Journal of Energy Storage 45 (2022) 103773

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Journal of Energy Storage

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Research Papers

Synthesis and thermophysical property evaluation of ionic semiclathrate

hydrate formed with tetrabutylphosphonium glycine as a chilling
temperature phase change material
Takashi Miyamoto , Naruki Kurokawa , Iku Ota , Atsushi Hotta , Ryo Ohmura *
Department of Mechanical Engineering, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: Ionic semiclathrate hydrate, which is formed under atmospheric pressure with sustainably safe properties, has a
Phase change materials potential for solid-liquid phase change materials(PCMs). In this study, the thermophysical property of tetrabu­
Ionic semiclathrate hydrate tylphosphonium glycine(TBPGly) hydrate containing no halogen guest compound, glycine (aminoacetic acid),
Aminoacetic acid
was investigated to evaluate the availability as an eco-efficient thermal energy storage medium. The phase
Dissociation heat
equilibrium temperature was obtained through visual observation method. The heat flow rate curve behavior
Phase equilibrium temperature
and dissociation heat were measured via differential scanning calorimetry(DSC). In the dissociation process, a
single hydrate dissociation peak emerged, indicating TBPGly hydrate has one type of crystallographic structure.
The concentration dependency of the TBPGly aqueous solution on the equilibrium temperature and the disso­
ciation heat was confirmed. The highest equilibrium temperature of 5.8 ◦ C was confirmed at the fraction range
wTBPGly =0.368 or xTBPGly =0.0306, and the largest dissociation heat was 177.7 kJ⋅kg− 1 at the fraction range
wTBPGly =0.377or xTBPGly =0.0318. The estimated hydration number in the congruent composition was found to
be in 31.2 to 32.5. In addition, based on the measured physical property, the optimum operating temperature and
volume fraction of TBPGly hydrate was evaluated to determine the concentration for the practical cooling sys­
tem. These data revealed TBPGly hydrate is available as a solid or slurry PCM under the operating temperature
range 2 ◦ C to 5.8 ◦ C. The experimental data as well as the illustrative calculations contribute to accelerate the
expansion in the application range, and provide the prospect in selecting the suitable composition toward the
actual hydrate-based cooling system.

1. Introduction consumption and 2.5% of greenhouse gas emmissions [1,4]. For

improving the efficiency of energy use toward decarbonization, it is of
To address increased demand due to population growth, food and great significance to study the energy savings and the power load
medical logistics need temperature control for the quality preservation. reduction of cold chain logistics.
A cold chain, comprising cold storage and refrigerated transportation of The thermal energy storage could provide the way of peak electrical
fresh food or temperature-sensitive medicines such as vaccines and loads shifting and the strategy for energy management in a variety of
blood, would play a key role in the agricultural and medical supply applications [5,6]. By storing the surplus electricity as a cold energy and
chains [1]. pre-cooling the stored items, it is possible to keep the refrigeration
One of the problems with the cold chain is energy consumption. In equipment idle during periods of high utility cost, and minimizing
the transition towards a carbon neutral society, the amount of power changes in environmental temperature [7–10]. In addition, stored cold
generation affecting global warming should be reduced. In contrast, energy could offer a backup solution to the unstable renewable energy
energy is required to maintain the chilling processes, and the generation supply to the chilling facilities. In energy storage system, Phase change
of this energy contributes to the increase of CO2 discharge [2,3]. materials (PCMs) has been attracted as thermal energy storage medium
Refrigeration of the products continued during the storage and the [11–14]. PCMs are capable of storing large amounts of energy caused by
transportation processes, resulting in 17% of global electricity the phase change process. In the transport applications, the high volume

* Corresponding author.
E-mail address: [email protected] (R. Ohmura).

https://doi.org/10.1016/j.est.2021.103773
Received 26 August 2021; Received in revised form 10 November 2021; Accepted 4 December 2021
Available online 13 December 2021
2352-152X/© 2021 Elsevier Ltd. All rights reserved.
T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

and mass can limit the energy efficiency [15]. Therefore, utilization of (DSC). The phase equilibrium temperature and dissociation behavior
PCMs could suppress the energy consumption and the required installed were investigated by visual observation with a CMOS camera and a
capacity of the refrigeration equipment. Recently, hydrates have been microscope. From these results, appropriate physical properties for the
suggested as thermal energy storage media with high energy density and TBPGly hydrate-based cooling system were discussed.
safety [16–25]. While water and ice are the most commonly used PCMs
for air cooling (10 ◦ C to 15 ◦ C) or frozen storage of cooked foods, fish and 2. Experiment and method
meat (less than 0 ◦ C), however, because of relying on only sensible heat
storage, water has a low cold carry capacity, and requires a large storage 2.1. Materials
tank. Though ice has a large thermal storage density, its operating
temperature range is limited. Owing to low melting point, ice is not The reagents used in this study are summarized in Table 1. Tetra­
suitable for chilling transportation of the perishable products which butylphosphonium glycine (TBPGly) aqueous solutions were obtained
require the temperature range from 2 ◦ C to 10 ◦ C [6,26–29]. Other by neutralizing glycine(aminoacetic acid) (0.99 content in anhydrous
representative materials, paraffin waxes and hydrated metal salts, have solid, FUJIFILM Wako Pure Chemical Co., Ltd.) with tetrabutylphos­
their disadvantages in flammability and corrosiveness, respectively [8, phonium hydroxide (TBPOH) aqueous solutions (0.40 mass fraction in
11–14]. Thus, various hydrates, such as hydro fluoro carbons, tetrahy­ aqueous solution, Sigma-Aldrich Co., LLC.). Glycine solid was added to
dropyran and cyclopentane have been studied for cold energy storage liquid water, and the mixture in the vessel was warmed with hot water
system [30–33]. Among them, ionic semiclathrate hydrates, formed until glycine was completely dissolved in the solution. The water was
under the atmospheric pressure and dissociated above the freezing deionized and distilled beforehand by the water distillation unit (WG
point, are highlighted. Its unique physical properties have been 222, Yamato Co. Ltd.). The distilled water was also used to adjust the
confirmed through laboratory scale experiments [34–38]. mass fraction in the neutralizing process. Since the mass fraction of
Clathrate hydrate is non-stoichiometric crystalline compounds, TBPOH aqueous solution had the uncertainty range from 0.38 to 0.43,
consisting of the space-filling cages of water molecules and other mol­ the detailed mass fraction of the regent was determined by the hydro­
ecules called guest compounds enclosed within the cages. Ionic semi­ chloric acid titration. The actual mass fraction of TBPOH aqueous so­
clathrate hydrate consists of ionic guest compounds: the cations of the lutions was 0.41. In this study, the mass fractions of TBPGly samples
guest compound are enclosed in a water framework of the cage, and the were made from 0.20 to 0.40. The mass of glycine, water and TBPGly
anions replace a part of hydrogen bonding. Ionic guest compounds are aqueous solution were measured using an electronic balance (IUW-200D
produced by the neutralization of various guest cations and anions. sefi, As One Co. Ltd.) with an expanded uncertainty of ± 0.1 mg
Quaternary ammonium or phosphate salts, tetrabutylammonium(TBA) (coverage factor k = 2). The total uncertainty of the mass fractions in
or tetrabutylphosphonium(TBP) salts have been mainly studied as guest TBPGly aqueous solution was estimated to be ± 2.0 × 10− 4 from the
cations [39–47]. With the strong interaction of the water -guest mole­ uncertainty of all mass measurements of the reagents during the
cules and the hydrogen bonding within the cage molecules, the ionic neutralization and adjusting process.
semiclathrate hydrate has a large dissociation heat [48]. For this ther­
mophysical property, many hydrates have been proposed for practical 2.2. Apparatus
use, however, most of them are limited to air conditioning temperature
range, around 10 ◦ C [39–41,45,46]. Since the thermophysical proper­ The phase equilibrium temperature measurements were carried out
ties, the phase equilibrium temperature and dissociation heat of the with an apparatus illustrated in Fig.1. A glass test tubes (external
hydrate, rely on the guest ionic compounds, various ionic semiclathrate diameter 10 mm, internal diameter 8 mm, height 90 mm) enclosing
hydrates containing different guest cations and anions should be TBPGly hydrate crystals were placed into the water bath (height 120 mm
investigated to expand the hydrate-based thermal energy storage ap­ and total volume 4032 cm3). The bath was filled with cooling liquid
plications in many fields and technologies. (ethylene glycol - water mixture). The temperature of the fluid was
As the selection of the guest compounds, heat capacity and envi­ controlled by a chiller (Tokyo Rikakikai Co., CTP-3000), and measured
ronmental acceptability are the most critical factors to sort the optimal by a platinum resistance temperature detector with an expanded un­
guest cations and anions of the hydrate. Focusing on the guest cations, certainty of ± 0.1 ◦ C (coverage factor k = 2). Images of hydrate crystals
TBP or TBA salts show different thermophysical property when the guest were taken with a CMOS camera(Edmund Optics Co., CMOS200-USB2)
anion is specified. Hydrates containing TBP salts tend to have a larger equipped with a computer and a microscope.
heat storage capacity and lower equilibrium temperature than hydrates In measuring heat flow rate and dissociation heat, these thermal
containing TBA salts [40,44]. Hence, incorporating TBP salts may in­ properties of TBPGly hydrate were measured by a differential scanning
crease the thermal energy storage capacity of ionic semiclathrate hy­ calorimetry (DSC) (TA Instrument, DSC25). The volume of the
drates. Halide anion-containing hydrates, such as TBAB, TBAF and TBAC aluminum cells in which TBPGly aqueous solutions were sealed, was 40
are well-known and characterized by their stability in the formation × 10− 3 cm3. Indium (purity 99.999%, Mettler Toledo Co.) and distilled
process [16,40,41,43,45]. Despite its large thermal energy capacity, water were used to calibrate the temperature and latent heat of the DSC.
halide anions will cause an environmental pollution, the production of By measuring the latent heat of water, we confirmed the uncertainty of
dioxins. As halogen-free ionic compounds, hydrates containing carboxyl enthalpy. The average of three measurements was 334.9 kJ⋅kg− 1, and
acid anions or amino acid anions have been reported [49–56]. However, the uncertainty of the dissociation heat measurements was estimated to
while research is progressing on carboxyl acid-based hydrates, few be 4.9 kJ⋅kg− 1 (coverage factor k = 2). It was consistent with the liter­
studies have been reported on amino acid-based hydrate. For further ature data within the experimental uncertainty [57].
development of the application of amino acid guest cations and ionic
semiclathrate hydrates, we propose glycine(aminoacetic acid), which is 2.3. Phase equilibrium temperature measurements
the simplest stable amino acid as a guest anion. To determine optimal
operating conditions and expand the potential of hydrate PCM, the In this study, the phase equilibrium temperature was measured by
thermophysical properties of TBP salts + Glycine hydrate should be visual observation method. The similar method was performed with an
clarified. alike apparatus in previous studies [23,39,40,44,47,52–56]. The reli­
In this study, the thermophysical properties of TBPGly hydrate, ability of this method was demonstrated via the measurement of the
which consists of an amino acid as a guest anion and TBP salt as a guest phase equilibrium temperature of ice and tetrahydrofuran (THF) hy­
cation, were investigated as a medium for cold storage applications. The drate [40]. Approximately 3 g of TBPGly aqueous solutions were
heat of dissociation was analyzed by a differential scanning calorimetry injected into a glass test tube with a silicon cap. These tubes were chilled

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T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

Table 1
Specifications of materials used in this study.
Name Chemical formula Supplier Purity

Glycine(aminoacetic acid) C2H5NO2 Sigma-Aldrich Co.LLC. 0.99 content in anhydrous solid

Tetrabutylphosphonium hydroxide (TBPOH) aqueous (CH3CH2CH2CH2)4POH Sigma-Aldrich Co.LLC. 0.40 mass fraction in aqueous solutiona
solutions
Water H2O Laboratory made Electrical conductivity was less than 0.1 μS•cm− 1
Tetrabutylphosphonium glycine (TBPGly) aqueous (CH3CH2CH2CH2)4PC2H4NO2 Laboratory made with above The standard uncertainty of mass fraction was ±
solutions materials 2.0 × 10− 4 b
Hydrochloric acid HCl Kanto Chemical Co. Inc. 0.01 mol•L− 1 c
a
This is the labeled mass fraction on the reagent bottle. The concentration with the uncertainty of TBPOH aqueous solution was measured by acid-based titration
with HCl. The actual mass fraction of TBPOH aqueous solution was 0.41. The standard uncertainty of the mass fraction was 3.0 × 10− 4.
b
The uncertainties of the mass fraction of TBPGly aqueous solution were estimated from the uncertainties of the mass measurements on TBPOH aqueous solution,
glycine solution and water on the neutralizing and adjusting processes.
c
HCl was utilized for the titration measurement to determine the uncertainty for mass fraction of TBPOH aqueous solution.

shown in Fig. 2. Before the cooling process, the temperature was kept for
20 ◦ C to dry the internal device. Then, the system temperature was
decreased from 20 ◦ C to − 20 ◦ C under a cooling rate of − 5 ◦ C min− 1, and
kept − 20 ◦ C for 10 min to convert all TBPGly aqueous solutions into the
hydrate form. In this study, hydrate nucleation has occurred under all of
the cooling runs, which indicates -20 ◦ C is sufficient to obtain repro­
ducible results on the hydrate formation and the resulting determination
of the heat of hydrate formation. In the next heating process, the tem­
perature was increased from − 20 ◦ C to 20 ◦ C at a heating rate of 2 ◦ C
min− 1 to dissociate the hydrate crystals. The reliability of the heating
rate of 2 ◦ C min− 1 in measuring the dissociation heat has been shown in
previous studies [46,52,54]. During the heating process, an endothermic
peak of the heat flow rate attributed to the dissociation of the crystals
emerged. Through the behavior of the heat flow curve, the composition
and the structure of hydrate crystals were inferred. The dissociation heat
of the hydrate was obtained by integrating the endothermic peaks,
which was normalized per unit mass. In performing the calculation, the
Fig. 1. Schematic diagram of the apparatus in the phase equilibrium temper­
ice melting and the hydrate decomposition peaks were completely
ature measurement.
separated. By integrating only the heat flow rate relevant to the hydrate,
the dissociation heat of the hydrate without the influence of ice was
at -20 ◦ C for 24 h to form the hydrate crystals. After visually confirming
obtained. The measurements were performed three times for a given
the hydrate formation, the tubes were set into a water bath under at­
mass fraction. For each experiment, three different TBPGly aqueous
mospheric pressure. The experimental temperature was kept constant
solutions were prepared to ensure accuracy.
for at least 4 h. The dissociation behavior of hydrate was observed with a
CMOS camera. If no remarkable changes were confirmed in the crystals,
3. Results and discussion
the system temperature was increased by 0.1 ◦ C. Once the hydrate began
to dissociate, the temperature was maintained constant again for 4 h. By
3.1. Phase equilibrium temperatures
repeating these procedures, the equilibrium temperature, the highest
temperature at which the hydrate exists without being complete disso­
The phase equilibrium temperatures of TBPGly hydrates were
ciated, was detected. The phase equilibrium temperature of the hydrate
is expressed by the following equation:
Teq ≡ (Tdiss − 0.1) ∘ C(1) where Teq was the phase equilibrium tem­
perature and Tdiss was the temperature at which the complete dissoci­
ation of the hydrate crystals was confirmed. The above measurements
were performed at least three times at each mass fraction. To confirm the
reproducibility, each sample were prepared from three different TBPGly
aqueous solutions for a given mass fraction.

2.4. Heat flow rate and dissociation heat measurements

Heat flow rates and dissociation heats of TBPGly hydrate in this

study were measured by a differential scanning calorimeter. As a sample
cell, approximately 15 mg of TBPGly aqueous solutions were injected
into the aluminum test sell. The reference cell was prepared by sealing
the empty sell containing only air. The masses of sample cell and
reference cell were measured with the same electronic balance as used in
the phase equilibrium temperature measurements. After placing these
two types of cells inside the DSC equipment, the device was filled with
dry N2 gas at 0.1 MPa to eliminate moisture. During the dissociation heat Fig. 2. Schematic diagram of the DSC temperature program in the heat flow
measurement, the system temperature of the DSC was controlled as rate and dissociation heat measurement.

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T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

measured by visual observation method under the atmospheric pressure. Table 2

TBPGly aqueous solutions were prepared at the concentration range The phase equilibrium temperatures of TBPGly hydrate.
0.198 ≤ wTBPGly ≤ 0.396. Fig. 3 presents the images of dissociation wTBPGlya xTBPGlyb Teq c / ◦ C Molar ratio of water to TBPGly
process of TBPGly hydrate crystals. For the mass fraction 0.377, the
0.198 0.0133 2.0 75.0
hydrate gradually dissociated over 5.1 ◦ C. It took several days to confirm 0.248 0.0176 3.1 56.5
a remarkable change in the amount of remaining crystals. The stepwise 0.278 0.0205 4.1 48.6
temperature increase was continued until the complete dissociation. All 0.297 0.0224 4.3 44.2
measurement results are listed on Table 2, where wTBPGly, xTBPGly, and 0.317 0.0246 4.5 40.3
0.347 0.0282 5.6 35.4
Teq indicate the mass fraction, the mole fraction of TBPGly aqueous 0.357 0.0293 5.3 33.9
solution, and the phase equilibrium temperature of TBPGly hydrate. The 0.368 0.0306 5.6 32.5
phase equilibrium temperature showed two trends, an increasing and 0.377 0.0318 5.8 31.2
decreasing parts. At the mass fraction range 0.198 ≤ wTBPGly ≤ 0.368, 0.386 0.0330 5.2 29.9
0.396 0.0344 5.0 28.8
the equilibrium temperature of the hydrate tended to be higher with the
increasing mass or mole fraction. Furthermore, the hydrate crystals were a
The standard uncertainty u (wTBPGly) is ± 2.0 × 10− 4.
b
immediately dissociated near the equilibrium temperature. In contrast, The standard uncertainty u (xTBPGly) is ± 3.0 × 10− 5. xTBPGly indicates the
in the mass fraction range from 0.297 to 0.386, the measured equilib­ mole fraction of TBPGly in aqueous solutions. These values of mole fractions
rium temperature showed close values, and hydrate dissociation rate were obtained by converting the mass fractions.
c
The expanded uncertainty U (Teq) is ± 0.1 K (k = 2).
became slower as described in Fig. 3. Above wTBPGly = 0.368 or xTBPGly
= 0.0306, the equilibrium temperature turned to drop. These results
indicated that thermodynamically stable hydrate would be formed near
mass fraction of 0.368.
As displayed in Fig. 4, the phase equilibrium temperature was closely
related to the mass fraction or mole fraction of TBPGly aqueous solution.
The dependence of phase equilibrium temperature on the composition
of ionic semiclathrate hydrate has been identified in the previous
experimental and theoretical studies [39–41,47,52–56,58]. In the case
of TBPGly hydrate, the melting point varied from 2.0 ◦ C to 5.8 ◦ C
depending on the TBPGly concentration. By adjusting the aqueous so­
lution to an appropriate composition, a hydrate with the property
required for the actual system can be obtained. The highest phase
equilibrium temperature of TBPGly hydrate was 5.8 ◦ C, which was
suitable for chilling transport of the thermosensitive food or medicine.
As a low temperature thermal energy storage medium, TBPGly hydrate
has the potential to contribute to the energy efficiency management, and
expand the application range of hydrate refrigerants in cold supply
chain.

3.2. Behavior of heat flow rate

Fig. 4. Dependency of the equilibrium temperature upon the mass fraction and
The heat flow rates of TBPGly hydrate were measured at the mass mole fraction of the TBPGly aqueous solutions.
fractions of TBPGly aqueous solution from 0.198 to 0.396, similar to the
equilibrium temperature experiment range. Reproducibility of the heat
wTBPGly ≤ 0.297 or 0.0133 ≤ xTBPGly ≤ 0.0224. Within this concentration
flow curve was confirmed at a given mass fraction by measuring the heat
range, the dissociation peak of hydrate was smaller than the other
flow rate from three different TBPGly aqueous solutions. Figs. 5 to 8
ranges, but sometimes another type of peak regarded as the ice melting
show the trend of the heat flow rate curve at the entire measurement
appeared below the freezing point. These ice melting peaks emerged
fraction range, at the low mass fraction range, at the range close to the
from residual water in the TBPGly aqueous solution that was not utilized
congruent composition, and at the high mass fraction range. As
for hydrate formation. The depth of these ice peaks should depend on
exhibited in Fig. 5, a single endothermic peak emerged over almost all
the amount of residual water in the solution. The aqueous solution of
concentration range of the TBPGly aqueous solutions. The single peak
wTBPGly = 0.198 contained more residual water than wTBPGly = 0.297,
was corresponded to the endothermic reaction that occurs in solid-liquid
which led to the appearance of the deep ice peak. For hydrate dissoci­
phase transition suggesting that TBPGly hydrate would have one type of
ation peak, the peak depth showed that the amount of hydrate produced
crystallographic structure. The polymorphism found in other ionic
at wTBPGly = 0.198 was smaller than that of wTBPGly = 0.297, as seen in
semiclathrate hydrate studies was not identified in TBPGly hydrate [16,
Fig. 6. Since the ice nucleation is a stochastic phenomenon, it is difficult
39,47,52,53,55,56]. The peak depth changed in response to the increase
to stably reproduce the ice formation. The heat flow data obtained in the
of mass or mole fraction. The deepest peak was confirmed at wTBPGly =
run with ice formation were not used to determine the heat of hydrate
0.368 or xTBPGly = 0.0306.
dissociation at mass fractions 0.198 and 0.297.
Fig. 6. presents the heat flow rate at the low concentration of 0.198 ≤

Fig. 3. Visual observation during TBPGly hydrate dissociation.

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T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

fraction range, the deeper hydrate peak was confirmed at the concen­
tration range 0.347 ≤ wTBPGly ≤ 0.368 or 0.0282 ≤ xTBPGly ≤ 0.0306.
Moreover, a single hydrate dissociation peak emerged, and no peak of
ice melting was observed at the composition neat the congruent point. In
this concentration range, the most of the water in the TBPGly aqueous
solution should be converted to hydrate, and the residual water seems to
be negligible, resulting in the decrease of ice melting peak. Further in­
crease of TBPGly hydrate formation resulted in the deep heat flow curve
during dissociation. A congruent point is that the ratio of water to
TBPGly in the aqueous solution is equal to the hydrate composition, and
at this mass fraction, all aqueous solution is fully converted to hydrate.
The maximum endothermic peak would appear with this composition.
Fig. 8 exhibits the hear flow rate in the high concentration range. Up
to wTBPGly = 0.368 or xTBPGly = 0.0306, the depth of the heat flow curve
increased as the mass fraction increased. On the contrary, the heat flow
curves showed a tendency to decrease with further increasing the mass
fraction and mole fraction over wTBPGly = 0.377 or xTBPGly = 0.0318,
Fig. 5. The heat flow rate at the mass fractions 0.20, 0.37, 0.38 and 0.39: blue indicating that wTBPGly = 0.368 or xTBPGly = 0.0306 is the closest
◆, w TBPGly= 0.20; red ▴, w TBPGly = 0.37; light green, ⬤ w TBPGly= 0.39; or­ aqueous solution to hydrate composition. When the mass fraction or
ange, ⬛ w TBPGly= 0.40.
mole fraction of TBPGly aqueous solution exceeded the hydrate
composition, the proportion of TBPGly in the solution increased, leading
to a shortage of water required for hydrate formation. Thus, the amount
of hydrate production decreased without further increase. In the high
mass or mole fraction range, more excess TBPGly which was not used for
hydrate formation remains in solution. These residual TBPGly should
affect the change in heat flow rate curve at wTBPGly =0.396 or xTBPGly =
0.0344.

3.3. Dissociation heat

The calculated dissociation heats of TBPGly hydrate were summa­

rized in Table 3. Large dissociation enthalpy was obtained from the
TBPGly concentration that showed the deep heat flow rate peak. The
maximum heat of dissociation was 177.7 kJ⋅kg− 1 confirmed at wTBPGly
= 0.368 or xTBPGly = 0.0306, where the largest amount of TBPGly hy­
drate would be formed. The energy density of TBPGly hydrate could be
compared with water cooling within the temperature range of chilled
transportation. The required temperature is from 2 ◦ C to 10 ◦ C. Under
Fig. 6. The heat flow rate at the mass fractions 0.20, 0.30: blue ◆, w TBPGly= these temperatures, water, which has a specific heat of 4.22 kJ⋅kg− 1⋅K −
0.20; red ▴, w TBPGly = 0.20 with ice; light blue ⬤, w TBPGly= 0.30; orange ⬛, w 1
[59], can storage 33.8 kJ⋅kg− 1 from temperature difference. TBPGly
TBPGly= 0.30 with ice.
hydrate also has the sensible thermal energy, which means that the total
energy density of TBPGly hydrate would be over 177.7 kJ⋅kg− 1. Hence,
Fig. 7 displays the change in peak depth, which indicate that the TBPGly hydrate has approximately more than five times the thermal
amount of hydrate formation tends to increase with the increasing of energy capacity of water, as the thermal storage for chilling
TBPGly concentration. Compared with the heat flow rate at the low mass temperature.

Fig. 8. The heat flow rate at the mass fractions 0.37, 0.38, 0.39 and 0.40: red
Fig. 7. The heat flow rate at the mass fractions 0.35, 0.36 and 0.37: green ◆, w ◆, w TBPGly = 0.37; blue ▴, w TBPGly= 0.38; light green ⬤, w TBPGly= 0.39;
TBPGly = 0.35; purple ▴, w TBPGly = 0.36; red ⬤, w TBPGly = 0.37. orange ⬛, w TBPGly= 0.40.

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T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

Table 3 are several previous studies on thermal or fluid property have been
The dissociation heats of TBPGly hydrate from differential scanning calorimetry conducted to utilize ionic semiclathrate hydrates as alternatives to
measurements. conventional cooling media, such as water and ice [42,55,56,60,61]. In
wTBPGlya xTBPGlyb ΔHd c / kJ•kg− 1
U d (ΔHd) kJ•kg− 1 particular, TBAB hydrate which is actually commercialized as a cooling
0.198 0.0133 56.0 ±1.9
medium for air conditioning systems is intensively studied. These ionic
0.248 0.0176 83.2 ±1.5 semiclathrate hydrates are used as solid-liquid PCMs for thermal energy
0.297 0.0224 117.6 ±6.3 storage medium in the cooling system. Depending on the operating
0.347 0.0282 159.1 ±6.0 condition of the hydrate, the cold storage and transportation system is
0.357 0.0293 167.2 ±4.3
basically divided into two types, a static type and a dynamic type
0.368 0.0306 177.7 ±0.6
0.377 0.0318 175.3 ±4.9 [62–65]. In this study, focusing on the measured thermal and physical
0.386 0.0330 172.9 ±3.9 property of TBPGly hydrate, practical application to these two cooling
0.396 0.0344 147.5 ±1.7 methods was discussed.
a
The standard uncertainty u (wTBPGly) is ± 2.0 × 10− 4. The static type is a method often used for ice thermal energy storage,
b
The standard uncertainty u (xTBPGly) is ± 3.0 × 10− 5. These values of mole in which the thermal storage medium is completely frozen for cooling. In
fractions were obtained by converting the mass fractions. this method, TBPGly hydrate solution was injected into the container,
c
The value do not include ice melting enthalpy. and refrigerated to form hydrate solid as a cooling medium. The system
d
The expanded uncertainty U (ΔHd) kJ•kg− 1 was obtained by the triplicate temperature will be decreased and kept constant by circulating a heat
measurements (k = 2). transfer medium such as water around the encapsulated hydrate. Since
cooling is performed without moving the refrigerant, the hydrate with
Fig. 9 shows the correlation between concentration of TBPGly hy­ high solid phase fraction and thermal stability is desirable in this system.
drate and its dissociation heats. Similar to the tendency in the equilib­ Hence, the fraction range of wTBPGly = 0.368 or xTBPGly = 0.0306 to
rium temperature of TBPGly hydrate and in the previous ionic wTBPGly = 0.377 or xTBPGly = 0.0318 near the congruent composition,
semiclathrate hydrate studies, the value of dissociation enthalpy was where all solutions are converted to hydrates, is suitable for the static
maximum near the estimated congruent composition, and tended to method. In addition, large amount of the hydrate with large dissociation
decrease thereafter [39,47,52–56]. From these results, the congruent enthalpy can provide a stable cold energy for a long time. TBPGly hy­
point would exist between wTBPGly = 0.368 or xTBPGly = 0.0306, which drate with the equilibrium temperature of 5.8 ◦ C, is desirable for cold
has the maximum equilibrium temperature, and wTBPGly = 0.377 or energy storage and transportation of temperature sensitive products.
xTBPGly = 0.0318, which has the maximum heat of dissociation. When While ice thermal energy storage system has a large melting enthalpy, its
the molecular composition of TBPGly-H2O was the same in the whole maximum operating temperature is limited to 0 ◦ C, which leads to high
hydrate produced from mass fraction 0.368 to 0.377 aqueous solution, power generation cost with low freezing efficiency. By selecting the
the estimated hydration number of the congruent composition should be range of physical properties with high thermal energy storage density,
in the range of 31.2 to 32.5. The hydration number is expressed by the the reduction of the storage tank volume and equipment can be realized.
following equation where n is the hydration number: In the dynamic method, the cold energy is transferred by flowing a
n = (1 − xTBPGly )/xTBPGly (2) hydrate slurry as the working medium. For its high fluidity and energy
According to the thermophysical characteristics obtained by these density, the slurry can provide the improvement in pumping power and
experiments, the optimum physical properties of TBPGly hydrate for the cooling efficiency [61,64]. The previous study revealed that hydrate
actual application will be discussed in the next section. slurries have cooling capacity of approximately two or three times larger
than cold water, and reduce power consumption by 36% [16,60]. To­
3.4. Determination of optimum physical property for TBPGly hydrate- ward the applicable use of hydrate slurry refrigerant, it is necessary to
based pcm retain the liquidness and select a concentration suitable for the cooling
temperature. The viscosity of an aqueous solution depends on the vol­
The hydrate-based PCM systems have advantages over other PCMs in ume fraction of the solid in the solution [66]. The volume fraction of
terms of non-corrosiveness, non-flammability, and eco-efficiency. There hydrates in the slurry has a great effect on fluidity, especially when the
volume fraction exceeds 0.40, the viscosity significantly increases
[67–69]. Therefore, the hydrate slurry with higher solid phase ratio
consequently requires a larger energy consumption to transport, such as
the need for a progressive cavity pump with a solid phase ratio of 0.60 or
higher [30]. To maintain the fluidity of the slurry, the concentration of
the hydrate solution should be less than the congruent composition at
which all the liquids crystalize [16,68]. In the congruent composition,
the concentration of the aqueous solution will keep constant after the
formation of hydrate crystals. However, if the concentration of the so­
lution is incongruent to the hydrate composition, the amount of salts(e.
g. TBAB or TBPGly) in the solution changes as the part of them are used
to form hydrates. Then, the equilibrium temperature of the hydrate may
drop as the salt concentration decreases from the initial concentration,
suggesting that lower temperature is needed to sustain the hydrate
crystallization.
Considering these phenomena, an appropriate concentration and an
operating temperature of TBPGly hydrate should be determined. Fig. 10
depicts the schematic phase diagram that explains the amount of TBPGly
incorporated into the hydrate caused by the temperature difference is
explained. On this diagram, the points A and B represent TBPGly mole
Fig. 9. Dissociation heat measured from TBPGly aqueous solution prepared in fraction in the solution that is actually used at the operating temperature
various mass fraction w TBPGly and the mole fraction x TBPGly;blue ◆, the (Top). As mentioned above, initial TBPGly mole fraction in the solution
dissociation heat of TBPGly hydrate. . should be smaller than the TBPGly mole fraction at the congruent

6
T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

to 0.34. At an operating temperature of 4 ◦ C, the optimum composition

of the solution was the concentration of 0.29 ≤ wTBPGly ≤ 0.31 or 0.0216
≤ xTBPGly ≤ 0.0237, and the solid phase ratio was 0.11–0.34.
The above results demonstrate that TBPGly hydrate can be utilized as
a solid-liquid hydrate PCM in the temperature range of 2–5.8 ◦ C. With
proper adjustment of these operating conditions and concentration of
aqueous solutions, TBPGly hydrate can surpass conventional cooling
system in temperature assurance and energy efficiency improvement.
Moreover, composed of non-halide substances, TBPGly hydrate is eco
and energy efficient materials in thermal energy storage for chilling
application.

4. Conclusion

In this study, TBPGly, halogen-free ionic semiclathrate hydrate

composed of TBP cation and glycine (aminoacetic acid) anion was
synthesized. Toward the practical application of hydrated-based PCM,
the phase equilibrium temperature, the heat flow rate and the dissoci­
ation heat of TBPGly hydrate were experimentally investigated via vi­
Fig. 10. The schematic phase diagram of the difference in TBPGly mole frac­ sual observation method and DSC measurement. The highest
tion related to the amount of hydrate formation. equilibrium temperature was 5.8 ◦ C at the fraction of wTBPGly = 0.368 or
xTBPGly = 0.0306, and the thermodynamically stable hydrates were
composition(xcon) as point A(xA < xcon). Thus, the aqueous solution with produced around that composition. During the heating process, a single
TBPGly mole fraction of xA was prepared. Moreover, the actual Top is hydrate dissociation peak of heat flow rate curve that was attribute to
required to be set below the equilibrium temperature of the used solu­ one type of crystallographic structure emerged at all fractions of TBPGly
tion to prevent the entire solution from being converted into hydrate. aqueous solutions. At the fraction of wTBPGly = 0.377 or xTBPGly =
Since the equilibrium temperature of a solution differs depending on the 0.0318, the largest dissociation heat of 177.7 kJ⋅kg− 1 was confirmed,
mole fraction of TBPGly, there is a difference in mole fraction of TBPGly which indicated that the large amount of hydrate would be formed at the
(Δx) between the points A and B(Δx = xA − xB ). At this state, TBPGly composition. The hydration number of TBPGly hydrate at the congruent
correspond to the mole fraction of point B(xB) can exist in a liquid. On composition was estimated to be 31.2–32.5. In the both equilibrium
the other hand, the excess mole fraction of TBPGly, which corresponds temperature and dissociation heat measurements, the dependence on
to Δx, is incorporated into hydrate when the solution is operated below the composition of TBPGly solution was revealed. In addition to the
the equilibrium temperature of the congruent composition(Tcon). The thermodynamic examinations, the conditions required for the actual
composition of the hydrate formed from the solution with TBPGly mole systems (operating temperature, initial concentration of the TBPGly
fraction of less than xcon should be consistent with the congruent solution and solid phase ratio of the TBPGly hydrate) were determined.
composition, even if the concentration of the solution is incongruent to Experimental and calculated results demonstrated that TBPGly hydrate
the hydrate composition. Hence, if Top is set below the congruent point, will be utilize as a solid–liquid PCM in the temperature range of 5.8 ◦ C
TBPGly mole fraction of the solution decreases with the formation of for solid hydrates and in the temperature range of 2–4 ◦ C for hydrate
hydrates, which leads to the decrease in the equilibrium temperature. slurries by adjusting the composition of the TBPGly solution.
The hydrate formation continues until the TBPGly mole fraction in the
solution is equal to that of the operating temperature(xB). As seen in CRediT authorship contribution statement
Fig. 10, when the equilibrium temperature drops to the point B, the
production of hydrate stops. Therefore, the amount of hydrate genera­ Takashi Miyamoto: Investigation, Conceptualization, Methodol­
tion can be controlled by determining the Top, leading to the adjustment ogy, Visualization, Writing – original draft, Formal analysis. Naruki
of the solid phase ratio of the solution that can be flowed as a slurry. The Kurokawa: Investigation, Formal analysis. Iku Ota: Investigation,
hydration number, n, of the hydrate generated here was 31.9, that is Formal analysis. Atsushi Hotta: Investigation, Formal analysis, Re­
estimated from the thermodynamic data obtained in the present study; sources. Ryo Ohmura: Validation, Data curation, Writing – review &
maximum equilibrium temperature was observed at n = 31.2 and the editing, Supervision, Resources, Formal analysis.
largest dissociation heat was measured at n = 32.5. The amount of hy­
drate formed with Δx is expressed as n × Δx in terms of mole. Based on
Declaration of Competing Interest
that value, the solid fraction of hydrate was calculated as follows.
In case of preparing 100 g of TBPGly solution, the suitable concen­
The authors declare that they have no known competing financial
tration and volume fraction were estimated under the setting tempera­
interests or personal relationships that could have appeared to influence
ture. From the results corresponding to operating temperature of 2 ◦ C, 3
the work reported in this paper.
◦
C and 4 ◦ C, the solid phase ratios of the hydrate slurry were obtained in
the practical range 0.11–0.36 with the concentration of 0.22 ≤ wTBPGly ≤
0.31. Under the temperature of 2 ◦ C, TBPGly aqueous solution with the Funding Sources
initial concentration of 0.22 ≤ wTBPGly ≤ 0.26 or 0.0150 ≤ xTBPGly ≤
0.0186 should be prepared. The solid phase ratio of the hydrate slurry This study was supported by a Keirin-racing-based research-promo­
was calculated to be 0.12–0.36, which may maintain fluidity of the tion fund from the JKA Foundation (2020M-195).
slurry. The composition of the hydrate produced here should be
consistent with the congruent point composition. When the operating
temperature was set to be 3 ◦ C, in light of the practical solid phase ratio, Acknowledgment
the concentration of 0.27 ≤ wTBPGly ≤ 0.29 or 0.0196 ≤ xTBPGly ≤ 0.0216
was appropriate as a fluid hydrate slurry with the solid fraction of 0.17 The authors gratefully acknowledge the Lab members for valuable
discussion and support.

7
T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

References to computational evaluation, Appl. Energy 89 (2012) 339–346, https://doi.org/

10.1016/j.apenergy.2011.07.039.
[27] W. Lu, S.A. Tassou, Characterization and experimental investigation of phase
[1] United Nations Environment Programme and International Energy Agency,
change materials for chilled food refrigerated cabinet applications, Appl. Energy
Cooling Emissions and Policy Synthesis Report. UNEP, Nairobi and IEA, Paris 2020.
112 (2013) 1376–1382, https://doi.org/10.1016/j.apenergy.2013.01.071.
[2] D. Coulomb, Refrigeration and cold chain serving the global food industry and
[28] L. Huang, U. Piontek, Improving performance of cold-chain insulated container
creating a better future: two key IIR challenges for improved health and
with phase change material: an experimental investigation, Appl. Sci. 7 (2017),
environment, Trends Food Sci. Technol. 19 (2008) 413–417, https://doi.org/
https://doi.org/10.3390/app7121288.
10.1016/j.tifs.2008.03.006.
[29] N. Ndraha, H.I. Hsiao, J. Vlajic, M.F. Yang, H.T.V. Lin, Time-temperature abuse in
[3] S.A. Tassou, G. De-Lille, Y.T. Ge, Food transport refrigeration - Approaches to
the food cold chain: review of issues, challenges, and recommendations, Food
reduce energy consumption and environmental impacts of road transport, Appl.
Control 89 (2018) 12–21, https://doi.org/10.1016/j.foodcont.2018.01.027.
Therm. Eng. 29 (2009) 1467–1477, https://doi.org/10.1016/j.
[30] T. Ogawa, T. Ito, K. Watanabe, K. ichi Tahara, R. Hiraoka, J. ichi Ochiai,
applthermaleng.2008.06.027.
R. Ohmura, Y.H. Mori, Development of a novel hydrate-based refrigeration system:
[4] J.A. Evans, E.C. Hammond, A.J. Gigiel, L. Reinholdt, K. Fikiin, C. Zilio, Assessment
a preliminary overview, Appl. Therm. Eng. 26 (2006) 2157–2167, https://doi.org/
of methods to reduce the energy consumption of food cold stores, Appl. Therm.
10.1016/j.applthermaleng.2006.04.003.
Eng. 62 (2014) 697–705, https://doi.org/10.1016/j.applthermaleng.2013.10.023.
[31] N. Xie, C. Tan, S. Yang, Z. Liu, Conceptual design and analysis of a novel CO2
[5] I. Dincer, M.A. Rosen, Energetic, environmental and economic aspects of thermal
hydrate-based refrigeration system with cold energy storage, ACS Sustain. Chem.
energy storage systems for cooling capacity, Appl. Therm. Eng. 21 (2001)
Eng. 7 (2019) 1502–1511, https://doi.org/10.1021/acssuschemeng.8b05255.
1105–1117, https://doi.org/10.1016/S1359-4311(00)00102-2.
[32] S. Takeya, R. Ohmura, Phase equilibrium for structure II hydrates formed with
[6] H. Selvnes, Y. Allouche, R.I. Manescu, A. Hafner, Review on cold thermal energy
krypton co-existing with cyclopentane, cyclopentene, or tetrahydropyran, J. Chem.
storage applied to refrigeration systems using phase change materials, Therm. Sci.
Eng. Data 51 (2006) 1880–1883, https://doi.org/10.1021/je060233r.
Eng. Prog. 22 (2021), https://doi.org/10.1016/j.tsep.2020.100807.
[33] W. Zhang, Y. Wang, X. Lang, S. Fan, Performance analysis of hydrate-based
[7] S.J. James, C. James, The food cold-chain and climate change, Food Res. Int. 43
refrigeration system, Energy Convers. Manag. 146 (2017) 43–51, https://doi.org/
(2010) 1944–1956, https://doi.org/10.1016/j.foodres.2010.02.001.
10.1016/j.enconman.2017.04.091.
[8] E. Oró, A. de Gracia, A. Castell, M.M. Farid, L.F. Cabeza, Review on phase change
[34] N.H. Duc, F. Chauvy, J.M. Herri, CO2 capture by hydrate crystallization - A
materials (PCMs) for cold thermal energy storage applications, Appl. Energy 99
potential solution for gas emission of steelmaking industry, Energy Convers.
(2012) 513–533, https://doi.org/10.1016/j.apenergy.2012.03.058.
Manag. 48 (2007) 1313–1322, https://doi.org/10.1016/j.enconman.2006.09.024.
[9] L.N. N, Assessment of latent heat thermal storage systems operating with multiple
[35] D. Zhong, P. Englezos, Methane separation from coal mine methane gas by tetra-n-
phase change materials, J. Energy Storage 23 (2019) 442–455, https://doi.org/
butyl ammonium bromide semiclathrate hydrate formation, Energy Fuels 26
10.1016/j.est.2019.04.008.
(2012) 2098–2106, https://doi.org/10.1021/ef202007x.
[10] J. Du, B. Nie, Y. Zhang, Z. Du, li Wang, Y. Ding, Cooling performance of a thermal
[36] S. Muromachi, S. Takeya, Y. Yamamoto, R. Ohmura, Characterization of tetra-n-
energy storage-based portable box for cold chain applications, J. Energy Storage 28
butylphosphonium bromide semiclathrate hydrate by crystal structure analysis,
(2020), https://doi.org/10.1016/j.est.2020.101238.
CrystEngComm 16 (2014) 2056–2060, https://doi.org/10.1039/c3ce41942h.
[11] B. Zalba, J.M. Marin, L.F. Cabeza, H. Mehling, Review on thermal energy storage
[37] M. Yang, W. Jing, J. Zhao, Z. Ling, Y. Song, Promotion of hydrate-based CO2
with phase change: materials, heat transfer analysis and applications, Appl. Therm.
capture from flue gas by additive mixtures (THF (tetrahydrofuran) + TBAB (tetra-
Eng. 23 (2003) 251–2833, https://doi.org/10.1016/S1359-4311(02)00192-8.
n-butyl ammonium bromide)), Energy 106 (2016) 546–553, https://doi.org/
[12] M. Thambidurai, K. Panchabikesan, N. Krishna Mohan, V. Ramalingam, Review on
10.1016/j.energy.2016.03.092.
phase change material based free cooling of buildings-The way toward
[38] H. Kiyokawa, H. Tokutomi, S. Ishida, H. Nishi, R. Ohmura, Thermal energy storage
sustainability, J. Energy Storage 4 (2015) 74–88, https://doi.org/10.1016/j.
performance of tetrabutylammonium acrylate hydrate as phase change materials,
est.2015.09.003.
Appl. Sci. 11 (2021), https://doi.org/10.3390/app11114848.
[13] C. Veerakumar, A. Sreekumar, Phase change material based cold thermal energy
[39] H. Sakamoto, K. Sato, K. Shiraiwa, S. Takeya, M. Nakajima, R. Ohmura, Synthesis,
storage: materials, techniques and applications - a review, Int. J. Refrig. 67 (2016)
characterization and thermal-property measurements of ionic semi-clathrate
271–289, https://doi.org/10.1016/j.ijrefrig.2015.12.005.
hydrates formed with tetrabutylphosphonium chloride and tetrabutylammonium
[14] Z. Khan, Z. Khan, A. Ghafoor, A review of performance enhancement of PCM based
acrylate, RSC Adv. 1 (2011) 315–322, https://doi.org/10.1039/c1ra00108f.
latent heat storage system within the context of materials, thermal stability and
[40] T. Suginaka, H. Sakamoto, K. Iino, S. Takeya, M. Nakajima, R. Ohmura,
compatibility, Energy Convers. Manag. 115 (2016) 132–158, https://doi.org/
Thermodynamic properties of ionic semiclathrate hydrate formed with
10.1016/j.enconman.2016.02.045.
tetrabutylphosphonium bromide, Fluid Phase Equilib. 317 (2012) 25–28, https://
[15] E. Oró, L. Miró, M.M. Farid, L.F. Cabeza, Improving thermal performance of
doi.org/10.1016/j.fluid.2011.12.010.
freezers using phase change materials, Int. J. Refrig. 35 (2012) 984–991, https://
[41] A. Fukumoto, P. Paricaud, D. Dalmazzone, W. Bouchafaa, T.T.S. Ho, W. FuLrst,
doi.org/10.1016/j.ijrefrig.2012.01.004.
Modeling the dissociation conditions of carbon dioxide + TBAB, TBAC, TBAF, and
[16] O. Hidemasa, S. Takao, Air-conditioning system using clathrate hydrate slurry, JFE
TBPB Semiclathrate Hydrates, J. Chem. Eng. Data 59 (2014) 3193–3204, https://
Tech. Rep. 3 (2004) 1–5.
doi.org/10.1021/je500243k.
[17] L. Fournaison, A. Delahaye, I. Chatti, J.P. Petitet, CO2 hydrates in refrigeration
[42] S. Muromachi, T. Abe, Y. Yamamoto, S. Takeya, Hydration structures of lactic acid:
processes, Ind. Eng. Chem. Res. 43 (2004) 6521–6526, https://doi.org/10.1021/
characterization of the ionic clathrate hydrate formed with a biological organic
ie030861r.
acid anion, Phys. Chem. Chem. Phys. 16 (2014) 21467–21472, https://doi.org/
[18] I. Chatti, A. Delahaye, L. Fournaison, J.P. Petitet, Benefits and drawbacks of
10.1039/c4cp03444a.
clathrate hydrates: a review of their areas of interest, Energy Convers. Manag. 46
[43] X. Wang, M. Dennis, An experimental study on the formation behavior of single
(2005) 1333–1343, https://doi.org/10.1016/j.enconman.2004.06.032.
and binary hydrates of TBAB, TBAF and TBPB for cold storage air conditioning
[19] J. Douzet, M. Kwaterski, A. Lallemand, F. Chauvy, D. Flick, J.M. Herri, Prototyping
applications, Chem. Eng. Sci. 137 (2015) 938–946, https://doi.org/10.1016/j.
of a real size air-conditioning system using a tetra-n-butylammonium bromide
ces.2015.07.042.
semiclathrate hydrate slurry as secondary two-phase refrigerant - experimental
[44] T. Kobori, S. Muromachi, T. Yamasaki, S. Takeya, Y. Yamamoto, S. Alavi,
investigations and modelling, Int. J. Refrig. 36 (2013) 1616–1631, https://doi.org/
R. Ohmura, Phase behavior and structural characterization of ionic clathrate
10.1016/j.ijrefrig.2013.04.015.
hydrate formed with tetra-n-butylphosphonium hydroxide: discovery of primitive
[20] X. Wang, M. Dennis, L. Hou, Clathrate hydrate technology for cold storage in air
crystal structure, Cryst. Growth Des. 15 (2015) 3862–3867, https://doi.org/
conditioning systems, Renew. Sustain. Energy Rev. 36 (2014) 34–51, https://doi.
10.1021/acs.cgd.5b00484.
org/10.1016/j.rser.2014.04.032.
[45] X. Wang, M. Dennis, Characterisation of thermal properties and charging
[21] B. Castellani, E. Morini, M. Filipponi, A. Nicolini, M. Palombo, F. Cotana, F. Rossi,
performance of semi-clathrate hydrates for cold storage applications, Appl. Energy
Clathrate hydrates for thermal energy storage in buildings: overview of proper
167 (2016) 59–69, https://doi.org/10.1016/j.apenergy.2016.01.032.
hydrate-forming compounds, Sustainability 6 (2014) 6815–6829, https://doi.org/
[46] J. Shimada, M. Shimada, T. Sugahara, K. Tsunashima, A. Tani, Y. Tsuchida,
10.3390/su6106815.
M. Matsumiya, Phase equilibrium relations of semiclathrate hydrates based on
[22] T. He, Z.R. Chong, J. Zheng, Y. Ju, P. Linga, LNG cold energy utilization: prospects
tetra- n-butylphosphonium formate, acetate, and lactate, J. Chem. Eng. Data 63
and challenges, Energy 170 (2019) 557–568, https://doi.org/10.1016/j.
(2018) 3615–3620, https://doi.org/10.1021/acs.jced.8b00481.
energy.2018.12.170.
[47] Y. Arai, R. Koyama, F. Endo, A. Hotta, R. Ohmura, Thermophysical property
[23] R. Koyama, Y. Arai, Y. Yamauchi, S. Takeya, F. Endo, A. Hotta, R. Ohmura,
measurements on tetrabutylphosphonium sulfate ionic semiclathrate hydrate
Thermophysical properties of trimethylolethane (TME) hydrate as phase change
consisting of the bivalent anion, J. Chem. Thermodyn. 131 (2019) 330–335,
material for cooling lithium-ion battery in electric vehicle, J. Power Sources 427
https://doi.org/10.1016/j.jct.2018.11.017.
(2019) 70–76, https://doi.org/10.1016/j.jpowsour.2019.04.055.
[48] S. Alavi, R. Ohmura, Understanding decomposition and encapsulation energies of
[24] C. Cheng, F. Wang, Y. Tian, X. Wu, J. Zheng, J. Zhang, L. Li, P. Yang, J. Zhao,
structure I and II clathrate hydrates, J. Chem. Phys. 145 (2016), https://doi.org/
Review and prospects of hydrate cold storage technology, Renew. Sust. Energy
10.1063/1.4964673.
Rev. 117 (2020), https://doi.org/10.1016/j.rser.2019.109492.
[49] H. Nakayama, S. Torigata, Hydrates of organic compounds. VIII. The effect of
[25] S.R. Rakkappan, S. Sivan, M. Naarendharan, P.S. Sudhir, D.S. Preetham,
carboxylate anions on the formation of clathrate hydrates of tetrabutylammonium
Experimental investigation on enhanced energy storage characteristics of
carboxylates, Bull. Chem. Soc. Jpn. 57 (1984) 171–174, https://doi.org/10.1246/
spherically encapsulated 1-decanol/expanded graphite composite for cold storage
bcsj.57.171.
system, J. Energy Storage 41 (2021), 102941, https://doi.org/10.1016/j.
[50] H. Nakayama, W. Kazuchi, Hydrates of organic compounds. III. The formation of
est.2021.102941.
clathrate-like hydrates of tetrabutylammonium dicarboxylates, Bull. Chem. Soc.
[26] L. Melone, L. Altomare, A. Cigada, L. de Nardo, Phase change material cellulosic
Jpn. 51 (1987) 2518–2522, https://doi.org/10.1246/bcsj.51.2518.
composites for the cold storage of perishable products: from material preparation

8
T. Miyamoto et al. Journal of Energy Storage 45 (2022) 103773

[51] H. Nakayama, H. Usui, H. Matsui, Hydrates of organic compounds. XIV. The [59] International Association for the Properties of Water and Steam. advisory Note
formation of clathrate-like hydrates of tetrabutylammonium amino carboxylates, No.5: industrial Calculation of the Thermodynamic Properties of Seawater 2013,
Bull. Chem. Soc. Jpn. 60 (1987) 4459–4461, https://doi.org/10.1246/ (2013). http://www.iapws.org/relguide/Advise5 [accessed 23 August 2021].
bcsj.60.4459. [60] G. Li, Y. Hwang, R. Radermacher, Review of cold storage materials for air
[52] Y. Yamauchi, Y. Arai, T. Yamasaki, F. Endo, A. Hotta, R. Ohmura, Phase conditioning application, Int. J. Refrig. 35 (2012) 2053–2077, https://doi.org/
equilibrium temperature and dissociation heat of ionic semiclathrate hydrate 10.1016/j.ijrefrig.2012.06.003.
formed with tetrabutylammonium butyrate, Fluid Phase Equilib. 441 (2017) [61] Z. Youssef, A. Delahaye, L. Huang, F. Trinquet, L. Fournaison, C. Pollerberg,
54–58, https://doi.org/10.1016/j.fluid.2017.02.001. C. Doetsch, State of the art on phase change material slurries, Energy Convers.
[53] Y. Yamauchi, T. Yamasaki, F. Endo, A. Hotta, R. Ohmura, Thermodynamic Manag. 65 (2013) 120–132, https://doi.org/10.1016/j.enconman.2012.07.004.
properties of ionic semiclathrate hydrate formed with tetrabutylammonium [62] A. Saito, Recent advances in research on cold thermal energy storage, Int. J. Refrig.
propionate, Chem. Eng. Technol. 40 (2017) 1810–1816, https://doi.org/10.1002/ 25 (2002) 177–189, https://doi.org/10.1016/S0140-7007(01)00078-0.
ceat.201600459. [63] T. Daitoku, Y. Utaka, Separation characteristics of clathrate hydrates from a
[54] Y. Arai, Y. Yamauchi, H. Tokutomi, F. Endo, A. Hotta, S. Alavi, R. Ohmura, cooling plate for efficient cold energy storage, Appl. Energy 87 (2010) 2682–2689,
Thermophysical property measurements of tetrabutylphosphonium acetate https://doi.org/10.1016/j.apenergy.2010.03.025.
(TBPAce) ionic semiclathrate hydrate as thermal energy storage medium for [64] P. Zhang, Z.W. Ma, R.Z. Wang, An overview of phase change material slurries:
general air conditioning systems, Int. J. Refrig. 88 (2018) 102–107, https://doi. MPCS and CHS, Renew. Sust. Energy Rev. 14 (2010) 598–614, https://doi.org/
org/10.1016/j.ijrefrig.2017.12.020. 10.1016/j.rser.2009.08.015.
[55] R. Koyama, A. Hotta, R. Ohmura, Equilibrium temperature and dissociation heat of [65] Y. Kozak, M. Farid, G. Ziskind, Experimental and comprehensive theoretical study
tetrabutylphosphonium acrylate (TBPAc) ionic semi-clathrate hydrate as a medium of cold storage packages containing PCM, Appl. Therm. Eng. 115 (2017) 899–912,
for the hydrate-based thermal energy storage system, J. Chem. Thermodyn. 144 https://doi.org/10.1016/j.applthermaleng.2016.12.127.
(2020), https://doi.org/10.1016/j.jct.2020.106088. [66] A.L. Graham, R.D. Steele, R.B. Bird, Particle clusters in concentrated suspensions.
[56] T. Miyamoto, R. Koyama, N. Kurokawa, A. Hotta, S. Alavi, R. Ohmura, 3. Prediction of suspension viscosity, Ind. Eng. Chem. Fundam. 23 (1984) 420–425,
Thermophysical property measurements of tetrabutylphosphonium oxalate https://doi.org/10.1021/i100016a007.
(TBPOx) ionic semiclathrate hydrate as a media for the thermal energy storage [67] M. Darbouret, M. Cournil, J.M. Herri, Rheological study of TBAB hydrate slurries as
system, Front. Chem. 8 (2020), https://doi.org/10.3389/fchem.2020.00547. secondary two-phase refrigerants, Int. J. Refrig. 28 (2005) 663–671, https://doi.
[57] R. Feistel, W. Wagner, A new equation of state for H2O Ice Ih, J. Phys. Chem. org/10.1016/j.ijrefrig.2005.01.002.
Ref. Data 35 (2006) 1021–1047, https://doi.org/10.1063/1.2183324. [68] P. Zhang, Z.W. Ma, Z.Y. Bai, J. Ye, Rheological and energy transport characteristics
[58] P. Paricaud, Modeling the dissociation conditions of salt hydrates and gas of a phase change material slurry, Energy 106 (2016) 63–72, https://doi.org/
semiclathrate hydrates: application to lithium bromide, hydrogen iodide, and tetra- 10.1016/j.energy.2016.03.025.
n-butylammonium bromide + carbon dioxide systems, J. Phys. Chem. B 115 [69] H. Zhou, C. Vasilescu, C.I. Ferreira, Heat transfer and flow characteristics during
(2011) 288–299, https://doi.org/10.1021/jp1067457. the formation of TBAB hydrate slurry in a coil heat exchanger, Int. J. Refrig. 64
(2016) 130–142, https://doi.org/10.1016/j.ijrefrig.2015.12.021.