Heat and Mass Transfer

https://doi.org/10.1007/s00231-020-02990-y

ORIGINAL

Paper title: thermochemical heat storage behavior of ZnSO4.7H2O

under low-temperature
Ata Ur Rehman 1,2 & Muhammad Khan 3,4 & Zheng Maosheng 1 & Ahsen Riaz Khan 1 & Asif Hayat 5

Received: 29 November 2019 / Accepted: 24 October 2020

# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
Thermochemical heat storage materials for space heating applications such as, ZnSO4 offer high energy storage density, low cost
and clean mean of long-term solar energy storage. Herein, we studied the ZnSO4 hydrated salt as potential heat storage material at
low temperature and furthermore observed the impact of temperature and concentration on the dehydration/hydration process and
enthalpy. The thermal behavior of ZnSO4•7H2O was investigated by applying various dehydration temperatures. The results
showed that 85% of water loosed at 100 °C temperature, which released 699 J/g (1.37 GJ/m3) in the dehydration process. The
hydration process of ZnSO4.7H2O at 100 °C recovered 541 J/g enthalpies, which delivered 1.1 GJ/m3. Similarly, the dehydration
result obtained at 150 °C was the same as showed at 100 °C. However, the enthalpy of hydration was 20% less than prior. The
XRD result showed that at higher temperatures agglomeration appeared followed by Van der Waals forces which affect the
hydration rate. The result of good cyclability and larger water sorption performance of ZnSO4 make them a promising and
suitable for heat storage in space heating application, which can be used as thermochemical heat storage material for thermal
storage devices.

Keywords Heat storage . Renewable energy . Hydration and dehydration . Zinc sulfate heptahydrate

1 Introduction of non-sustainable power sources to sustainable power sources

which are more energy efficient and environment-friendly in
The expanded interest in energy, the ascent in the cost of fuel the procedure as compared to carbon-based systems. Previous
related to the consumption of petroleum derivatives, and the studies suggested that the required percentage of thermal ener-
impact of greenhouse gasses on our climatic needs replacement gy in the residential area was in between 40 and 50% of the
final energy [1]. Since to avoid carbon-based technologies, the
required amount of space heat energy can be covered through
* Ata Ur Rehman
ataurrehman257@gmail.com
renewable energy sources such as tidal energy [2], wind energy
[1], and solar energy [2–4]. Among these sources, solar energy
* Muhammad Khan
mkhanchemistry@yahoo.com
application is an emerging research field with increasing atten-
tion for their high thermal energy potential, easiest availability
1
and with an advantage of zero greenhouse gasses emission [1].
Institute for Energy Transmission Technology and Application, Although solar energy exhibits some serious drawbacks, such
School of Chemical Engineering, Northwest University,
Xi’an, Shaanxi, People’s Republic of China as the unpredictability of energy supply and the disparity be-
2 tween heat demands (winter) and optimum solar energy supply
Department of Chemistry, Bacha Khan University,
Charsadda, Pakistan (summer) [2, 4–7]. In order to match the energy gap, thermal
3 energy storage (TES) technology, based on solar energy is a
School of Materials Science and Engineering, Northwestern
Polytechnical University, Xi’an 710072, Shaanxi, People’s Republic perfect choice. TES system is a highly promising technology,
of China particularly in the view of long-term heat storage. In commer-
4
Department of Chemistry, University of Okara, Renala Khurd, cial space heating application, storage of thermal energy is re-
Okara, Punjab, Pakistan quired, especially, when the supply of energy from renewable
5
College of Chemistry, Fuzhou University, Fuzhou, People’s sources is low (i.e. thermal energy demand is high in the winter
Republic of China and low in the summer). Thus, TES can be used to bridge the

gap between supply and demands. The storage of TES in do-
mestic space heating application can be stored in three know
systems including sensible heat storage (SHS) [8, 9], latent heat
storage (LHS) [10, 11] and thermochemical energy storage
(TCES), [12–14]. Based on larger storage density and econom-
ical view point, TCES has the potential to store 10–15 time
larger thermal energy than other conventional systems Fig. 1
[8, 15, 16], and almost loss free for an indefinite amount of
time. Additionally, thermal storage based on thermochemical
reaction from solar energy is a key element in increasing energy
storage for future use. Energy storage density (GJ/m3) of TCMs
is 5–14 times higher than SHS, LHS and the traditional water
storage methods [18]. Since TCE storage technology is an ad-
vanced and reliable process which is still unexplored. In this
technology, heat loss during charging and discharging is almost
negligible, because of energy stored in the form of chemical
potential [7, 9, 17–20]. The thermochemical energy storage is a
reversible chemical process with charging and discharging be-
tween solid and gas as shown in Fig. 2.
Numerous candidates were perversely investigated for pos-
sible thermochemical heat storage materials TCMs. Among
these, salt hydrates offer lower dehydration temperature,
non-toxic, larger theoretical energy density, good cyclability
and conductivity which is a better choice for seasonal solar
heat storage application. The charging/discharging principal
of Salt-H2O pair is simple and convenient for solar thermal
storage (Fig. 2). In summer, during heat peak (charging), salt
hydrates loss water with heat energy (ΔH) in a closed chamber
connected with solar radiation trapping device and in winter
(discharging), the water vapor is allowed to react with dehy-
drate salt, and in the result of chemical reaction heat energy
Fig. 1 Storage density versus
physical phenomena involved [8]
Heat Mass Transfer
(ΔH) is obtained. It should be noted that presently the solar
heat trapping device (medium solar heat collector) can only
increase temperature of material up to 150 °C. Many salt hy-
drates including hydrates of MgSO4 [15], MgCl2 [16], CaCl2
[14], CuSO4 [6], and SrBr2 [18, 21] are well-known thermo-
chemical heat storage materials (TCMs) studies in previous
literatures.
Sulfate based salt hydrates (CuSO4•5H2O, FeSO4•7H2O,
LiSO4•H2O, MgSO4•7H2O) is a major class of promising re-
versible TCMs [22]. In the sulfate-based salt hydrates,
Magnesium sulfate heptahydrate hydrate (MgSO4•7H2O)
have been extensively investigated as an appropriate candi-
date for solar thermal storage. Rehman at al [8], suggested
that dehydration of MgSO4 involve two water loss steps with
88% H2O and contain 2.8 GJ/m3 and good cyclability.
However, at practical circumstances, the hydration reaction
of MgSO4 become very slow, this subsequent low enthalpy
upgrade and low H2O uptaking ability under practical condi-
tion. Additionally, at ambient temperature (25 °C), MgSO4 its
self-discharging drawback. Moreover, poor cyclability is also
a drawback, which is due to structural instability, during de-
hydration of MgSO4 at 55 °C the material slightly transforms
to amorphous state. These disadvantages of MgSO4 limit the
heat storage ability and motivate the researcher to search new
thermochemical heat storage material.
Zinc sulfate heptahydrate (ZnSO4•7H2O) (ZSHh) is an un-
explored TCM candidate which has the potentially of high
theoretical energy density (1.97 GJ/m3), low market price
and easily achievable dehydration temperature (< 100 °C)
with an advantage of maximum hydration energy at realistic
conditions (25 °C and 1 atm) [23–26]. Our study reported that
Heat Mass Transfer
Fig. 2 Thermochemical storage
process cycle: charge, storage and
discharge
ZnSO4 showed similar behaviour likewise MgSO4 with max-
imum water sorption performance, good cyclability and ex-
cellent hydration/dehydration enthalpy. Previous study sug-
gested that due to its undefined dehydration/hydration (DH)
pathway zinc sulfate show water sorption and undefined DH
pathway disadvantage [6]. Rabbering et al., investigated the
dehydration of ZSHh and identified that hexahydrate and
tetrahydrate are unstable stages between hepta and
monohydrate stage through thermogravimetric analysis
(TGA) [6, 27]. On the other hand, Spiess and Gruehnet al.,
founded that hexahydrate is not an intermediate between hepta
and monohydrate [28]. Chihara and Seki et al., test their var-
ious dehydration through TGA and found transition stage
7 → 6β, 6β → 6α (spontaneously), 6α → 6γ, 6γ → 4, 4 →
1, 1 → 0 [29]. Besides dehydration, hydrations of zinc sulfate
heptahydrate face also pathway problems. For hydration pro-
cess, Posern et al., proposed various hydration pathway of
ZSHh and found that possible hydration will follow anyone
pathway mentions in Fig. 3 [23].
According to Hess’s Law, the total enthalpy of a reaction is
indefinite from pathway i.e. in the ideal case the dehydration
enthalpy is always equal to hydration enthalpy but opposite in
sign. Since on the basis of all contradictory literature and
interesting facts about ZnSO4 as TCMs, it attracts us to inves-
tigate the various sides of ZnSO4 for seasonal solar heat stor-
age in the form of the chemical method (TCES).
The aim of the present study investigated hydration/
dehydration for mass and heat transfer, water sorption perfor-
mance and cyclability of ZnSO4•7H2O as potential heat stor-
age material for seasonal heat storage devices.
2 Experimental
2.1 Materials
Analytical grade ZnSO4•7H2O was selected for this study, on
the basis of their interesting properties, i.e. high crystal storage
density, low cost, non-toxicity, easy availability, and favor-
able temperature range. TGA technique was used to confirm
the hydration level of pure salts. Analytical grade ZSHh was
purchased from Guangdong Guanghua Sci-Tech Co., Ltd.
China.
2.2 Instrument and method
2.2.1 Instruments
The instruments used in the method are the same as used in
previous literature [30, 31].
2.2.2 Dehydration
The water desorption capacity and dehydration heats in
ZnSO4 material was measured through thermogravimetric
analysis (TG) coupled to a differential thermal analysis
(DTA) (Henven HTC-1) [30, 31]. Since in the previously
study it was suggested that there are various dehydration path-
ways. In order to follow the validate dehydration pathway,
10–15 mg of sample was used in a dynamic method from
25 °C up to 300 °C with two different heating rate 1 °C/min
and 5 °C/min, respectively. All the TG-DTA experiment was

Fig. 3 Possible hydration
pathways of ZnSO4·H2O
conducted at realistic conditions (RC). TG was used to mea-
sure the number of dehydrated water in moles per ZnSO4
using Eq. (1) [32] where Nw is the number of water lost per
moles, mw is the mass of water lost, Msalt is the molecular
weight (ZnSO4: 161 g mol−1), msalt is the mass of the salt
and MH2O is the molecular weight of water (18 g mol−1).
mw ⋅M salt
Nw ¼
msalt •M H 2 O
2.2.3 Hydration experiment
Prior to the hydration process, a dehydration experiment was
needed to complete the DH cycle. Ten grams (10 g) (M1) of
zinc sulfate heptahydrate was placed in an electro-thermal
oven (DHG-9070A) at two different constant temperatures
100 °C and 150 °C for two hours (2 h) at the same realistic
condition. Selection of lower limits (100 °C) was selected on
the basis of ZSHh maximum dehydration at a lower which can
be easily achievable through any solar collector while upper
limit (150 °C) was chosen due to a maximum temperature rise
of medium solar heat collector. The resultant masses of
Fig. 4 The preparation procedures of ZnSO4 for Dehydration and hydration
Heat Mass Transfer
partially dehydrated samples were weighed through digital
balance (digital balance: JJ 124 BC with ±0.1 error) called M2.
As showed in Fig. 4, the DH procedures are divided into
three steps. Step 1): Analytical grade 10 g of ZnSO4·7H2O
was weighted for the experiment. Step 2): Weighted sample
was put into the electro-thermal oven and isothermally heated
for 2 h at a heating rate of 5 °C min−1. In the 1st group, the
ð1Þ temperature in the oven was fixed for 100 °C and in the 2nd
group, the temperature was fixed at 150 °C. Step 3): This step
is a hydration step in which the dehydrated sample was first
weighted (M2) through a digital balance and then a required
amount of water (Mw) (25 ml) was allowed for chemical sorp-
tion as a result thermal energy are produced for the required
application. Before adding water, the initial temperature of the
water was recorded (T1), and then added into partially
dehydrated salt. The addition of water makes positive changes
in the internal temperature, due to which heat energy are re-
leased, which continuously make changes in temperature and
record on a digital thermometer (apuhua TM-902C, −50 °C ~
1300 °C, accuracy 0.1 °C). In the recorded temperatures a
single highest temperature was noted, called T2. The amount
of sorption heat in the form of enthalpy was calculated man-
ually with the help of Eq. 2 [33].
Heat Mass Transfer
Q ¼ ðM w þ M 2 ÞC P *ðT 1 −T 2 Þ ð2Þ
In which Q is enthalpy during hydration experiment and Cp
is water heat capacity 4.2 J/g °C. Hydration procedure for each
sample was repeated three times.
2.2.4 X-ray powder diffraction
Crystalline structure information and phase identification in
ZnSO4.nH2O salts at various temperature (25 °C, 100 °C,
120 °C, 140 °C, 150 °C) were characterized through X-ray
powder diffraction (PXRD). The X-Ray measurements were
carried out on a Rigaku Smart Lab II powder diffraction
(PXRD (Rigaku Co., Tokyo, Japan), scanning from 5 to 90°
(2θ) at a rate of 0.02 s−1 using Cu Kα1 + Kα2 radiation (λ =
0.15418 nm) source. The applied voltage and current were
40 kV and 40 mA, respectively.
2.2.5 Scanning electron microscope
Field emission-scanning electron microscope (Uanta FEG
250) (SEM) was used to study microstructural changes and
surface topography of ZSHh at 25 °C and 100 °C temperature.
ZnSO4 samples were placed on a carbon tape and mounted on
a bronze stub. In the apparatus magnifications ranging from
50 to 1500 was used in a low-pressure 10−6 – 10−7 mbar. The
beam accelerator voltage was set between 5 kV and 15 kV.
2.2.6 Reusability study
Reusability of material was investigated by taking 100
hydration/dehydration cyclic round of ZnSO4 using TGA-
DSC3+. The temperature program used for dehydration of
sample prior to the hydration was set to ramp rate of
10 °C min−1, and then to cooling down at −15 °C min−1.
2.2.7 Influence of relative humidity and temperature on water
sorption
Water uptaking performances of the hydrate salts are evaluate
at various relative humidity (RH) at fixed hydration tempera-
ture in a chamber at a range of 50 to 90% at 25 °C. During the
test, RH and temperature in the experimental chamber are set
to the reaction conditions. Therefore, to preserve the hydration
status of salt hydrates, we store it at 70% RH under 25 °C.
3 Result and discussion
The dehydration reaction of solid state ZnSO4.7H2O from one
phase to another phase is a complex process. Due to a large
number of various stable and metastable stages, the
identification of specific dehydration stable stage was calcu-
lated through Eq. 1 [32]. The dehydration process of
ZnSO4.nH2O stable stage was calculated from mass loss ob-
tained from the TG curve, and on the basis of the possible
calculated results obtained by calculations, we conclude vari-
ous stable stages of ZnSO4.7H2O. Since the dehydration of
zinc sulfate heptahydrate was performed through TG-DTA
apparatus, using a temperature ramp rate of 1 °C/min and
5 °C/min from 25 °C up to 300 °C, under the realistic condi-
tion (Fig. 5).
3.1 Dehydration of zinc sulfate heptahydrate
To investigate the heat storage ability of ZnSO4•7H2O it is
important to analyze the dehydration steps, enthalpy and water
loss per step. Additionally, the influence of heating rate is also
an important parameter of heat storage material for the real life
application. Therefore, the ZnSO4•7H2O was studied using
TGA coupled with DTA at 1 °C/min and 5 °C/min from
25 °C up to 300 °C, under the realistic condition.
The shape of the TG curve indicated (Top of the Fig. 5) that
mass loss occurred in three distinct steps, each accompanied
by a change in the DTA signal. Both the TG-DTA dehydra-
tion rate showed 7 → 6, 6 → 1, 1 → 0, stable stages which are
in agreement with [24]. The TGA curve of ZnSO4•7H2O
showed several decomposition steps. However, three steps
are weight loss and one step is a transition step. From the
DTA curve of ZSHh, a small transition step was observed,
where a negligible amount of enthalpy is released [24]. Due
to the curve observed in the TGA, we included this transition
step into our first step. Initial dehydration step starts at 42 °C,
accompanied with 14% mass loss and complete at 60 °C. The
calculated amount of dehydrated mass loss was associated
with one mol of water. First dehydration reaction of hydrated
zinc sulfate is an interesting reaction for seasonal heat storage.
The dehydration enthalpy and mass loss of zinc sulfate
showed better potential for heat storage. Moreover, the first
transition temperature of ZnSO4 is above than ambient tem-
perature level, which is an additional advantage. Second de-
hydration step followed same behavior with further loss of
5 mol of water starting at 63 °C and completed at below
75 °C, accompanied with 71% of total mass loss per mol of
ZnSO4•7H2O [23]. This step is an interesting and important
step for compact seasonal heat storage due to their large
amount of desorption enthalpy, which quantifies 0.9 GJ/m3
energy density. The advantage of the second dehydration re-
action is that it can be easily achievable at a low temperature
(< 100 °C) by any solar heat collector. Since based on low
dehydration temperature and larger energy released, the max-
imum rehydration enthalpy and energy of zinc sulfate has an
advantage over other thermochemical heat storage salts when
comparing with other heat storage material such as MgSO4,
MgCl2 and FeSO4 [22] (Table 1).
 Heat Mass Transfer

Fig. 5 Experimental enthalpies of

reaction, energy densities for
dehydration and decomposition
temperature range of zinc sulfate
hydrates

Finally, the last dehydration step occurred at a high tem- second dehydration step at 65 to 110 °C which loss 60% of
perature (223 °C) accompanied with 13% mass loss. total mass. Finally, the last step was occurred at 220 to 280 °C
However, in TCES point of views, the final dehydration tem- associated 14% of mass loss. The DTA curve of zinc sulfate
perature is far away from the achievable required boundary heptahydrate (Fig. 5. below part) at 1 °C/min and 5 °C/min
line of TCMs through medium solar heat collector. Similarly, showed that all peaks were associated with endothermic pro-
the dehydration result of ZnSO4•7H2O was also investigated cesses [23]. Peak enthalpy at 1 °C/min of first dehydration
at heating rate of 5 °C/min. The thermogravimetric analysis step was concerned with 270.60 J/g and secondly followed
(TG) result highlighted that in the first dehydration step 13.8% by a further DTA peak, associated with 431.32 J/g which
of mass was loosed at a range of 42 to 62 °C followed by corresponds to 0.90 GJ/m 3 energy density at 100 °C.
Similarly, the enthalpy obtained at heating rate of 5 °C/min
was 230.12 J/g, 403.45 J/g and 283.87 J/g for first, second and
third steps, respectively.
Table 1 Hydration enthalpies of reaction, energy densities at 100 °C for
salt hydrates The TG-DTA analysis showed, that the dehydration enthal-
py of ZnSO4•7H2O, especially first and second water loss step
S/ Salt hydrate at (100 °C) Enthalpy (J/g) Energy density (GJ/m3) is enough for the heat storage application. Additionally, both
No
first and second dehydration temperature can be easily
1 ZnSO4•7H2O 636.10 1.25 achieved by a solar collector which is an important and inter-
2 MgSO4•7H2O 310.86 0.52 esting step for compact seasonal heat storage. Moreover, the
3 FeSO4•7H2O 420.30 0.84 influence of different heating rate (1 °C/min and 5 °C/min)
4 MgCl2•7H2O 537.45 1.01 increase the dehydration temperature however it decreases the
water loss.
Heat Mass Transfer
3.2 Dehydration of ZnSO4 crystal
TG-DTA investigation of ZnSO4·7H2O showed that increased
in temperature dehydrated water molecules. Since to investi-
gate and validate TG-DTA analysis an addition characteriza-
tion experiment was employed for more detailed dehydration
study through In-situ microscopic at 1 atm water vapor pres-
sure at a heating rate of 1 °C/min shown in Fig. 6.
For the better understating, we synthesized ZnSO4 crystal.
The study indicated that the mass of water is present inside the
crystals before the temperature lifts to 80 °C. maximum water
was dehydrated at above 80 °C which turns transparent crystal
into white color. However, the impact of high temperature
(>80 °C) has a negligible effect on the crystal. The observation
of In-situ microscopic result obtained for ZnSO4 crystal is the
validation of the TG-DTA experiment [24].
3.3 X-ray diffraction measurements
X-ray diffraction patterns of all five samples at 150 °C (a),
140 °C (b), 120 °C (c), 100 °C (d) and 25 °C (e) are presented
in Fig. 7 (a-e). It is essential to validate the crystallinity and
phase present of the water and ZnSO4 in each sample, as the
level of hydration/dehydration will impact the amount of heat
released/stored. The main reflections observed in Fig. 7 (a-e)
are assigned to that of ZnSO4.7H2O phase, where two visible
reflection at 26.1° and 29.4° 2θ (Peak Y) matched to the
water, which was presented in all five samples, and rising in
intensity with increasing temperature. The presence of such a
partially hydrated phase was to be expected, as the dehydra-
tion >100 °C (4–10 h) leads to the loss of six H2O molecules
(Fig. 7 (a-d)). It was also reported that for the material at high-
temperature, the main reflection was observed at 18.6°, 23.7°,
26.1°, 26.8°, 35.0° and 35.9°, which matched for ZnSO4
structural. The X-Ray diffraction study suggests that effect
of temperature over ZnSO4.7H2O content showed 85% of
water molecules (calculated six moles of H2O per ZnSO4
mol) dehydration occurred during desorption process which
was possible due to various strength of water bonding with
zinc sulfate. However, zinc sulfate was not completely
dehydrated at mentioned temperatures; a small amount of wa-
ter was still attached with the base molecule (ZnSO4). The
Fig. 6 In-situ microscopic observations of the dehydration process of a ZnSO4.7H2O crystal under a realistic condition with a heating rate of 1 °C/min
advantages of attached water molecule prevent ZnSO4 to split
it into ZnO and SO3 [24], which was also confirmed through
XRD result invisible peak concerned to zinc sulfate by-
products.
3.4 SEM characterization of zinc sulfate
Zinc sulfate various hydrated state were analyzed at two dif-
ferent temperatures; (a) at a relative temperature (25 °C) and
(b) after dehydration (100 °C) for 2 h using Field emission-
scanning electron microscope (Uanta FEG 250) (SEM) shown
in Fig. 8. The SEM images of hydrated ZnSO4 clearly showed
that the formation of cracks was due to a temperature (100 °C)
treatment in which water molecules are dehydrated.
Additionally, the SEM (image c) also showed that water mol-
ecules not only leave the external surface but also escaped
from the inner surface of zinc sulfate molecules. The cracking
in ZnSO4 crystal showed an indication for uniform dehydra-
tion of water molecules during the dehydration process.
3.5 Hydration of salt hydrates
Hydration of material is an important step for measuring the
amount of power, which can be provided to a system for
complete its challenges, with a determined temperature level.
Partially dehydrated ZnSO4 was investigated for hydration at
normal practical conditions (Fig. 4 (3)). Before hydration
analysis, dehydration of materials was first done through elec-
trical oven at a heating rate of 5 °C/min. The oven was pro-
grammed to heat up material from room temperature to 100 °C
and 150 °C in two different zones. All the hydration experi-
ment was carefully tested three times. Sorption enthalpy was
calculated manually using Eq. 3. In the first round, zinc sul-
fate is dehydrated at 100 °C and in second round material was
heated at 150 °C with mention procedure above (Fig. 4), keep-
ing the experimental parameters same.
3.6 Hydration of dry salts at 100 °C and 150 °C
Hydration measurements of zinc sulfate showed promising
results. The observed result indicated that 541 J/g enthalpy
was released at 100 °C and 432 J/g enthalpy was released at

Fig. 7 X-Ray diffraction of
ZnSO4•7H2O. A: 25 °C, B:
100 °C, C: 120 °C, D: 140 °C and
E: 150 °C
150 °C. In the first hydration experiment, higher heat released
value was observed for ZnSO4. As discussed in the previous
TGA section 3.1, that 71% of energy is stored in the second
dehydration step, which was completed below 100 °C. This
means that at 100 °C zinc sulfate was able to give rise higher
hydration enthalpy (541 J/g), due to their maximum dehydra-
tion below 100 °C, which is also confirmed by TG-DTA and
X-Ray diffraction measurement.
Unfortunately, in the second hydration experiment, (before
dehydrating sample was heated up to 150 °C) the calculated
hydration enthalpy value was 432 J/g, which is lower than the
first hydration process. This unexpected behavior of ZnSO4
was also validated through X-Ray diffraction. The X-Ray dif-
fraction study in Fig. 7 showed that the intensity of each peak
gradually increased with high temperature. Thereby, all the
observed results indicated that there might be some weak
forces are involved which give rise such small changes.
From these observations, we proposed that this force might
be Van der Waals forces which affect the hydration rate [35,
Fig. 8 SEM pictures of ZnSO4•7H2O (a) 25 °C (b, c) 100 °C
Heat Mass Transfer
36]. Meanwhile, hydration of ZnSO4 was also affected by
layer thickness.
3.7 Cyclability and heat of hydration
Cyclability of ZnSO4 compared with MgSO4 were performed
using TGA-DSC at a dehydration ramp rate of 10 °C min−1
and cooling ramp rate of −15 °C min−1 under 1 atm vapor
pressure and 25 °C hydration temperature. The reusability of
both materials was tested on the basis of their heat of hydration
values against cyclic repetition. To get stable impression of
MgSO4 and ZnSO4 samples, 100 consecutives recycle steps
were repeated, where after every 10 cycle we record their
result, presented in Fig. 9.
The test result highlighted that both MgSO4 and ZnSO4
released highest enthalpy 1405 J g−1 and 1298 J g−1, while
compare to first cyclic step next cyclic steps are 10–20% low-
er. Mostly the difference between first and other steps is due to
lower water sorption lower at ambient temperature. In
Heat Mass Transfer
Fig. 9 Cyclability of MgSO4 and
ZnSO4 (hydration enthalpy is
function of cyclic repetition)
summary, the cyclability results demonstrated that both salt
shows same heat released behaviour, which proof the good
cyclability of ZnSO4•7H2O.
3.8 Hydration performance of salt hydrates at relative
humidity and temperature
Rehman et al. [6], and Xu et al. [34], suggested that relative
humidity (RH) has a significant effect on water sorption abil-
ity of material in the hydration process. To investigate the
impact of RH on the H2O uptaking ability of ZnSO4, various
specific RH including 65%, 75% and 85% were selected at
constant air temperature (25 °C). Result of Fig. 10 shows that
at 65% and 75% RH, 0.13 g/g and 0.143 g/g mass were up-
takes after 26 and 16 h, respectively. On the other side, the
75% relative humidity result shows that after 10 h 0.11 g/g
Fig. 10 Effect of relative humidity on the water sorption of ZnSO4 at
25 °C
mass is uptake, while a sharpe decrease was observed and the
salt transform to aqueous solution.
The above result indicates that as the RH increase from
lower (65%) to maximum (75%) the mass of water sorption
increase with increase RH and faster hydration rate, while
further increase in RH (85%) sharply decrease water sorption
mass to minimum level with more faster hydration rate. The
reason of this irregularity can be explain as follow. When RH
touched to 85% humidity level, larger number of H2O vapour
are absorb than saturation point of zinc sulfate and conse-
quently the ZnSO4 transform into aqueous. The resultant salt
solution is unable to uptake further H2O. This observation was
also reported by Rehman et al. [6], and Posern et al. [35].
Thus, the better water sorption performance of ZnSO4 was
recoded at 75% RH, which is an evidence of their better heat
storage ability.
In summary, from the thermochemical heat storage point of
view, ZnSO4 shows similar heat storage performance likewise
MgSO4. Both materials are energy efficient and shows larger
cyclability, maximum water sorption and much higher calcu-
lated energy density. Moreover, the heating relative humidity
and water sorption will change the water sorption performance
of the material. However, during dehydration of MgSO4, low
dehydration temperature, amorphous state transformation,
larger difference between first and second rehydration enthal-
py drawbacks limits the use of magnesium sulfate
heptahydrate for seasonal storage, On the other hand,
ZnSO4•7H2O showed better heat storage performance such
as larger activation air temperature, good cyclability, low re-
hydration temperature, maximum water sorption and enough
hydration/dehydration enthalpy of material proofed that
ZnSO4•7H2O is a promising TCM candidate Therefore, it is
suggested that a brief study is needed on ZnSO4•7H2O for
heat storage application in further.

4 Conclusions
From this study, it can be revealed that zinc sulfate
heptahydrate is a promising candidate for solar seasonal heat
storage long-term material. The energy involved in the ZnSO4
dehydration process at 100 °C is 1.37 GJ/m3 and the enthalpy
recovered in the hydration process at the same parameters are
1.1 GJ/m3 at 100 °C. The cyclic study showed better perfor-
mance and larger water sorption was recorded at 75% RH.
The conclusion of study also reviewed that the Vander
Waals forces affect the hydration rate, which induces higher
dehydration enthalpy (541 J/g) at 100 °C than dehydrated at
150 °C (432 J/g).
Acknowledgments Financial support from NSFC (51672208), National
Key R&D Program of China (2018YFB1502902), Key Program for
International S&T Cooperation Projects of Shaanxi Province
(2019KWZ-03), and Sci-Tech R&D Program of Shaanxi Province
(2010 K01-120, 2011JM6010 and 2015JM5183) is greatly acknowl-
edged. The project was partly sponsored by SRF ((2012)940) for
ROCS, SEM.
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