Thermal Science and Engineering Progress 13 (2019) 100397

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Thermal Science and Engineering Progress

journal homepage: www.elsevier.com/locate/tsep

A theoretical and experimental study of a TBAB salt hydrate based cold T

thermal energy storage in an air conditioning system
⁎
Xiaolin Wanga, , Xiaoqiang Zhaib, Huanqi Zhanga, Lei Zhouc
a
Research School of Engineering, The Australian National University, Canberra 2601, Australia
b
Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai 200240, China
c
School of Mechanical Engineering and Automation, Harbin Institute of Technology, Shenzhen 518055, China

A R T I C LE I N FO A B S T R A C T

Keywords: Various phase change materials (PCMs) have been studied in the past decade for cold thermal energy storage
Tetrabutylammonium bromide hydrate (CTES), among which semi-clathrate hydrates of quaternary ammonium salts have aroused great interests.
Cold thermal storage Tetrabutylammonium bromide (TBAB) hydrates can form at temperatures applicable for air conditioning ap-
Air conditioning plications. Based on the results of former studies on a TBAB hydrate based PCMs, this paper investigates the
Influencing factor
influencing factors of a lab-scale CTES tank based on this self-developed PCM in an emulated air conditioning
TRNSYS
system. The effect of chilled water temperature and flowrate on charge, and the effect of return water flowrate
and cooling load on discharge are experimentally studied. A model of the CTES was developed using ε-NTU
method, through which its performance are evaluated in terms of charging/discharging rate, charging/dis-
charging capacity and efficiency. In addition, influencing factors such as return water temperature and flowrate,
initial PCM liquid fraction, and the number and material of the heat transfer coils are analysed using TRNSYS
simulation employing the developed CTES model. According to the results, it is suggested in the actual use of
TBAB hydrate based CTES to apply 2.0 °C chilled water for charge with initial solids and 4.0 °C chilled water for
charge without initial solids. The optimal chilled water flowrate, 12 g s−1 for charge with initial solids and
18 g s−1 for charge without initial solids, can also be employed. In addition, in the design of a CTES the heat
transfer coils are suggested to have a thermal conductivity close to 16 W m–1 K−1 but no need to exceed this
value.

1. Introduction
Cold thermal energy storage (CTES) conserves cooling by extracting
heat from a storage medium, such as water, ice and phase change
materials (PCMs). It has become one of the primary means of load le-
velling of electricity demand, and meanwhile offers many other bene-
fits, such as providing solar cooling into evening, reducing chiller ca-
pacity and enhancing chiller efficiency for running at night.
The feasibility of PCM thermal storage has been addressed. By
Mehdaoui et al. [1] the heat transfer within a vertical enclosure con-
taining PCM in a test cell was studied experimentally. In addition, a
simulation using Transient System (TRNSYS) Simulation Tool was built
to evaluate the feasibility of integrating the PCM enclosure in a real
building envelop. It was found that during the heating phase the tem-
perature in the test cell equipped with the PCM enclosure was 28 °C;
without the PCM enclosure the cell temperature ranged between 29 and
40 °C. Stritih et al. [2] presented the use of latent heat thermal storage
heated by a hot air solar energy collector. A numerical model of the
storage was built and implemented as a component in TRNSYS, and was
validated by experimental results. It was found that the average cov-
erage ratio in the heating season for the system with and without sto-
rage was 67% and 53%, respectively. In the work of Stritih et al. [3], a
composite wall filled with different PCMs was developed using TRNSYS
for the purpose of integration into passive near zero buildings. It was
shown that the PCMs in the wall reduced building energy consumption
on daily basis. A model of a building with ordinary radiant floor was
built by Lu et al. [4] to compare the differences in its temperatures to
that of a building with PCM floor coupled with solar water heating
system (PFCSS). The PCM floor is a cement floor structure on the
ground which has a cement motar screed-coat layer containing double
tubes of PCM and circulating water. It was found that the PFCSS
building’s temperature fluctuation was smaller and the heating process
was longer. At an indoor temperature of 20 °C, the PFCSS building had
5.87% lower energy consumption. By McKenna et al. [5] a simulation

⁎
Corresponding author.
E-mail address: xiaolin.wang@anu.edu.au (X. Wang).

https://doi.org/10.1016/j.tsep.2019.100397
Received 7 February 2019; Received in revised form 21 August 2019; Accepted 21 August 2019
2451-9049/ © 2019 Elsevier Ltd. All rights reserved.
X. Wang, et al.
Nomenclature
English alphabet
A heat transfer area, m2
Cp specific heat of the HTF, kJ/(kg·K)
hHTF heat transfer coefficient of the HTF, W/(m2·K)
kPCM thermal conductivity of PCM, W/(m·K)
kWALL thermal conductivity of the tube wall, W/(m·K)
L tube length, m
ṁ mass flowrate of HTF, kg/s
RHTF thermal resistance of the HTF, K/W
Ri inner radius of the tube, m
Rmax max radius of frozen PCM between the phase change in-
terfaces of adjacent tubes, m
was conducted to study the potential for geo-cooling, with and without
thermal storage, in a Mediterranean climate. A model of spherically-
encapsulated PCM CTES tank was developed and validated in the
TRNSYS environment. Using a small, lightweight commercial building
in the case study, it was found that electricity savings of 24–45% was
possible from combining geo-cooling with PCM CTES, when compared
to a reference system based on ground-source heat pump.
Studies have been presented to study PCM thermal storage perfor-
mance using modelling and experimental methods and to optimise the
design of PCM thermal storage units and systems. Korti et al. [6] pre-
sented an experimental study on a PCM CTES unit using three different
types of paraffin. The effect of heat transfer fluid (HTF) temperature,
flowrate and the type of PCM on the charging and discharging time
were discussed. It was found by increasing the inlet HTF temperature
from 74 to 78 °C, the charge was accelerated by 54.5% and the dis-
charge was extended by 48.5%. The performance of CTES system using
packed bed containing spherical capsules filled with n-tetradecane was
studied by Wu et al. [7]. A 40 vol% ethylene glycol aqueous solution
was used as HTF. A mathematical model was established to study the
effect of HTF temperature and flowrate, porosity of packed bed and
capsule diameter on the melting and freezing time, and charging and
discharging rate. Using the same method, the discharging character-
istics of a CTES system with coil pipes were studied [8]. The effect of
inlet HTF temperature and flowrate and the coil diameter on the HTF
outlet temperature, melt fraction and discharging rate were discussed.
It was showed that higher HTF flowrate and higher inlet HTF tem-
perature resulted in higher discharging rate. In addition, the pipe dia-
meter had less influence on the discharging process. In a study of
Zarajabad et al. [9], a numerical study for optimal PCM volume was
conducted on a CTES system mounted in a freezer. NaCl-H2O was used
as the PCM with a melting temperature of −21 °C. PCM boxes with the
maximum exposed area and various PCM thicknesses were simulated
using computational fluid dynamics (CFD). When the PCM thickness
was raised from 2 to 3 cm, discharging time per unit of PCM mass in-
creased significantly to 45% and slightly afterward. Container with
3 cm thickness was found most optimal. By Abdelsalam et al. [10]
rectangular PCM modules with coil heat exchangers in a modular sto-
rage tank of 200 L were studied. The effect of PCM volume fraction and
spacing between the modules on the heat transfer and the charging rate
were analysed. Two-dimensional CFD simulations showed an 85% in-
crease in the charging rate by increasing the PCM volume fraction from
0.025 to 0.150. For a certain coil heat exchanger design, further in-
crease of the charging rate necessitated increasing the surface area of
the heat exchanger. For tube-in-tank arrangements, the impact of the
boundary condition of the PCM surroundings on the heat transfer was
studied by Belusko et al. [11]. HTF was set as parallel flow, counter
flow or in a serpentine arrangement. This work identified that the cri-
tical influencing factor was the loss of heat transfer area once the phase
2
Thermal Science and Engineering Progress 13 (2019) 100397
Ro outer radius of the tube, m
RPCM thermal resistance of the PCM, K/W
RT total thermal resistance, K/W
RWALL thermal resistance of the tube wall, K/W
Ti CTES inlet HTF temperature, °C
To CTES outlet HTF temperature, °C
TPCM phase change temperature, °C
U overall heat-transfer coefficient, W/(m2·K)
Greek alphabet
δ phase change fraction
ε heat exchanger effectiveness
interfaces between parallel tubes met. It was significant for parallel
flow but eliminated for the counter flow arrangement, which delivered
a more uniform phase interface parallel to the tube wall. A mathema-
tical model of an encapsulated PCMs based thermal storage was de-
veloped [12], considering the simplified non-equilibrium energy
equations coupled with enthalpy technique. A PCM thermal storage was
fabricated to evaluate the effect of charging and discharging tempera-
ture and flowrate. It was found that the charge and discharge were both
faster for smaller capsule diameter and higher porosity. The maximum
storage efficiency was 75.69% when the inlet HTF temperature of
charging and discharging were 180 and 120 °C respectively and the
flowrate was 8.2 lpm. The effect of phase change temperature on the
coefficient of performance (CoP) of an air conditioning system was
investigated [13]. The system performance with different PCMs was
studied by using a validated dynamic model in Modelica. It was found
higher PCM melting temperature resulted in higher power consumption
during cooling operation, but lower power consumption during the
recharge operation. By using a selected PCM, an increase of 11% in the
CoP was observed. It was noted that high thermal conductivity com-
ponents, such as metal foam, can be used to enhance thermal con-
ductivity [14]. A conjugate numerical fluid flow and heat transfer
method was used to characterise a tube-in-tank design. The results
showed that there was an optimum compactness factor (CF) for PCM at
any finite thermal conductivity, and the optimum CF and maximum
effective energy storage ratio were higher at a higher PCM thermal
conductivity. It is also indicated that enhancement of heat transfer in
the fluid side may further improve the effective energy storage ratio. By
Jia et al. [15] a spherical PCM capsule with circular pin-fins was pro-
posed and its temperature variation, liquid fraction distribution, and
charging rate with various pin-fin configurations were numerically
studied. Good agreement was achieved between the model and ex-
perimental data with a deviation of < 6.9%. It was found that the
thermal performance can be improved by optimizing geometric para-
meters of pin-fins. Cheng et al. [16] designed a three-stage cascaded
cold storage unit (CCSU). Its solidification process was compared to that
of a single-stage cold storage unit (SCSU). The results showed that,
although the energy and exergy stored in CCSU were 2–5% and 4–8%
less than those stored in the SCSU, the cold charging rate was enhanced
by 11–35% in the CCSU and its exergy efficiency was higher. In addi-
tion, cascaded PCMs can reduce the amount of material used and ensure
optimal storage utilisation. By Li et al. [17] a one dimensional transient
model for PCM capsules was developed to predict the performance of a
cascaded cold storage unit by using equivalent specific heat method and
entransy theory. From the results, the optimized parameters including
stage number of 3–6, solidification temperature offset of 2.5 °C and the
dimensionless capsule diameter of 0.05–0.1 were recommended. With
the optimized structure, the average equivalent thermal resistance was
reduced by 75.7%. By Tehrani et al. [18], the performance of various
X. Wang, et al.
thermal storage alternatives integrated into a 19.9 MWe Gemasolar
concentrated solar power plant were compared with a conventional
two-tank system through a validated numerical analysis. It was found
by changing the filler portions, cascaded PCM group did not sig-
nificantly change the annual performance of the system. By Li et al.
[19,20] an open-air swimming pool was studied to minimise the vo-
lume of the PCM tank while keeping its capability to maintain the water
temperature inside the thermal comfortable range in winter. A simu-
lation platform was developed using TRNSYS and MATLAB to in-
vestigate the effect of the decision-making variables on the tank volume
regarding its control, energy performance, thermal comfort and eco-
nomic performance. Case studies showed that the proposed optimisa-
tion was able to efficiently reduce the tank volume and the operational
cost without sacrificing the storage capacity.
Simple methods for modelling a PCM thermal storage system were
proposed. A developed approach was similar in concept to the bypass
factor method, widely used in air conditioning applications to estimate
the outlet air conditions from a coil [21]. The results exhibited a good
agreement with the experimental results. The method was applicable to
any PCM thermal storage, thereby simplifying the performance char-
acterisation of such systems in energy analysis tools such as TRNSYS. In
recent years, a simplified method is being proposed for characterising
PCM thermal storage, which is based on the effectiveness-number of
transfer units (ε-NTU) technique. The effectiveness, which refers to how
much of the volume is used to store useful energy, was defined by Amin
et al. [22] to represent the expected energy storage density of a PCM
thermal storage system. The technique was validated in various system
configurations. It was proven that the ε-NTU method is applicable for
PCM encapsulated in spheres and flat containers through experimental
validation [23–25]. Using the ε-NTU method, a two-dimensional re-
presentation was developed to predict the heat transfer during phase
change. A correlation was developed, revealing the validity of the ε-
NTU method for packed bed PCM systems. By Aziz et al. [26] three
configurations of PCM container were investigated, including a plain
sphere, a sphere with conducting pins, a copper-plated sphere with
conducting pins. The results showed that the local effectiveness values
were increased by an average of 65% for the embedment of 32 pins. The
average effectiveness was further improved by almost 256% when
using copper plated sphere. The results also suggested that the heat
flow through the pinned sphere predominately followed a parallel path,
while through the copper plated sphere was predominately isothermal.
An investigation into optimising useful latent heat within a tube-in-tank
PCM thermal storage system was conducted, with particular reference
to off-peak thermal storage applications for space cooling [27]. The
process involved the determination of actual useful energy to be stored
in a PCM storage system coupled to a night-time cooling system using a
cooling tower. The useful energy to be stored in PCM was determined
using a validated ε-NTU model. This storage effectiveness was opti-
mised to deliver a storage effectiveness of 68% and 75%. A new sim-
plified two-dimensional model, based on the ε-NTU technique, was
built to characterise tube-in-tank PCM systems with radial round fins
Table 1
Properties of the TBAB and other PCMs for air conditioning applications.
PCMs
Hexadecane–tetradecane (2:3–0:1 by volume)
Hexadecane–tetradecane (2:1–2:3 by volume)
Hexadecane–tetradecane (6.5:1–2:1 by volume)
Caprylic acid–lauric acid (9:1 by mole)
Caprylic acid–palmitic acid (9:1 by mass)
Dodecanol–caprylic acid (40.6:59.4 by mass)
C14, C15, C16, C17, C18 (33.4:47.3:16.3:2.6: 0.4 by mass)
76% Na2SO4·H2O
40% TBAB water solution
Capric acid–lauric acid (65:35 by mole) with 10% secondary additives
Capric acid–lauric acid
Thermal Science and Engineering Progress 13 (2019) 100397
[28]. In addition, a simplified mathematical representation was devel-
oped using the ε-NTU technique for a cylindrical tank filled with PCM,
with HTF flowing through tubes inside the tank [29]. The results
showed that this technique can readily be used as a design tool for
sizing and optimising a thermal storage unit with PCMs. The average
heat exchange effectiveness of the thermal storage system was achieved
with a large heat transfer surface area. An experimental study was
undertaken on a direct contact PCM thermal storage using air as the
HTF and water as the PCM [30]. Unity heat exchange effectiveness was
identified over the entire phase change process demonstrating the ex-
cellent heat transfer characteristics of the concept. It was found if
pumping losses was reduced, gas based direct contact PCM storage
could potentially achieve a higher useful storage density than conven-
tional PCM systems which also relied on a large heat transfer area.
Tetrabutylammonium bromide (TBAB) semi-clathrate hydrates offer
a large latent heat that leads to size and weight advantages. They also
provide large latent heat and suitable phase change temperatures in the
range of 5–12 °C, which suits to the characteristics of conventional air
conditioning systems. The properties of TBAB and other widely-studied
PCMs for air conditioning cold storage applications are compared in
Table 1. However, the hydrate formation has many uncertainties. One is
the induction delay in the hydrate formation that extends the charging
process and incurs extra energy consumption of the chiller. Due to the
uncertainties, the charging and discharging performance of TBAB hy-
drate based CTES are seldom studied in a practical systems. This paper
presents a study on the use of a PCM based on modified TBAB hydrates
[31,32] in a lab-scale experimental CTES system and in TRNSYS si-
mulation. The charge and discharge process were conducted at various
operating conditions to study the influencing factors. The charging
capacity and efficiency at various chilled water temperatures and
flowrates, and the discharging capacity at various cooling demands and
return water flowrates are experimentally studied. The effect of HTF
flowrates, initial PCM phase and heat transfer coils is studied using
TRNSYS simulation tools with a CTES model developed based on the ε-
NTU method.
2. Experimental system
The internal structure of the lab-scale demonstration of TBAB hy-
drate based CTES system is shown in Fig. 1. It is mainly composed of a
CTES tank (total inner volume of 100 L) with helical coils (total length
of 36.5 m), a thermostatic bath (HX-1030) and an external HTF loop. It
is based on an internal melt ice-on-coil system. The CTES tank is made
of high-density polyethylene (HDPE) with 380 mm in width and length,
and 960 mm in height. The helical coils are made of low-density
polyethylene (LDPE) with an internal diameter of 15 mm and a thick-
ness of 1 mm. They were spiralled and located at the centreline of the
tank. The CTES tank is initially filled with 75 L liquid PCM which is a
self-developed recipe with a phase change temperature of 12 °C. The
CTES tank has a rated latent heat storage capacity of 3.75 kWh with the
contained PCM. In the loop, water (the HTF) passes through the helical
Phase change temperature (°C) Latent heat (kJ kg−1) Supercooling degree (°C) Ref.
1.7–5.3 > 148 1–2 [33,34]
5.3–10 148
10–14.5 148–183
3.77 152 / [35]
6.54 117 2.2
7 179 2.5
7 158 / [36]
9.3 114 / [35]
12 193 ~5 [37,38]
12.5–13.9 112–127 / [39]
14.7–15.1 100–151 0.2–0.5 [40]
3
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

Inlet Outlet UA 1
NTU = =
̇ p)
(mC RT mĊ p (5)
Liquid surface
For the coils with HTF passing through inside and PCM outside, the
total thermal resistance RT can be expressed as
Temperature
measuring point #1 RT = RHTF + RWALL + RPCM
1
(δ (Rmax 2 − Ro2) + Ro2) 2
1 ln (Ro / Ri ) ln [ Ro
]
Temperature = + +
measuring point #2 2πRi LhHTF 2πkWALL L 2πkPCM L (6)

Helical coils
Tank wall
Fig. 1. The internal structure of the CTES tank.
coils to cool or heat the TBAB solution/hydrate. Two thermocouples are
mounted at the centreline of the CTES tank, respectively at 350 mm and
600 mm from the bottom of the tank. There are thermal resistances at
the inlet and outlet of the tank and the thermostatic bath. The un-
certainty of temperature measurement is ± 0.1 °C. The water flowrate
is controlled in the range between 6 and 24 g s−1 using the pump inside
the thermostatic bath and an external circulating pump, and is mea-
sured by flowmeters (Micro Motion® Compact Density Meters).
PCM used in this study was 35% TBAB and 0.675 wt% tetra-n-bu-
tylammonium fluoride (TBAF) aqueous solution, with its main prop-
erties detailed in Table 2. The purpose of adding minor amount of TBAF
was to lift the phase change temperature and decrease the supercooling
degree without reducing its formation enthalpy. A previous work has
shown TBAB and TBAF mixtures are stable with no phase separation
[41].
The GHS classification of TBAB is: Acute Toxicity (Oral) Category 4;
Skin Corrosion/Irritation Category 2; Serious Eye Damage Category 1;
Acute Aquatic Hazard Category 2. There are investigations about the
corrosion behaviour of metals used to make the pipelines, valves, and
heat exchangers of air-conditioning system in TBAB aqueous solution
containing aggressive bromide anion. This could be alleviated by using
inhibitors [42]. Polyethylene, polypropylene and glass containers are
most suitable for TBAB storage. In this experiment the tank and coils
are both polyethylene.
The experimental system can be operated in charging or discharging
mode, as shown in Fig. 2. In the charging operation, the thermostatic
bath acts as a chiller to deliver cooling capacity to the CTES tank; in the
discharging operation, the CTES tank discharges to deliver cooling ca-
pacity to the fan-coil. The charging and discharging cooling capacity
can be calculated using Eqs. (1) and (2) respectively. The charging ef-
ficiency refers to the ratio of stored cooling capacity to the total cooling
capacity delivered by the chiller (the thermostatic bath), which can be
found using Eq. (3).
̇
Qcharge ̇ p, water (Toutlet − Tinlet )
= mC (1)
̇
Qdischarge ̇ p, water (Tinlet − Toutlet )
= mC (2)
̇ / Qchiller
ηcharge = Qtank ̇ (3)
The heat transfer between HTF and PCM can be correlated to the
heat gain and loss through the HTF. Consequently, the heat transfer rate
and outlet HTF temperature can be calculated from
̇ p (Ti − TPCM ) = mC
Q = εmC ̇ p (To − Ti ) (7)
Based on the ε-NTU method, a CTES model was built using the
properties of the self-developed TBAB hydrate material as the PCM
(shown in Table 2) and the dimensions of the experimental CTES tank.
The model was compiled as a component in the transient simulation
environment TRNSYS 16.1 [Thermal Energy System Specialists (TESS)].
The TRNSYS deck file mainly consists of an electric chiller (Type 655), a
fan-coil (Type 32) and the modelled CTES tank (Type 62).
4. Results and discussions
4.1. Experimental results
Charging operations were conducted at various chilled water tem-
peratures and flowrates in different initial conditions – charge “from
TBAB solution with formed hydrate” or “from complete liquid TBAB
solution”. Solid hydrate particles are believed to shorten the induction
time in hydrate formation as they provide nuclei seeds to assist to
overcome the metastability in phase equilibrium. Besides, in the be-
ginning of most charging cases, solids may exist in CTES tanks as the
PCMs are not often melt completely in the discharge. Therefore, in this
study charge “from TBAB solution with formed hydrate” was carried
out. The two initial conditions are compared. Discharging operations
were studied at different return water flowrates and cooling loads. A
heater of 750 W was used to increase the cooling load of the ambient.
4.1.1. Effect of chilled water temperature on the charge
In the charge “from TBAB solution with formed hydrate” or “from
complete liquid solution”, at various chilled water temperatures (from
2.0 to 6.0 °C), the charging capacity and charging efficiency are shown
in Fig. 3. It was illustrated that lower chilled water temperatures
(2.0–4.0 °C) resulted in higher charging capacity during the same
period of time. In the charge from solution with solids (a), the average
charging capacity in 3.5 h for 5.0 and 6.0 °C chilled water was respec-
tively 14.5% and 25.0% lower than that for the three lower chilled
water temperatures. In the charge from complete liquid solution (b), the
average charging capacity in 5 h for 5.0 and 6.0 °C was respectively
12.5% and 16.3% lower than that for the other three lower chilled
water temperatures.
Table 2
Properties of the self-developed TBAB hydrate material.

3. CTES tank modelling and TRNSYS simulation Material 35% TBAB and 0.675 wt Ref.
% TBAF

A CTES tank component was programmed using the validated ε- Latent heat (kJ kg−1) 209 [41]
NTU model. The effectiveness is defined as a ratio of the actual dis- Density (kg m−3) 1100 This work
charged heat to the theoretical maximum amount of heat that can be Specific heat, liquid (kJ kg–1 K−1) 3.60 [43]
discharged. It describes the average NTU of the CTES, which can be Specific heat, solid (kJ kg–1 K−1) 2.60 [37]
Thermal conductivity, liquid 0.35 [44]
presented by the average thermal resistance between the HTF and PCM
(W m–1 K−1)
at phase interface. Thermal conductivity, solid 0.38 [45]
(W m–1 K−1)
ε = 1 − exp (−NTU ) (4)

4
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

(a) tank charging from chiller (b) tank discharging to load

Fig. 2. Operating modes of the experimental emulated air conditioning system with CTES.

Comparing the two cases, the existence of solid hydrate was not chilled water flowrate resulted in higher charging capacity during the
found to obviously accelerate the hydrate formation. Although adding same time period. In the charge from solution with solids (a), the
pre-produced TBAB hydrate into supercooled TBAB aqueous solution charging capacity of 18, 15, 12 and 9 g s−1 in 9 h were respectively
could immediately induce the crystallisation of TBAB hydrate crystals 39.6%, 40.2%, 28.0% and 26.4% higher than that of 6 g s−1 chilled
[45], as the solid hydrates on the coils also reduce the thermal con- water flowrate. In the charge from complete liquid solution (b), in 7 h
duction in the bulk of liquid, the cooling capacity of case (a) was lower the charging capacity of 18, 15, 12 and 9 g s−1 were respectively
than that of case (b) during the same time period. This was more ob- 48.8%, 15.3%, 13.0% and 12.9% higher than that of 6 g s−1 flowrate.
vious at lower chilled water temperatures. In addition, the lack of The charging capacity grew much faster in the case (b) than that in
sensible heat exchange at the initial stage of case (a) also led to less the case (a) showing again that hydrate solids did not accelerate the
cooling capacity to be stored. On the other hand, the charging efficiency charging process as expected. In fact, the induction time, which was
of case (b) (averagely 0.706, 0.794, 0.797, 0.719 and 0.692 respectively proven to be shortened by adding nuclei seeds, is no longer a dominant
for 2.0, 3.0, 4.0, 5.0 and 6.0 °C) was in general higher than that of the factor in a large-scale CTES tank; therefore the charge starting with
case (a) (averagely 0.736, 0.735, 0.665, 0.641 and 0.647 respectively hydrate solids will not bring significant advantages. In addition, the
for 2.0, 3.0, 4.0, 5.0 and 6.0 °C). It was also found the charging effi- charge from complete liquid solution (b) had obviously higher charging
ciency did not increase with the decrease in chilled water temperature efficiency (0.753, 0.711, 0.695, 0.693 and 0.708 in average respectively
constantly. The optimal chilled water temperature for case (a) and (b) for 18, 15, 12, 9 and 6 g s−1) than the charge from solution with solids
were respectively 2.0 and 4.0 °C. (b) (0.596, 0.636, 0.702, 0.597 and 0.592 in average respectively for
18, 15, 12, 9 and 6 g s−1). For the charging efficiency, the optimal
chilled water flowrate for case (a) and (b) were respectively 12 g s−1
4.1.2. Effect of chilled water flowrate on the charge and 18 g s−1.
Similarly, the effect of chilled water flowrate (from 6 to 18 g s−1) on
the charging capacity and efficiency is shown in Fig. 4. All the cases
were conducted at 3.0 °C chilled water temperature. Generally, higher

0.8 1.0 1.2 1.0

0.9 1.1 0.9
0.7
1.0
0.8 0.8
Charging capacity (kWh)
Charging capacity (kWh)

0.6 0.9
0.7 0.7
Charging efficiency
Charging efficiency

0.8
0.5 0.6 0.6
0.7
0.4 0.5 0.6 0.5
0.4 0.5 0.4
0.3 Capa. Effi. Capa. Effi.
0.4
o o
2C 0.3 o o
2C 0.3
0.2 o
3oC 0.3 o
3oC
0.2 o
4oC
0.2
o
4oC 0.2
0.1 o
5oC 0.1
o
5oC 0.1
0.1
o
6oC
o
6oC
0.0 0.0 0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (hour) Time (hour)

(a) charge from TBAB solution with formed hydrate (b) charge from complete liquid TBAB solution
Fig. 3. Effect of chilled water temperature on the charging capacity and efficiency.

5
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

1.2 1.0 1.6 1.0

0.9 1.4 0.9

1.0 0.8

Charging capacity (kWh)

0.8
Charging capacity (kWh)

1.2
0.7

Charging efficiency
0.7

Charging efficiency
0.8
1.0 0.6
0.6
0.6 0.5 0.8 0.5

0.4 0.6 0.4

Capa. Effi. Capa. Effi.
0.4 0.3
-
18 g s -1
0.3 -
18 g s-1
-
15 g s-1
0.4 -
15 g s-1
0.2 0.2
0.2
-
12 g s-1
-
12 g s-1
-
9 g s-1 0.2 -
9 g s-1 0.1
0.1
-
6 g s-1
-
6 g s-1
0.0 0.0 0.0 0.0
0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7
Time (hour) Time (hour)

(a) charge from TBAB solution with formed hydrate (b) charge from complete liquid TBAB solution
Fig. 4. Effect of chilled water flowrate on the charging capacity and efficiency.

26 1.0 0.20
#1(higher) #2(lower)
24 24 g s-1 0.9 0.18
20 g s-1

Disharging capacity (kWh)

0.8 0.16
22 16 g s-1

Discharging rate (kW)

0.7 0.14
Temperature (oC)

20
0.6 0.12
18
0.5 0.10
16
0.4 0.08
14 0.3 0.06
Capa. Rate
12 0.2 - 0.04
24 g s-1
-
10 0.1 20 g s-1 0.02
-
16 g s-1
8 0.0 0.00
0 1 2 3 4 5 6 7 8 9 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5

Time (h) Time (hour)

(a) PCM temperature (heater off) (b) discharging rate and capacity (heater off)

26 1.0 0.40
#1(higher) #2(lower)
24 24 g s
-1 0.9 0.36
-1
20 g s
Disharging capacity (kWh)

22 -1
0.8 0.32
16 g s

Discharging rate (kW)

Temperature ( oC)

0.7 0.28
20
0.6 0.24
18
0.5 0.20
16
0.4 0.16
14 0.3 0.12
Capa. Rate
12 0.2 - -1 0.08
24 g s
10 0.1
-
20 g s-1 0.04
-
16 g s-1
8 0.0 0.00
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

Time (h) Time (hour)

(c) PCM temperature (heater on) (d) discharging rate and capacity (heater on)
Fig. 5. Effect of return water flowrate and cooling load on the discharging performance.

4.1.3. Effect of return water flowrate and cooling load on the discharge and (c). It was noticed that the temperature increase at position #1 was
The discharge was operated from complete solid state at three dif- much faster and more sensitive than that at position #2, since the re-
ferent return water flowrates (16, 20 and 24 g s−1) and a constant fan turn water passed through the CTES tank from the top (closer to #1).
speed. The discharge with or without an additional cooling load of Without an additional cooling load (a), the PCM temperature curves
750 W was compared. The variations of PCM temperature, discharging dispersed greatly at various return water flowrates. The PCM tem-
rate and capacity are shown in Fig. 5. perature remained at 12.0 °C (phase change temperature) for the
The PCM temperature at position #1 and #2 are shown in Fig. 5(a) longest time at 16 g s−1 flowrate. With an additional 750 W cooling

6
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

5 Table 4
Simulation Experiment Thermal conductivity of studied coil material.
3oC
5oC Material Thermal conductivity (W m–1 K−1)
4
LDPE 0.33
Charging capacity (kWh)

Stainless steel 16.0

Aluminium 205
3
Copper 401

2 respectively, indicating the simulation results were in good agreement

with experimental ones. Therefore, a series of simulations were con-
ducted using the scheduled conditions shown in Table 3. The thermal
1 conductivity of various helical coil materials are shown in Table 4.

4.2.2. Influence factors on the charging performance

0
0 5 10 15 20
Time (hour)
Fig. 6. Validation of simulation results with experimental results.
load (c), the temperature curves were quite close to each other at
various flowrates. The PCM temperatures at position #1 increased ra-
pidly to 19.0 °C in 1.6 h and the temperatures at position #2 departed
from 12.0 °C in only 4 h, indicating a much faster discharge than that
without extra cooling load.
The discharging rate and discharging capacity without and with an
additional cooling load are compared in Fig. 5(b) and (d). The dis-
charging rate dropped gradually in all the cases with time. It was found
that without an additional cooling load (b), higher return water flow-
rate led to higher discharging rate, and as a result higher discharging
capacity was accumulated during the same period of time. The dis-
charging capacity for 24 and 20 g s−1 flowrates were respectively
47.7% and 19.8% higher than that for 16 g s−1 return water flowrate. In
the case with extra cooling load (d), the effect of 16 and 20 g s−1
flowrates on the discharge was quite similar. Moreover, the discharging
rate in case (d) were averagely 59.1%, 69.9% and 110.5% higher than
those without extra cooling load for 24, 20 and 16 g s−1 flowrates re-
spectively. Moreover, it was noticed that the cooling load affected more
significantly at lower return water flowrates. The fluctuation in dis-
charging rate in Fig. 5(b) came from the fluctuation in the flowrate,
which was more obvious when a larger flowrate was applied.
4.2. Simulation results
4.2.1. Calibration of simulation
The charging process was also carried out using the modelled CTES
tank in the TRNSYS environment. The CTES tank model based on the ε-
NTU method employing the parameters from the experimental tank.
In Fig. 6, the charging capacity from experimental data and simu-
lation results for 3 °C and 5 °C HTF temperature are compared. The
error of the simulation was 6.61% for 3 °C and 9.97% for 5 °C
Effect of HTF temperature on the PCM temperature, charging rate
25
and capacity is shown in Fig. 7. The initial PCM temperature is set at
25 °C. The average charging rate for 2.0, 3.0, 4.0, 5.0 and 6.0 °C HTF
temperature are respectively 0.331, 0.300, 0.263, 0.229 and 0.194 kW.
The charging time for 2.0, 3.0, 4.0, 5.0 and 6.0 °C HTF temperature are
respectively 14.6, 16.1, 18.3, 21.0 and 24.5 h. The charging capacity at
the end of simulation is close for all the HTF temperatures. The slight
difference in the final charging capacity is led by various sensible heat
storage of solid PCM.
Effect of HTF flowrate on the charging process is shown in Fig. 8. As
can be seen, the charging rate for 7 g s−1 HTF flowrate (0.154 kW) is
dramatically lower than that of the other three flowrates (0.269 kW in
average); as a result, the charge for 7 g s−1 HTF flowrate does not
complete in 25 h. The charging rate and capacity for 14, 21 and
28 g s−1 flowrates are close, from which it is believed that 14 g s−1 is
the optimal HTF flowrate for charging among the flowrates studied.
Effect of initial PCM liquid fraction on the charging process is shown
in Fig. 9. In Fig. 9(a) the PCM temperature starts from 25 °C for 100%
liquid case, and from 12 °C (the phase change temperature) for 25–75%
liquid cases as the phase change has already started in the beginning of
simulation. The charging rate is not obviously affected by the initial
liquid fraction. The final charging capacity at 25 h is approximately in
proportion to the corresponding initial liquid fraction.
Effect of the number of heat transfer coils on the charging perfor-
mance is shown in Fig. 10. The average charging rate for 30, 40, 50 and
60 coils are respectively 0.151, 0.207, 0.262 and 0.317 kW, showing
that the increase of charging rate is linear to the increase of coils’
number. Effect of heat transfer coil material on the charging perfor-
mance is shown in Fig. 11. The charging rate and charging capacity for
coils made of copper, aluminium and stainless steel are quite similar
(1.09 kW in average) when the thermal conductivity of the three ma-
terials are all above 16.0 W m–1 K−1. The obviously lower charging rate
occurs in the case of LDPE coils (averagely 0.262 kW).
4.2.3. Influence factors on the discharging performance
The discharge is simulated with the HTF from the CTES tank flowing
to an air–water heat exchanger (the fan-coil). Influence of flowrate (7,

Table 3
Schedule of simulation on the charge and discharge of CTES.
Process Influencing factor studied PCM volume (L) Number of coils Material of coils HTF temperature (°C) HTF flowrate (g s−1) Initial phase

Charge HTF temperature 75 50 LDPE Various 21 100% liquid

HTF flowrate 75 50 LDPE 5 Various 100% liquid
Initial liquid fraction 75 50 LDPE 5 21 Various
Number of coils 75 Various LDPE 5 21 100% liquid
Material of coils 75 50 Various 5 21 100% liquid

Discharge HTF flowrate 75 50 LDPE / Various 100% solid

Initial liquid fraction 75 50 LDPE / 21 Various
Number of coils 75 Various LDPE / 21 100% solid
Material of coils 75 50 Various / 21 100% solid

7
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

25 1.0 6
2oC Capacity Rate
3oC
o
C 2oC
4oC
o
C 3oC 5
20 0.8

Charging capacity (kWh)

5oC
o
C 4oC

Charging rate (kW)

o
C 5oC
Temperature (oC)

6oC 4
o
C 6oC
15 0.6
3
10 0.4
2

5 0.2
1

0 0.0 0
0 5 10 15 20 25 0 5 10 15 20 25
Time (hour) Time (hour)

(a) temperature variation (b) charging rate and capacity

Fig. 7. Effect of HTF temperature on the charging process.

25 1.0 6
7 g s -1 Capacity Rate
14 g s -1 o
C 7 g s-1
21 g s -1 o
14 g s-1
5
20 0.8 C

Charging capacity (kWh)

28 g s -1 o
C 21 g s-1
Charging rate (kW)
Temperature (oC)

o
CC 28 g s-1 4
15 0.6
3
10 0.4
2

5 0.2
1

0 0.0 0
0 5 10 15 20 25 0 5 10 15 20 25
Time (hour) Time (hour)

(a) temperature variation (b) charging rate and capacity

Fig. 8. Effect of HTF flowrate the charging process.

25 1.0 6
liquid Capacity Rate
75% liquid liquid
50% liquid 75% liquid 5
20 0.8 Charging capacity (kWh)
25% liquid 50% liquid
Charging rate (kW)

o
CC 25% liquid
Temperature (oC)

4
15 0.6
3
10 0.4
2

5 0.2
1

0 0.0 0
0 5 10 15 20 25 0 5 10 15 20 25
Time (hour) Time (hour)

(a) temperature variation (b) charging rate and capacity

Fig. 9. Effect of initial liquid fraction on the charging process.

14, 21 and 28 g s−1) on the discharge is shown in Fig. 12. The initial the discharge for 7 g s−1 flowrate does not complete in 30 h, which can
temperature of PCM is 5 °C. As can be seen, the discharging rate for be viewed from Fig. 12(a) that at 30 h the PCM temperature for 7 g s−1
7 g s−1 HTF flowrate (0.127 kW) was lower than that of 14, 21 and still stays at its phase change temperature.
28 g s−1 flowrates (0.159, 0.173 and 0.181 kW respectively). Therefore Effect of initial liquid fraction on the discharging process is

8
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

25 1.0 6
30 coils
40 coils
50 coils 5
20 0.8

Charging capacity (kWh)

60 coils

Charging rate (kW)

Temperature ( oC)

4
15 0.6

Capacity Rate 3
30 coils
10 0.4
40 coils
50 coils 2
o
CC 60 coils
5 0.2
1

0 0.0 0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
Time (hour) Time (hour)

(a) temperature variation (b) charging rate and capacity

Fig. 10. Effect of number of heat transfer coils on the charging process.

25 8 6
LDPE
Stainless steel 7
Alumium
5
20

Charging capacity (kWh)

Copper 6
Charging rate (kW)
Temperature ( oC)

4
5
15
4 3
Capacity Rate
10 3 LDPE
2
Stainless steel
2 Alumium
5 Copper 1
1

0 0 0
0 5 10 15 20 25 0 5 10 15 20 25
Time (hour) Time (hour)

(a) temperature variation (b) charging rate and capacity

Fig. 11. Effect of material of heat transfer coils on the charging process.

25 1.0 5
7 g s-1 Capacity Rate
14 g s-1 o
C 7gs -1

20 21 g s-1 14 g s-1
o
Disharging capacity (kWh)
0.8 C 4
28 g s-1 o
C 21 g s-1
Disharging rate (kW)
Temperature ( oC)

o
CC 28 g s-1
15 0.6 3

10 0.4 2

5 0.2 1

0 0.0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (hour) Time (hour)

(a) temperature variation (b) discharging rate and capacity

Fig. 12. Effect of HTF flowrate on the discharging process.

9
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

25 1.0 5

Capacity Rate
solid

Discharging capacity (kWh)

20 0.8 25% liquid 4

Discharging rate (kW)

50% liquid
Temperature ( oC)

o
CC 75% liquid
15 0.6 3

10 0.4 2

solid
5 25% liquid 0.2 1
50% liquid
75% liquid
0 0.0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (hour) Time (hour)

(a) temperature variation (b) discharging rate and capacity

Fig. 13. Effect of initial liquid fraction on the discharging process.

25 1.0 5
30 coils Capacity Rate
40 coils 30 coils

Discharging capacity (kWh)

50 coils 40 coils
20 0.8 4
60 coils 50 coils
Discharging rate (kW)
o
CC 60 coils
Temperature (oC)

15 0.6 3

10 0.4 2

5 0.2 1

0 0.0 0
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Time (hour) Time (hour)

(a) temperature variation (b) discharging rate and capacity

Fig. 14. Effect of number of heat transfer coils on the discharging process.

25 1.0 6
LDPE
Capacity Rate
Stainless steel
Alumium LDPE 5
20 0.8
Discharging capacity (kWh)
Copper Stainless steel
Discharging rate (kW)

Alumium
Temperature (oC)

Copper 4
15 0.6
3
10 0.4
2

5 0.2
1

0 0.0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (hour) Time (hour)
(a) temperature variation (b) discharging rate and capacity
Fig. 15. Effect of material of heat transfer coils on the discharging process.

10
X. Wang, et al. Thermal Science and Engineering Progress 13 (2019) 100397

36 28

Charge Charge

Charging / discharging time (hour)

Charging / discharging time (hour)
32 24
Discharge Discharge

20
28
16
24
12
20
8

16 4

12 0
5 10 15 20 25 30 solid 25% liquid 50% liquid 75% liquid lqiuid
-1
HTF flowrate (g s ) Initial state of PCM

(a) effect of HTF flowrate (b) effect of initial state of PCM

36 28
Charging / discharging time (hour)

Charge Charge

Charging / discharging time (hour)

32 Discharge 24 Discharge

20
28

16
24
12
20
8

16
4

12 0
25 30 35 40 45 50 55 60 65 LDPE stainless steel alumium copper
Number of coils Coil material

(c) effect of number of coils (d) effect of coil material

Fig. 16. Effect on the charging and discharging time.

illustrated in Fig. 13. The initial PCM temperature is 5 °C for 100% solid
case and at 12 °C (phase change temperature) for 25–75% liquid frac-
tion cases. Similar to the charge process, the average discharging rate is
not affect significantly by the initial liquid fraction. The discharging
capacity at 30 h is approximately in proportion to the initial solid
fraction.
Effect of the number of heat transfer coils on the discharging per-
formance is shown in Fig. 14. The average discharging rate for 30, 40,
50 and 60 coils are respectively 0.113, 0.137, 0.159 and 0.178 kW,
indicating that the increase of discharging rate is linear to the increase
of coils’ number. Effect of heat transfer coil material on the discharge is
shown in Fig. 15. The discharging rate and capacity for coils made of
copper, aluminium and stainless steel are similar (0.213 kW in average)
and much higher than that for LDPE coils (0.159 kW in average). A
slight increase in the discharging rate at the end of phase change can be
viewed for all the cases, which results from the reduced thermal re-
sistance along with the dissociation of solid hydrate on the heat transfer
coils.
4.2.4. Charging and discharging time
The charging and discharging time refer to the duration from the
start of cooling/heating to the completion of phase change. The CTES
tank model presents the effect of HTF flowrate, initial PCM state,
number and material of heat transfer coils on the charging and dis-
charging time, as illustrated in Fig. 16.
As shown in Fig. 16(a), the HTF flowrate influences on the charging
and discharging time significantly, especially as it reduces from 14 to
7 g s−1 the charging and discharging time increase by 94.0% and
32.7%. At a low HTF flowrate of 7 g s−1, both the charging time and
discharging time become as long as about 32 h. It is also found that HTF
flowrate affects more greatly on the charging process at lower HTF
flowrates, which is in agreement with the literature [6]; while the HTF
flowrate affects more greatly on the discharging process at higher HTF
flowrates. As can be seen from Fig. 16(b), the variations in the charging
and discharging time are non-linear with the initial liquid fractions. The
increase of charging time becomes more rapid as the initial liquid
fraction rises; the increase of discharging time gets more rapid as the
initial solid fraction rises.
From Fig. 16(c) and (d), both charging and discharging time reduce
as either the number of heat transfer coils or the thermal conductivity
of the coil material increases. In this study the influence of coil material
is negligible when its thermal conductivity is higher than
16 W m–1 K−1. The effect of the number and material of coils on the
charging time is more dramatic than that on the discharging time. This
is due to the fact that the temperature difference between HTF and PCM
is smaller in the charge and heat transfer is a key restraint during PCM

11
X. Wang, et al.
solidification in the studied CTES tank design.
5. Conclusion
Based on the results of a self-developed PCM using TBAB hydrate,
this paper investigates the influencing factors of a lab-scale CTES tank
in an emulated air conditioning system. The charging/discharging rate,
charging/discharging capacity and efficiency are studied using both
experimental and simulation methods. The influence of chilled water
temperature and flowrate on charge and the effect of return water
flowrate and cooling load on discharge are studied experimentally. The
effects of HTF temperature and flowrate, initial liquid fraction of PCM,
and the number and material of the heat transfer coils are studied in a
self-programmed CTES model in TRNSYS simulation. Main findings are
concluded:
(1) From the experimental results, the existence of formed hydrates
was not found to accelerate the hydrate formation; instead, as the
formed hydrates on heat transfer coils led to thermal resistance, the
charging rate initially with solids was lower, especially at low
chilled water temperatures. The induction issue in large-scale CTES
tanks is no longer dominating, thus it is not advantageous to form
hydrate starting from a solution with hydrate solids.
(2) The charging efficiency did not always increase with the drop of
chilled water temperature and the increase of chilled water flow-
rate. The optimal chilled water temperature for charge with/
without solids were 2.0 °C and 4.0 °C respectively. The optimal
chilled water flowrate for charge with and without solids were
12 g s−1 and 18 g s−1 respectively in the experiment.
(3) The discharge process with an additional 750 W cooling load was
much faster than that without an additional cooling load. The
cooling load affected more at lower flowrates.
(4) From the simulation results, the HTF flowrate affects more greatly
on the charging process at low HTF flowrates; it affects more largely
on the discharging process at high flowrates.
(5) The increase of charging time becomes more rapid as the liquid
fraction in the initial PCM rises; the increase of discharging time
becomes more rapid as the solid fraction in the initial PCM rises.
(6) The effect of coil material at a thermal
conductivity > 16 W m–1 K−1 (stainless steel) is negligible; the ef-
fect of the number and material of coils on the charging time is
more dramatic than that on the discharging time.
Overall, according to the simulation results, the performance of
PCM is of significance to the efficiency of the CTES system, on which
not only the thermal properties of the PCM but also its cost and che-
mical compatibility with containers have a great impact. This study
employed TBAB hydrate as the PCM mainly for its proper thermal
properties. In addition, the cost of raw TBAB is relatively low, which is
$60–80 USD per kWh cooling capacity storage. However, for compat-
ibility with metal containers, more insights into the corrosion are
needed. In addition, the economic aspects, system lifespan, optimisa-
tion of the CTES to shorten the payback period remain important topics
for future work that would bring this technology to an advanced pilot
stage for commercialisation.
Declaration of Competing Interest
The authors declared that there is no conflict of interest.
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