for successful
long-term operation of the hybrid sulfur electrolyzer. Long-
ð3Þ
term degradation, either from sulfur deposition or other
mechanisms, are not addressed here but need to be
investigated.
In order to improve the mass-transfer limitations of
ð4Þ
dissolved SO2 in sulfuric acid, thus increasing current
densities and decrease electrolyzer size and cost, we
developed a patented process by which we feed SO2 as a
gas to the anode and liquid water to the cathode [10]. The
water required at the anode in Reaction 2 is supplied from
the cathode via transport across the membrane (see Fig. 3).
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832 J Appl Electrochem (2016) 46:829–839

Fig. 2 A schematic of how the Savannah River National Laboratory envisions the hybrid-sulfur (HyS) process would be link to solar energy [9]

We discuss here the effect of operating conditions (e.g., Nafion of three thicknesses; N117 (7 mil extrusion cast
current, temperature) and design variations (e.g., catalyst film), N115 (5 mil extrusion cast film) and N212 (2 mil
type and loading, membrane type and thickness) that must dispersion cast film). The standard catalyst loading was
be balanced in order to achieve the three general design 0.5 mg/cm2 Pt black and carbon cloth gas diffusion layers
goals stated above. from Etek were placed between the MEA and the carbon
flow channels. When using Nafion-based MEAs, dry SO2
gas was fed to the anode and liquid water to the cathode.
2 Experimental For acid-doped polybenzimidazole-based MEAs, the gas-
eous SO2 was humidified and the cathode was dead-ended
When using NafionÒ-based membrane-electrode assem- with only an outlet.
blies (MEAs), the experimental setup and operating con- Sulfonated PBI (s-PBI) membranes (thickness con-
ditions were similar to that reported previously [11–15]. trolled to 500 lm) were prepared as described previously
The electrolyzer cell was a standard 10 cm2 cell purchased [16]. The only difference between the already-reported PBI
from Fuel Cell Technologies, Inc. This cell was modified membranes [17] and those used in this study is an addi-
so that the electrolyzer reactants and products were passed tional acid exchange step. After casting from (polyphos-
through Kynar plates instead of the standard aluminum phoric acid) PPA and hydrolysis to phosphoric acid, the
endplates to avoid corrosion by H2SO4. The membrane was PBI membranes were soaked in deionized water at room
Fig. 3 Schematic of the model SO2(g) SO2(g) + H2SO4 + H2O
system under consideration Anode Flow Channel
[13]. Dry SO2 gas and liquid
water are fed to the anode and Anode
cathode, respectively. Water Catalyst SO2 + 2H2O H2SO4 + 2H+ + 2e- GDL
diffuses across the NafionÒ x = δM
Layer
membrane from the cathode to H2O
the anode due to a gradient in
Membrane diffusion
the water activity. Water also +
H (H2O)n migration
moves to the anode with a
pressure gradient and is Cathode
2H+ + 2e- H2 x=0
transported back to the cathode Catalyst GDL
via electro-osmotic drag
Layer
Cathode Flow Channel
H2O H2O + H2

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temperature for 5 days to remove the phosphoric acid. The
leached PBI membranes were then immersed in 5 M sul-
furic acid for 2 days prior to use.
Membrane specific-area resistance was measured by the
current interrupt technique, in which the current of the
operating electrolyzer was abruptly changed, and the
transient potential response monitored. During cell opera-
tion, the sulfuric acid was collected at the exit of the cell
and titrated against sodium hydroxide to determine the
concentration.
3 Results and discussion
The polarization curves for electrolyzers using MEAs
made from Nafion 117, 115 and 212 membranes are given
in Fig. 4 [13]. The symbols are experimental data and the
lines are smooth curve fits to the data. As expected, the cell
voltage decreases as the membrane thickness decreases.
For example, at 0.6 A/cm2 the voltage decreases from 0.92
to 0.75 V as the membrane thickness is decreased by a
factor of 2.5. The thinner membranes are also able to go to
much higher currents before the voltage rises exponen-
tially. The N212 membrane can reach 1.2 A/cm2 before the
voltage hits 1.0 V, where the N115 membrane only reaches
half this current density.
Although thinner membranes achieve higher current
densities at lower voltage, they also produce weaker sul-
furic acid. Figure 5 shows the sulfuric acid concentration
leaving the cell as a function of membrane thickness and
current density (data points). Also shown in Fig. 5 are the
model predictions (lines) using a model for water transport
Fig. 4 Polarization data for 1.4
electrolyzers using MEAs made
from the Nafion 117, 115 and
212 membranes [13]. The 1.2
Nafion 212 electrolyzer can be
operated at lower cell voltages
than the thicker membrane due 1.0
to lower membrane resistance.
Nafion® 117
Cell Voltage (V)
The thinner membrane can also
be operated at higher current 0.8
densities due to increased water
diffusion through the thinner
membrane 0.6
0.4
0.2
0.0
0.0
833
across the cell [15]. There is good agreement between the
model simulations and the data, especially at higher current
densities where the experimental error is minimal. As
expected, the sulfuric acid concentration decreases as
membrane thickness decreases due to increased water flux
through the thinner membranes.
To better understand why the amount of water crossing
the membrane increases with current, the model predictions
of the contributions to the total water flux are plotted in
Fig. 6 [13]. At low current densities, the molar flux of
water increases with increasing current density due to an
increase in the amount of H2SO4 produced at the anode.
The presence of H2SO4 reduces the water activity and leads
to an increase in concentration-driven diffusion from the
cathode. As the current density increases, however, this
phenomenon is increasingly offset by the electro-osmotic
drag, which pulls water back across the membrane to the
cathode. A situation then exists in which the flux due to
diffusion competes with electro-osmotic drag. The pres-
sure-driven flux is the same over all current densities.
To see if it was possible to decouple high voltage and
high sulfuric acid concentration, the membrane conduc-
tivity as a function of sulfuric acid concentration was
measured via the four-point measurement technique.
Combining these data with the water uptake data measured
previously [18] gives the conductivity as a function of
water content, which is shown in Fig. 7 [15]. The data are
for solutions of sulfuric acid concentration ranging from
9 M (k = 8.5) to pure water (k = 18). The data reported in
the literature are also shown in Fig. 7 for experiments in
which the membrane water content was controlled by the
water content of the air in contact with the membrane [19,
Nafion® 115
Nafion® 212
0.2 0.4 0.6 0.8 1.0 1.2 1.4
Current Density (A/cm2)
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834 J Appl Electrochem (2016) 46:829–839

Fig. 5 Experimental data 8.0

(symbols) and model predictions
(lines) for the concentration of
H2SO4 leaving the electrolyzer 7.0
Nafion® 212
[13]. The sulfuric acid
Nafion® 115
concentration increases with 6.0

H2SO4 Concentration (M)

current density because a the
rate of H2SO4 production Nafion® 117
increases with current density 5.0
and b the electro-osmotic drag
of water back to the cathode 4.0
increases with current density
(see Fig. 6). The cell
temperature was 80 °C 3.0

2.0

1.0

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Current Density (A/cm2)

Fig. 6 Contributions of 5.00

diffusional flux and electro-
osmotic drag to the net water
flux in Nafion 212 [13]. The 4.00
Diffusion
lines are model predictions. The
diffusion and pressure effects 3.00 Net Water Flux
Water Molar Flux to Anode

work to offset the electro-

osmotic drag effect. The cell
(mol/cm2 s) x 105

temperature was 80 °C 2.00

Differential Pressure
1.00

0.00

-1.00

-2.00
Electro-osmotic Drag

-3.00
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
2
Current Density (A/cm )

20]. The following empirical expression was fit to our data
and is plotted in Fig. 7.
r ¼ 0:0012k2  0:0083k
Coupling Eq. 6 to the equations used to generate the
curves in Fig. 6, the area-specific resistances (ASR) were
predicted [15] and shown in Fig. 8 for three different
membrane thicknesses as a function of current density. The
data in Fig. 8 were obtained by the current interrupt tech-
nique on working electrolyzers at discrete current densities.
The increase in membrane resistance with current density
is nearly linear at low currents, and then increases dra-
matically. For example, the N115 membrane ASR increa-
ses linearly from approximately 0.05 X cm2 at 0.05 A/cm2
ð6Þ
to 0.18 X cm2 at 0.4 A/cm2. At current densities higher
than 0.4 A/cm2, however, the membrane ASR increases
exponentially. This increase in membrane resistance is due
to the increased concentration of sulfuric acid produced at
the anode at high current density. The concentration of
sulfuric acid produced at the anode in a N115 electrolyzer
operated at temperature T = 80 °C at 0.8 A/cm2 is about
8 M, which corresponds to a membrane water content of

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Fig. 7 Membrane conductivity 0.35

as a function of water content
[15]. Our data (filled circle)
from N115 equilibrated with 0.30
sulfuric acid at 80 °C and a line
(Eq. 5) fit through that data are
shown. The other N115 data 0.25

Conductivity (S/cm)
(times) were equilibrated with
humidified air at 80 °C [19].
The N117 data (opened square) 0.20
were equilibrated with
humidified air at 30 °C [20]
0.15

0.10

0.05

0.00
0.0 5.0 10.0 15.0 20.0 25.0
Membrane Water Content (λ, mol H 2O/mol SO3- )

Fig. 8 Membrane area-specific 0.70

resistance (ASR) as a function
of current density [15]. The
points [N212 current interrupt 0.60
(opened circle) and N115
Area-Specific Resistance (Ω•cm2)

current interrupt (filled circle)] Nafion® 117

are experimental data. The cell 0.50
temperature was 80 °C and the
Nafion® 115
lines are model predictions
0.40

0.30

0.20
Nafion® 212
0.10

0.00
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40
2
Current Density (A/cm )

k \ 10. Hence, as the sulfuric acid concentration produced
at the anode increases, the membrane water content
decreases. Because the conductivity of Nafion is strongly
dependent on membrane water content (Fig. 7), a decrease
in the water content leads to a dramatic decrease in the
membrane conductivity. Thus, operating the Nafion-based
electrolyzer at high current densities or with a thick
membrane, where a high concentration of sulfuric acid is
produced at the anode, increases membrane resistance, and
results in high cell potential.
With the complicated membrane resistance accurately
predicted, the total cell potential can be separated into
ohmic and activition overpotentials, as shown in Fig. 9
[15]. The V—iRA curves have been obtained by using the
ASR in Fig. 8. Assume the cathodic overpotential (i.e.,
hydrogen evolution) is negligible, and using the equilib-
rium potential obtained previously [21], anodic overpo-
tential, ga, can be identified. To minimize ga, either a
better catalyst is needed or the cell needs to be run at higher
temperatures. From the breakdown of the total cell

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836 J Appl Electrochem (2016) 46:829–839

Fig. 9 Contributions of the

total cell voltage for N212 [15].
The points (opened circle) are
experimental data and the lines
are model predictions. The total
cell potential was predicted as
the sum of the individual
potential contributions. The cell
temperature was 80 °C

Fig. 10 Total cell potential of

the SO2-depolarized
electrolyzer as a function of
current density and membrane
thickness [15]. The model
predictions (lines) are composed
of the individual contributions
(i.e. Ueq, iRA and ga). The cell
temperature was 80 °C

potential shown in Fig. 8, one can see that the most sig-
nificant contributions to the total cell potential are the
reversible cell potential, Ueq, the ohmic losses, iRA, and the
anodic overpotential, ga. In turn, all these voltage losses
can be added to the equilibrium potential over a range of
operating conditions to predict the total cell potential, as
shown in Fig. 10.
The conclusion from operating the SDE with a perflu-
orinated sulfonic acid membrane like Nafion that requires
water to enhance proton conductivity is that simultaneously
achieving low voltage, high current, and high acid con-
centration is not possible. Therefore, we investigated
membranes whose conductivity is not adversely affected
by the concentration of sulfuric acid produced at the anode.
The anodic overpotential also could be improved by
operating at higher cell temperatures. Hence we turned our
attention to acid-doped polybenzimidazole (PBI) mem-
branes as an alternative to state-of-to Nafion because they

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Fig. 11 Area-specific
resistance (ASR) for N212
(opened circle) [15] and s-PBI
all at 80 °C (opened square)
[16] as a function of sulfuric
acid concentration produced at
the anode. Lines for N117 and
N212 are model predictions [15]
and the one for s-PBI is
connecting the symbols
do not rely on water for their proton conductivity, and
therefore they offer the possibility of operating at high acid
concentrations and/or elevated temperatures to minimize
voltage losses (e.g., kinetic and ohmic resistances) [16].
Early studies for fuel-cell applications relied on doping the
as-cast PBI membranes with concentrated solutions of
phosphoric acid (up to 11 M) to impart conductivity to the
membrane [22, 23]. The phosphoric acid-doped PBI
membranes exhibited good conductivity and mechanical
integrity at temperatures [100 °C, low gas permeability
and low electro-osmotic drag [23]. While this approach
yields sufficiently conductive PBI membranes for high
temperature fuel cell operation, leaching of the phosphoric
acid over time resulted in a gradual loss of conductivity.
More recently, an new casting and doping procedure for
many PBI membranes, termed the PPA process was
developed [24, 25]. This process relies on PPA as the
polycondensation agent, the polymerization solvent, and
the casting solvent. The polymerized PBIs are cast directly
from the PPA solution and membrane formation occurs
when moisture is absorbed from the atmosphere, which
hydrolizes the PPA to phosphoric acid in the membrane.
Sulfonated PBI (s-PBI) membranes were prepared using
the same process starting with sulfonated monomers to
impart an additional acid molality in the polymer structure
to enhance conductivity [17, 26, 27].
Figure 11 shows the ASR of s-PBI compared to that of
Nafion as a function of sulfuric acid concentration [16].
The broken lines for N117 and N212 are the model pre-
dictions shown in Fig. 8 but plotted versus the acid con-
centration generated at the anode. Also shown is the ASR
837
for s-PBI measured at 80 °C. From Fig. 11, it is clear that
the ASR of s-PBI is higher than that of N212 (i.e.,
0.105 X cm2 at about 2.0 M sulfuric acid versus
0.04 X cm2), but is lower than N117 (i.e., 0.14 X cm2);
despite the relative thickness of s-PBI membranes (about
500 lm thick, vs. 175 and 50 lm for N117 and N212,
respectively). In addition, our data show that the ASR of
s-PBI is relatively constant with increasing sulfuric acid
concentrations. Unfortunately the highest acid concentra-
tion measured for s-PBI is approximately 4 M due to
limitations of our cell. However, conductivity data on PBI
shows that it retains its high conductivity at much higher
acid concentrations. Further, its conductivity increases with
temperature and maintains good mechanical integrated up
to 150 °C [24, 25].
These s-PBI membranes were used in our SDE and
current–voltage (i–V) curves are shown in Fig. 12 from 80
to 110 °C operated with a dry cathode and humidified SO2
anode. Also shown for comparison are i–V curves for N117
at 80 °C, operating with a liquid cathode and dry anode.
From the i–V curves, the s-PBI operates at lower cell
voltages than N117 over the full range of current densities
even though the former is almost three times thicker. For
example, at 0.3 A/cm2, the cell voltage of the N117 elec-
trolyzer is 0.776 V, while for s-PBI at the same tempera-
ture (80 °C) and current density, the voltage is 0.698 V, an
improvement of 0.078 V. At 110 °C, where conductivity
and electrode kinetics are improved, the s-PBI cell voltage
at 0.3 A/cm2 is 0.60 V, an improvement of 0.098 V over
the 80 °C operation. The thickness of the s-PBI membrane
is not varied because unlike the Nafion membrane, it does
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838
1.00
0.90
Nafion 117, T = 80 C
0.80
0.70
0.60
Cell Voltage (V)
0.50
0.40
0.30
0.20
0.10
0.00
0.00 0.10 0.20
Current Density (A/cm2)
Fig. 12 Current-voltage (i–V) curves from SO2-depolarized elec-
trolyzer using NafionÒ N117 (filled diamond ) at 80 °C, with a liquid
cathode and dry anode [13]. Also shown are i–V curves for the
not play a role in water management (i.e., the resulting acid
concentration). Therefore, the thickness of the s-PBI
membrane is made as thin as possible while retaining
mechanical integrity. The temperature was limited to
110 °C due to our experimental set up and it is not a
limitation on the membrane. Also, this set up becomes less
stable at higher currents due to poor control of water in the
anode feed. Improvements in our experimental set up are
underway and they should enable us to go to higher tem-
peratures, higher current densities, and higher acid
concentrations.
4 Conclusion
We developed and patented a gas-fed SDE that we tested
over a range of operating conditions (e.g., current, tem-
perature, SO2 flow rate) and design variations (e.g., catalyst
type and loading, membrane type and thickness) for use in
a solar HyS process. A key insight from our work was that
the concentration of sulfuric acid increases with current
density, which dehydrates perfluorinated sulfonic acid
membranes like Nafion and increases cell resistance. This
creates a challenge when using an SDE with commercial
membranes (e.g., Nafion). That is, concentrated sulfuric
acid is necessary to achieve the desired overall process
123
J Appl Electrochem (2016) 46:829–839
s-PBI, T = 80 C
s-PBI, T = 90 C
s-PBI, T = 100 C
s-PBI, T = 110 C
0.30 0.40 0.50 0.60
electrolyzer using s-PBI membrane from 80 to 110 °C (closed
square), with a dry cathode and humidified anode. The lines connect
the symbols
efficiency, but high acid concentrations dehydrate the
membrane and reduces the efficiency of the electrolysis
step. Another major disadvantage of a membrane like
Nafion is that it loses its mechanical integrity above
100 °C. Using sulfonated acid-doped polybenzimidazole
(s-PBI) membranes represent an alternative material
because they do not rely on water for their proton con-
ductivity, and therefore they offer the possibility of oper-
ating at high acid concentrations and/or elevated
temperatures to minimize voltage losses (e.g., kinetic and
ohmic resistances). Work continues on using s-PBI at
elevated temperature (130–150 °C) and pressure (2–10
atm) to achieve the design goal of simultaneously achiev-
ing low voltage, high current, and high acid concentrations
for use in a solar HyS process.
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