Simulation of electrical and thermal behaviors of
Paraffin nanocomposite used for energy storage.
Hiba MHIRI
Laboratory of Energy and Materials (LR11ES34)
University of Sousse, ESSTHSousse, Abbassi Lamine
Street, 4011 HSousse, Tunisia.
mhirihiba@yahoo.fr
Abstract— Electrical Thermal Storage (ETS) is the technology of
converting off-peak electricity to heat, storing it at low cost, and
then releasing it later at peak hours.
In the present work, new smart composites are developed by
associating a carbon nanofiber (CNF) as conductive element with
paraffin wax which is used simultaneously as storage media and
polymer matrix dielectric.
The voronoi tessellation random construction is used to simulate
the real structure of nanocomposite in the aim to identify current
distribution in nanofibers. (And) The finite element method was
used to solve the coupling equations of vaious physical
phenomena: electric current, heat transfer and solid to liquid
phase change of the paraffin.
The effects of some parameters are thus investigated such as
time, concentration level of CNF and temperature, on both the
electrical-thermal properties of the CNF/paraffin composite.
The effects of the structured distribution of conductive
nanoparticles are analyzed to predict the ideal percolation
threshold and the effective electrical conductivity of the
composite system.
We prove from these results that the CNF/paraffin composites
have both thermal storage and electrical heating functions and
can achieve a high thermal storage capacity at relatively low
temperature. They have a great potential application in the area
of ETS.
Keywords_ Electrical Thermal storage; nanocomposite
nanocomposite; voronoi tessellation; effective electrical
conductivity; self-heating.
INTRODUCTION
Research in electric thermal storage (ETS) has lately
attracted an increased attention. In particular, when the electric
current flows through a solid or liquid with finite conductivity,
electrical energy is converted to heat through resistive losses
in the material (Joule effect)[1].
Combining these materials is particularly important to
ensure this storage. These materials could have both thermal
storage and electrical conduction characteristics.
Phase change materials (PCM) offer challenging options to
be employed as effective energy storage [2].
Paraffin wax has been found to exhibit many desirable
characteristics as phase change material for thermal energy
storage applications such as high latent heat of fusion,
Afef JEMNI, Habib SAMMOUDA
Laboratory of Energy and Materials (LR11ES34)
University of Sousse, ESSTHSousse, Abbassi Lamine,
Street 4011 HSousse, Tunisia.
negligible super cooling, low vapor pressure in the melt,
chemically inert and stable, self nucleating, no phase
segregation and commercially available at low cost. However,
it also has some inherent limitations such as low thermal and
electrical conductivity and large volume change during phase
transition.
The low thermal and electrical conductivity of paraffin
wax could be enhanced by using (a) metal fillers, (a) carbon
additives, and/or fins [3, 4–7]. Carbon nanofibers (CNF) have
a strong resistance to corrosion and chemical attack, which
makes them compatible with paraffin wax. They also have a
good electrical and thermal conductivity [8] .So far a new
composite developed by associating a carbon nanofiber (CNF)
as conductive element with paraffin wax which is used
simultaneously as a storage media and a polymer matrix
dielectric.
These kinds of materials are sometimes multifunctional
and they can modify their mechanical or physical properties
when a stimulus (thermal, electric, magnetic, etc.) is applied,
and return to their original properties when the stimulus is
withdrawn.
In this work, a numerical setup was built to investigate the
electro-thermal behaviors of paraffin wax as a phase change
material reinforced by carbon nanofiber used for energy
storage applications.
Our main aim is to propose a pioneering approach to
simulate the random nature of fiber packing geometry in real
composites based on Voronoi function and B-Spline
curves.[26] These processes are flexible in controlling the
nanofiber shapes and distribution in the composite .
Then, the Time Domain Finite Element Method (TDFEM)
is used for the simulation.
The aim of this study is to investigate the feasibility of
using electrically conductive CNF/paraffin wax composites
for ETS. The effects of percolation, concentration level of
CNF and temperature on the electrical conductivity of the
CNF/paraffin wax composites are also investigated.
MICROSTRUCTURE MODELING
In recent years, different image-analysis techniques have been
applied using optical microscopy or scanning electron
microscopy (SEM in order to identify the non-homogeneous
1
microstructures of carbon nanofiber reinforced composites) E : Electric field
[5–7].
The electrical properties (that are pas besoin) included in the
In this work, we present a method that (il manqué un verbe ici,
model are the permittivity of vacuum, the relative permittivity
peut etre uses) numerically modeling electron images via a
of the insulation e r, and the electrical conductivity s.
stochastic micro-pattern. The underlying idea is to use this
The temperature distribution is given by the heat conduction
method to generate the distribution of the nanofiber filled with
equation in Eq (2):
PCM composite materials.
When
The first step of structural modeling is to determine the
random generation of different points in the material. These J : The current density
points will be connected together to create irregular convex
and concave polygons (where the assembly of these polygons E : Electrical field
form the Voronoi structure which the vertices are modeled as
control points of closed B-Spline curves) ???. The B-Spline The electrical properties (that are pas besoin) included in the
curves are then used to allow for a closer fit of observed model are the permittivity of vacuum, the relative permittivity
structures with irregular cell size and shape. This normally of the insulation e r, and the electrical conductivity s.
results in non-linear boundaries between cells. The temperature distribution is given by the heat conduction
Consequently, this enables a more realistic simulation of the equation in Eq (2): (paragraphe repetee)
properties of the materials. Furthermore, the generation of
‘virtual’ structure becomes possible and can ultimately be
used to optimize the existing alignment of carbon nanofiber
  Cp 
T
t

 . k T  +Sheat
and to virtually design new materials. With a source heat (is pas besoin) given by Eq
As shownin Fig. 1, the pore size, shape, topology and (3): 2
distribution are closely related to the following parameters: J
S   E 2
-The distribution of the Voronoi generator (a); heat 
-The B-spline curve associated with each Voronoi cell (b)
-The effect of values of scale factor (c). T is the temperature, J is the current density, and E (r, t) = −∇
(r, t) is the electrical field associated with an electrical
potential V (r, t). The material properties of density ρ, heat
capacity Cp, and thermal conductivity κ are specific to each
material of the nano system. These properties are dependent
on the temperature, where ρ = ρ (T(r, t)), Cp = Cp (T(r, t)),
a) b) and κ = κ (T(r, t)), σ = σ (T(r, t)) is the temperature-dependent
electrical conductivity.
IV. PHYSICAL MODEL
The physical model used for the studied composite material
(paraffin/carbon nanofiber) is shown in fig2.
A square piece L 50µm wide encloses the paraffin wax, which
c) is filled with the carbon nanofiber.
The electrical currents interface applies a voltage between the
two contact boundaries (top and bottom) of the composite
III. GOVERNING EQUATIONS
material and the other sides are left electrically isolated.
The model includes coupling between the electrical field The related thermo-physical properties of the paraffin wax are
distribution and the temperature due to heat generation by given in table 1.
the electrical current passing through the material when the
heat conduction equation contains a source term that Table1: Thermal physical properties of PCM
depends on the electrical conductivity and the electrical
field. Therefore, the temperature affects the properties of the Materials Parameters Value
materials. l (kg/m3 ) 910
PCM 782.5
 s (kg/m 3 )
3.65*10-3
The electrical current equation is given by the Eq (1): l ( Ns / m 2 ) 0.3
D ks (W/(mK)) 0.1
J   .E  J 1.021*105
t e kl (W/(mK))
3.085*10-4
L (J/kg)
 (1 / K ) 58°C
Tm (K) 2850
When
CP ( J / (kg K ))
s

J : The current density

2

For the non-linear behavior of the phase change in the paraffin
wax, transient analysis was used.
A very dense mesh was required in the composite material to
ensure convergence during phase changes. It consists of
around 15.000 domain elements and 74500 degrees of
freedom.
V. RESULTS AND DISCUSSIONS
A. Percolation Effect
Percolation theory takes into account the distribution of minor
phase in the microstructure of the composite, which depends
on its shape, size, and orientation. Percolation theory is one of
the easiest mechanisms to model disordered systems because
it has little statistical dependency, is an easy concept to realize
even for the most complex systems, and its outcomes are
realistic for qualitative predictions of random composites. ( . )
The percolation model describes the interconnectivity of
carbon nanofiber along the edges of the particles with voronoi
type.
a)
b)
Effect of percolation in electrical potential and current
density.
The nanofiber can be described as separate domains or as
boundary conditions.
Fig ??? shows a schematic (do you mean scheme or sketch?)
of the geometric model as well as two possible filler
distributions in a partially connected filler distribution and a
disconnected filler distribution and a disconnected filler
distribution ( repetition). We can observe the changes in the
electrical potential and electrical density for the different filler
distributions due to??? the electrical path.
B. Concentration effect
Effective properties of the nanocomposites can be calculated
using COMSOL Multiphysics®, a finite element method
(FEM) based on simulation software. The primary goal of
simulation in this research is to calculate the effective
conductivity of the composite medium made of paraffin wax
and carbon nanofibers.
Figs ??? show the electrical conductivity of the composite
with different concentration (non pas concentrations) levels of
CNF.
Since paraffin wax itself is an insulator, the electrical conductivity of
the CNF/paraffin wax composites strongly depends on the
concentration of CNF, which dominates the conductive network in
the composites due to the percolation threshold (i.e., the
transition between the electrical insulator and conductor).
The percolation threshold (φc ) of composites depends on the
structural factors (e.g. size and shape) of the fillers used. The
φc of composites tends to decrease with increasing aspect ratio
of the fillers???
The alignment of CNF will enhance the electrical conductivity
of the composites along the direction of the electrical field.
With a low concentration level of CNF, the average distance
between CNF is large; the conductive path is thus difficult to
form.
As a result, the paraffin wax composites with 0.45 vol. % CNF
maintain a low electrical conductivity. With the concentration
level of CNF increasing to 0.9 vol. %, the average distance
between adjacent CNF in composites decreases and the
electronic transition by tunneling conduction becomes easier.
The main conduction mechanism between adjacent nanofibers
is probably electron hopping when their separation distance is
small???
The improvement effect of the CNF on the electrical
conductivity of the composites is due to the formation of a
conductive network in paraffin wax.
Figs??? show the thermal conductivity of the composite with
different concentration (no s) levels of CNF.
3
 D. Self Heating

The Joule heating effect also occurs when an electrical current

is applied on the Paraffin wax/CNF composite, the self-
The effective thermal conductivity of the composite increases heating behavior was also investigated in this research. When
as the concentration of the nanofibers increases. This behavior the electrical current passed through the fibers, the
can be explained by the decrease (no s) and increase of the temperature of the composite fibers was increased by Joule
distance and interactions between the nanofibers . heating effect and transformed to the paraffin wax, which
caused melting.
C. Temperature effect E. Alternative Current

02
2
24
0, 0,
021
0, 22
0,
Thermal Conductivity
Electric Conductivity

0
02
0,
20
01
9
0,
0,
8
01 18
0, 0,
7
01
0, 16
6 0,
01
0,
5 14
0,
01
electric conductivity
0, In the material, the top face is set to the port where input
4
0,
01 thermal conductivity 12 alternating voltage (sine function is considered in simulations
0,
3
01 with unit amplitude) is applied, while its opposite face is
0,
290 295 300 305 310 315 320
maintained at ground level. The remaining sides are
Temperature (K) maintained at periodic condition.
Fig?? shows the effect of the temperature in the electrical and After creating the geometry, defining its physical properties
thermal conductivity. and its guiding equations and constant, the final step before
The electrical conductivity of carbon nanofiber composites simulating the model is setting the variables. For this end, a
was enhanced by the annealing process at different parametric solver is used in COMSOL Multiphysics®. The
temperatures and changed with time. The electrical solution is obtained from simulations by setting the variables
conductivity of fibers can be changed when the fibers are and their possible values through a parametric solver.
exposed to different temperatures or stretched. This module was preferred because it enables a frequency
This research covers the discussion on the influence of sweep to be conducted for different loadings of the nanofiller
temperature and stretching processes on the electrical at different frequencies.
conductivity of composite fibers. It’s decreasing with increase In fig????, we notice that the current density changes with
in annealing temperature???. This phenomenon can be different frequencies. At low frequency the electrical path is
explained by two factors; one is the change in volume of the only in the CNF domains and the paraffin becomes insulator,
paraffin wax matrix, and the other is the electrical field- whereas at high frequency, the effect of the boundary
induced alignment of CNF. disappears and the composite material becomes conductor.
The rise in temperature increases the volume of paraffin wax,
which leads to an increase of tunneling barrier through by V. CONCLUSION
electrons????. The present study includes a stochastic Voronoi diagram and a
In addition, the rise in temperature transorms paraffin wax B-spline distribution to predict stochastic fiber networks
from solid phase to liquid. The CNF in liquid paraffin wax starting from the behavior of individual fibers and the
will trend to alignment??? under the external electrical field. multiscale structure by using Matlab software and a finite
But for the same reasons, the thermal conductivity of the element method (FEM) for solving the electro-thermal
composite increases with the rise in temperature. behaviors in the composite material (paraffin wax/CNF).

4
Based on the simulation results;
 The CNF was incorporated into paraffin wax matrix to
develop electrically conductive composites for ETS
application.
 Carbon nanofiber (CNF) can exhibit electrical
conductivity and introduce electrical current into paraffin.
 The temperature affects the distribution of the electrical
field through the conductivity and the electrical field
affects the temperature distribution in turn.
 The electrical conductivity of CNF/paraffin wax
composites increases with the concentration level of CNF,
presenting regular percolation characteristics.
These findings indicate that the developed smart materials can
convert electrical energy into thermal energy via electrical
heating and have higher thermal storage performance.
ACKNOWLEDGMENT
This research project was supported by the Tunisian
Ministry of High Education and Scientific Research under
Grant LabEM – ESSTHSousse - LR11ES34.
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