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Latent heat storage using a PCM-graphite composite material

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 Latent heat storage using a PCM-graphite composite material
by * H. Mehling, S. Hiebler, F. Ziegler
ZAE Bayern, Walther-Meissner-Str. 6, 85748 Garching, Germany, fax +49-89-329442-12,
email: hmehling@ph.tum.de

KEY-WORDS
Latent heat, phase change, heat flux, graphite

Abstract
Latent heat storage in phase change materials (PCM) is preferable to sensible heat storage in applications with
small temperature swing, because of a comparably high storage density. However, common PCMs with a solid-
liquid phase transition suffer from a small thermal conductivity especially in the liquid state, usually below 0.5
W/(mK). Therefore, even though heat can be stored efficiently, it is not accessible in short times and with large
heat flux densities. In the last few years the ZAE Bayern has developed a PCM-graphite composite material that
combines the high heat storage capacity of the PCM and the large thermal conductivity of graphite.
In this paper we present experimental data on the thermal conductivity and wall heat transfer coefficient of the
composite material. Based on these data, the heat flux in a simple 1-dimensional cooling cycle is calculated and
compared to measured data. It is shown that using the composite material significantly shorter loading and
unloading times can be achieved than with the pure PCM.

Introduction
To discuss basic features of the heat transfer in a latent heat store a simple one-dimensional model can be used.
The phase change material (PCM) is initially at the phase change temperature Tph as shown in Fig. 1 on the left.
After the temperature at the surface is lowered to Tunload heat is extracted from the PCM and the phase front moves
away from the surface. If the latent heat at the phase transition ∆H is much larger than the sensible heat cp⋅(Tph-
Tunload) the temperature gradient is constant.

temperature T temperature T
liquid solid liquid

Tph Tph

Tunload

0 distance from surface 0 distance from surface

Figure 1: Initial temperature profile in the PCM (left) and upon unloading / cooling (right).
Latent heat storage using a PCM-graphite composite material AUTHOR: Mehling
TERRASTOCK 2000, Stuttgart, Germany PNO: A-070
August 28 until September 1, 2000

This problem with neglecting the specific heat was first solved by (STEFAN 1891). The distance of the phase front
from the surface as a function of time s(t) is

T ph − Tunload
(eq.1) s (t ) = 2 ⋅ λ ⋅ t ⋅
∆H
and the heat flux at the surface is

λ ⋅ (T ph − Tunload ) ∆H ⋅ λ ⋅ (T ph − Tunload )
(eq.2 ) q (t ) = =
s (t ) 2⋅t
As long as the phase front does not encounter any other unloaded region, the heat flux density as a function of time
q(t) is, therefore, proportional to the square root of λ. However, for a given heat exchanger geometry the distance
between heat exchanger surfaces limits s. At the time when the phase boundaries from opposite heat exchanger
surfaces meet, the final heat flux density q(smax) is proportional to λ. Vice versa, for fixed final heat flux the
maximum allowable distance between heat exchanger surfaces is proportional to λ. A common approach to
increase heat transfer in the storage material is to add materials with a high thermal conductivity to the PCM. For
example VELRADJ et al. (VELRADJ et al. 1999) investigated the heat transfer in a latent heat store with a
paraffin as storage material. Using metallic rings to enhance heat transfer, the effective thermal conductivity was
increased from 0.2 W/(mK) to about 2 W/(mK). This increase in the effective thermal conductivity by an order of
magnitude results in an increase in the heat flux as a function of time by about a factor of 3. In this paper we will
report on experiments which were conducted with another heat transfer enhancement technique.

Description of the PCM-graphite composite material

During the last years the ZAE Bayern developed a PCM-graphite composite material that combines the high
thermal conductivity of the graphite with the heat storage capability of the PCM. Fig. 2 shows the appearance and
structure of the composite material. The composite material consists of roughly 80 Vol.-% PCM, 10 Vol.-% of a
special, highly porous graphite produced by SGL TECHNIK (available in large quantities), and 10 Vol.-%
remaining air. The thermal conductivity is increased from 0.2-0.5 W/(mK) for the pure PCM to values in the 20-30
W/(mK) range with only little loss in heat storage capacity.

highly porous PCM

Air
graphite particles 80 Vol%
10 Vol%
10 Vol%

Figure 2: Picture of a PCM-graphite composite block and schematic, microscopic structure.

Measurement setup for thermal conductivity and wall heat transfer coefficient
For the construction of a heat store using the new material its thermal conductivity λ and the wall heat transfer
coefficient α have to be known. Both values can be determined by a single measurement using the setup described
in fig. 3.

x
weight
TH
heater
δT
δx

sample
∆x ∆T
thermocouples

δT

cooler
TC
temperature T

Figure 3: Schematic measurement setup and temperature profile for determination of thermal conductivity λ and
wall heat transfer coefficient α from sample to heater / cooler surface.

The sample is fixed between an electric heater at the top and a water cooler at the bottom. If heat losses are
negligible the heat flux Qtherm through the sample equals the electric heat Qel supplied, which can easily be
determined. After thermal equilibrium is reached, the heat flux is given by
∆T Qtherm ⋅ ∆x
(eq.3) Qel = Qtherm = A ⋅ λ ⋅ ⇒λ =
∆x A ⋅ ∆T
where A is the sample cross section and ∆T the temperature drop at a distance ∆x in the sample. The wall heat
transfer coefficient from the sample to the heater (or cooler respectively) is defined as
A ⋅ δT
(eq.4 ) ⇒α =
Qtherm
where δT is the temperature difference between the heater surface and the sample surface. As the heater is made
from a material with high thermal conductivity it is practically isothermal and its surface temperature can be
determined by a single thermocouple. The surface temperature of the sample is calculated from the temperature
gradient ∆T/∆x within the sample and the distance δx between the sample surface and the closest thermocouple by
extrapolation. In order to ensure good contact between walls and sample a decent pressure has to be applied. This
pressure, which is an important parameter for the wall heat transfer coefficient, is controlled by a weight on top of
the heater. Experiments have shown that for typical samples and temperature gradients the heat loss was up to
15%. By a first order estimation of heat losses this error was further reduced.
Latent heat storage using a PCM-graphite composite material AUTHOR: Mehling
TERRASTOCK 2000, Stuttgart, Germany PNO: A-070
August 28 until September 1, 2000

The system was tested on steel 1.4301 with λ=15 W/(mK) (WEGST 1998) using samples with different geometry.
Tab. 1 shows the results. For small sample height, the thermal resistance between heater and cooler via the sample
is negligible compared to the one via the insulation. With increasing sample height the thermal resistance of the
sample increases and significant heat is transferred through the insulation leading to an increasing measurement
error. For samples with 50 mm ⋅ 50 mm ⋅ 10 mm and using the first order correction of heat losses the error is
smaller than 1%. This geometry was used for the measurements on the composite. As the thermal conductivity of
the composite is larger than that of steel, heat losses will be smaller and the error will be of the order of 1%.

Table 1: Test results for the thermal conductivity measurement.

sample geometry determined λ [W/mK] deviation from literature value [%]
90 mm⋅∅20 mm 17.24 14.9
50 mm⋅50 mm⋅10 mm 15.03 0.2
50 mm⋅∅50 mm 14.95 0.3

Samples
Two different PCMs were investigated: an eutectic salt PCM 72 (MgNO3/LiNO3⋅6H2O) manufactured by Merck
KGaA Darmstadt and a paraffin RT50 manufactured by Schümann Sasol Hamburg. The thermodynamic data of
these materials (BAUMANN and HECKENKAMP 1997, SCHÜMANN SASOL 1999) and of graphite are shown
in Tab. 2. Compared to graphite the thermal conductivity of the PCMs is about two orders of magnitude lower.
With these materials the PCM-graphite composites samples in Tab. 3 with different graphite density ρGr were
produced.

Table 2: Thermodynamic data of the base materials used. Thermal conductivity data of graphite (CALLISTER
1997) strongly depend on graphite composition.
ρ [kg/L] cp [kJ/LK] λ [W/(mK)] ∆H [kJ/L] Tph [°C]
Graphite 2.3 1.4 25-470 - -
Paraffin RT 50 0.8 2.0 0.2 153 54
Eutectic salt PCM 72 1.6 2.2 0.5 290 72

Table 3: Prepared properties of the PCM-graphite composite samples. ∆H and cp are calculated.
ρGr [kg/L] Vol. % Gr Vol. % PCM ∆H [kJ/L] cp [kJ/LK]
Paraffin RT 50 0.200 9 85 130 1.83
Paraffin RT 50 0.175 8 85 130 1.81
Eutectic salt PCM 72 0.175 8 75 217 1.76

Results and discussion

Thermal conductivity
The results of the thermal conductivity measurements are shown in Fig. 4. Due to the manufacturing process the
samples have an uneven surface, leading to an error in the cross section A (eq.3) of about 10%. The total error for
the thermal conductivity therefore is up to 15%. It is generally seen that the composite material has a significantly
higher thermal conductivity than the pure PCM (Tab. 2), about 50 times for the eutectic and more than 100 times
for the paraffin. No significant difference is observed for the composite material, no matter if the PCM is in the
solid or in the liquid state. One of the samples was investigated after thermal cycling and showed an increase in the
thermal conductivity, but the effect is still within the experimental error. The eutectic was not measured in the
liquid state, because the measurement set up cannot be heated to the required temperature.

30
thermal conductivity [W/(mK)]

25

20 pure
solid
15
liquid
10 225 cycles solid

0
RT50, 200g/l RT50, 175g/l PCM 72, 175g/l

Figure 4: Results of the thermal conductivity measurements on the different PCM-graphite composite samples
compared to values for the pure PCM (Tab. 3).

Wall heat transfer coefficient

6
heat transfer coefficient [kW/(m K)]
2

4
solid
3 liquid
225 cycles solid
2

0
RT50, 200g/l RT50, 175g/l PCM 72, 175g/l

Figure 5: Results of the wall heat transfer coefficient on the different PCM-graphite composite samples.
Latent heat storage using a PCM-graphite composite material AUTHOR: Mehling
TERRASTOCK 2000, Stuttgart, Germany PNO: A-070
August 28 until September 1, 2000

The results for the wall heat transfer coefficient are shown in Fig. 5. They are generally subject to larger errors as
δT is small (large relative error) and the results are very sensitive to the sample surface preparation. The applied
pressure was 5 kPa. Generally, results fall into the 1-6 kW/(m2K) range. Again, the eutectic was not measured in
the liquid state.

The Temperature-step experiment

To compare a pure PCM with the new material in a situation similar to a real heat store, an experiment was
performed where the temperature at the surface/heat exchanger was changed suddenly from 55°C to about 23°C
according to fig. 1. The samples were pure paraffin RT 50 (Tab. 2) and the RT 50-graphite composite material
with ρGr = 175g/L (Tab. 3). The temperature-time curves were measured at 3 different distances from the surface.
Tab. 4 lists the times when the phase front reaches a certain distance s from the heat exchanger determined by
experiment and also by simulation. For the pure paraffin the phase front needs one hour to move 2 cm. This is in
reasonable agreement with the simulation (according eq. 1) within the experimental errors. For the composite, the
phase front moves much faster. A length of 2 cm is reached after less than 2 minutes. However in this case
experiment and simulation (according eq. 1) show no agreement within the experimental errors. A simulation with
a more advanced model taking the wall heat transfer coefficient α into account shows better agreement.

Table 4: Comparison of experimental and simulated values for the temperature-step experiment.
Material method s = 1 cm s = 2 cm s = 3 cm
pure RT 50 experiment 15 min 60 min
simulation eq.1 20 min 80 min 180 min
RT 50, 175 g/L Graphite experiment 75 s 115 s 150 s
simulation eq.1 8s 33 s 75 s
simulation α = 1 kW/(m2K) 50 s 115 s 200 s

Conclusions
The experiments we discussed in this paper show that the new composite material shows a significant
improvement in the heat transfer within latent heat storage materials. The thermal conductivity in the composite
material is up to 100 times higher than in the pure PCM, leading to the phase front moving between 10 and 30
times faster. The conventional analytic model becomes inaccurate, as for the new material thermal resistances that
could be neglected for the low conducting pure PCM now become significant. A more advanced model has to be
developed to accurately describe heat transfer in heat stores using the new composite material.

Acknowledgements
This work was supported by the BAYERISCHE FORSCHUNGSSTIFTUNG, within the project ISOTEG. We thank our project
partners Merck KGaA (www.merck.de), SGL TECHNIK GmbH (www.sglcarbon.com) and SHK (www.shk-web.de).
References
BAUMANN H. and HECKENKAMP J., 1997, Sonderdruck aus Nachrichten Chemie, Technik und Laboratorium, Wiley VCH
no. 11, pp 1075.
 CALLISTER W. D. 1997, “Materials science and engineering: an Introduction”, 4th ed., Wiley & Sons.
SCHÜMANN SASOL 1999, website: http://www.schuemann-sasol.com/index_produkt.html.
STEFAN 1891, Ann. Phys. U. Chem., Vol. 42, pp. 269 – 286.
VELRADJ R., SEENIRAJ R.V. HAFNER B., FABER C. and SCHWARZER K., 1999, “Heat transfer enhancement in a latent
heat storage system”, Solar energy, Vol. 65, No. 3, pp. 171 – 180.
WEGST C.W. 1998, Stahlschlüssel, Verlag Stahlschlüssel Wegst GmbH, Marbach.

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