Applied Thermal Engineering 22 (2002) 1141–1151

www.elsevier.com/locate/apthermeng

Heat transfer enhancement in water when used as PCM

in thermal energy storage
a,*
L.F. Cabeza , H. Mehling b, S. Hiebler b, F. Ziegler b,1

a
Universitat de Lleida, Escola Universita
ria Polit

ecnica, Jaume II, 69, E-25001 Lleida, Spain
b
Bavarian Center for Applied Energy Research, Division of Energy Conversion and Storage, Walther-Meißner-Str. 6,
D-85748 Garching, Germany
Received 1 August 2001; accepted 18 January 2002

Abstract
Efficient and reliable storage systems for thermal energy are an important requirement in many appli-
cations where heat demand and supply or availability do not coincide. Heat and cold stores can basically be
divided in two groups. In sensible heat stores the temperature of the storage material is increased signifi-
cantly. Latent heat stores, on the contrary, use a storage material that undergoes a phase change (PCM)
and a small temperature rise is sufficient to store heat or cold. The major advantages of the phase change
stores are their large heat storage capacity and their isothermal behavior during the charging and dis-
charging process. However, while unloading a latent heat storage, the solid–liquid interface moves away
from the heat transfer surface and the heat flux decreases due to the increasing thermal resistance of the
growing layer of the molten/solidified medium. This effect can be reduced using techniques to increase heat
transfer. In this paper, three methods to enhance the heat transfer in a cold storage working with water/ice
as PCM are compared: addition of stainless steel pieces, copper pieces (both have been proposed before)
and a new PCM-graphite composite material. The PCM-graphite composite material showed an increase in
heat flux bigger than with any of the other techniques.
2002 Elsevier Science Ltd. All rights reserved.

Keywords: Phase change material; Thermal energy storage; Heat flux enhancement; Experiment

*
Corresponding author. Tel.: +349-73-702-742; fax: +349-73-702-702.
E-mail addresses: lcabeza@diei.udl.es (L.F. Cabeza), hmehling@ph.tum.de (H. Mehling), shiebler@ph.tum.de
(S. Hiebler), fziegler@tu-berlin.de (F. Ziegler).
1
Present address: Inst. Energy Technology, Technical University of Berlin, Sect. BH10, Ernst-Reuter-Platz 1,
D-10857 Berlin, Germany. Fax: +49-30-31422253/89-32944212.

1359-4311/02/$ - see front matter
2002 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 4 3 1 1 ( 0 2 ) 0 0 0 3 5 - 2
1142 L.F. Cabeza et al. / Applied Thermal Engineering 22 (2002) 1141–1151

1. Introduction

Efficient and reliable thermal storage systems are an important requirement for many appli-
cations due to the non-coincidence of heat demand and supply or availability. Among the thermal
energy storage concepts, sensible heat, latent heat, and thermochemical heat are under investi-
gation. The major advantages of the phase change stores are their large heat storage capacity and
their isothermal behavior during charging and discharging process.
In a latent heat thermal storage (LHTS) system, during phase change the solid–liquid interface
moves away from the heat transfer surface. During this process, the surface heat flux decreases
due to the increasing thermal resistance of the growing layer thickness of the molten/solidified
medium. In the case of solidification, conduction is the only transport mechanism, and in most
cases it is very poor. In the case of melting, natural convection can occur in the molten layer and
this generally increases a bit the heat transfer rate compared to the solidification process (if the
layer is thick enough to allow natural convection to occur). However, the generally low heat
transfer rate can be increased considerably by using a suitable heat transfer enhancement tech-
nique.
There are several methods to enhance the heat transfer in a LHTS system. The use of finned
tubes with different configurations has been proposed by various researchers as an efficient means
to improve the charge/discharge capacity of a LHTS system [1–7].
Other heat transfer enhancement techniques for LHTS systems are having the PCM inserted in
a metal matrix [8–14], using PCM dispersed with high conducting particles [15] and micro-
encapsulation of PCM [16,17].
A quite recent method to improve heat flux in PCMs is to use a PCM-graphite composite
material, developed at the ZAE Bayern and produced by SGL CARBON GmbH (Germany). It
features both high storage density and large heat flux. The high heat storage capacity is due to 80–
85% (vol) content of PCM; a 10% (vol) content of special, highly porous graphite gives the
composite material a thermal conductivity in the 20–30 W/mK range [18–21].
The objective of the research work which is presented in this paper was to compare the heat flux
in a near-commercial energy storage device working with water/ice as the PCM by observing the
moving of the phase boundary. The flux was increased as compared to pure ice by inserting
stainless steel or copper pieces, or using the graphite composite material previously described.

2. Materials and methodology

The experiments were carried out in an experimental storage tank designed for this purpose
(Fig. 1). The dimensions of it are 107 mm height, 105 mm width, and 430 mm length. It was made
from metacrylate and has a capacity of 4 l. An aluminum intercooler (4 mm thick) was used as
heat exchanger placed in the middle of the storage and the inlet and outlet were connected to a
thermostatic bath.
To measure the heat transfer, six thermocouples were used. One thermocouple was at the inlet
and one at the outlet of the brine going through the heat exchanger. Four thermocouples were
placed inside the storage, one in contact with heat exchanger on each side of it and one at a
distance of 1 cm away of heat exchanger on each side. The thermocouples next to the heat ex-
 L.F. Cabeza et al. / Applied Thermal Engineering 22 (2002) 1141–1151 1143

Fig. 1. Thermal energy storage design. Thermocouples in store: one in contact with the heat exchanger and one located
1 cm away of it, on each side.

changer were used to see if there was any temperature difference between the brine inside it and
the PCM outside. The distant thermocouples allow to observe the arrival of the phase front at this
very distance.
In the experiments deionized water was used as PCM. The brine used for heating and cooling
was a mixture of water and antifreezing agent, with the temperature in the thermostatic bath set at
15 C for heating and at
15 C for freezing.
Having one thermocouple at each side of the heat exchanger allowed to use one side of the
container as a reference store. Pure ice was used as reference material.
All experiments were performed in the same procedure. The fluid in the thermostatic bath was
set to the cooling temperature and the valve at the entrance of the heat exchanger was opened.
When freezing was complete the fluid circulation was stopped to heat up the thermostatic bath to
the heating temperature. When this temperature was reached, the fluid circulation in the heat
exchanger was restarted. The experiment was stopped when the PCM temperature was at most 5
K below the heating temperature.
To enhance the heat transfer in the PCM, three different methods were used:

• Addition of stainless steel pieces: tube pieces of 16 mm of internal diameter, 18 mm of external

diameter and 25 mm of length.
• Addition of copper pieces: tube pieces with the same dimensions as above.
• Addition of graphite matrix impregnated with PCM.

The stainless steel and copper pieces were selected attending the necessity of using metal pieces
with a commercially available size [12–14]. The characteristics of the materials are presented in
Table 1.
In the first set of experiment, no enhancement was used. This was done to check if the ex-
periment did operate symmetrically, i.e. if the boundary conditions on both sides of the plate were
the same.
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Table 1
Material properties of the materials used for heat transfer
Base material q (kg/l) DH (kJ/l) cp (kJ/l K) k (W/m K)
Stainless steel 7.8 – 3.9 45
Copper 8.9 – 3.4 393
Graphite matrix 2.3 – 1.4 25–470
Water 1.0 330 4.1 0.6–2.4
Sensible heat (kJ/l)
Storage material Vol% water Latent heat Cooling Heating Effective k
(kJ/l) (DT ¼ 20 K) (DT ¼ 15 K)
Water 100 330 84 63 0.6–2.4
Water þ stainless steel 97 319 81 57 ?
Water þ copper 97 319 66 50 ?
Water–graphite 90 297 78 59 20–30
composite material

In the second set of experiments, the enhancement materials were added to only one side of the
heat exchanger. In this way the velocity of the movement of the phase front of PCM with and
without enhancement can be compared. In the third set of experiments, two different enhancement
materials were used in the same experiment to compare these materials directly. The uncertainty
and reproducibility is in the order of 1 K.

3. Results

The results obtained in these experiments are presented in Figs. 2–5. The evolution of the
temperature in freezing and melting in each experiment are plotted in two different graphs. Each
graph presents the temperatures measured in six points of the store, as described above: the
measurements at the inlet and outlet of the fluid flowing through the heat exchanger (HE in; HE
out; no symbols) the measurements just outside of the heat exchanger on both sides (R 0 cm; L 0
cm; square symbols) and the measurements at 1 cm of the heat exchanger on both sides (R 1 cm; L
1 cm; triangles). Full symbols are used in the side where an enhancement material is added, and
hollow symbols when the ice is by itself.
Table 2 lists the times that elapsed until the temperature at 1 cm distance from the plate rose to
þ2 C upon heating/melting and to
2 C upon cooling/freezing.
When the storage was filled with PCM alone, there was no difference between left and right side
of the heat exchanger (Fig. 2a and b). In these experiments, the freezing front of the PCM was
always a well defined plane in the whole container moving away from the heat exchanger. The
symmetry between both sides of the heat exchanger is very satisfactory. In the following, one side
with inserts is compared to the second side without.
 L.F. Cabeza et al. / Applied Thermal Engineering 22 (2002) 1141–1151 1145

Fig. 2. (a) Freezing stage of the experiment with water as PCM alone. (b) Melting stage of the experiment with water as
PCM alone.

In the freezing experiment the phase front reaches 1 cm after 15 min, when the temperature has
dropped to zero. At this point, a significant change in the temperature curve is observed. Melting
takes much longer, about 1 h.
On the contrary, when stainless steel was added, almost no improvement (beyond the uncer-
tainity threshold) was observed (Fig. 3a and b). The only change seen was that the temperature
1146 L.F. Cabeza et al. / Applied Thermal Engineering 22 (2002) 1141–1151

Fig. 3. (a) Freezing stage of the experiment with water on the right side and with stainless steel pieces on the left side.
(b) Melting stage of the experiment with water on the right side and with stainless steel pieces on the left side.

during melting of ice did not show the quick change seen at the 1 cm thermocouple when ice was
alone (Fig. 2a) but the change in temperature was more smooth. In the experiments, we visually
observed that the phase front of the freezing of PCM did not change its shape when stainless steel
was added.
The addition of copper to the water (in the right side of the heat exchanger) did accelerate the
heat transfer especially during melting (Fig. 4b). Fig. 4a shows that the temperature in the side
 L.F. Cabeza et al. / Applied Thermal Engineering 22 (2002) 1141–1151 1147

Fig. 4. (a) Freezing stage of the experiment with water on the left side and with copper pieces on the right side. (b)
Melting stage of the experiment with water on the left side and with copper pieces on the right side.

with copper is somewhat lower than when there is only ice, but this is only a bit above the un-
certainty threshold. The velocity of the phase front is unchanged. Fig. 4b demonstrates that the
melting of the PCM with copper at 1 cm distance starts 30 min earlier than when working with
PCM alone (Table 2).
The visual observation shows that there is no linear phase front any more, but the PCM freezes
and melts around the metal pieces. However, this is not reflected in the freezing curve.
1148 L.F. Cabeza et al. / Applied Thermal Engineering 22 (2002) 1141–1151

Fig. 5. (a) Freezing stage of the experiment with water on the right side and with graphite composite on the left side. (b)
Melting stage of the experiment with water on the right side and with graphite composite on the left side.

When the graphite composite was used, there was a big difference to the other experiments (Fig.
5a and b). After approximately 5 min the freezing phase front has reached 1 cm distance. The heat
transfer rate is so large is that the cooling liquid in the thermostatic bath (HE in) does not reach
the set temperature. If this would have been the case, the phase front would have moved even
faster.
Fig. 5b also shows that the melting process with the graphite composite is at least as fast as with
using copper.
 L.F. Cabeza et al. / Applied Thermal Engineering 22 (2002) 1141–1151 1149

Table 2
Observed times for the melting/freezing front to proceed 1 cm upon cooling and heating and calculated average power
Storage material Time (min) Average power (W/m2 )
Heating Cooling Heating Cooling
Water 55 30 1.1 2.2
Water þ stainless steel 45 30 1.5 2.1
Water þ copper 25 20 2.6 3.1
Water–graphite composite material 15 10 4.2 5.9

4. Discussion

A first feature that has to be compared is the energy density, which comprises both latent heat
and sensible heat, for each of the thermal enhancement methods studied (Table 1). The addition
of any thermal enhancement material decreases the energy density of the store, because of the
reduction of volume of PCM in it. In all cases, the sensible heat is only a small fraction of the
latent heat. For water alone the sensible heat amounts to 25% of the total energy density in
cooling and 20% in heating, very similar to the results when stainless steel or the graphite com-
posite material is used. The insertion of copper pieces decreases the influence of sensible heat to
20% in cooling and to 15% when heating.
For this data, it can be seen that in pure water the energy density is highest and with the
graphite composite it is lowest. However, due to the low conductivity the high energy density
cannot be utilized in high-flux applications.
A result that has been withdrawn from the experiments is the time needed for the melting and
freezing front of the PCM to reach the thermocouple located at 1 cm from the heat exchanger, as
shown in Table 2. It can be seen, that the addition of stainless steel does not give much im-
provement, while copper and the graphite composite material gave an improvement of 120% and
250%, respectively in heating, and of 50% and 150%, respectively in cooling.
Table 2 also presents the average power for heating and cooling for the thermal enhancement
methods studied. In these results it is obvious to see that the addition of stainless steel does not
give any advantage to the store, while the addition of copper pieces gives and increase of 98% in
the average power on heating and of 40% on cooling. The addition of the graphite composite
material shows a much higher increase in the average power of the store, that is, 280% on heating
and 170% on cooling.

5. Summary and conclusions

Experiments were performed in a small thermal energy storage device to study heat transfer
improvement in PCM with three different heat transfer enhancement methods. These were ad-
dition of stainless steel pieces, copper pieces, and a graphite matrix impregnated with PCM. The
PCM used was water. The volume content of water was always bigger or equal to 90% volume of
the store. It could be seen that the heat or cold stored was dominated by latent heat, since sensible
heat in all cases was between 15% and 25% of total heat stored.
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The main conclusions are:

• Addition of stainless steel pieces in the PCM does not increase the heat flux significantly.
• Addition of copper pieces enhances heat transfer significantly, especially in the melting period
(discharge of the store).
• The use of graphite composite allows an even larger increase in heat transfer than with copper.
The heat flux is about four times larger on heating and three times larger on cooling as com-
pared to using pure ice.
• With the addition of stainless steel pieces, the melting/freezing front does not show any change.
This corresponds to the unchanged heat flux.
• With the addition of copper pieces, the melting/freezing front is not regular but is strongly in-
fluenced but the metal pieces.
• With the addition of the graphite matrix composite, the movement of the phase front cannot
be seen, because the pores in it are too small. But it is reasonable that the phase front is also
irregular.

In conclusion, the fin effect, which is expected by inserting metal pieces into the PCM, is only
relevant if really highly conductive material is being used. This is the case for copper and the
graphite matrix. The latter features an additional benefit because it forms a consolidated block
with many uninterrupted heat flux paths, which is no the case in a loose packing of the metal
pieces. This is the reason for the graphite matrix being a very effective heat flux enhancement
material.

Acknowledgements

The present work was partially supported by a project of the University of Lleida (Spain).

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