Journal of Energy Storage 27 (2020) 101166

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Journal of Energy Storage

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Thermal conductivity enhancement of sodium thiosulfate pentahydrate by T

adding carbon nano-tubes/graphite nano-particles
⁎
Rabi Ibrahim Rabady , Dua'a S Malkawi
Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110, Jordan

A B S T R A C T

Phase change materials are great thermal energy storage medium, while their low thermal conductivity presents the main obstacle for their potential applications.
Improvement of the thermal conductivity and specific heat of Sodium Thiosulfate Pentahydrate as a base phase change material with joining Carbon Nano tubes CNT
and Graphite Nano particles GNP as Nano-fillers was investigated in this work. CNT and GNP Nano-fillers added in a mass fraction of 1, 3, 5 and 7% in Sodium
Thiosulfate Pentahydrate. Thermal conductivity and specific heat were measured by Hot Disk Thermal Constants Analyzer Instrument. Results have shown that
increasing the mass fraction of Nano-fillers increases the composite's thermal conductivity. Thermal conductivity of the composite containing: 7% GNP was 2.944 W/
m.k with 155.33% enhancement, in the other hand, thermal conductivity of the composite containing: 7% CNT was 4.031 W/m.k with 249.61% enhancement.
Moreover, the charging/discharging rates have been enhanced by adding Nano-fillers to Sodium Thiosulfate Pentahydrate.

1. Introduction PCM and the surrounding medium. Recently, induced by the extra-
ordinary interest and advances in the technology, researchers proposed
Using Phase Change Material PCM as storage media for latent enhancing the PCMs’ thermal conductivity by adding nanoparticles
thermal energy is an effective way for using thermal energy. PCMs may [9–15]. Comparison for the findings of previous research studies which
involve only sensible heat, latent heat or a combination of both. PCMs investigated adding nanoparticles to PCM to improve the thermal
give a high energy storage capacity by absorbing or releasing latent conductivity is of interest. Nevertheless, it was difficult to make com-
heat during phase change process during isotherm conditions. PCMs prehensive and solid comparison due to various PCM and nanoparticles
classified into two types: Organic (Paraffins and nonparaffin) and sizes and thicknesses used in these investigations. Zeng et al. present
Inorganic (Salt hydrate and metallics). The main characteristics that results of an experimental investigation of melting of nanoparticle en-
choosing organic and nonorganic PCM depends on them are: Suitable hanced phase change materials. Multi-walled carbon nanotubes (CNT)
phase-transformation temperature, high latent heat, high specific heat were dispersed in 1-dodeconal to prepare samples with various weight
and high thermal conductivity [1–5]. Recently, inorganic type of PCMs percentages (0, 1 and 2 wt.%). The thermal conductivity increases with
such as salt hydrates have been investigated as thermal energy storage increasing the weight percentages of the CNTs; for instance, the relative
and found with favorable thermal properties [6]. They have a higher enhancement is 4.6% for the 1 wt.% [14]. He et al. present the pre-
thermal conductivity, a higher latent heat, and lower cost relative to paration and thermal characterization of Myristic acid as PCM en-
organic phase change materials [7]. On the other hand, inorganic PCMs hanced by multi-walled carbon nanotubes (MWCNTs) and nano-gra-
(salts and salt hydrates) have phase segregation and supercooling pro- phite (NG). It was found that the thermal conductivity of the PCM
blems, which will reversibly affect the energy storage capacity [8]. composites can be improved by 47.30% and 44.01%,% respectively, by
Another key property of PCMs is the thermal conductivity, since it di- adding MWCNTs and NG with a concentration of 3 wt.% for the
rectly affects the charging/discharging rates of the PCM with heat en- MWCNT [15]. In this paper, further experimental investigation is per-
ergy. Higher thermal conductivities are favorable in order to facilitate formed in order to examine the performance improvement due to
convenient use of stored heat energy. However, most PCMs suffer low adding nano-fillers such as: Carbon Nanotubes or Graphite Nano-Par-
thermal conductivities that negatively affect their effectiveness. Dif- ticles to Sodium Thiosulfate Pentahydrate at different mass fraction.
ferent suggestions were proposed and investigated in order to overcome The purpose of this paper is to evaluate and compare the heat transfer
the low thermal conductivity issue by incorporating a metallic mesh enhancement of the phase change nanocomposites using different nano-
into the PCM volume or by small size spherical capsulation of the PCM, fillers and to develop nano-PCM composites with desired character-
which effectively increases the interacting surface area between the istics, especially with high thermal conductivity, to facilitate for

⁎
Corresponding author.
E-mail address: rrabady@[Link] (R.I. Rabady).

[Link]
Received 25 September 2019; Received in revised form 2 December 2019; Accepted 17 December 2019
Available online 28 December 2019
2352-152X/ © 2019 Elsevier Ltd. All rights reserved.
R.I. Rabady and D.S. Malkawi Journal of Energy Storage 27 (2020) 101166

Table 1 temperature is maintained at 50–60 °C. Sodium thiosulfate penta-

Specifications of nano-fillers. hydrate should be melted until is converted to liquid phase. The
MWCNT GNP measured amount of nano-fillers is added to liquid Sodium thio-
sulfate pentahydrate, and then the composites were prepared by
Diameter 50–80 nm 40 nm shear mixing with a magnetic stirrer for 20 min, followed by ultra-
Purity > 90% > 95%
sonic shaking for 50 min. To the above solution, Carboxymethyl
Ash < 0.8% < 0.5%
Color Black Black
cellulose (CMC) and sodium dodecyl sulfate (SDS) were mixed and
thoroughly stirred. The CMC used as a stabilizing or nucleating
agent, which helps in preventing phase segregation and super-
effective thermal energy storage. The thermal conductivities and spe- cooling problems, a main problem encountered in salt hydrates.
cific heat capacity of these nanocomposites are measured by Hot Disk SDS used as surfactant solution to help nano-fillers to dispersed in
thermal constants analyzer. Finally, the charging and discharging salt hydrate. During this step, the temperature was kept above the
period performances of these different phase change nanocomposites melting temperature of Sodium thiosulfate pentahydrate.
are also investigated. (4) The molten composite is poured gently into a rectangular mold then
put it in hydraulic press to take the mold shape without bubbles and
2. Experimental allowed to solidify at room temperature.

2.1. Materials 2.3. Instruments

Sodium thiosulfate pentahydrate as PCM with melting point of The used instruments for the experimental work were as follow:
about 48 °C was purchased from US Research Nanomaterials. Inc.
(Houston, USA). Because of its melting point and charging/ discharging • Hot plate was used to raise the temperature of the samples until they
cycling durability, such salt hydrate can be suitable in solar hydronic melt with magnetic stirrer.
systems which find broad application in domestic use as clean source of • Supersonic shaker was used to mix the nanoparticles with Sodium
hot water. thiosulfate pentahydrate homogeneously.
Multi-walled carbon nanotube MWCNT and Graphite nano-powder • The samples were prepared by casting molding then pressed by
are the two types of nano-fillers were used, with specification listed in hydraulic press, the average thickness of the sample is 3 mm, and
Table 1. Fig. 1 presents the SEM graphs of these nano-fillers. All ma- can be immediately used for thermal transport measurements.
terials were utilized as supplied without further treatment or purifica- • Hot Disk Thermal Constants Analyzer shown in Fig. 2 was used to
tion. measure the thermal conductivity, specific heat and diffusivity of
the samples. A Hot Disk thermal analyzer uses the Transient Plane
2.2. Preparation of composite PCM Source (TPS) method based on a transient technique. The sensor of
this device includes an electrically conducting model in the shape of
Various samples were prepared with weight fractions of 1, 3, 5, and a double spiral, which is engraved on a very thin Nickel foil. This
7% of MWCNT and GNP nanoparticles. The preparation of composites spiral is surrounding by two thin insulating sheets. This sensor is
has been characterized by five steps: placed between two sample pieces to perform a thermal transport
measurement.
(1) Pre-melting of pure PCMs, to homogenize the pure PCM. Sodium
thiosulfate pentahydrate has been put in suitable Vials to assist the 3. Results and discussion
handling of the preparation steps of composites.
(2) Weighing of a solid PCM with and nano-fillers to prepare the 3.1. Thermal conductivity analysis
samples. For each type of the nano-fillers, the mass fractions in
samples are 1, 3, 5, and 7%. The temperature variations of phase change materials are used for
(3) The Vial is placed in hot plate within a water beaker with thermal energy storage. The energy storage rate depends mainly on the

Fig. 1. SEM micrographs of: (a) MWCNT, (b) GNP. (Source: US Research Nanomaterials. Inc.).

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R.I. Rabady and D.S. Malkawi Journal of Energy Storage 27 (2020) 101166

Fig. 2. Hot disk thermal constants analyzer that was used to measure the thermal conductivity.

thermal conductivity of materials; therefore, the thermal conductivity Table 3

of PCMs is an important property that must be investigated in order to Thermal conductivity of Sodium thiosulfate pentahydrate /CNT composites.
be improved by proper method. Thermal parameters Mass
The thermal conductivity of Sodium thiosulfate pentahydrate was fraction
measured as reference value as 1.153 W/m.K. The experimental result 1% 3% 5% 7%
for the thermal conductivity of the composite PCMs with 1%, 3%, 5%
Thermal conductivity (W/m K) 2.824 3.107 3.603 4.031
and 7% nano-fillers are listed in Tables 2 and 3; which are also fitted as The relative thermal conductivity 144.93 169.47 212.49 249.61
shown in Fig. 3. It is clear that the thermal conductivity of the com- enhancement (%)
posite PCM increased remarkably with the increasing of the nano-fillers
content. Relative thermal conductivity enhancement factor defined as:
(k-k0)/k0 is used in order to describe the quantitatively enhancement of
nano-filler in increasing of thermal conductivity. Adding Carbon Nano
tubes to Sodium thiosulfate pentahydrate yields better thermal con-
ductivities than adding the GNP. Moreover, increasing the CNT mass
fraction maintain thermal conductivity enhancement of the composite,
but it becomes almost steady with the GNP addition as depicted from
Fig. 3. These two aspects propose that incorporating CNT to Sodium
thiosulfate pentahydrate would be more advantageous and promising
for useful application.
Based on the above experimental results of the two types of used
nanoparticles, it can be concluded that the enhancement of thermal
conductivity is directly related to the nanomaterial microstructure
shown in Fig. 1. For instance, PCM with CNT can form columnar
structure layer on the nanoparticle surface, which helps in producing
effective heat conduction paths, hence enhanced thermal conductivity.
Whereas, for PCM with GNP case, the spherical sheet structure helps to
form nano-layer that facilitates better heat conduction since the
thermal conduction in the transversal direction is much lower than that
in the longitudinal direction. Fig. 3. Thermal conductivity of the composite PCMs versus the mass fraction of
the nanoparticles.

Table 2
Thermal conductivity of Sodium thiosulfate pentahydrate/GNP composites. Enhancement of thermal conductivity consequently affects directly
from the charging time that is required to reach certain temperature,
Thermal parameters Mass
fraction which is critical thermal energy storage applications, as depicted in
1% 3% 5% 7% Figs. 4 and 5 presents. Apparently, increasing the CNT mass fraction
enhances both the thermal conductivity as well as the charging time
Thermal conductivity (W/m K) 2.208 2.578 2.611 2.944
which was decreased from 30 min to 7 min only with 7% mass fraction.
The relative thermal conductivity 91.5 123.59 126.45 155.33
enhancement (%) Whereas, adding 7% of GNP decreased the charging time from 30 min
to about 11 min.

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R.I. Rabady and D.S. Malkawi Journal of Energy Storage 27 (2020) 101166

Fig. 7. STP with GNP composites behavior during discharging time.

Fig. 4. STP with CNT composites [Link] charging time.

Fig. 5. STP with GNP composites behavior during charging time. Fig. 8. Comparison between studies added GNP.

Fig. 6. STP with CNT composites behavior during discharging time.

Fig. 9. Comparison between studies added GNP.

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R.I. Rabady and D.S. Malkawi Journal of Energy Storage 27 (2020) 101166

Fig. 10. DSC analysis for PCM with 7%GNP: (a) Melting curve, (b) Solidified curve.

Figs. 6 and 7 present the effect of adding CNT and GNP to Sodium additive wt.% of the nano filers.
Thiosulfate Pentahydrate on discharging time when the samples cooled
at room temperature (18 °C). For CNT case the discharging time was
3.2. DSC analysis
decrease from 40 min for Sodium Thiosulfate Pentahydrate to 15 min
with 7% CNT. Whereas, for mass fraction of 7% GNP the discharging
Melting and solidified temperature of the Sodium thiosulfate pen-
time was decrease from 40 min to 18 min.
tahydrate was investigated using DSC for maximum mass percent of
Figs. 8 and 9 present a comparison results between our recent study
two types of nanoparticles, 7% GNP and 7% CNT. The melting tem-
and that of M. He et al [15]. Obviously, not only that our findings in
perature and enthalpy of Sodium thiosulfate pentahydrate is 48 °C and
enhancing the relative thermal conductivity by nano filters addition are
210 kJ/kg, respectively.
far better than that of He et al, but also it covers wider range for the
The DSC curves of Sodium thiosulfate pentahydrate with 7% of GNP

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R.I. Rabady and D.S. Malkawi Journal of Energy Storage 27 (2020) 101166

Fig. 11. DSC analysis for PCM with 7%CNT: (a) Melting curve, (b) Solidified curve.

are shown in Fig.10, which shows that the melting temperature of the slight increase in the melting temperature was observed as depicted
7% GNP composite is about 53.1 °C. It can be concluded that the from the DSC curves of the CNT/ sodium thiosulfate pentahydrate
melting temperature is almost not affected by the concentration of the composite compared to that melting temperature of the pure sodium
added GNPs since slight decrease in the melting temperature was ob- thiosulfate pentahydrate as observed in Fig. 11. Moreover, the melting
served when compared with that of pure sodium thiosulfate pentahy- temperature of the 7% CNT/ sodium thiosulfate pentahydrate compo-
drate. The solidified DSC curves show that the composite exhibits su- site was 55.8 °C. The adding of CNT also shows positive influence on
percooling phenomenon with solidified temperature as 25.6 °C. easing the effect of the supercooling phenomenon where the solidified
Similar to the GNP/ sodium thiosulfate pentahydrate composite, temperature was 20.1 °C. The supercooling effect was improved

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R.I. Rabady and D.S. Malkawi Journal of Energy Storage 27 (2020) 101166

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