210 Energy & Fuels 2003, 17, 210-215

Instability of Sulfate and Selenate Solid Acids in Fuel

Cell Environments
Ryan B. Merle, Calum R. I. Chisholm, Dane A. Boysen, and Sossina M. Haile*
California Institute of Technology, Materials Science, Mail Code 138-78,
Pasadena, California 91125
Received May 28, 2002

The chemical and thermal stability of several solid acid compounds under fuel cell operating
conditions has been investigated, primarily by thermogravimetric methods. Thermal decomposi-
tion of CsHSO4, a material which has shown promise as an alternative electrolyte for proton
exchange membrane (PEM) fuel cells, initiates at ∼175°C under inert conditions. The overall
decomposition process can be expressed as 2CsHSO4 f Cs2SO4 + H2O + SO3 with Cs2S2O7
appearing as an intermediate byproduct at slow heating rates. Under reducing conditions,
chemical decomposition can occur via reaction with hydrogen according to 2CsHSO4 + 4H2 f
Cs2SO4 + 4H2O + H2S. In the absence of fuel cell catalysts, this reduction reaction is slow;
however, materials such as Pt, Pd, and WC are highly effective in catalyzing the reduction of
sulfur and the generation of H2S. In the case of M3H(XO4)2 compounds, where M ) Cs, NH4, or
Rb and X ) S or Se, a similar reduction reaction occurs: 2M3H(XO4)2 + 4H2 f 3M2XO4 + 4H2O
+ H2X. In an operational fuel cell based on CsHSO4, performance degraded with time, presumably
as a result of H2S poisoning of the anode catalyst. The performance loss was recoverable by
exposure of the fuel cell to air at 160 °C.

Introduction form of steam, which is harmless to the otherwise water-

soluble electrolyte.
It has recently been demonstrated that CsHSO4, a
While numerous advantageous features of solid acid
prototypical “superprotonic” solid acid, can be utilized
electrolytes have been noted, it was also reported that
as a fuel cell electrolyte, despite its solubility in water
fuel cell degradation occurred during operation.1 In that
and unusual mechanical properties.1 Solid acids can be
first work, the focus was on the possible negative impact
regarded as chemical intermediates between normal
of steam in the environment. Accordingly, fuel cell
acids, such as H2SO4, and normal salts, such as Cs2SO4.
performance was measured both prior to and after 18
Those with superprotonic properties undergo a struc-
h of exposure of the cell to humidified air, but not after
tural transformation at slightly elevated temperatures
prolonged exposure to standard fuel cell gases (humidi-
to a highly disordered state. Accompanying this trans-
fied H2 at the anode and humidified O2 at the cathode).
formation is an increase in protonic conductivity by
Degradation under these conditions was slight, but
several orders of magnitude.2-9 Such materials offer
measurable. It was suggested that the cause was the
several advantages over polymeric electrolytes in fuel
reduction of sulfur in the solid acid at the anode to form
cell applications such as operability at slightly elevated
dihydrogen sulfide, rather than detrimental interactions
temperatures, no humidification requirements, and,
with water. In the present work, we examine the
given their solid nature, presumably impermeability to
thermal stability of CsHSO4 and explore the possibility
methanol. The key to successful implementation of
that reduction of superprotonic solid acid sulfates and
superprotonic solid acids in a fuel cell, as has been
selenates occurs under hydrogen gas and can cause
demonstrated for CsHSO4, is simply operation above
degradation in fuel cell performance.
100 °C. At these temperatures, H2O is present in the
* Corresponding author. Experimental Section
(1) Haile, S. M.; Boysen, D. A.; Chisholm, C. R. I.; Merle, R. B.
Nature 2001, 410, 910-913. The chemical stability of several known superprotonic solid
(2) Baranov, A. I.; Shuvalov, L. A.; Shchagina, N. M. JETP Lett. acid compounds was examined. These were CsHSO4, (NH4)3H-
1982, 36, 459-462.
(3) Moskvich, Yu. N.; Sukhovskii, A. A.; Rozanov, O. V. Sov. Phys. (SO4)2, (NH4)3H(SeO4)2, Rb3H(SeO4)2, and the mixed sulfate
Solid State 1984, 26 (1), 21-25. phosphate, Cs2(HSO4)(H2PO4). In addition, the salt Cs2SO4 was
(4) Pawlowski, A.; Pawlaczyk, Cz.; Hilczer, B. Solid State Ionics also studied for comparison. The solid acid sulfates were
1990, 44, 17-19. synthesized in-house according to standard recipes, see refs 6
(5) Ramasastry, C.; Ramaiah, A. S. J. Mater. Sci. Lett. 1981, 16,
2011-2016. and 10, for example, whereas the solid acid selenates were
(6) Gesi, K. Phys. Status Solidi A 1976, 33, 479-482. provided by the Russian Institute of Crystallography. The
(7) Chisholm, C. R. I.; Haile, S. M. Solid State Ionics 2000, 136- mixed sulfate phosphate was prepared from a solution of Cs2-
137, 229-241. CO3, H2SO4, and H3PO4, in which the Cs:S:P ratio was fixed
(8) Haile, S. M.; Calkins, P. M.; Boysen, D. Solid State Ionics 1997,
97, 145-151.
(9) Haile, S. M.; Lentz, G.; Kreuer, K.-D.; Maier, J. Solid State Ionics (10) Boysen, D. A.; Chisholm, C. R. I.; Haile, S. M.; Narayanan, S.
1995, 77, 128-134. R. J. Electrochem. Soc. 2000, 147, 3610-3613.

10.1021/ef0201174 CCC: $25.00 © 2003 American Chemical Society

Published on Web 11/28/2002
Sulfate and Selenate Solid Acids in Fuel Cell Environments Energy & Fuels, Vol. 17, No. 1, 2003 211

Table 1. Physical Characteristics of Catalyst Materials

surface
catalyst source particle size area, m2/g
Pt black Alfa Aesar N/A 27
RuO2 [Ru] Alfa Aesar <1 µm 45-65
Pd black Aldrich N/A 40
Au Aldrich 100 nma N/A
Ir black Alfa Aesar N/A 30-60
Ni/Al “Raney Ni” Alfa Aesar 200 mesh (<74 µm) N/A
WC Alfa Aesar <1 µm 1.2-1.4
a With agglomerates of ∼1-2 µm.

at 2:1:1. The solution was heated to 50 °C and continuously

stirred until a precipitate formed, which was then filtered and
rinsed with methanol. The sulfate salt was obtained com-
mercially and used as-received (Alfa Aesar, 99.9%).
To establish the thermal dehydration/decomposition tem-
perature of CsHSO4, this material was examined by thermal
gravimetric analysis (TGA) under flowing argon (40 cm3/min)
using a Netzsch STA 449. Samples were used in the form of
lightly crushed single crystals so as to minimize effects due to
surface water. Heating rates were varied from 0.5 to 40 °C/
min, and data collected up to 400 ( 2 °C. The sample mass
was kept constant at 16 mg. The impact of Pt catalyst material
on the dehydration process was examined by performing TGA
analysis under similar conditions, but for CsHSO4 powders
containing 35 wt % platinum powder, the properties of which
are detailed in Table 1.
To establish chemical stability under reducing conditions,
TGA measurements were carried out under flowing H2. The
majority of these experiments were performed isothermally
at 160 ( 10 °C (the temperature at which the earlier fuel cell
results were obtained 1) using a Perkin-Elmer TGA 7. The
hydrogen flow rate was 20 cm3/min. For temperature-depend-
ent measurements (1 °C/min), a Netzsch STA 449 was utilized
and the gas was 4% H2 in argon (40 cm3/min). The evolved
gases were analyzed using a Balzers Thermostar AMU200
quadrupole mass spectrometer (MS). Prior to exposure to H2,
powders were equilibrated under flowing nitrogen to eliminate
weight changes due to loss of surface water. Sample quantities
were on the order of 20-30 mg. Cesium hydrogen sulfate was
examined both as-synthesized and mixed with a variety of
typical fuel cell catalyst materials (35 wt %). Weight changes
for all other compounds were measured (only) in the presence
of Pt, again, in mixtures containing 35 wt % catalyst. Ad-
ditional catalysts examined in the case of CsHSO4 were Ru,
Pd, Au, Ir, Ni/Al, and WC. The characteristics of the catalyst
powders are presented in Table 1. For experiments with Ru,
the metallic powder was obtained by reduction of RuO2 under
flowing H2 165 °C for 13 h. In some cases, the reaction product
(of the solid acid with H2) was examined by X-ray powder
diffraction. For this, a Scintag Pad-V diffractometer, equipped
with a sealed tube Cu KR X-ray source, was utilized.
Performance of CsHSO4-based fuel cells over a prolonged
period of time under typical operating conditions has also been
measured. A single cell membrane electrode assembly (MEA)
was fabricated as reported earlier.1 Briefly, a layer of the solid
acid was sandwiched between two electrocatalysis layers
comprised of CsHSO4, Pt black, carbon black, and the volatile
organic naphthalene, in a mass ratio of 6:10:1:1 (approximate
volume ratio of 4:1:2:2). These layers were, in turn, placed
between two sheets of porous graphite current collectors. The
entire assembly was uniaxially pressed at 490 MPa, to yield
a dense electrolyte membrane (1.3 mm in thickness) with good
mechanical contact to the electrocatalyst layers. The MEA was
placed in a standard graphite test station and fuel cell
polarization curves obtained at 154 ( 2 °C. Upon heating to
the measurement temperature, the organic phase in the
electrode evaporated, leaving behind a porous electrode struc-
ture. The Pt loading was ∼15 mg/cm2.
Figure 1. (a) Weight change in CsHSO4 as a function of
temperature at heating rates as indicated and under flowing
argon (40 cm3/min); and (b) weight change in CsHSO4, with
and without 35 wt % Pt catalyst, as a function of temperature
at at 1 °C/min and under flowing argon (40 cm3/min). Note
the difference in scales. Inset in (a) shows the temperature at
which 0.05% of weight is lost as a function of heating rate. A
total weight loss of 3.92% corresponds to the loss of 1/2 mole of
H2O and the formation of Cs2S2O7.
Results and Discussion
The thermal behavior of CsHSO4 under inert atmo-
sphere is shown in Figure 1. In Figure 1a, the thermo-
gravimetric data for the material alone are presented,
whereas in Figure 1b the weight loss curve at 1 °C/min
for samples with and without Pt catalyst are presented.
In addition, the inset in Figure 1a shows the tempera-
ture at which 0.05% of the initial weight has been lost
as a function of (heating rate)1/2. Plotting the data in
this manner allows one to extrapolate to zero heating
rate and determine at which temperature this magni-
tude of weight loss will be encountered even under
isothermal conditions.11 The results here demonstrate
that CsHSO4 is generally stable against dehydration to
∼175 °C. The erratic behavior of the data in Figure 1a,
however, indicates that the initial dehydration steps are
rather sample dependent. Moreover, for ground powder
samples, a slight, but measurable, weight loss under
inert atmosphere was occasionally observed under
isothermal conditions for temperatures as low as 145
°C. The diffraction pattern of such samples was identical
to that of standard CsHSO4. Thus, this small weight
change is likely attributable to loss of H2O from the
surface region of CsHSO4 particles. In the case of the
slowest heating rate, 0.5 °C/min, a plateau in the TGA
(11) Gray, A. P. Analytical Calorimetry; Plenum Press: New York,
1968; pp 209-218.
212 Energy & Fuels, Vol. 17, No. 1, 2003 Merle et al.

Figure 2. Weight loss isotherm of CsHSO4 under flowing H2

(20 cm3/min) and at a temperature of 160 °C with and without
35 wt % Pt catalyst. To allow for direct comparison, the weight
of Pt has been accounted for in the curve for CsHSO4 + Pt.

curve at ∼96 wt % corresponds to the loss of 1/2 mole of

H2O (per mole CsHSO4), and is consistent with the
formation of Cs2S2O7. Examination of the data in Figure
1b clearly reveals that the Pt in the system strongly
influences the dehydration process. The onset of CsH-
SO4 dehydration is significantly decreased while the
rate at which dehydration occurs is greatly increased
in the presence of the catalyst material.
In Figure 2 the weight loss isotherms (T ) 160 °C) of
CsHSO4, both alone and in the presence of platinum
catalyst material, under reducing atmospheres are
presented. In the absence of any catalyst material, the
solid acid exhibits a weight loss of 0.03% over a 10 h
period during the isothermal hold. In the presence of
Pt, however, the sample loses 4.4 wt %, or 6.8 wt % of
solid acid. These results demonstrate quite clearly that,
whatever the reaction between H2 and CsHSO4, it is
highly catalyzed by Pt.
The temperature-dependent measurement, Figure 3,
reveals that weight loss is steady but slight at temper-
atures between 120 and 140 °C (<0.01%/°C), and then
increases rapidly beyond ∼140 °C to a much more severe
rate of 0.07%/°C. The differential scanning calorimetry
(DSC) curve exhibits an exothermic peak at this tem-
perature, which closely corresponds to the superprotonic Figure 3. Combined thermal and evolved gas analysis of
transition, reported to occur at 141 °C.2 The rapid CsHSO4 mixed with 35 wt % Pt catalyst, under flowing 4%
weight loss beyond the transition suggest that the H2/96% Ar (40 cm3/min) and a heating rate of 1 °C/min; (a)
kinetics of the reaction are correlated to the structural thermal gravimetric and differential scanning calorimetry
state of the solid acid, perhaps being enhanced by the traces; (b) mass spectrometry signals for H2O and H2S; and
(c) ratio of the intensities of the mass spectra signals for these
dynamics of the SO4 group reorientation in the high- two species.
temperature, disordered phase. At higher temperatures,
an anomaly is evident in the DSC, TGA, and MS data as a consequence of the reaction of the hydrogen with
at ∼198 °C. The precise chemistry associated with this residual oxygen in the experimental apparatus. Defining
feature is unclear, but it is again apparent that the the background signal as the value at 120 °C, the ratio
decomposition of CsHSO4 under reducing conditions is of the water to hydrogen sulfide signals, after back-
much more severe than under inert conditions and in ground subtraction, is as high as ∼26:1 at the transition
the absence of a catalyst material. and decreases gradually with increasing temperature,
The mass spectrometry results show a dramatic Figure 3b. The observed ratio is significantly greater
increase in both the H2S and H2O content of the evolved than the 4:1 value expected for reaction 1, and only some
gas at precisely the position of the first DSC peak. This of this discrepancy can be explained by differences in
result is in general agreement with the reaction pro- sensitivity of the MS detector to these species. A likely
posed earlier1: explanation is that, in addition to catalyzing the reduc-
tion reaction, Pt also catalyzes the simple dehydration
2CsHSO4 + 4H2 f Cs2SO4 + 4H2O + H2S (1) reaction:
2CsHSO4 f Cs2SO4 + H2O + SO3 (2)
Quantitative analysis of the H2O and H2S contents as
determined from the mass spectrometry experiments is as suggested by the results in Figure 1b. It should be
difficult because the background H2O signal was high noted that at temperatures above ∼140 °C, SO and SO2
Sulfate and Selenate Solid Acids in Fuel Cell Environments Energy & Fuels, Vol. 17, No. 1, 2003 213

Figure 4. X-ray powder diffraction pattern of the reaction byproduct of H2 with CsHSO4 (in the presence of Pt catalyst).

(but no SO3) were also detected, as might be expected

from an overall decomposition reaction that includes
both reactions 1 and 2.
While these mass spectrometry experiments were
repeated several times to ensure reproducibility, it
should be noted that, on occasion, the mass spectrom-
etry data showed a sharp peak rather than a simple
increase in the H2O and H2S signals at 140 °C and that
the H2O:H2S signal ratio was extremely high (∼200:1).
Moreover, beyond 140 °C, the intensity of the H2S signal
gradually increased, whereas that of the H2O signal
gradually decreased, and, simultaneously, the DSC
signal was measurably endothermic at these high
temperatures. These observations are consistent with
a reduction process that generates H2S that is heavily
adsorbed onto the surface of the Pt particles, and then Figure 5. Weight loss isotherms of solid acid and salt
compounds (as indicated) under flowing hydrogen (20 cm3/min)
gradually desorbs with increasing temperature. In such in the presence of Pt catalyst at 160 °C.
cases, the SO and SO2 signals were much higher than
in the “standard” case. It could not be established to reaction 2. However, at this low reaction temperature,
whether the differences in these experimental results dehydration alone, even in the presence of the catalyst,
were due to residual oxygen in the system, or true Figure 1b, would not be expected to proceed to comple-
sample-to-sample variations. tion.
The diffraction pattern of the byproduct of the reac- The reduction reaction 1 can be expressed generally
tion between hydrogen and cesium hydrogen sulfate is for MHXO4 and M3H(XO4)2 compounds (where M )
shown in Figure 4. The sample was examined after ∼15 alkali metal or ammonium ion and X ) S or Se):
h of reaction at 160 °C in the presence of Pt catalyst
(again, 35 wt %). Prior to exposure to H2, the diffraction 2MHXO4 + 4H2 f M2XO4 + 4H2O + H2X (3a)
pattern of the as-synthesized material corresponded
exactly to that of CsHSO4 phase III (not shown), 2M3H(XO4)2 + 4H2 f 3M2XO4 + 4H2O + H2X (3b)
whereas after reduction, Figure 4, the diffraction peaks
correspond to those of Pt and Cs2SO4. This result is in A comparison of the stabilities of various sulfate and
agreement with the reaction 1. Complete thermal selenate compounds is presented in Figure 5 (atm )
decomposition of CsHSO4 under inert atmosphere would flowing H2, T ) 160 °C, catalyst ) 35 wt % Pt). Each of
also yield Cs2SO4 as the final reaction product according the acid compounds undergoes a superprotonic transi-
214 Energy & Fuels, Vol. 17, No. 1, 2003
Figure 6. Weight loss isotherms of CsHSO4 under flowing
hydrogen (20 cm3/min) in the presence of various (potential)
fuel cell catalysts (as indicated) at 160 °C.
tion at a temperature below the measurement temper-
ature. It is apparent that the simple salt, Cs2SO4, is
stable under reducing conditions, despite the 6+ oxida-
tion state of sulfur and thus it is likely the final reaction
product. Disappointingly, from an applications perspec-
tive, none of the sulfate or selenate solid acids is stable
under these conditions. The rate of weight loss follows
the sequence (NH4)3H(SO4)2 > CsHSO4 > Rb3H(SeO4)2
> (NH4)3H(SeO4)2 > Cs2(HSO4)(H2PO4). Given the
fractional weight change per formula unit reacted, eq
3, one would expect weight loss to occur more quickly
for MHXO4 than M3H(XO4)2 compounds. The rapid
degradation of (NH4)3H(SO4)2 reveals that this material
is particularly unsuitable for fuel cell applications.
Indeed, attempts to demonstrate fuel cell performance
using (NH4)3H(SO4)2 were uniformly unsuccessful.12 The
lower reactivity of Cs2(HSO4)(H2PO4) may be a result
of the lesser tendency of phosphorus to form H3P than
sulfur to form H2S.
The effect of alternative catalyst materials on the
stability of CsHSO4 is evident in Figure 6. Here again,
the results are undesirable for fuel cell applications.
Even relatively inactive catalysts such as Au lead to a
significant increase of the rate of reaction 1 compared
to its rate in the absence of catalysts. In general, the
reaction rate increases according to the sequence Au <
Ni/Al < RuO2 < Pt < WC < Pd < Ir. Given the wide
variation in specific surface areas of the catalyst materi-
als employed, Table 1, it is not possible to establish
whether this sequence is a direct consequence of catalyst
chemistry. Nevertheless, it is surprising that WC, with
a relatively low specific surface area, serves as a very
effective catalyst for sulfur reduction. There is no reason
to expect these catalyst materials would have a lesser
impact on alternative superprotonic solid acids of sul-
fates or selenates that might be considered for fuel cell
applications.
The performance of a typical CsHSO4-based single-
cell fuel cell is shown in Figure 7. Upon initial examina-
tion, the peak power was 12 mW/cm2, and the current
density at short circuit 45 mA/cm2. Damage to the fuel
cell under operating conditions was rapid. After 5 h of
continuous operation, the performance fell to a peak
power of 6 mW/cm2, and a current density at short
(12) Boysen, D. A.; Merle, R. B.; Chisholm, C. R. I.; Haile, S. M.
Unpublished results.
Merle et al.
Figure 7. (a) Potential and (b) power density for a CsHSO4-
based single cell fuel cell. Initial curves (circles) obtained
immediately upon reaching the measurement temperature of
154 °C, post-degradation curves (triangles) obtained after 5 h
of operation, and post-recovery curves (squares) obtained after
an additional 3 h of exposure to stagnant air.
circuit of 17 mA/cm2. After flushing both the anode and
cathode with compressed air and then holding the
system in stagnant air for 5 h, the fuel cell performance
recovered to a level close to that measured initially.
Peak power was 10 mW/cm2 and current density at
short circuit 41 mA/cm2. These results indicate that the
loss in performance cannot be associated with degrada-
tion of the membrane directly, which would be irrevers-
ible, but some other reversible process. Adsorption of
small quantities of H2S onto the surface of the Pt
catalyst, as generated according to reaction 1, and its
desorption upon exposure of the anode to air, is consis-
tent with the observed fuel cell behavior, although other
possibilities cannot be unequivocally ruled out. It has
been established, in the case of phosphoric acid fuel
cells, that as little as 50 ppm H2S in the incoming fuel
stream significantly degrades anode performance, and
that this degradation is similarly reversible.13
Concluding Remarks
In the experiments carried out here the catalyst
content (35 wt %) is much greater than is used in a
typical fuel cell. Thus, the loss of electrolyte in a solid
(13) Chin, D.-T.; Howard, P. D. J. Electrochem. Soc. 1986, 133,
2447-2450.
Sulfate and Selenate Solid Acids in Fuel Cell Environments
acid based fuel cell can be expected to be significantly
less than shown in Figures 4 and 5. Accordingly, the
decrease in performance of CsHSO4-based fuel cells with
time is not a direct consequence of electrolyte damage,
but rather, a consequence of the generation of H2S
which acts as a highly effective catalyst poison. Thermal
desorption of hydrogen disulfide from the platinum
catalyst surface is likely responsible for the recovery of
fuel cell performance after exposure of the electrodes
to (humid) air. Identification of a fuel cell anode catalyst
that is not susceptible to H2S poisoning thus emerges
as one strategy for enhancing the lifetime of solid acid
sulfate or selenate fuel cells. An alternative strategy is
to increase the water partial pressure at the anode so
as to drive reactions 2 and 3 to the left. Indeed, the high
water concentrations needed to operate direct methanol
fuel cells14 may suffice to prevent H2S formation. In such
a case, however, the anode liquid (methanol plus water)
must be fed to the fuel cell in vapor form so as to prevent
(14) Wasmus, S.; Kuver, A. J. Electroanal. Chem. 1999, 461 (1-2),
14-31.
Energy & Fuels, Vol. 17, No. 1, 2003 215
dissolution of the electrolyte. The most ideal solution
to the stability problem is to develop completely alter-
native superprotonic solid acids based on different
oxyanion (XO4n-) groups, in particular PO43- groups.
Efforts along these lines are underway, however, it must
be noted that the high-temperature behavior of CsH2-
PO4, the most likely candidate, simply based on its
chemical and structural similarity to CsHSO4, is not
well-understood.15 Thus, a broad-based exploratory
synthetic effort may be necessary to develop solid acids
that combine high conductivity with good stability.
Acknowledgment. Dr. Tregubchenko kindly pro-
vided the selenate crystals examined here. This work
was supported by the California Energy Commission
through the PIER grant program, by the California
Institute of Technology through the Grubstake program
and by the Office of Naval Research.
EF0201174
(15) Lee, K.-S. J. Phys. Chem. Solids 1996, 57 (3), 333-342.