Solar Energy 139 (2016) 695–710

Contents lists available at ScienceDirect

Solar Energy
journal homepage: www.elsevier.com/locate/solener

Exploitation of thermochemical cycles based on solid oxide redox

systems for thermochemical storage of solar heat. Part 4: Screening
of oxides for use in cascaded thermochemical storage concepts
Christos Agrafiotis ⇑, Martin Roeb, Christian Sattler
Deutsches Zentrum für Luft- und Raumfahrt/German Aerospace Center (DLR), Linder Höhe, 51147 Köln, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Air-operated Solar Tower Power Plants store the excess solar energy during on-sun operation as sensible
Received 22 February 2016 heat in porous solid materials that function as recuperators during off-sun operation. Their storage
Received in revised form 18 April 2016 capacity can be extended by coating or manufacturing the porous heat exchange modules with oxides
Accepted 20 April 2016
of multivalent metals undergoing reduction/oxidation (redox) reactions accompanied by significant heat
Available online 27 April 2016
effects (e.g. Co3O4/CoO, BaO2/BaO, Mn2O3/Mn3O4, CuO/Cu2O). Furthermore, to maximize the amount of
redox material that can be thermochemically exploited efficiently in a given thermochemical reactor vol-
Keywords:
ume, the idea of employing cascades of porous structures, incorporating different redox oxide materials
Solar energy
Cascaded thermochemical heat storage
and distributed in a certain rational pattern in space tailored to their thermochemical characteristics and
Redox pair oxides the local temperature of the heat transfer medium is set forth.
Thermogravimetric analysis studies with the oxides above were performed to identify the most
suitable ones for further cascaded operation. The Co3O4/CoO redox pair has been already proven capable
of stoichiometric, long-term, cyclic reduction–oxidation under a variety of conditions. The Mn3O4/Mn2O3
redox pair was found herein to be characterized by a large ‘‘temperature gap” between reduction
(
940 °C) and oxidation (
780–690 °C) temperature, whereas the CuO/Cu2O and BaO2/BaO pairs could
not work reproducibly and quantitatively.
Thermal cycling tests with the Co3O4/CoO and Mn3O4/Mn2O3 powders operating together under the
conditions required for complete oxidation of the less ‘‘robust” Mn3O4/Mn2O3, demonstrated that both
powders can be reduced and oxidized in complementary temperature ranges, extending thus the
temperature operation window of the whole storage cascade.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction regenerative thermal energy storage (TES) systems (Glück et al.,

Generation of Solar Thermal Electricity from Concentrating
Solar Power (CSP) plants offers significant advantages from a sys-
tem perspective, mostly because of its built-in thermal storage
capabilities (International Energy Agency, 2014). In a series of pre-
vious publications by the authors (Agrafiotis et al., 2014, 2015b;
Agrafiotis et al., 2015c) the idea of exploiting redox oxide pairs
coated on or shaped into porous structures like honeycombs and
foams, as hybrid sensible-thermochemical solar energy storage
means in air-operated Solar Thermal Power Plants (STTPs), was
set forth. The concept is based on the storage principles of such
plants like the Solar Tower Jülich (STJ) in Germany (Fig. 1a). In
such plants, similarly to existing industrial high-temperature
⇑ Corresponding author.
E-mail address: christos.agrafiotis@dlr.de (C. Agrafiotis).
1991; Tamme et al., 1991), sensible heat is the preferred heat stor-
age type: thermal energy is transferred from a hot working fluid to
a solid in the storage unit during the so-called ‘‘charging” stage and
from the solid to the cold working fluid during ‘‘discharging” (Zunft
et al., 2011).
Regenerative sensible heat storage can be ‘‘hybridized” with
either Latent Heat Storage (LHS) via Phase Change Materials
(PCMs) (Glück et al., 1991) or with ThermoChemical Storage
(TCS): in addition to sensible-only-effects the heat effects of
phase changes or chemical reactions can be exploited within the
same storage module volume. With respect to TCS, among the pos-
sible reversible reactions (e.g. decomposition of metal hydroxides,
carbonates or oxides) with substantial thermal effects, the
utilization of a pair of redox reactions involving solid oxides of
multivalent metals, is most attractive for large-scale deployment
in STPPs using air as the heat transfer fluid. In this case air can

http://dx.doi.org/10.1016/j.solener.2016.04.034
0038-092X/Ó 2016 Elsevier Ltd. All rights reserved.
696 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710

HTF flow when charging

HTF flow when discharging

4CuO → 2Cu2O+O2 4CuO 2Cu2O+O2
T = 1120 oC T = 1120 oC
ΔH= 64 kJ/molreact ΔH= 64 kJ/molreact

6Mn2O3 → 4Mn3O4+O2 6Mn2O3 4Mn3O4+O2

T = 1000 oC T = 1000 oC
ΔH= 32 kJ/molreact ΔH= 32 kJ/molreact

2Co3O4 → 6CoO+O2 2Co3O4 6CoO+O2

T = 870 oC T = 870 oC
ΔH= 202 kJ/molreact ΔH= 202 kJ/molreact

2BaO2 → 2BaO+O2 2BaO2 → 2BaO+O2

T = 690 oC T = 690 oC
ΔH= 81 kJ/molreact ΔH= 81 kJ/molreact

(a) (c)

(b)
Fig. 1. (a) The Solar Tower power plant of Jülich, schematic of its operating principle and plant layout (from (Zunft et al., 2011)); (b) schematic of operation principle of
Cascaded Latent Heat Storage (CLHS) with five Phase Change Materials (from (Dinter et al., 1991)); (c) schematic adaption of the idea in the case of hybrid sensible-TCS
storage: an exemplary Cascaded ThermoChemical Storage (CTCS) employing four different redox oxide materials, cascaded according to decreasing reduction temperature
showing the principle of operation during charging and discharging.

be used as both the heat transfer fluid and the reactant (oxygen)
and therefore can come to direct contact with the storage material
(oxide) with the two reduction/oxidation reactions producing sim-
ply oxygen-rich or oxygen-lean air. The potential of such oxides
was extensively investigated (Wong, 2011). Equilibrium thermo-
dynamic studies with the HSC Chemical Reaction and Equilibrium
Software (Roine, 2002) of 74 such single-metal solid oxide – air
systems, under nominal air at atmospheric pressure as the carrier
gas combined with economic potential evaluations, have narrowed
the redox pair systems suited to the operating temperature range
of current as well as future air-operated STPPs, to the ones listed
below in increasing order of equilibrium reaction temperature,
together with their respective storage densities (i.e. heat effects
per kg of solid oxide reactant) and the maximum weight change
with respect to the solid oxide reactant corresponding to stoi-
chiometric reactions:
2BaO2 þ DH ¢ 2BaO þ O2 Tequilibrium ¼ 690  C
DH ¼ 474 kJ=kg DWstoich ¼ 9:45%
2Co3 O4 þ DH ¢ 6CoO þ O2 Tequilibrium ¼ 870  C
DH ¼ 844 kJ=kg DWstoich ¼ 6:64%
6Mn2 O3 þ DH ¢ 4Mn3 O4 þ O2 Tequilibrium ¼ 1000  C
DH ¼ 204 kJ=kg DWstoich ¼ 3:38%
4CuO þ DH ¢ 2Cu2 O þ O2 Tequilibrium ¼ 1030  C
DH ¼ 811 kJ=kg DWstoich ¼ 10:01%
Emphasis on such ThermoChemical Storage (TCS) with redox
oxides has been placed on the Co3O4/CoO pair. Upon heating
Co3O4 is reduced to CoO at
885–905 °C (depending on the heating
rate and the powder characteristics). Oxidation of CoO to Co3O4
takes place at a slightly lower temperature upon subsequent cool-
ing. This pair undergoes stoichiometric, long-term, cyclic redox
operation under a variety of ramp rates without requiring dwelling
at either the reduction or the oxidation temperature. Relevant
research started from loose powders (Agrafiotis et al., 2014) and
has reached the level of small-size redox-oxide coated honey-
combs and foams (Agrafiotis et al., 2015b,c; Tescari et al., 2014)
as well as larger-scale porous structures either made entirely of
Co3O4 or being Co3O4-rich composites (Karagiannakis et al.,
2014; Pagkoura et al., 2015, 2014). Other studies have dealt with
the Mn3O4/Mn2O3 (Carrillo et al., 2014a,b; Wokon et al., 2014),
the CuO/Cu2O (Alonso et al., 2015) and the Fe2O3/Fe3O4 (Block
and Schmücker, 2016) pair. In addition to single-metal oxides,
multi-metal combinations of the cations above have been tested
to reduce the operation temperature range and/or cost like e.g. of
Co–Fe (Block et al., 2014), Cu–Co (Block et al., 2013), Cu–Cr, Cu–
Mn (Block and Schmücker, 2016), Mn–Fe (Block and Schmücker,
ð1Þ 2016; Carrillo et al., 2015). Mixed compositions corresponding to
spinel Ni, Mg and Cu cobaltates were not proved capable of cyclic
redox operation (Agrafiotis et al., 2014). Co- or Ca-containing per-
ovskites (Babiniec et al., 2015, 2016) have also been recently
ð2Þ
tested.
However TCS as well as LHS share the common characteristic of
taking place isothermally, i.e. at the equilibrium temperature of
ð3Þ the oxide material and at the temperature of fusion/solidification
of the PCM respectively. To exploit the full potential of both meth-
ods the entire mass of the storage medium should be above or
below this constant temperature (during on- or off-sun operation,
ð4Þ
respectively). In other words, throughout the duration of on-sun
operation, not only the heat supplied from the heat transfer fluid
to the storage medium should be sufficient to melt/reduce the
entire mass of the storage material but also to maintain it at a
 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710
temperature above its melting/reduction temperature; if at some
region or after some time the temperature drops below the melt-
ing/reduction temperature of the heat storage medium, solidifica-
tion/oxidation will respectively occur and this storage region will
become useless. Therefore a common problem for the two routes
is that when during on-sun operation the entire volume of the stor-
age module is not above the melting/reduction temperature
respectively the processes will consequently not take place/cease
in these regions.
To tackle this problem, in the case of LHS, the so-called
‘‘Cascaded Latent Heat Storage” (CLHS) concept has been proposed,
where salts with different melting temperatures are cascaded as
PCMs from the lower operating temperature upwards to the max-
imum operating temperature. A particular combination of five salts
in a series as shown in Fig. 1b for parabolic trough power plants
was discussed (Dinter et al., 1991). The salt with the highest melt-
ing temperature is selected for the hot end of the CLHS and the salt
with the lowest one for the cold one. The idea is conceptually sim-
ple: during charging (on-sun operation) the hot heat transfer fluid
enters the cascade at a temperature higher than the melting point
of the MgCl2/KCl/NaCl mixture providing the necessary heat of
fusion. Even though the heat transfer fluid will eventually come
out of this module at a lower temperature, this temperature is
enough to provide the heat of fusion and melt the second material
of the cascade and so on. In this way a higher utilization of the pos-
sible phase changes and a more uniform outlet temperature over
time can be achieved. The concept has been verified experimen-
tally and numerically by DLR in a cascade of three PCMs, namely
KNO3, KNO3/KCl and NaNO3, where the positive effects of a CLHS
compared to a non-cascaded LHS were affirmed (Michels and
Pitz-Paal, 2007).
Similarly a simple inspection of reactions (1)–(4) and the regen-
erative heat storage system of STJ (Fig. 1b) has led to the concept of
Cascaded ThermoChemical Storage (CTCS) (Agrafiotis and Pitz-
Paal, 2013). Just like the PCMs, various oxides can be cascaded with
increasing reduction temperature from the cold to the hot end; an
exemplary schematic of the operation concept employing the four
oxides of reactions (1)–(4) is shown in Fig. 1c. The analogy to
Fig. 1b is obvious: during on-sun operation air coming out of the
first module of the cascade is cooled, but nevertheless its temper-
ature is above the reduction temperature of the second material in
the cascade and therefore sufficient to dissociate it also to its
reduced form, and so on. In this respect, just like in the case of
CLHS, the full enthalpy of the heat transfer fluid – despite the fluid
becoming progressively cooler – can be stored in individual
‘‘discretized” parts of the cascade and recovered in a similar
fashion in off-sun operation.
The first three parts of the work have dealt with the Co3O4/CoO
redox pair, which due to its favourable characteristics, is consid-
ered as the starting point for the proposed application. The current
work involves the evaluation of other redox oxide pair powders
among those listed above in a more extensive and systematic
way than already initially reported (Agrafiotis et al., 2015a). Issues
like operational temperature range, peculiarities of redox opera-
tion advantages and limitations in view of their suitability for com-
bined incorporation in such a cascaded concept, are identified.
2. Experimental
Single oxides Co3O4, CuO and Mn2O3 were employed as-
received from the respective suppliers. To obtain BaO2, Ba(NO3)2
powder was calcined in alumina crucibles in a furnace under air
atmosphere at 950 °C for 4 h. In addition to single-oxide redox
pairs, a perovskite of targeted stoichiometry La0.3Sr0.7FeO3, shown
to have high, reversible oxygen uptake/release (Evdou et al., 2010),
697
Table 1
Properties of powders employed as provided by the suppliers.
Powder Supplier Purity Size
Co3O4 Materion Advanced Chemicals 99.5% 325 mesh
CuO No 1 Merck Chemicals P96.0 <160 lm
CuO No 2 Beijing Cerametek Materials Co., Ltd. 99.9% 200 mesh
Mn2O3 Materion Advanced Chemicals 99.9% 325 mesh
Ba(NO3)2 Alfa Aesar 99.0% 325 mesh
La2O3 Alfa Aesar 99.0% 325 mesh
SrCO3 Alfa Aesar 99.0% 325 mesh
Fe2O3 Alfa Aesar 99.0% 325 mesh
was synthesized via solid-state synthesis. The respective quantities
of the powder raw materials La2O3, SrCO3 and Fe2O3 were dry-
mixed and calcined at 1050 °C for 10 h, with a heating rate of
5 °C/min. The characteristics of the powders employed as provided
by the suppliers are summarized in Table 1.
Thermogravimetric Analysis and Differential Scanning
Calorimetry (TGA/DSC) experiments were performed with a Net-
zsch STA 449 F3 JupiterÒ instrument. In several experiments the
process gas effluent was diverted to a mass spectrometer (Pfeiffer,
Omnistar) via which the Oxygen concentration was recorded. The
details and the experimental protocol have been described in detail
previously. The basic approach is that during heat-up the reduction
reactions (forward schemes of reactions (1)–(4) above) start at a
specific temperature (hereafter to be denoted as Tred) whereas dur-
ing subsequent cool-down the reverse, oxidation reactions take
place at another temperature (hereafter to be denoted as Tox) that
can be different than Tred due to either hysteresis phenomena or
peculiarities of the particular oxide systems under study as will
be discussed below. The extent of reduction/oxidation can be mon-
itored by comparing the weight loss/gain vs. the stoichiometric
percentages in schemes (1)–(4). Under such conditions, reduction
was practically complete for most systems. However, the oxidation
extent depends on the particular system and can be controlled via
two ways: either by prolonged dwell at a particular temperature
where the oxidation rate is significant or by slow heating/cooling
rates during cycling from the upper to the lower temperature limit,
so that the materials spend enough time within the temperature
range of sufficiently fast oxidation kinetics. In all experiments,
unless stated otherwise, the last cooling step to room temperature
has taken place under Argon gas to ‘‘freeze” the reduced state of
the oxide and post-analyse it comparatively to the initial, oxidized
state via X-ray Diffraction (XRD) performed with a Siemens (Karl-
sruhe, Germany) D-500 Kristalloflex X-ray powder diffractometer
(Cu Ka radiation) in the diffraction angle (2 theta) range of 10–80°.
3. Results – discussion
The single-oxide systems tested are presented below in
sequence of decreasing theoretical reduction temperature (Wong,
2011), starting from the higher-temperature end.
3.1. The CuO/Cu2O redox pair
The reduction temperature for CuO has been calculated at

1030 °C (Wong, 2011). In Fig. 2a the results of TGA experiments
with two CuO powders from different sources where cycles were
performed between 1090 and 1000 °C with ramp rates of 5 and
1 °C/min and no dwell at either temperature level are shown. The
upper temperature limit was selected just slightly above the reduc-
tion temperature of CuO to avoid possible melting of Cu2O (m.p.
1232 °C). In order not to prolong extensively the experiment time,
the initial heat-up to 900 °C was performed with a high ramp rate,
30 °C/min. During heat-up both CuO powders exhibit intense
698 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710

(a) 102 1200

Tred = 1040 oC Tox= 1035 C o
Tmax= 1090 oC

100
1000
Tmin= 1000 oC
98
Weight change (%)

800
96

Temperature (oC)
94 Wt. loss:
10.3 %
10.3 % Wt re-gain: 600
5.0 %

92
Wt re-gain:
2.4 %
400
90

88 CuO No1, 1090-1000oC, 1oC/min

CuO No1, 1090-1000oC, 5oC/min 200
, Weight change (%)
CuO No2, 1090-1000oC, 5oC/min , Temperature
86
0 100 200 300 400 500 600
Time (min)

1200
(b) 102
Tred = 1045 oC CuO No1 vs. No2, 1090-1020oC, 5oC/min
Tox= 1030 oC Tmax= 1090 oC
100
Tmin= 1020 oC 1000
t=2 hrs
98

800
Weight change (%)

96 Temperature (oC)

94 600

92
400

90

200
88 Wt. loss: Wt re-gain:
11.8 % 5.0 %

Wt. loss: Wt re-gain: Wt. loss:

Weight change (%)
Wt re-gain: Wt. loss: Wt re-gain:
10.2 % 9.6 % 9.7 % 9.2 % 9.4 % 8.1 % Temperature
86 0
0 100 200 300 400 500 600 700 800 900
Time (min)
Fig. 2. Comparative weight change curves during TGA of the two CuO powders tested: (a) ramp rates of 1 and 5 °C/min without dwell; (b) ramp rate of 5 °C/min and dwell at
oxidation temperature of 1020 °C.

reduction when a temperature of about 1040 °C is reached (very Powder No1, it is clear that the ramp rate did not have any effect
close to the literature value) accompanied by a weight loss of on the extent of re-oxidation within the temperature limits exam-
10.0–10.3% corresponding to complete reduction stoichiometry ined; the weight increase for both ramp rates was limited to only
(scheme (4) above) and recorded almost instantaneously within a about 2.4 wt%. On the contrary, a difference with respect to the
very narrow temperature range. From the two experiments with powder source was observed: at the higher ramp rate of 5 °C/min,
 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710
the two powders exhibited almost identical behaviour during
reduction but Powder No 2 recovered a higher percentage of its
weight (
5.0 wt%) during subsequent re-oxidation. However, it
was clear that under these conditions complete re-oxidation of
CuO could not be achieved.
To possibly improve the re-oxidation extent, the approach of
prolonged dwell at the oxidation temperature was tested with
both powders. Experiments were performed raising further the
lower temperature limit to 1020 °C – narrowing very much thus
the temperature span – and setting the dwell time at this (oxida-
tion) temperature at 2 h, raising at the same time the number of
cycles to 5. Since reduction was fast and quantitative no dwell
was set for it. The ramp rate between 1090 and 1020 °C was set
to 5 °C/min. The results under these conditions are shown in
Fig. 2b and corroborate the trends observed in Fig. 2a. During the
first heat-up both powders undergo a fast, complete reduction.
During cool-down from the maximum temperature after the first
step of complete reduction the materials start oxidizing abruptly
from 1030 °C. Initially a steep weight increase is recorded between
when Tox is crossed until when the lower limit plateau temperature
is reached; oxidation is further accomplished during dwell at
1020 °C, however with a slower rate and recovering only a percent-
age of the total weight lost during reduction. A first conclusion is
that re-oxidation extent was improved for both powders vs. that
observed in the previous experiment. Furthermore, during the re-
oxidation steps powder No 2 systematically recovered a higher
percentage of the weight lost during reduction. However, even
though during the first re-oxidation step the material recovered
almost quantitatively its initial weight lost (9.6 vs. 10.2 wt%
(a) 9000
8000
7000
Intensity (arbitrary units)
6000
5000
4000
3000
2000
1000
0
10
(b)
Fig. 3. (a) XRD spectra comparison between the as-received CuO powder No 1 and its reduction product after TGA and last cooling step under Argon; (b) same powder on the
TGA holder before (left) and after (right) the experiment where significant shrinkage and densification can be observed.
699
respectively), gradual weight loss is taking place in the next cycles
and both the upper and the lower bounds of the weight curve shift
to lower values. In addition, the oxidation extent is always lower
than that of the previous reduction. These trends are common for
both powders. It seems that this is the ‘‘best” that can be done with
CuO since the dwell temperature is only
10–15 °C lower than that
of where oxidation starts. An overall weight loss more than the
(expected) stoichiometric was recorded at the end of the experi-
ment. This can only be attributed to any volatilization, especially
since XRD analysis of the product (Fig. 3a) indicated the reduced
phase Cu2O (JCPDS card 05-0667) as the only detectable phase
after reduction. In all cases the product was characterized by a sig-
nificant volume reduction and was highly sintered in the form of
small hard globules (Fig. 3b). From all the results for CuO so far,
it can be concluded that, even under the best possible and practical
conditions it seems that CuO cannot work reproducibly and quan-
titatively even for few cycles.
3.2. The Mn2O3/Mn3O4 redox pair
The calculated reduction temperature for Mn2O3 has been
reported as Tred = 1000 °C (Wong, 2011); recent experimental stud-
ies have identified it at
950 °C with slight deviations above or
below that value depending on the heating rate and the Mn2O3
source employed (Carrillo et al., 2014b). Thus the first experiment
with Mn2O3 powder was run between 1000 and 550 °C with ramp
rate of 10 °C/min without dwell at either temperature, based on
the behaviour of Co3O4. The results are shown in Fig. 4a (top). Just
like the other oxide systems, the material exhibits intense
o CuO reactant
o After reduction stage at TGA
o : CuO
* : Cu2O
*
o
o oo
o o
*
o * o o
*
*
*
20 30 40 50 60 70 80
Diffraction angle (2 theta) (o)
700 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710

1100
(a) Mn2O3
100 600
Tred = 940oC
Tox= 660oC Wt. (%)
Wt loss:
Wt re-gain:
T ( oC) 0
3.46 %
98 0.64 %

96 1000-550oC 10 oC/min
1100
Weight change (%)

Temperature (oC)
100 600
Tred = 925oC
o
Tox= 710 C Wt loss:
3.47 %
0
Wt re-gain:
98 3.13 %

96 1000-600oC 5 oC/min

1100
100 600
Tred = 920oC
Tox= 745 C o
Wt loss:
3.62 %
0
Wt re-gain:
98 3.41 %

96 1000-600oC 2 oC/min

0 200 400 600 800 1000 1200

Time (min)

101 1200
(b) Mn2O3, 10 oC/min, effect of Tdwell oxidation

100 1000

Tred = 940oC

99 800
Weight change (%)

Temperature (oC)
Wt loss:
3.68 %

Wt loss:
3.70 %

98 600
Wt re-gain:
3.51 %

97 400

96 Tdwell oxidation: 900oC 200

750oC
720oC
690oC Wt. (%)
650oC T ( oC)
95 0
0 100 200 300 400 500 600 700 800 900 1000
Time (min)
Fig. 4. Comparative weight change curves during TGA of the Mn2O3 powder tested: (a) effect of ramp rate (10, 5 and 2 °C/min) without dwell during cycling; (b) effect of
oxidation dwell temperature with a ramp rate of 10 °C/min, on oxidation performance.

reduction during heatup when a temperature
940 °C is reached, increases, especially when 660 °C are exceeded. Around 870 °C oxi-
accompanied by a weight loss of 3.38% corresponding to the stoi- dation rate reaches a peak; thereafter is reduced again. This trend
chiometry of complete reduction (scheme (3) above) and recorded is repeated during the second cycle, in which, though a lower level
almost instantaneously within a very narrow temperature range of oxidation is observed compared to that during the first cycle.
even before the sample has reached the upper limit temperature This system is not characterized by a narrow temperature differ-
of 1000 °C. However, during cool-down from the upper tempera- ence between reduction and oxidation like the Co3O4/CoO pair
ture limit, a practically recordable oxidation starts to take place (for which is about 20–30 °C) but rather from an oxidation temper-
only when the temperature reached is as low as 840 °C – signifi- ature much lower than its reduction temperature (
940 °C), as it
cantly lower than the Tred of 940 °C. As the temperature is further has also been observed in previous studies (Carrillo et al., 2014b).
decreased the rate of oxidation remains low. After the lower tem- Again one way to increase the re-oxidation extent is to increase
perature limit is reached and heat-up starts, the oxidation rate the dwell time in the temperature range where the oxidation rate

is high. The results by lowering the ramp rate from 10 to 5 and
2 °C/min are shown also in Fig. 4a. The extent of re-oxidation
increases with decreasing ramp rate and weight re-gain almost
reaches the one lost during reduction. In addition, the upper parts
of the weight curves become ‘‘flatter” and the curves tend to be
more symmetric with respect to cool-down and heat-up. Neverthe-
less, oxidation is always slower than reduction and the relevant
curves are ‘‘skewed” to the right.
To identify more precisely the temperature where oxidation
rate is maximum, experiments were performed with ramp rate of
10 °C/min for long dwell times at different lower level plateau tem-
perature values. Five representative such experiments are summa-
rized in Fig. 4b; it can be concluded that the oxidation rate for the
particular Mn2O3 powder under the specific conditions is signifi-
cant in the range 690–750 °C, maximum around 720 °C (olive
curve) where the weight gained during re-oxidation is just margin-
ally lower than that lost during reduction, and minute outside this
temperature range above (e.g. either at 900 or at 650 °C). This
range of oxidation onset temperature determined here (depending
on the cooling rate) is in agreement with results reported in the lit-
erature for this system in several studies either in the form of pow-
der (Carrillo et al., 2014a,b; Wokon et al., 2014) or in the form of
porous pellets (Karagiannakis et al., 2014). It should be also men-
tioned that the exact temperature ranges and the shape of the
(a)
Mn2O3
5000
Intensity (arbitrary units)
4000
3000
2000
1000
0
10
(b)
Fig. 5. (a) XRD spectra comparison between the as-received Mn2O3 powder and its reduction product after characteristic TGA experiments of Fig. 4 with last cooling step
under Argon (colour of XRD spectrum same as weight curve in Fig. 4); (b) Mn2O3 powder on the TGA holder before (left) and after (right) an experiment where the reddish
reduced phase of Mn3O4 is clearly visible. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710 701
weight change curves have been reported to depend on the source
of powder (as also observed in the present study with the two CuO
powders mentioned above) attributing the differences in beha-
viour to particular powder characteristics, like particle size distri-
bution and/or morphology (Carrillo et al., 2014b).
XRD spectra of representative final products from both sets of
experiments, with and without dwell, are shown in Fig. 5a (with
the same line colour as their respective TGA weight curves in
Fig. 4). The practically stoichiometric extent of reduction is evi-
dent: the initial product was single-phase Mn2O3 and the reduction
product in all cases single-phase Mn3O4. Reduction can also be
observed visually, since the reduction product is reddish-like in
colour in contrast to the black colour of the reactant (compared
on the TGA holder before and after an experiment in Fig. 5b). The
extent of re-oxidation seems to affect the crystallinity of the final
product: it is interesting to note the lower crystallinity of the prod-
ucts from both temperature schedules (with/without dwell) under
the conditions where the weight gain was maximized in contrast
to the other two experiments where oxidation took place only
marginally in both cycles. The two powders which were reduced
almost stoichiometrically to Mn3O4 during the first reduction but
exhibited very low re-oxidation percentage in the first oxidation
(black and grey curves in Fig 4a, b respectively) and thereafter
‘‘oscillated” between much lower levels of weight span are of much
as-received, before TGA
after TGA between 1000-550 oC, 10oC/min
after TGA between 1000-600 oC, 2oC/min
after TGA between 1000-720 oC (plateau)
after TGA between 1000-900 oC (plateau)
--- Ref. Mn3O4 --- Ref. Mn2O3
20 30 40 50 60 70 80
Diffraction angle (2 theta) (o)
702 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710

(a) 1000
BaO2
100 T = 720 oC
720

Weight change (%) 98 Wt loss:

Temperature (oC)
~ 6.8 %
Weight (%) T( oC)
heating/cooling 5oC/min
Wt loss:
~ 8.0 % heating/cooling 2oC/min
96 heating 5oC/min, cooling 1oC/min
0

94
Wt re-gain: Wt re-gain:
2.0 % 3.5 %

92

0 250 500 750 1000 1250 1500

Time (min)

(b) 1000
BaO2
100 T = 720 oC
720

T = 580 oC
98
Weight change (%)

Temperature (oC)
96 0

94 o
Weight T( C)
2oC/min, T low = 300oC
2oC/min, T low = 450oC
2oC/min, T low = 500oC
92 2oC/min, T low = 550oC
2oC/min, T low = 650oC

0 200 400 600 800

Time (min)
Fig. 6. Cyclic TGA of BaO2 powder: (a) effect of heating and cooling rates on weight change; (b) effect of lower temperature limit on weight change with ramp rate of 2 °C/min
without dwell.

higher crystallinity than their respective counterparts (violet1 and
olive curves in Fig 4a, b respectively) which ‘‘oscillated” within prac-
tically the full stoichiometric weight span.
3.3. The BaO2/BaO redox pair
The powder from the calcination of Ba(NO3)2 at 950 °C was
shown by XRD to be single-phase Barium peroxide BaO2 (see
below). According to the literature (Bowrey and Jutsen, 1978)
reduction of BaO2 to BaO takes place at
740–760 °C and is com-
pleted below 900 °C, whereas oxidation of BaO starts at about
600–650 °C and continues even at temperatures lower than
400 °C. Thus a first TGA experiment was run between 850 and
500 °C with a ramp rate of 5 °C/min throughout and no dwell
1
For interpretation of colour in Figs. 4, 6 and 9, the reader is referred to the web
version of this article.
(orange curves in Fig. 6a). After an initial weight loss at low tem-
peratures possibly due to absorbed moisture or carbon dioxide
not detectable by XRD, upon reaching
720 °C reduction takes
place in accordance to literature and just like all other oxides
tested, abrupt weight loss is recorded almost instantaneously
within a very narrow temperature range even before the sample
has reached the upper limit temperature of 850 °C. The overall
maximum weight loss associated with this reduction though is

6.8%, significantly less than the 9.45% expected from the stoi-
chiometry of reaction (1). Further heat-up to 850 °C does not have
an additional effect on the reduction extent and the weight
remains constant. During subsequent cool-down from 850 °C the
material starts gaining weight abruptly when the same tempera-
ture of
720 °C is reached, but oxidation rate at some point during
further cooling is almost negligible and the weight remains practi-
cally constant; during heat-up from the lower temperature limit
the weight increases further but the heating rate is too high and

the material reaches the reduction temperature of
720 °C before
oxidation is completed. The behaviour is repeatable from step to
step. Just like in the case of Mn2O3/Mn3O4, to prolong the material
dwell in the temperature range favourable for oxidation, a lower
ramp rate of 2 °C/min was selected and the lower temperature
limit was set to 450 °C (blue curves in Fig. 6a). The behaviour is
qualitatively identical but in this case the weight re-gain during
oxidation has been increased from
2.0% to
3.5% of the initial
weight, being though still far from that lost during the first reduc-
tion. Thereafter, the behaviour is repeatable from step to step: the
weight lost during each reduction is re-gained during each subse-
quent oxidation – but with slightly decreasing extents of both
reduction and oxidation. A third experiment with heating rate of
5 °C/min and even lower cooling rate of 1 °C/min (grey curves)
from the reduction temperature changed the shape of the weight
curves but did not improve the overall weight gain during
oxidation.
To investigate whether oxidation takes place at lower tempera-
tures at any further extent as reported in the literature, a series of
experiments was performed with the heating rate of 2 °C/min
varying the lower temperature limit of the cycle between 300
and 600 °C. The first cycles of these experiments are shown in
Fig. 6b. In some of these experiments the upper temperature limit
was set to 800 °C; this had no effect on the reduction extent. It is
clear that oxidation rate is almost negligible during cooling at tem-
peratures lower than
580 °C where the weight remains practi-
cally constant; when the lower temperature limit was set at
650 °C (magenta curve) the ‘‘flat” segment of the weight curve is
not observed. However, in all cases the over-all weight gain during
oxidation is of the order of 50% of the initial weight loss during
reduction. Even though after the first step the extents of reduction
and oxidation coincide, they are still much lower than the theoret-
ical, stoichiometric one. Similarly to the Mn2O3/Mn3O4 pair, oxida-
tion is always slower than reduction and the relevant curves are
also ‘‘skewed” to the right.
The XRD spectra of the products of several TGA experiments
where the last cooling step was performed either under Ar or
under air are shown in Fig. 7, together with that of the ‘‘initial”
material before TGA (product of calcination of Ba(NO3)2 at
200
0
200
Intensity (arbitrary units)
0
300
0
400
0
1000
500
0
10
Fig. 7. XRD spectra comparison of various TGA products vs. that of the as-synthesized BaO2 powder from calcination of Ba(NO3)2 at 950 °C for 4 h (TGA ‘‘reactant”).
C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710 703
950 °C, shown to be single-phase Barium peroxide BaO2 – JCPDS
card 86-0070). The TGA products are of much lower crystallinity
compared to the initial powder before TGA, whereas their phase
composition spans a wide range: from single-phase Barium
Carbonate (BaCO3 – JCPDS card 05-0318) to Barium Hydroxide
Hydrate(s) (Ba(OH)⁄2H2O – JCPDS cards 39-1304, 26-0154) and Bar-
ium Oxide-Peroxide ((BaO)0.25(BaO2)0.75 – JCPDS card 85-1768).
The last, oxide phase form was detected only on samples with
the final step performed under air; on the contrary, the common
characteristic of all products with the last step under Ar is the
absence of not only the ‘‘reduced” oxide BaO but of any oxide
phase. Since the TGA experiments were run with synthetic air, this
indicates that after the TGA experiment, the reduced phase of the
oxide BaO might have reacted with moisture and/or CO2 from
atmospheric air to form BaCO3 or hydrated Ba(OH)2 until the trans-
fer of the samples to the XRD instrument for analysis or even dur-
ing the XRD measurement itself, since no extra precautions for
avoiding their contact with air were taken (after TGA, each sample
was weighted in atmospheric environment and stored in a closed
vile until XRD analysis). This reactivity of BaO vs. steam and carbon
dioxide has already been reported (Bowrey and Jutsen, 1978).
The combined results from above, i.e. the non-stoichiometric
re-oxidation extent as well as the difficulty in avoiding the Barium
oxide hydration/carbonation under realistic conditions where the
air flowing through the redox storage medium cannot be com-
pletely purified from moisture or CO2, render this pair not strategi-
cally suited for this application.
3.4. The LaxSr1xFeO3/LaxSr1xFeO3d redox pair
XRD analysis of the La2O3/SrCO3/Fe2O3 mixture calcined at
1050 °C for 10 h (Fig. 8a) has shown La0.3Sr0.7FeO3 as the major
phase (JCPDS card 82-1964) as well as minor peaks corresponding
to Sr3Fe2O6 (JCPDS card 45-399) in accordance to previous relevant
studies (Nalbandian et al., 2009). The TGA results of this sample
cycled twice between 1200 and 800 °C with heating/cooling rate
of 5 °C/min are shown in Fig. 8b (the initial heat-up to 600 °C
was performed with a higher ramp rate of 30 °C/min). In contrast
to the single oxides tested above, the material is not characterized
Product of TGA 850-550 oC, heatup 5oC/min, cooldown 1oC/min, last step in air
--- Ref BaO0.25(O2)0.755 (JCPS 85-1768)
Product of TGA 850-500 oC, 5oC/min, last step in air
--- Ref Ba(OH)2*H2O-JCPS 39-1304; --- Ref Ba(OH)2*H2O-JCPS 26-0154
--- Ref (BaO)0.25(BaO2)0.755-JCPS 85-1768
Product of TGA 850-300 oC, 2oC/min, last step in Ar
--- Ref Ba(OH)2*H2O-JCPS 39-1304; --- Ref Ba(OH)2*H2O-JCPS 26-0154
Product of TGA 850-450 oC, 2oC/min, last step in Ar
--- Ref BaCO3-JCPS 05-0378
Ba(NO3)2 calcined at 950 oC-4 hrs, before TGA
--- Ref BaO2
20 30 40 50 60 70
Diffraction angle (2 theta) ( o)
704 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710

(a) 500
After calcination at 1050oC, 4 hrs
--- Ref. La0.3Sr0.7FeO3; --- Ref Sr3Fe2O6

400

Intensity (arbitrary units)

300

200

100

0
10 20 30 40 50 60 70 80
Diffraction angle (2 theta) (°)

(b) 101
Tmax = 1200 oC
1200

100 1000
Weight change (%)

Temperature (°C)
Wt loss:
1.35 % Tmin= 800 oC
99 800
Wt re-gain:
0.6 %
600
98
400

97
200
La0.3Sr0.7FeO3 1200-800oC, 5oC/min
Weight change (%)

96
Temperature
0
0 100 200 300 400 500 600
Time (min)

Fig. 8. (a) XRD spectrum of the as-synthesized perovskite powder showing La0.3Sr0.7FeO3 as the major phase and minor peaks of Sr3Fe2O6; (b) weight change curves during
cyclic TGA of La0.3Sr0.7FeO3 powder, tested between 1200 and 800 °C with ramp rate of 5 °C/min without dwell.

by a specific reduction and oxidation temperature value where 3.5. Combination of Co3O4/CoO–Mn2O3/Mn3O4 redox pairs
‘‘abrupt” weight loss or gain takes place; instead weight loss is
observed from the early stages of heating and proceeds in a Based on the findings above, the CuO/Cu2O and the BaO2/BaO
quasi-linear mode until the highest temperature is reached. During pairs were excluded from further studies. The perovskite systems
cool-down to 800 °C this trend is reversed: the material gains although being in principle suitable for a cascaded configuration,
weight in the same fashion. Even though the amount gained during need further research especially with respect to their redox reac-
the first cool-down is less than originally lost during the first heat- tions heat effects. This leaves practically only the two pairs
up from ambient temperature to 1200 °C, the behaviour in the next Co3O4/CoO and Mn2O3/Mn3O4 among the single-oxide redox pairs
steps is totally reversible: when cycled between 1200 and 800 °C for further investigation. It should be noted that the reduction tem-
the material gains and loses exactly the same amount of Oxygen peratures of these systems were identified as
895 and
940 °C
upon cooling/heating respectively. This characteristic is in princi- respectively, i.e. both higher than that of the air provided currently
ple favourable for a cascade configuration since the redox reactions from STJ; however a target in future STPPs is to supply air of higher
can take place throughout the cascade irrespective of its particular temperature. The Mn2O3/Mn3O4 pair has a very peculiar behaviour,
temperature. However the overall weight loss is rather small, characterized by a large temperature gap between reduction
something that implies that also the heat effects of these reactions (
940 °C) and oxidation (
780–690 °C) temperature. In addition,
will be small as well. A similar quasi-linear weight loss/gain has there exists only a very narrow temperature range (
690–
been observed in a series of Co-containing perovskites (Babiniec 750 °C) within which Mn2O3 oxidation proceeds with a significant
et al., 2015), where also the weight change for one cycle under rate, this oxidation is in general slow and needs extended dwell at
air was very small and Argon atmosphere was employed to aug- the optimum temperature (range) for completion.
ment it. The highest reaction enthalpy has been calculated from A comparison of the reaction enthalpies of the two systems was
these experiments as 250 kJ/kg-ABO3 for a La0.3Sr0.7Co0.9Mn0.1O3d performed via DSC experiments. Samples of equal weight of Mn2O3
stoichiometry. and Co3O4 powder were cycled under the same conditions, for 2
 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710 705

cycles between 1000 and 600 °C, without dwell, with low ramp
rates of 2 and 4 °C/min to ensure almost complete oxidation of
Mn3O. The ‘‘corrected” DSC curves (subtracting the curves from
those of blank experiments under the same conditions) for the
experiments with the two ramp rates of 2 and 4 °C/min are shown
in Fig. 9a and b respectively, together with the relevant TGA curves
(blue for cobalt oxide). Under such conditions, after applying the
correction, in one hand the baselines of the plots for the two pow-
ders under the same ramp rate practically coincide in regions
where no reactions accompanied from significant heat effects take
place; in the other hand the intensities of the endothermic and
exothermic peaks of the two systems provide a direct qualitative
comparison between the enthalpy effects of reactions of equal
masses of powders.
The reaction enthalpies for Co3O4 have been calculated from DSC
experiments as a function of ramp rate in Part I of this publication
series (Agrafiotis et al., 2014) in the range 480–560 kJ/kg, about 57–
66% of its theoretical. In the case of Mn2O3 with both rates of 2 and
4 °C/min the DSC signals for exothermic/endothermic reactions
were very small. During the first heat up and the first reduction
point – 928 °C for 4 and 917 °C for 2 °C/min – a small, but neverthe-
less visible peak upwards (endothermic) can be observed in both
graphs. Thereafter, during all other subsequent reductions/
oxidations as recorded from weight change, the DSC signals are
non-distinguishable. Based on that, the only calculations and
comparison of heat effects that could be made were for the first
reduction peak. A comparison for the two ramp rates, with the
respective plots truncated after this point and after subtracting
the respective baselines is shown in Fig. 10. Just like in the case of
Co3O4, as the ramp rate increases the DSC peaks become sharper
but the heat effects recorded are lower, as an integration of the area
under the relevant curves demonstrates. The calculated areas
are provided in Table 2; they were converted to kJ/kg to be
compared to the theoretical value taken as 202 kJ/kg (Wong,
2011) in the last column of the table, ranging between 42% and
68% of it (85–140 kJ/kg). These values are in the same range with
reduction enthalpies reported recently (160–170 kJ/kg) obtained
from similar experiments with the same system (Carrillo et al.,

(a) 101
Co3O4, Mn2O3, 1000-600oC, 2 oC/min
1

T 1000
, TGA
100
0
99
Weight change (%)

800
98 -1

Temperature (oC)

DSC (mW/mg)
97
600 -2
96

95 -3
400

94
-4
93 200
, DSC corr

92 -5
0 200 400 600 800 1000 1200 1400
Time (min)

(b) 101
Co3O4, Mn2O3, 1000-600oC, 4 oC/min
1
T
, TGA 1000
100
0
99
Weight change (%)

800
98 -1
Temperature (oC)

DSC (mW/mg)

97
600 -2
96

95 -3
400

94
-4
93 200
, DSC corr
92 -5
0 100 200 300 400 500 600 700
Time (min)

Fig. 9. Comparison of TGA and corrected DSC curves between the Mn2O3 and Co3O4 powders between 1000 and 600 °C with heatup/cooldown rate of (a) 2 and (b) 4 °C/min.
706 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710
101
Mn2O3, 1000-600oC, 2 and 4 oC/min
100
99
Weight change (%)
98
97
96
95
T 2 oC/min
T 4 oC/min
94
0 50 100
Fig. 10. Comparison of TGA and ‘‘smoothed” DSC curves for Mn2O3 during the first reduction step between 1000 and 600 °C without dwell and heatup/cooldown rates of 2
and 4 °C/min.
Table 2
Heats of reduction reactions of Mn2O3 calculated per step from the relevant areas
under the curves of the DSC experiments, as a function of ramp rate and comparison
to the theoretical value (taken as 202 kJ/kg).
Powder Ramp rate Calculated area under DH (kJ/kg)
(°C/min) the 1st peak of DSC
curve (mW/mg)
Mn2O3 4 1.41 84.6
2 2.31 138.6
2014b), where the authors also noticed sharp reduction peaks but
much broader oxidation peaks, similarly to the present study. It
has recently been shown though, that at least in the case of the
Co3O4/CoO pair, such deviations from the theoretical heat of reac-
tion can occur due to additional reactions accompanied by heat
effects that take place during the actual heating/cooling TGA exper-
iments like the Co3+ spin state change (Block and Schmücker, 2016)
but are not taken care of in the theoretical calculations.
To investigate the combined behaviour of these two redox pairs,
at first experiments with quantities of both powers not touching
each other (Fig. 11a) placed on the TGA holder were performed
under conditions where the Mn2O3/Mn3O4 pair exhibited the best
oxidation performance, either with slow ramp rate and no dwell, or
with higher ramp rate and extended dwell at the oxidation
temperature.
In Fig. 11b, the weight curves of experiments corresponding to
the first case i.e. with a low ramp rate of 2 °C/min between 1000
and 600 °C and no dwell are shown, in comparison to the ‘‘plain”
Co3O4, and Mn2O3 powders. In one hand, the differences between
the two ‘‘plain” powders are clearly distinguishable: in the case
of Co3O4 both reduction and oxidation take place almost instanta-
neously, to the same stoichiometric extend and the weight curves
are perfectly symmetric in contrast to the ‘‘skewed” ones of Mn2O3
which, however, under these conditions also proceed to almost
stoichiometric oxidation. In the other hand it is obvious that the
curve corresponding to the two powders placed simultaneously
on the TGA holder is a ‘‘superposition” of the curves of the two
individual powders. Reduction takes place almost instantaneously,
whereas oxidation in two consecutive steps: one fast due to the
oxidation of CoO and one much slower due to the oxidation of
2.0
1000
T=917oC
1.5
800
Temperature (°C)
DSC (mW/mg)
1.0
600
0.5
400
0.0
200
TGA, 2oC/min DSC, 2oC/min
TGA, 4oC/min DSC, 4oC/min
-0.5
150 200 250 300 350 400 450
Time (min)
Mn3O4 recovering almost fully the total weight lost during
reduction, in a reproducible pattern during six consecutive cycles.
The reduction product after TGA is shown in Fig. 11a, where again
the red colour of the Mn oxide after TGA indicates clearly reduction
DH (% th.) to Mn3O4. The results are shown together with the respective
mass-spectrometer signals analysing for compound of atomic mass
units (a.m.u.) of 32 (O2), (bottom half of Fig. 11b). A characteristic
41.9% ‘‘magnification” of the second cycle is shown in Fig. 11c. It is clear
68.6% that the Co3O4/CoO pair uptakes and releases Oxygen during heat-
up and cool-down respectively. However, distinct oxygen peaks for
the Mn2O3 powder, either alone or in the experiment together with
the Co3O4 can only be observed during its reduction step. During
its oxidation, even if a weight gain is clearly recorded, any oxygen
signal attributable to Mn2O3 re-oxidation is practically indistin-
guishable in both experiments. During the heating steps the two
powders are reduced instantaneously, yet consecutively; their
reduction temperatures are close to each other, but nevertheless
distinct, as it can be clearly observed in Fig. 11c.
The two-powder configuration was also tested with a ramp rate
of 10 °C/min between 1000 and 720 °C with 3 h dwell time at oxi-
dation. A relevant experiment with Co3O4 was not performed,
since, based on the previous results during such a cycle, complete,
cyclic reversible reduction–oxidation of the Co3O4/CoO pair is also
expected. For comparison purposes though, a mixture of the two
powders (Co3O4 + Mn2O3) in the same analogies as in the TGA
experiment above was prepared and comparatively tested under
the same schedule to check for any differences in behaviour, possi-
ble reactions between Co3O4 and Mn2O3 etc. The TGA results are
shown in Fig. 12a compared to the respective experiment with
‘‘plain” Mn2O3 (olive curve as in Fig. 4b) under the same conditions.
The powder mixture, even though it exhibits an abrupt weight loss
during the first heat-up to 1000 °C, gains weight upon further heat-
ing, even during dwell at the high-temperature limit of 1000 °C.
The sample continues to gain weight with a different rate upon
cooling from 1000 °C until T = 865 °C is reached. At this point the
sample’s weight stabilizes and remains at this value throughout
the subsequent dwell period at the lower temperature of 720 °C.
In the next cycle the phenomena are similar, but much less intense
in scale and they tend to attenuate with increasing number of
cycles, where only minor changes in weight are further recorded.
The XRD spectra of the Co3O4/Mn2O3 powder mixture before and
 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710 707

(a)

101 1100
(b)
100
600
99

Temperature (°C)
Weight change (%)

98
0
97
96
95
94 1000-600oC; 2 oC/min; no dwell
Co3O4
Mn2O3
93
Weight change (%) Co3O4-Mn2O3 non-mixed
Temperature
92 1100 3.0x10
-8

600
-8
0 2.0x10

amu 32, O 2
-8
1.0x10

32 amu, O2
0.0

0 400 800 1200 1600 2000 2400 2800

Time (min)

(c) 101 1100 1.9x10

-8

o
o
T = 870 C
T = 955 C
100 o
T = 930 C
600
99
Weight change (%)

98
0
97
-8
1.5x10

96
Temperature (°C)

95
amu 32, O

94
2

93
Temperature
Weight change (%) 32 amu, O 2
92 1.1x10
-8

550 600 650 700 750 800 850 900 950

Time (min)
Fig. 11. (a) Co3O4 and Mn2O3 powders placed together and non-mixed on the TGA holder before (left) and after (right) cyclic TGA between 1000 and 600 °C with ramp rate
2 °C/min without dwell during cycling, with the reddish reduced phase of Mn3O4 clearly visible after the experiment; (b) comparative weight change curves during such
experiments with Co3O4, Mn2O3, and non-mixed Co3O4 and Mn2O3 powders in conjunction with gas effluent analysis of emissions of amu 32 (O2) via a mass-spectrometer; (c)
‘‘magnification” of the second cycle.

after TGA are shown in Fig. 12b, from where it can be concluded demonstrated in the TGA graph is not capable of significant oxygen
that the two powders have reacted with each other: the product release/uptake.
after TGA is a low-crystallinity, mixed Co–Mn spinel oxide On the contrary the two non-mixed powders exhibited again
(Co,Mn),(CoMn)2O4 (JCPDS card No 14-808) which, as repeatable and ‘‘additive” redox behaviour. The results of the
708 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710

1200
(a) 101
T = 950 oC
100
Wt loss:
3.54 %
600
99

Temperature (°C)
98
Weight change (%)

Wt re-gain:
0
3.51 %
97

96

95

94 Co3O4-Mn2O3
10 oC/min; Tdwell oxidation: 720oC
93 Mn2O3
Co3O4-Mn2O3, non-mixed
Weight change (%)
Co3O4-Mn2O3, mixed
Temperature
92
0 200 400 600 800 1000 1200 1400
Time (min)

150
(b) Co3O4-Mn2O3 mixture after TGA between 1000-720 oC
--- Ref (Co,Mn)(Co,Mn)2O4 -18-408

100
Intensity (arbitrary units)

50

0
Co3O4-Mn2O3 mixture as-prepared before TGA
--- Ref Co3O4 --- Ref Mn2O3

200

100

0
10 20 30 40 50 60 70 80
Diffraction angle (2 theta) (°)
Fig. 12. (a) Comparative weight change curves during four TGA cycles between 1000 and 720 °C with ramp rate 10 °C/min and dwell times of 1 h at 1000 °C and 3 h at 720 °C,
of Mn2O3, non-mixed and mixed Co3O4 and Mn2O3 powders; (b) XRD spectrum of the mixed powder before and after TGA, with the latter being a mixed Co–Mn spinel (Co,
Mn), (CoMn)2O4.

non-mixed powders are shown together with the mass-
spectrometer signal for O2, in Fig. 13a; characteristic ‘‘magnifica-
tions” of two steps, one at the beginning and another towards
the end of the experiment are shown in Fig. 13b, c. It is again clear
in the ‘‘magnifications” of Fig. 13b, c that during all heat-up steps
the two powders are reduced instantaneously and consecutively.
During the first cool-down after the dwell at the upper tempera-
ture limit (Fig. 13b), there is a distinct abrupt weight gain accom-
panied by sharp oxygen uptake corresponding to Co3O4 (its re-
oxidation temperature is slightly lower than its initial reduction
temperature); this weight gain is not equal to the total weight loss
that occurred during reduction. During the next, isothermal step at
720 °C, even though a further increase of the sample’s weight is
recorded – obviously due to Mn3O4 oxidation – this is not accom-
panied by a visible Oxygen uptake. Before the end of this isother-
mal stage, the sample’s weight has been stabilized to a level just
marginally lower than its initial value before reduction. During
the next steps the phenomena are exactly repeated. Only during
the last the isothermal oxidation stage (Fig. 13c) a ‘‘broad” peak
evidently corresponding to Oxygen uptake from Mn3O4 can be
somehow distinguished. The same trend of ‘‘shift” of the weight
curve to lower absolute values with increasing number of cycles
typical for all experiments involving Mn2O3 can also be observed
here. Entirely similar in shape oxygen concentration profiles
including very sharp peaks during reduction and very broad and
low peaks during oxidation have been also obtained in other recent
studies with the Mn2O3/Mn3O4 (Karagiannakis et al., 2014)
employing 10 g pellets and dwell at oxidation temperature levels.
 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710 709

(a) 101 1200 4.0x10 -9

100
3.0x10 -9
600

Weight change (%)

99
2.0x10 -9
98

amu 32, O 2
0
97
1.0x10 -9
96
0.0

Temperature ( oC)
95 Wt loss: Wt re-gain:
5.08 % 4.80 %
Wt loss: Wt re-gain:

94 5.04 % 4.73 % Wt loss:

4.54 %
Wt re-gain:
4.69 %
-1.0x10-9
Wt loss: Wt re-gain: Wt loss:
4.99 % 4.74 % 4.88 %

o o
Co3O4-Mn2O3; 10 C/min; Tdwell oxidation: 720 C
93 Mn2O3
Weight change (%)
Temperature
Co3O4-Mn2O3, non-mixed
32 amu, O2
-2.0x10-9
92
0 200 400 600 800 1000 1200 1400
Time (min)
-9 -9

(b) 101
1200 4.0x10 (c) 101 1200 4.0x10

100 100 T = 965 oC

T = 955 oC
99 T = 935 oC o
99
T = 840 C T = 940 oC
Temperature (°C)

Weight change (%) T = 840 oC

Weight change (%)

Temperature (°C)
-9 -9
98 800 2.0x10 98 O2 from Co3O4 800 2.0x10
O2 from Mn2O3

amu 32, O2
97 O2 from Co3O4 97

96 96 O2 from Mn2O3
O2 to Mn3O4

95 400 0.0 95 400 0.0

amu 32, O2

94 94 O2 to CoO
O2 to CoO

Co3O4-Mn2O3; 10 oC/min; Tdwell oxidation: 720oC

93 Mn2O3
Weight change (%) 93 Co3O4-Mn2O3; 10 oC/min; Tdwell oxidation: 720oC Weight change (%)
Temperature Mn2O3 Temperature
Co3O4-Mn2O3, non-mixed Co3O4-Mn2O3, non-mixed
32 amu, O2 -9 32 amu, O2 -9
92 0 -2.0x10 92 0 -2.0x10
60 80 100 120 140 160 180 1000 1100 1200 1300
Time (min) Time (min)

Fig. 13. (a) Same weight change curves as in Fig. 12a in conjunction with gas effluent analysis of emissions of amu 32 (O2) via a mass-spectrometer; (b), (c) ‘‘magnifications”
of the first and last cycles respectively.

4. Conclusions operation of current and future air-operated STPPs, besides

Co3O4/CoO only Mn2O3/Mn3O4 is capable of cyclic operation. How-
The current solar heat storage concept in air-operated Solar ever, whilst the Co3O4/CoO system undergoes stoichiometric, cyclic
Tower Power Plants as sensible heat in porous solid materials oper- reduction–oxidation under a variety of heating/cooling rates and
ating off-sun as regenerators can be rendered to a ‘‘hybrid” sensi- within a narrow temperature range, Mn2O3/Mn3O4 is characterized
ble/thermochemical one via coating the porous heat exchange by a lower reaction heat effect especially during oxidation, slower
modules with oxides of multivalent metals for which their reduc- oxidation rate and a large temperature gap between reduction
tion/oxidation reactions can take place within the plant’s air tem- (
940 °C) and oxidation (
780–690 °C) temperature. Furthermore,
perature operating range and are accompanied by significant heat the CuO/Cu2O and BaO2/BaO pairs cannot work reproducibly and
effects or by manufacturing them entirely of such oxides. Further- quantitatively due to different reasons. The former is characterized
more, the construction modularity of current state-of-the-art sen- by a reduction temperature high enough to cause extensive sinter-
sible storage systems provides for the implementation of concepts ing and shrinkage of the material. The reduced phase of the latter,
like spatial variation of redox oxide chemistry and solid materials BaO, reacts even with traces of any moisture and/or CO2 present in
porosity along the storage module, to enhance the utilization of the surrounding atmosphere to hydrated Barium hydroxides and
the heat transfer fluid and the storage of its enthalpy. In this per- Barium carbonate respectively, a fact severely limiting the poten-
spective the idea of employing cascades of various porous struc- tial implementation of this pair in the particular application under
tures, incorporating different redox oxide materials and realistic on-site conditions. In the other hand perovskite systems
distributed in a certain rational pattern in space tailored to their that are not characterized by a distinct reduction/oxidation tem-
thermochemical characteristics and to the local air temperature perature range but they release/gain oxygen in a continuous mode
has been set forth and tested. during the heating/cooling stages respectively are in principle
TGA studies were performed among those redox systems iden- favourable for a cascaded configuration like the one mentioned
tified as in-principle suitable via thermodynamic calculations, herein, together with any other current or future mixed oxide
namely CuO/Cu2O, Mn2O3/Mn3O4 and BaO2/BaO as well as with compositions, provided that they can operate in a reversible,
one perovskite system, to determine their operational temperature multi-cyclic redox mode with significant reaction heat effects.
range, cyclability, limitations and peculiarities of redox operation. A combination of two single-oxide systems, namely Co3O4/CoO
These experiments have shown that among the single-oxide and Mn2O3/Mn3O4 has been further explored. Thermal cycling tests
systems exhibiting redox behaviour in the temperature range of with these two powders together under the conditions required for
710 C. Agrafiotis et al. / Solar Energy 139 (2016) 695–710
complete oxidation of the less ‘‘robust” one, Mn3O4/Mn2O3,
demonstrated in principle the proof-of-concept of the cascaded
configuration, i.e. that both powders can be reduced and oxidized
in complementary temperature ranges, extending thus the temper-
ature operation window of the whole storage cascade. However
the heat effect of Co3O4 per unit volume is much higher than that
of Mn2O3. Therefore, to maximize the amount of heat generated
per unit volume of a cascaded storage module during discharging,
the region of the cascade containing Mn2O3 should be limited only
to where the temperature during discharging cannot reach the oxi-
dation temperature of Co3O4; this naturally depends on the flow
rate and temperature of the air stream introduced in the cascade
during the discharging step. The demonstrated chemical reaction
between the Co3O4 and Mn2O3 powders to a redox-inert phase
induces the necessity of some physical separation. This, for exam-
ple, could be just a ‘‘thin slice” of non-coated porous supports
between the Co3O4- and the Mn2O3-coated ones, operating as
sensible-only heat storage modules. Such aspects, including the
relevant materials cost, are currently under consideration for the
design of a larger-scale unit.
Acknowledgements
Dr. C. Agrafiotis would like to thank the European Commission
for funding of this work within the Project ‘‘FP7-PEOPLE-2011-IEF,
300194; Thermochemical storage of solar heat via advanced reac-
tors/heat exchangers based on ceramic foams (STOLARFOAM)”
under the Intra-European Fellowship Marie Curie Actions of the
7th Framework Programme and to DLR Programmdirektion Ener-
gie (PD-E) for funding through the Project ‘‘Thermochemical stor-
age for CSP-applications based on Redox-Reactions – from
materials to processes (REDOXSTORE)”.
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