J Therm Anal Calorim
DOI 10.1007/s10973-016-5474-y
On the low- to high proton-conducting transformation
of a CsHSO4CsH2PO4 solid solution and its parents
Physical or chemical nature?
E. Ortiz1 I. Pineres1 C. Leon2
Received: 21 January 2016 / Accepted: 9 April 2016
 Akademiai Kiado, Budapest, Hungary 2016
Abstract The first-order transition from low to superpro-
tonic conducting phase (at 119 \ Tsp \ 145 C) of a solid
solution of CsHSO4 and CsH2PO4 [Cs3(HSO4)2(H2PO4)]
was carefully examined by using modulated and conven-
tional differential scanning calorimetric, simultaneous
thermogravimetric and differential scanning calorimetric,
simultaneous thermogravimetric and mass spectroscopy,
impedance spectroscopy, and temperature evolution of
X-ray diffraction and scanning electron microscopy. Our
results show evidence that at this temperature, the
endothermic anomaly associated with the physical trans-
formation is, instead, the response of a chemical-surface
thermal decomposition. One of its products is water: part of
it is evaporated and part is strongly bonded to the other
decomposition products. Given that these are of polymeric
nature, they constitute a host matrix that contains liquid
water regions. Therefore, as part of liquid water dissolves a
superficial portion of salt (providing protons), this system
behaves in similar manner to a polymer electrolyte mem-
brane (located over the salt surface) where the proton
transport mechanism might include the vehicle type, using
H3O? as a charge carrier. A discussion that favors the
non-existence of the superprotonic conducting phase of
CsH2PO4 is also presented.
& E. Ortiz
everortiz@mail.uniatlantico.edu.co
1
GFM, Department of Physics, Faculty of Basic Sciences,
Universidad del Atlantico, Km 7 Antigua va Puerto
Colombia, Barranquilla, Colombia
2 long time was required for the voltage to equilibrate
GFMC, Department of Applied Physics III, Faculty of
Physics, Universidad Complutense de Madrid, 28040 Madrid,
Spain
Keywords KDP-type crystals  Superprotonic phase
transition  Decomposition reactions  Thermal analysis
Introduction
Polymer electrolyte membrane fuel cells constitute one of
the most promissory clean energy technological strategies
for transportation, mobile, and stationary applications [1].
Nevertheless, their efficiency is reduced because the
proton-conducting membrane is permeable to hydrogen
and due to the low operation temperature below 100 C,
which is imposed by the requirement of liquid water for
proton conduction [2]. This is because this system does
not correspond to a truly solid phase; it contains liquid-
like regions between the polymer molecules and, more-
over, does not conduct protons exclusively [3]. In con-
trast, a truly solid compound, such as acid salts CsHSO4
(CHS) and CsH2PO4 (CDP), has been proposed by
Hailes research group [2, 4] as an electrolyte for fuel
cells. When these salts are heated through 140 and
230 C, respectively, an anomalous phase transition from
low- to high proton-conducting phase takes place [5, 6],
with conductivity values in the 10-2 S cm-1 order of
magnitude. This offers three fuel cell technical advan-
tages: its electrolyte is a solid material, it uses an anhy-
drous proton transport mechanism, and has intermediate
operating temperature range (200300 C) [7]. However,
like polymer electrolyte membrane fuel cells, they are
also not free of operating problems: from the electromo-
tive force measurements generated across a CHS sample
placed in an oxygen concentration cell at 145 C, a very
(about 5 h) [8]; furthermore, hydration of the feeding
gases by partial water pressure must be used to avoid
123

possible decomposition, e.g., a CDP fuel cell requires a
value of 0.4 atm [7].
Although the existence of the superprotonic conducting
phase of CDP above 230 C is now widely accepted, it
was not always so. For example, Haile et al. [9] proposed
mixing, in different proportions, the superprotonic CHS
conductor with the non-superprotonic CDP to examine
whether the phosphorous atom destroys its superprotonic
conducting state. While pursuing this goal, the new
superprotonic conductor, Cs3(HSO4)2(H2PO4), was dis-
covered. This system, with a superprotonic conducting
phase transition temperature, Tsp, of 119 C [9] is an
important aspect of the present research work. The
assumption that CDP was not a superprotonic conductor
[9] was supported by the fact that while the sole work by
Baranov et al. [10] suggests the presence of such a
transition at 230 C into a cubic phase, numerous other
studies reveal the onset of decomposition at this tem-
perature [1113]. Nevertheless, since the discovery of this
researcher, many solid acid superprotonic conductors
have been reported; probably, the most recent is
Cs2(SO4)0.9(HAsO4)0.1Te(OH)6 [14].
Even though much research supports the existence of a
superprotonic phase transition in CDP [7, 1517], it is still a
controversial issue [7, 16, 17]; if when CDP is heated above
230 C, it presents a physical or chemical transformation. In
other words, it is the high conductivity observed above
230 C due to an intrinsically bulk solid physical protonic
transport mechanism, or is it due to a (surface) chemical
decomposition? CHS is not free of the same debate [18].
Some authors believe that a physical transformation
takes place when CDP (CHS) is heated through 230 C
(141 C), consisting of the monoclinic structural phase
transition to the cubic (tetragonal) phase. This transition to
a higher structural symmetry would largely enhance proton
transport, governed by the Grotthuss mechanism, which
includes two stages: proton transfer and reorientation of the
tetrahedron [1922]. The first consists of a proton dis-
placement along the hydrogen bond closer to one of the
PO4 (SO4) groups participating in the bond; the second
corresponds to a breaking of the longest half of the
hydrogen bond followed by a reorientation of the HPO4
(HSO4) group to a new position. The reorientation con-
tinues until a second PO4 (SO4) group is found in an
appropriate orientation to form a new hydrogen bond.
Then, the process is repeated, and, as a result, long-range
proton transport through the lattice is possible. On the other
hand, following the hypothesis by Lee [23], other authors
believe that a chemical transformation occurs when CDP is
heated above 230 C, giving rise to partial thermal
decomposition (polymerization) at reaction sites on the
surface of the crystal, according to the following chemical
reaction:
123
E. Ortiz et al.
nCsH2 PO4 s ! Csn H2 Pn O3n1 s n  1H2 Ov 1
Here, n is the number of molecules participating in thermal
decomposition; s or v in parentheses denote that the cor-
responding compound is in the solid or vapor state,
respectively. This statement is partially supported on Thi-
los [24] earlier review on polymerization of phosphates
and arsenates. According to Taninouchi et al. [25], the
stable phase just above the dehydration temperature is the
full dehydrated product of solid CsPO3, but partially
dehydrated products, such as solid Cs2H2P2O7 and an
unknown phase, appeared as transient phases in the course
to complete dehydration. Park [26] described the mass loss
at the 230245 C temperature range as difficult to explain,
given that polymerization processes depend on temperature
and on an unstable intermediate product. However, the
author concludes that around 230 C, an onset of thermal
decomposition of CDP in CsnH2PnO3n?1 takes place at the
crystal surface, but probably with n  1, [(CsPO3)n]. A
similar interpretation was proposed for CHS by Ortiz et al.
[18], who found that when it is heated through 141 C the
chemical reaction
2CsHSO4 ! Cs2 S2 O7 H2 O 2
takes place at the crystal surface. A parallel explanation for
the case of CsHSeO4 has also been presented by the same
research group [27].
The aim of the present work was to study a CHS and
CDP solid solution [Cs3(HSO4)2(H2PO4)] to examine
whether it could be object of the same controversial subject
of its parents (CDP and CHS); if this is so, we hope to
contribute to shed light on the dilemma regarding the
nature (physical or chemical) of the transformation of all
these salts.
Experimental
Cesium carbonate (Cs2CO3, 99.9 %) and sulfuric acid
(H2SO4, 9597 %) were obtained from Sigma-Aldrich Co.,
USA, and phosphoric acid (H3PO4, 85 %) from Merck,
Germany. Cs3(HSO4)2(H2PO4) crystals and crystalline
powder samples were grown by slow evaporation of the
aqueous solution containing stoichiometric amounts of
Cs2CO3, H2SO4, and H3PO4. The sample was vacuum-
dried at room temperature and transferred into a test tube
that was placed into a hermetic glass bottle with moisture
indicator silica. After keeping the samples during more
than 2 months in this condition, they were pre-treated
during 1 hour at 65 C (under 99.999 pure helium gas),
before starting any experiment.
Conventional (DSC) and modulated differential scan-
ning calorimetric measurements (MDSC) were conducted
On the low- to high proton-conducting transformation of a CsHSO4CsH2PO4 solid solution and its
on this salt with a TA Instruments 2920 analyzer. The DSC
curves were collected from several samples by using dif-
ferent heating rates. Similarly, thermogravimetric analysis
(TG), on three samples, was performed with a TA Instru-
ments 2050 analyzer at different heating rates. For one of
these TG experiments (using a heating rate of 2 C min-1),
a Balzers Thermostar mass spectrometer was coupled to
the TG equipment to execute a simultaneous TGMS
experiment. Also, simultaneous thermogravimetric and
differential scanning calorimetric (TGDSC) measure-
ments were obtained with a TA Instruments SDT 2960 by
using a heating rate of 1 C min-1. The MDSC thermo-
grams were made on sealed (using a Loctite Superflex Red
High-Temp silicone adhesive sealant) and unsealed crys-
tals with an average heating rate, amplitude, and modula-
tion period of 0.2 C min-1, 0.2 C, and 60 s, respectively.
Regarding the DSC, MDSC, and SDT experiments, the
equipment was carefully calibrated for each heating rate,
including temperature, enthalpy, and onset slope (thermal
resistance). Pure helium gas (99.999 %) with a
60 mL min-1 flux was used for all these experiments.
Conducting silver paint on both faces of a flat crystal was
used as electrodes for the complex impedance measurements,
which were performed by means of a Solartron 1260A ana-
lyzer, using an average heating rate of 0.2 C min-1. The
dc conductivity was calculated from the frequency depen-
dence of the real part of the complex conductivity following a
well-established procedure [28, 29].
The temperature evolution of X-ray powder diffraction
patterns at different isotherms (from 25 to 170 C) was
taken by using a Bruker-AXS D8 Advance X-ray diffrac-
tometer equipped with an Anton Paar HTK-1200 high-
temperature furnace. These data were obtained by using
CuKa1 radiation (k = 1.5406 A) with a 2h scan step of
0.02 every 5 s. A scanning electron microscope (FEI
XL30 ESEM) was used to obtain surface sample images at
different temperatures (from 25 to 143 C) under 5-mbar
pressure.
Results and discussion
A DSC heatingcooling cycle on a Cs3(HSO4)2(H2PO4)
crystal, using 1 C min-1 as heating rate, is plotted in
Fig. 1. The upper temperature limit was imposed by the
reported value of 150 C, where the salt starts to decom-
pose [30].
On heating, an endothermic anomaly with 127.5 and
135.2 C, as respective onset and peak temperature values,
was registered. The corresponding enthalpy change value,
DH, was 44.0 J g-1. Comparing this result with that by
Suzuki and Hayashi [31], who reported an endothermic
DSC peak at 135 C, and that by Haile et al. [9] who
71.4 C
1
106.6 C
H = 26.4 J g1 127.5 C
H = 44.0 J g1
Heat flow/mW
1
103.1 C
Endothermic
2
3 135.2 C
10 30 50 70 90 110 130 150
Temperature/C
Fig. 1 DSC curve for a Cs3(HSO4)2(H2PO4) crystal under a 5150
5 C heatingcooling cycle. The heating rate was fixed at 1 C min-1
measured an DH of 40 J g-1, this event should be associ-
ated with the first-order transition from low to superpro-
tonic conducting phase, discovered by Haile et al. [9, 30].
This transition is a consequence of a simultaneous struc-
tural phase transition from a monoclinic to a cubic (CsCl
type) symmetry [9]. The latter is isostructural with the
superprotonic conducting phase of CDP [31, 32]. Checking
the DSC baseline, the small thermal response at the peak
temperature of 103.1 C could be interpreted as part of the
earlier thermal behavior of the endotherm. A similar
observation was reported, but at 110 C [30]. On cooling,
the curve shows a flat, broad exothermal peak with onset
and peak temperature values of 106.6 and 71.4 C,
respectively. This sample thermal response could be related
to the observation that the cubic superprotonic conducting
phase remains down to 87 C on the cooling cycle [33].
However, it should be noted that the DH value of the
cooling exothermic peak does not correspond to that of the
heating endothermic one; it is about 40 % less. So that,
according to this measurement, the reported first-order
phase transition is not of the reversible type. Additionally,
from literature data, a wide dispersion of the Tsp value (into
a 26 C temperature range) is found: 119 [9], 131 [34], 135
[31], 143 [9], and 145 C [30]. This behavior is not
exclusive to this CHSCDP solid solution salt. Although in
lesser proportion, it is also present in its parents; while the
Tsp value on CDP spreads from 126 [35] to 231 C [32];
CHS does the same, but from 140 [36] to 147 C [37].
According to the fundamental thermodynamic first-order
phase transition theory, when a system is heated (under
standard pressure conditions) through its respective tem-
perature phase transition, it must correspond to a constant
value independent of the heating rate used. However, it is
not the case for any of these salts. If instead, the DSC peak
enthalpy is related to a partial thermal decomposition
123
 E. Ortiz et al.

(polymerization) at reaction sites on the surface of the 100.0

70 90 110 130 150 170 190
crystal, the wide literature dispersion on the reported Tsp
values of Cs3(HSO4)2(H2PO4) and its parents could be well (a) TG
explained. When a sample with a higher surface quality 0.25 %
99.8
(less concentration of surface structural defects) is heated 150.0 C

Mass/%
with a higher heating rate (less time for the thermal kinetic 150 C
reaction process), the onset decomposition temperature is 100
99.6
expected to be higher. Therefore, we propose that the DSC 5.2 %

Mass/%
95
peak of Cs3(HSO4)2(H2PO4) corresponds to a chemical 373 C 16.6 %
transformation instead of a physical one. As indicated in 90 650 C
99.4
the introduction, a similar hypothesis was suggested for its 85
parents, concluding that instead of a physical transforma- 75 150 225 300 375 450 525 600
Temperature/C
tion, a surface chemical decomposition takes place at
230 C for CDP [23, 26, 38, 39], and 141 C for CHS [18], 135.4 C
0.5
according to Eqs. (1) and (2), respectively. Given that (b) DSC 2
Cs3(HSO4)2(H2PO4) is a solid CHS and CDP solution, it is

Endothermic

DTG/(102)% C1
likely that its thermal decomposition products involve the

Heat flow/mW
1.0
same as its parents. If the proposed hypothesis was true, a 170.0 C
mass-loss step, related to the evolution of water vapor as a 113.5 C
1
product of decomposition, should be detected in the same 1.5
temperature range where the DSC peak is registered.
The temperature dependence of the mass loss for the DTG
wide temperature range from 35 to 650 C, using 2.0
135.2 C 0
1 C min-1 as heating rate, is shown in the insert in
Fig. 2a. At first glance, the TG curve might be described as 70 90 110 130 150 170 190

the sequence of two big mass-loss steps with subtotal Temperature/C

values of 5.2 and 16.6 % at around 373 and 650 C,
respectively. However, careful examination allows seeing a
small additional earlier temperature mass-loss step below
150 C. In order to increase the graphic resolution, the
small area marked with a dashed ellipse has been amplified
in Fig. 2a. Now, a clear mass-loss step of 0.25 % at 150 C
is evident. Also, the DSC curve of another crystal sample
using the same heating rate of the TG experiment
(1 C min-1) is plotted in Fig. 2b. Because the temperature
scales for these data plots (Fig. 2a, b) are the same, it is
clear that the DSC endothermic peak temperature at
135.2 C fits almost exactly with the peak temperature
(135.4 C) of the temperature derivative of the thermo-
gravimetric (DTG) curve, meaning that the DSC
endothermic peak is directly associated with the mass-loss
step.
To confirm that the DSC and TG events occur simul-
taneously, we measured these two signal responses from
the same crystal by using simultaneous DSCTG equip-
ment, using the same heating rate used in Fig. 2. The exact
coincidence of their respective DSC and DTG temperature
peak values of 135.0 and 135.1 C confirms the direct
relation between these signals. Given that the results
exhibit very similar data as that shown in Fig. 2, we
decided not to present it. These results show that decom-
position starts well below the temperature reported by
Haile et al. [30] (150 C). By comparing the starting
Fig. 2 The insert shows the TG curve of a Cs3(HSO4)2(H2PO4)
crystal, under the wide temperature range from 35 to 650 C.
a amplified 70190 C temperature range marked with the dashed
ellipse, in the insert. b DSC curve of another dry Cs3(HSO4)2(H2PO4)
crystal overlapped with the derivative curve, DTG, of a. The heating
rate of these experiments was fixed at 1 C min-1
temperature where the DSC and DTG signals leave their
respective baseline, it can be noted that decomposition
begins at around 113 C. If it is assumed that the whole
constitutional water is thermally removed from the salt, we
propose the following chemical reaction:
Cs3 HSO4 2 H2 PO4 s ! Cs2 S2 O7 s CsPO3 s
2H2 Ov 3
where s and v in parentheses have the same meaning as in
Eq. (1). The respective theoretical sample mass loss cor-
responds to 5.22 %. This value agrees with the first major
mass loss of 5.2 % at 373 C. This proposed decomposi-
tion is consistent with the fact than CDP decomposes to
CsPO3 at around 380 C [40] and CHS to Cs2S2O7 at
around 400 C, when it is heated using a low heating rate
[41], as the one used here for Cs3(HSO4)2(H2PO4). If the
sample is heated to higher temperature values (above
447 C), the cesium pyrosulfate decomposes forming
cesium sulfate (Cs2SO4) and sulfur trioxide (SO3) [41]. The
whole reaction requires a total mass loss of 16.84 %. This

123
On the low- to high proton-conducting transformation of a CsHSO4CsH2PO4 solid solution and its

value also agrees with our measured value of 16.6 % at
650 C and with that reported by Haile et al. [9] (16.5 %).
However, because our interest is related to the small mass-
loss step, we focused on the low temperature range,
70190 C.
To confirm whether water corresponds to a decomposition
product, a simultaneous TGMS experiment was performed
on a crystal by using a heating rate of 2 C min-1 (Fig. 3).
Overlapped with these data, Fig. 3b also shows a DSC
experiment of a crystal heated under the same experimental
conditions. The results in Fig. 3 are quite similar to those
shown in Fig. 2: a DTG peak (Fig. 3a) appears simultane-
ously with the DSC anomaly, it can be noticed that both
temperature peaks are very close (137.8 and 137.3 C,
respectively). Hence, these measurements are interpreted in
the same way as those shown in Fig. 2. Moreover, the
m/z = 18? amu MS ion current signal presents an event with
a temperature peak value (138.0 C) that also coincides with
the DSC and DTG temperature peaks. This confirms that
water is one of the decomposition products obtained from a
chemical transformation whose maximal rate (at this heating
rate) is reached at the average temperature value of 137.7 C.
70 90 110 130
100.0
TG
137.8 C
99.8 (a)
Note that this temperature is higher than the respective value
for the case when lower heating rate is used, see Fig. 2b.
In order to check the effect of the heating rate and the
samples morphology, we compared the DSC and TG ther-
mal response of crystalline powder samples (as grown)
heated at 0.2 C min-1 (Fig. 4) with those crystal samples
heated at 2 C min-1 of Fig. 3. To assist this task, Figs. 34
have been edited by using the same temperature and mass
scales. For comparison, a dc conductivity measurement of a
flat crystal, but with the same (average) heating rate of 0.2 C
min-1 used on the experiments shown in Fig. 4 has been
overlapped (Fig. 4b). While Fig. 4a presents a mass loss of
0.80 % at 150 C, Fig. 3a exhibits 0.23 % mass loss at this
same temperature value. Furthermore, while Fig. 4b pre-
sents a 99.5 J g-1 broad endothermic anomaly, essentially
composed of three peaks (covering the whole temperature
range associated with the mass-loss step), Fig. 3b shows a
44.5 J g-1 single-endothermic peak (covering around half of
the corresponding mass-loss step temperature range). The
higher mass-loss step of 0.80 % (Fig. 4a) compared to the
0.23 % mass loss in Fig. 3a is a consequence of the sum of
two effects: the first sample (shown in Fig. 4) had a higher
specific surface area and more time to yield more chemical
product (during the kinetics of the reaction) than the second
150 170 190
sample (shown in Fig. 3). The same reason also explains why
1.5
0.23 % the DH measured value is higher for the first sample: given
150.0 C that it yields larger amounts of chemical products, it requires
more energy to break up chemical bonds. Considering that
DTG/(102)% C1

99.6
1.0 the first two peaks of the DSC curve in Fig. 4b are within the
Mass/%

99.4 reported temperature range where the superprotonic phase

99.2
transition takes place, one of these could be assigned to this
0.5 physical transformation. Nevertheless, both have their
99.0 respective DTG peak at quite the same DSC peak tempera-
DTG
ture values. In addition, the last DSC peak at 171.3 C does
98.8
0.0
not have a homologous peak on the DTG curve, probably at
138.0 C 188.5 C. However, it is 17.2 C above. Because thermal
0.5
128.4 C
DSC
decomposition phenomena usually tend to occur on surfaces
H = 4.6
1.0 where heat contact is direct and chemical binding is weaker,
44.5 J g1
Heat flow/mW

rather than on the bulk crystal [26], we believe that at the very
Ion current/nA

MS
1.5 earlier decomposition stage (at the onset of the first DSC
4.5
177.5 C endodermic anomaly), a big proportion of the water pro-
2.0 +
m/z = 18 aum duced from the most external surface easily transforms to gas
and evaporates. However, when the chemical reaction front
2.5 4.4 migrates below the most external surface, part of the water
(b) 137.3 C diffuses to the surface to evaporate, but another significant
3.0
part of it, as a liquid phase, is strongly bonded to the other
70 90 110 130 150 170 190
decomposed products or even to the salt. Liquid water
Temperature/C
might dissolve parts of the salt providing protons to the
Fig. 3 Simultaneous TGMS and DSC measurements of two Thermal Surface Decomposition Products System (TSDPS)
Cs3(HSO4)2(H2PO4) crystals, respectively, in the 70190 C temper- of Cs3(HSO4)2(H2PO4). Taking into account that except for
ature range. a TG and its corresponding DTG curve. b DSC overlapped
the liquid water, its composition is not exactly known, we
with the m/z = 18? amu MS ion current signal. The heating rate was
fixed at 2 C min-1. For comparison purposes, the mass and temper- prefer to use this definition. Probably, in addition to the
ature scales of this figure are the same as those of Fig. 4 liquid, this system contains Cs2S2O7 and decomposition

123
 E. Ortiz et al.

100.0
70 90 110 130 150 170 190 range, where the transition is found to occur, is also not
188.5 C consistent with the thermodynamic first-order phase transi-
TG
99.8
125.2 C 4
tion theory where the low- and high-temperature phases can
(a) coexist only at the phase transition temperature. Considering

DTG/(102)% C1
99.6 134.7 C 0.80 % that except the liquid water, all the products constituting the
Mass/%

150 C
99.4 TSDPS of Cs3(HSO4)2(H2PO4) are of polymeric nature; it
2
DTG could behave similar to a polymer electrolyte membrane
99.2 111.6 C
(located over the salt surface), where the polymers constitute
99.0 a host matrix that contain liquid water regions. Therefore, as
0 part of liquid water dissolves a superficial portion of salt
98.8 (providing protons) [18, 27], the proton transport mechanism
1
0.0 H = 99.5 J g1 of TSDPS of Cs3(HSO4)2(H2PO4) might include the vehicle
DSC
type, using H3O? as a charge carrier. If the sample is heated
(b) 2
further (Fig. 4), a second-stage chemical-surface decompo-
0.2 126.0 C
sition takes place but the DTG peak temperature presents a

Log/S cm1
Heat flow/mW

Endothermic

0.4
111.0 C
0.6
IS
125.1 C
70 90 110 130
Temperature/C
Fig. 4 TG and DSC measurements of two Cs3(HSO4)2(H2PO4)
crystalline powder samples (as grown), respectively, in the
70190 C temperature range. a TG and its corresponding DTG
curve. b DSC overlapped with a dc conductivity measurement of a
crystal sample. Heating rate of all these experiments was fixed at
0.2 C min-1
products of CDP as oligomer transient decomposition
products to CsPO3 [23, 25] or even long chains of CsPO3
monomers [CsnH2PnO3n?1 polymer with n  1, (CsPO3)n],
as proposed by Park [26]. From conductivity data (Fig. 4b), it
can be seen that conductivity increases by 300 times. How-
ever, it does not correspond to an abrupt conductivity jump,
as that observed through the well-known first-order transi-
tion from low to superionic conducting phase of AgI salt at
147 C [42, 43]. Instead, through a wide temperature range
of 15 C, a gradual monotonically conductivity increase
from 111 to 126 C is observed. This measurement agrees
with that reported by Haile et al. [9], who indicated that the
temperature range (14 C) over which this transition occurs
corresponds to 111125 C. Certainly, by comparing the
temperature value where the DTG and DSC signals leave
their respective baselines (Fig. 4a, b, respectively), both
coincide with the onset temperature value where conduc-
tivity starts to jump. Similarly, the respective DSC and DTG
temperature peaks of 125.1 and 125.2 C coincide with the
offset temperature where the conductivity stops jumping. At
this temperature, the highest first-stage chemical-surface
decomposition rate takes place. This wide temperature
3
delay of 6.5 min (1.3 C) with respect to the respective DSC
171.3 C
peak temperature. A similar, but more pronounced, effect
4
133.4 C corresponds to the third-stage chemical decomposition,
where the corresponding DTG peak temperature is delayed
5 86 min (17.2 C) with respect to the respective DSC peak.
This suggests that the total additional water produced in this
6 event is strongly bonded to the hygroscopic products of
150 170 190
decomposition. This explains the fact that the corresponding
DTG peak temperature around 188.5 C appears at a higher
temperature value where no DSC peak appears. This DTG
peak could also involve the release of part of the liquid water
formed at the first two DSC peaks. This phenomenon is also
evident in the results shown in Figs. 23 where after the DTG
peak (associated with the endothermic DSC peak), a second
DTG peak starts to appear at 170.0 and 177.5 C, respec-
tively, without any associated endothermic DSC peak. Note,
also, that while the DSC baseline stays flat, a second MS
water vapor increase starts simultaneously with its respective
DTG signal at 177.5 C (Fig. 3b). This evidence confirms
the existence of liquid water strongly bonded to the TSDPS
of Cs3(HSO4)2(H2PO4). Otherwise, our proposed proton
conduction mechanism cannot be possible.
The fact that liquid water is present at the temperature
range where the existence of the superprotonic conduction
phase of Cs3(HSO4)2(H2PO4) has been reported is evident
from the Suzuki and Hayashi [31] 1H solid-state NMR
studies. On heating the salt, at 127 C, two narrow signals
coexist, where one of these (with a chemical shift value at
around 6.4 ppm) was ascribed to physically absorbed
water. At 137 C, the two signals collapse into one sharp
signal. From Fig. 3, it can be seen that this temperature
corresponds to the same value where the higher decom-
position rate of the surface of the crystal, heated to
2 C min-1, is reached. On the other hand, a room tem-
perature 1H NMR study [35] of a wet powdered CDP
sample, than was pretreated isothermally at 200 C for a
day, shows three peaks with the main chemical values of
14.5, 10.5, and 6.6 ppm, respectively. The first two peaks

123
On the low- to high proton-conducting transformation of a CsHSO4CsH2PO4 solid solution and its
correspond to two crystallographically distinct hydrogen
atoms of the salt and the last one to chemically surface-
absorbed water, which (as noted) was particularly difficult
to remove. In addition, from the respective 1H NMR data
by Yamada et al. [33], when CDP is heated through the
superprotonic phase transition, a single peak that appears at
the average chemical shift value of the first two peaks,
reported by Boysen et al. [35], decreased to 6.5 ppm.
Therefore, we believe this peak corresponds to the 1H
NMR response of protons from the liquid water produced
as a consequence of thermal decomposition. Certainly, this
statement is consistent with Lees [44] optical observations
of non-equilibrium processes at the CDP sample surface,
where a liquid-like behavior, such as water flow, takes
place when the sample is heated above Tsp. Therefore, we
trust that when CDP is heated through the reported
superprotonic phase transition, instead of this physical
transformation a chemical one takes place at its surface,
following Lees [23] reaction (1). However, we must
emphasize that not all the H2O evaporates because part of
the liquid water is strongly bonded to the other polymeric
product(s) and to the salt. Hence, we propose the following
chemical reaction:
nCsH2 PO4 s ! Csn Hn Pn O3n1 s 1  xn
 1H2 Ol xn  1H2 Ov 4
Here, n and x are the number of molecules participating in
thermal decomposition and the fraction of the water that
evaporates, respectively. The letters s, l, or v in parentheses
denote solid, liquid, or vapor. Herein, it is important to
point out that the strongly bonded liquid water may affect
the dry structure of the polymeric product(s). The high
conductivity values reported above 230 C could be
interpreted as proposed here for Cs3(HSO4)2(H2PO4).
Returning to the comparison from the measurements of
Figs. 3 and 4, where the endothermic DSC anomaly on the
latter corresponds to an overlapping of three peaks while
on the former it corresponds to only one, it is explained by
the fact that at a lower heating rate (when the reaction has
10 times more time to develop), the sequence of decom-
position events is better resolved. Also, the well-matched
(125.1 and 125.2 C, respectively) first DSC and DTG
peak temperatures of the samples heated at low heating rate
(0.2 C min-1) shift together to a higher temperature value
(12.2 C above) when the crystals are heated at a higher
heating rate (2 C min-1). This is the usual behavior of the
kinetic nature of a chemical transformation. Moreover, it
demonstrates that the whole enthalpy of the DSC peak
must be associated with the chemical decomposition
reaction.
Given that the low to superprotonic conducting phase
transition is of the first-order type [9], when the tempera-
ture dependence on entropy thermodynamic function, S, is
135 47
80
S
45
S/J mol1 K1
76
H/J g1
Tonset/C
130
43
72
41
Tonset
125 H
68
39
0 2 4 6 8 10 12 14 16
Heating rate/C min1
Fig. 5 Heating rate dependence of the onset temperature, Tonset,
enthalpy change, DH, and entropy change, DS, of the endothermic
peak associated with the first-order superprotonic conducting phase of
Cs3(HSO4)2(H2PO4). Five crystals were heated to 0.2, 2, 5, 10, and
15 C min-1, respectively
plotted, a discontinuous change, DS, takes place at the
respective transition phase temperature. This is equal to the
corresponding DH or latent heat, Q, divided by this tem-
perature. Thereby, independent of the heating rate used,
DS and its respective DH should be constant. Certainly,
because the theoretical DS calculated by Haile et al. [9]
(51.5 J mol-1 K-1) corresponds to the difference between
the configurational entropy associated with the protonic
configuration at the cubic superprotonic conducting phase
(57.3 J mol-1 K-1) and that associated with the room
temperature monoclinic phase (5.8 J mol-1 K-1), it does
not depend on any particular heating rate value.
In this sense, an additional kinetic DSC experiment is
presented in Fig. 5. Here, the onset temperature, Tonset,
enthalpy, DH, and entropy changes, DS, of the thermal
anomaly are measured from five crystals heated to 0.2, 2, 5,
10, and 15 C min-1, respectively. It can be seen that none
of these quantities remains constant. Comparing the result
associated with the extreme heating rate values of 0.2 and
15 C min-1, it is observed that while Tonset shifts 11.3 C
to higher temperatures from 123.5 to 134.8 C, DH de-
creases 6.2 J g-1 (13.5 %) from 46.0 to 39.8 J g-1, and
DS decreases 12.7 J mol-1 K-1 (15.9 %) from 80.0 to
67.3 J mol-1 K-1. This experiment proves that the DSC
anomaly is governed by a chemical instead of a physical
transformation. As indicated above, higher heating rates
mean less time to start the chemical bond breaking process
(higher Tonset) and less broken chemical bonds (lower DH).
This also explains the wide spread of the values reported in
the literature for the superprotonic conducting phase tran-
sition temperature.
Chisholm [45] reported an extended research of several
mixed CHSCDP compounds, and the X-ray powder
123
 E. Ortiz et al.

Figure 6 indicates that the enthalpy change associated with

H = 45.9 J g1 the thermal event at around 123.5 C, as measured from
0.6 Total heat flow
the kinetic component, corresponds to 99.1 % (45.5 J g-1)
of the total DH value measured from the total heat flow
signal (45.9 J g-1). Considering that decomposition reac-
Heat flow/mW

tions are time-dependent phenomena, the results suggest

0.0
Non kinetic component H = 0.4 J g1
that 99.1 % of the total DH is associated with chemical
123.5 C
H = 45.5 J g1 processes. The remaining 0.9 % measured value for the
Kinetic component
heat capacity component (0.4 J g-1) of the very small
MDSC peak could be associated with the physical trans-
0.6 formation in the crystal from low to superprotonic con-
ducting phase. However, using our Tonset value (123.5 C),
126.2 C 135.3 C
the enthalpy change associated with this transformation is
75 90 105 120 135 150
much lower than that required by the theoretical config-
Temperature/C
urational DS calculated by Haile et al. [9],
Fig. 6 Total heat flow and its time-dependent (kinetic component) DH = 29.6 J g-1. Consequently, from our MDSC mea-
and time-independent (heat capacity component) components of a surements, the non-kinetic component of the enthalpy
sealed Cs3(HSO4)2(H2PO4) crystal under a heating cycle from 75 to change value (0.4 J g-1) cannot be related to a superprotonic
150 C. The heating rate was fixed at 0.2 C min-1
conducting phase transition of the Cs3(HSO4)2(H2PO4)
crystal. Further, Fig. 7a shows the MDSC cooling cycle of
1.2 the sealed crystal shown in Fig. 6, presented together with
0.9 H = 45.2 J g1 a cooling cycle from another unsealed crystal (Fig. 7b) that
Total heat flow
0.6
was previously heated to the same maximum temperature
Non kinetic component
H = 0.2 J g1
used in Fig. 6 (150 C). On the cooling cycle of the sealed
Heat flow/mW

0.3 (a)
0.0
Kinetic component
0.3
0.6
0.4
0.3 (b)
Total heat flow
0.2
0.1
15 30 45 60 75
Temperature/C
Fig. 7 a Total heat flow and its time-dependent (kinetic component)
and time-independent (heat capacity component) components of a
sealed Cs3(HSO4)2(H2PO4) crystal under the cooling cycle from 150
to 5 C, immediately after the heating cycle shown in Fig. 6. b Total
heat flow of an unsealed Cs3(HSO4)2(H2PO4) crystal under a cooling
cycle, after having been heated to 150 C. The cooling rate of these
experiments was fixed at 0.2 C min-1
diffraction patterns measured in the temperature transition
regions [around 30 C for Cs3(HSO4)2(H2PO4)] showed a
reproducible mixture of the room and high-temperature
phases. Therefore, he concluded that the transition appears
to be a thermodynamic, rather than kinetic, phenomenon.
To examine this last statement, the thermal results for a
heatingcooling cycle of a sealed Cs3(HSO4)2(H2PO4)
crystal, using the MDSC technique, are shown in Figs. 6
7a, respectively. This technique allows separation of the
time-dependent (kinetic) component from the time-inde-
pendent (heat capacity) component of the thermal
response of the sample to a modulated heat flow [46].
and unsealed samples, practically 100 % of the total heat
flux corresponds to the kinetic component. By comparing
H = 45.0 J g1
the DH of the total heat flux endothermal anomaly for the
heating (45.9 J g-1, Fig. 6) cycle with those cooling cycles
of the sealed (45.2 J g-1, Fig. 7a) and unsealed samples
(30.1 J g-1, Fig. 7b), we may conclude that when the
H = 30.1 J g1 sample is sealed it seems that the transformation is rever-
90 105 120 135 sible, but if it is unsealed it is not reversible (similar to the
results presented in Fig. 1). Given that the elastic cover
cannot alter the configurational entropy change, DS (which
only depends on the intrinsic structural properties of the
low- and high-temperature phases), it constitutes a physical
unrealistic phenomenon interpretation. For the sealed
sample, the total water produced on heating (as a conse-
quence of the chemical reaction) is kept with the sample,
and when cooled, the reverse chemical reaction can take
place; thus, the DH value is the same as when the sample
was heated. But if the crystal is not sealed, a fraction of the
water is evaporated, and in the cooling cycle, the liquid
water is not enough to react with the total amount of the
other products. Therefore, the measured DH value is lower
than when the sealed sample is cooled. Moreover, the
unsealed endotherm anomaly has a different shape and
appears at lower temperatures (covering a wider tempera-
ture range) than the sealed one. When the water produced
is not enough in the unsealed sample, under a dry atmo-
sphere, the inverse reaction is more sluggish than when
there is abundant liquid in the sealed one. In the unsealed
sample, it is, then, possible that other types of reactions

123
On the low- to high proton-conducting transformation of a CsHSO4CsH2PO4 solid solution and its

take place, which could explain why new peaks become 9

(110)
visible on cooling to 98 C, giving rise to an extremely 6

(200)
(100)

(210)
(111)
3
complicated pattern [9] on further cooling to 70 C. 170 C
Before proceeding with our XRD results, it is important to 9
6
examine previous results by Chisholm [45]. According to
3
this author, the X-ray powder diffraction patterns, some 160 C
9
Celsius degrees, above Tsp (taken at around 140 C) of
6
low-phosphate-content mixed CHSCDP compounds [like 3
150 C
Cs3(HSO4)2.5(H2PO4)0.5 or Cs3(HSO4)2.25(H2PO4)0.75]
9
consist of a combination of two phases: a tetragonal and a 6

Intensity/a.u.
cubic one. The first was associated with the well-known 3
140 C
tetragonal phase of the superprotonic high-temperature 9
phase of CHS. It appears as a consequence of a partial 6
thermal decomposition of the mixed CHSCDP system, 3 130 C
where sulfate and phosphate tetrahedral migrate into dif- 9
ferent phase domains. From our point of view, given that Tsp 6
of CHS is 141 C, this assumption is reasonable. However, it 3 120 C
is not the case for the other decomposed product: CDP. At 9
140 C, its thermodynamic stable phase is the low-temper- 6
ature monoclinic one, but no XRD peaks for this phase 3
110 C
appear. Therefore, the cubic phase observed of this CHS 9

(220) (402)

(023)(331)

(214)(114)
(330)(313)
(221)

(511)
(600)

(421)
6

(204)
(112)

(621)
CDP solid solution was associated with an isostructural

phase with the superprotonic cubic one of CDP [45]. If this
interpretation is correct, why does not the XRD pattern from
the decomposed phosphate product(s) appear? Taking into
account our interpretation that the 141 C XRD pattern of
CHS corresponds to the XRD response of the TSDPS of CHS
[18], the 140 C XRD pattern form the low-phosphate-
content mixed CHSCDP compounds may correspond to
an overlapped XRD pattern from the TSDPS of CHS and
the TSDPS of CDP. The mass-loss step registered at
around Tsp on Cs3(HSO4)2.5(H2PO4)0.5 supports this
interpretation [47]. The superprotonic conducting state of
a high-phosphorous content mixed CHSCDP compound,
like Cs3(HSO4)2(H2PO4), is purely cubic [45]. From ear-
lier studies on pre-heated (during 1030 min at 210 C)
highly SiO2 content composites of (1 x)CsHSO4 - xSiO4,
it was concluded that an amorphous phase of CHS is formed
[48]. We trust that the amorphous phase might correspond
to an amorphous phase, but of TSDPS of CHS. Then, the
fact that only the cubic phase of a high-phosphorous content
mixed CHSCDP compound is present could be explained
by assuming that TSDPS of CDP plays a similar role as
SiO2 does on TSDPS of CHS.
Figure 8 shows high-temperature XRD patterns of
powdered crystalline Cs3(HSO4)2(H2PO4) at several iso-
therms from 25 to 170 C, under stagnant ambient atmo-
sphere. The 25 C diffraction pattern corresponds to that
reported (ICSD 079,789) for a room temperature mono-
clinic symmetry with space group P21/n. No other phase
was detected. According to this reported data, Miller
indices of (intensity-relevant) reflection peaks of this phase
were assigned. By heating from 25 to 110 C, some peaks
(202)
3
25 C
18 21 24 27 30 33 36 39 42
2 /
Fig. 8 XRD patterns of a Cs3(HSO4)2(H2PO4) powdered sample at
25, 110, 120, 130, 140, 150, 160, and 170 C, respectively. Miller
indices of (intensity-relevant) reflection peaks of the room temper-
ature phase (25 C) has been indicated, as well as those of the 170 C
pattern, associated with the isostructural superprotonic conducting
phase of CDP. The peaks for the 25 C pattern that remain on
subsequent high-temperature patterns and those new ones are marked
with solid and dotted arrows, respectively
increase their intensity, probably by the order increase of
the atomic planes induced by the thermal atomic binding
relaxation. From 110 to 170 C, a general behavior is
observed. The monoclinic peaks become weaker until
170 C when they completely disappear. Certainly, the

peaks at 2h = 24.4 [(220) (402)] and 27.8 (600) persist
even until 160 C. New peaks appear (all those of the
170 C pattern, which have been associated with the
isostructural phase of the superprotonic cubic phase of
CDP [45]) with a general temperature intensity increase.
The 2h = 31.5 (111) peak is present from the early tem-
perature of 120 C. The most evident pattern that shows the
phase coexistence of the monoclinic room temperature and
that responsible for the new peaks phase(s) is that of
150 C. Even if we hypothetically assume that the low- to
high proton (superprotonic)-conducting phase transition is
time-dependent, the very low average heating rate used in
this experiment (0.17 C min-1) does not offer the
opportunity for a phenomenon, like superheating. It should

123
 E. Ortiz et al.

be noted that the higher reported Tsp (145 C, [30]) is
15 C below 160 C; however, at this last high tempera-
ture, the sample still contains a room temperature mono-
clinic phase. By heating at such a low heating rate, how is
it possible to have a low-temperature phase 15 C above
the higher reported first-order phase transition tempera-
ture? This constitutes one of the most robust evidence that
Cs3(HSO4)2(H2PO4) undergoes a chemical instead of a
physical transformation. If we compare this result with the
TG curve of Fig. 4a, which shows the mass loss for a
powder crystalline sample heated at similar heating rate
(0.2 C min-1) used in this experiment, at 130, 140, 150,
160, and 170 C, the sample contains 7.6, 13.4, 15.3, 17.8,
and 19.7 % of thermal decomposition products. Here, we
have assumed a total water mass loss of 5.2 %. However, if
we consider that after thermal decomposition the sample
maintains 60 % of the water produced, a rough estimation
of the amount of decomposed product implies 2.5 times
these values. Therefore, at 170 C, where the respective
pattern is composed entirely by the new XRD peaks, about
50 % of the sample corresponds to decomposed products
from which a third part belongs to TSDPS of CDP and the
other two-thirds to the amorphous TSDPS of CHS. The
remaining 50 % of the sample belongs to the salt, which is
not detected because all the X-ray energy is absorbed by
the decomposed product located at the sample surface.
According to Ikeda [49], the Tsp of CDP, measured form
the DSC onset temperature, occurs at 227 C. However,
from his temperature evolution of XDR patterns, the strong
low monoclinic peaks kept their intensity until phase
transition started at 232 C. If the sample if heated further,
these peaks decrease, but even at 238 C, they do not
disappear. Otomo et al. [50] have observed a similar but
more pronounced behavior. From their XRD data, they
conclude that the monoclinic phase of CDP was still pre-
sent at 243 C. This means that the low-temperature phase
is present even 12 C above the higher reported Tsp
the cubic cell constant, a, for CDP from 230 to 290 C.
According to these data, the thermal expansion coefficient
of the cubic phase of CDP [Da/ao = a(T - To) with ao =
4.9724(2) and To = 260 C] was a = 3.92 9 10-5 K-1.
Although we know the superprotonic cubic phase of CDP
is thermodynamically not stable below the Tsp, using these
data, the ao(T) linear relation has been extrapolated to room
temperature. Comparing, in their order, the CDP a values
reported by Ikeda et al. [49, 52], Bronowska [32], and
Yamada [33] (marked with a rectangle) at around the same
temperature of 240 C, a progressive reduction of the
a value is clearly noted. Because all powdered samples are
pure CDP and are exposed to quite the same atmospheric
pressure (the XRD chamber used by Ikeda et al. [49, 52] is
equipped with a check valve to limit the system pressure to
2 atm) the a value should be the same, the bar error of this
data is smaller than the symbol size. The unique different
parameter between these experiments was the water partial
pressure. While Ikeda et al. [49, 52] exposed the sample to
a higher water partial pressure around 1 atm, Bronowska
[32] exposed it to H2O-saturated atmosphere and Yamada
[33] made the experiment under the usual non-humidified
atmosphere. From these results, it seems that the cubic cell
constant, a (and therefore the volume cell value), rises with
increase in water partial pressure. This behavior is more
akin to that of a crystalline phase of a polymeric material
than of an ionic solid compound.
Considering that cell constant values for the CHSCDP
mix compounds (Fig. 9) were measured under a similar
atmosphere as used by Yamada [33] for CDP, we used the
same ao(T) linear relation (the same slope) obtained by
Ikeda et al. [49, 52] in their CDP experiment under high
4.98 Ikeda et al. [44, 47]
(water partial pressure ~ 1 atm)
237 C
4.97
Bronowska [28]
(saturated water atmosphere)
CsH2PO4

(231 C [32]) for the superprotonic first-order phase tran- 4.96 140 C
Cell constant a/

Cs5(HSO4)3(H2PO4)2 242 C
sition of CDP. As for the Cs3(HSO4)2(H2PO4) case, this 4.95 130 C Yamada [29]
Cs3(HSO4)2.50(H2PO4)0.50
also constitutes one of the most overwhelming evidence 170 C
4.94 This work
that CDP undergoes a chemical transformation instead of a Cs3(HSO4)2(H2PO4)
physical transformation that leads to high proton conduc- 4.93

tivity. A similar behavior has also been registered on CHS 4.92 140 C
[18] and CHSe [27], where their respective (012) and (021) 119 C Cs3(HSO4)2(H2PO4)
4.91 50 C Cs2(HSO4)(H2PO4)
peaks persist 13 and 7 C above their corresponding higher Cs2(HSO4)(H2PO4)
reported Tsp of 147 C [37] and 128 C [51]. 4.90
0 50 100 150 200 250 300
Ikeda et al. [49, 52] built a high-temperature sealed
Temperature/C
XRD chamber with 150 C tempered walls to prevent
water condensation. Seeking to avoid the thermal decom- Fig. 9 Temperature and humidity dependence of the cell constant
position of a powdered CDP sample, a drop of water was value, a, associated with the cubic superprotonic conducting phase of
CDP [28, 29, 43, 46] and its comparison with the, respective, a values
placed inside the chamber, so, under a heating cycle above
of the high-temperature cubic phase of some CHSCDP solid
100 C, the water evaporates providing humidity. Figure 9 solutions [40]. The a value calculated from our 170 C XRD pattern,
shows the Ikeda et al. [49, 52] temperature dependence of of a Cs3(HSO4)2(H2PO4) powdered sample, is also indicated

123
On the low- to high proton-conducting transformation of a CsHSO4CsH2PO4 solid solution and its
Fig. 10 Temperature evolution
of SEM Cs3(HSO4)2(H2PO4)
surface images from 25 to
143 C, under 5-mbar pressure
humidified atmosphere, but subtracting the required dif-
ference to match the Yamada [33] a value. As noted, the
indicated cell constant values of the mixed CHSCDP solid
solutions agree with the new ao(T) linear relation, even
with that calculated by our XRD pattern at 170 C for
Cs3(HSO4)2(H2PO4). Supported on this observation and the
extreme high coincidence between all the high-temperature
XRD patterns (above their reported Tsp values) of the dif-
ferent mix CHSCDP solid solutions (Fig. 4.3 of Ref.
[45]), we propose that all the cubic high-temperature
phases from all these samples correspond to the same
system: the TSDPS of CDP.
Finally, Fig. 10 shows the temperature evolution of SEM
Cs3(HSO4)2(H2PO4) surface images from 25 to 143 C.
Even though the images were gotten from an under-atmo-
spheric pressure, it helps to understand the thermal evolution
behavior of the sample surface. At room temperature, the
image shows a uniform surface containing some powder
particles. At 101 C, this seems to decompose and it is
observed that small white bubbles are formed, probably
from polymeric material. At 107 C, the image shows
intense surface chemical decomposition where entities like
volcanos seem to eject a liquid. A less amplified image, at
120 C, shows a smooth surface rounded by some volcano
craters. The imagen at 126 C shows a bigger portion of the
smutted area. The image at 143 C shows a not so smooth
surface, but looks like a membrane covering the salt.
According to our research presented here, the liquid ejected
from volcanos at 107 C corresponds to the water. Proba-
bly, the smoothed area at 120 and 126 C is a polymeric
matrix with very high water content. At 143 C, this system
is in the course of drying.
The thermal decomposition process observed from our
SEM result is analogous with that described for KH2PO4,
KDP (and CDP) [28]. When this salt is heated stepwise, to
higher temperatures, a solid crust of high-molecular
polyphosphate forms around the crystallites, which breaks
down if the internal pressure of water produced becomes
sufficiently high. Moreover, our microscopy images are
also consistent with Lees [44] optical observation (at
atmospheric pressure) of the crystal surface of several solid
acids, including CDP. By heating through their respective
transformation temperatures, the scene that comprises
various kinds of patterns, such as cracks, pores, sheaves,
spherulites, and flow of liquid (water), was compared to the
corresponding geological phenomena that involve earth-
quakes and volcanos in eruption with lava flow production.
Summary and conclusions
Under a heating cycle of the CHSCDP solid solution
Cs3(HSO4)2(H2PO4), a clear mass-loss step was simultane-
ously observed with the DSC endothermic peak, which has
been associated with the low to superprotonic conducting
phase transition. When heating rate increases, the DSC and
DTG peaks move together to higher temperature values.
Another DSC kinetic experiment shows that when heating
rate increases, the Tonset (associated with the superprotonic
conducting phase transition temperature, Tsp) increases but
123

entropy and enthalpy changes decrease. These experiments
explain the broad literature Tsp value dispersion
(119145 C). The MDSC experiment verified that practi-
cally, the total enthalpy of the endothermic anomaly is of
kinetic nature. The simultaneous TGMS signals evidenced
that water is a chemical product of the surface thermal
chemical decomposition of the salt and (compared to DSC
curves) that part of it is strongly bonded to other polymeric
products. The temperature evolution of SEM images con-
firms the chemical reaction at the surface of the sample,
including the production of water and a polymeric material.
All these experiments suggest that the observed high proton
conduction, above Tsp, is a consequence of the chemical
transformation of Cs3(HSO4)2(H2PO4). Probably, the
TSDPS of Cs3(HSO4)2(H2PO4) behaves similar to a poly-
mer electrolyte membrane (located over the salt surface),
where the polymers constitute a host matrix that contains
liquid water regions. Therefore, as part of liquid water
dissolves a superficial portion of salt (providing protons)
[18, 27], the proton transport mechanism of this system
might include the vehicle type, using H3O? as a charge
carrier.
The highest reported Tsp value, where the monoclinic
room temperature phase of Cs3(HSO4)2(H2PO4) transforms
to the superprotonic cubic phase, is 145 C [30]. Because
this phase transition is of the first-order type, the only
temperature where the low- and high-temperature phases
may coexist is Tsp. According to our temperature evolution
of the XRD patterns (using a very low heating rate average
of 0.17 C min-1), the sample still contains room tem-
perature monoclinic phase 15 C above the highest repor-
ted superprotonic temperature phase transition. From the
thermodynamic point of view, this probably constitutes the
most robust evidence that Cs3(HSO4)2(H2PO4) undergoes a
chemical transformation that leads to high proton conduc-
tion instead of being due to a superprotonic physical
transformation (first-order structural phase transition).
By using this same behavior, interpretation for the
Cs3(HSO4)2(H2PO4), the fact that the low-temperature
monoclinic phase of CDP was still 12 C above the highest
reported Tsp for the superprotonic first-order phase transi-
tion of CDP [50], permits us to propose this as the most
overwhelming evidence that CDP undergoes a chemical
instead of a physical transformation. Certainly, taking into
account our early results [38, 39] that CDP presents a clear
mass-loss step when heated above 230 C, and the fact
that the high-temperature cubic phase of our XRD mea-
surement of Cs3(HSO4)2(H2PO4) at 170 C is, essentially,
identical to the high-temperature cubic phase of CDP (by
Yamada [33]) at 242 C (except for the thermal expansion
effect), we conclude that the XRD signal responses of CDP
and Cs3(HSO4)2(H2PO4) at 242 and 170 C, respectively,
correspond to the same system: the TSDPS of CDP.
123
E. Ortiz et al.
Therefore, the high-temperature cubic phase observed
when CDP is heated above 231 C does not correspond to a
superprotonic conducting phase of CDP.
Acknowledgements We are grateful to Professor Bengt-Erik Mel-
lander (Department of Applied Physics, Chalmers University of
Technology, Gothenburg-Sweden) for the useful discussions about the
design of the project that generated, as a product, this contribution.
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