Energy Conversion & Management 41 (2000) 1543±1556

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Thermal conductivity enhancement of energy storage media

using carbon ®bers
Jun Fukai*, Makoto Kanou, Yoshikazu Kodama, Osamu Miyatake
Department of Chemical Systems and Engineering, Kyushu University, 6-10-1, Hakozaki, Higashi-ku, Fukuoka 812-
8581, Japan
Received 17 March 1999; accepted 20 September 1999

Abstract

Carbon ®bers with a high thermal conductivity are used to enhance the thermal conductivities of
energy storage media. Two types of enhancement techniques were studied. One is the technique using
randomly oriented ®bers, while the other is that of using a ®ber brush. The carbon ®bers essentially
enhance the e€ective thermal conductivity of ®ber/paran composites. For the random type, the ®ber
length has little e€ect on the e€ective thermal conductivity. The ®ber brush increases the e€ective
thermal conductivities to the maximum values predicted which is theoretically. The ®ber brush is also
useful for enhancing the e€ective thermal conductivities of packed beds of particles. 7 2000 Elsevier
Science Ltd. All rights reserved.

Keywords: Thermal conductivity enhancement; Carbon ®ber; Paran; Packed beds

1. Introduction

Phase change materials (PCMs) are prime candidates for use as thermal energy storage
media because of their superior energy storage capacities. They should possess a high
density, high speci®c heat, high thermal conductivity, congruent melting, small volume
change, little supercooling and so on [1]. However, it is practically dicult to ®nd or
develop PCMs that satisfy all desirable qualities. In many cases, unsuitable properties are

* Corresponding author. Tel.: +81-92-642-3515; fax: +81-92-642-3519.

E-mail address: jfukai@chem-eng.kyushu-u.ac.jp (J. Fukai).

0196-8904/00/$ - see front matter 7 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 9 6 - 8 9 0 4 ( 9 9 ) 0 0 1 6 6 - 1
1544 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556

Nomenclature

b radius of cylinder (m)

CP speci®c heat (J/kg)
dP mean diameter of solid particles (m)
f initial temperature (K)
g wall temperature (K)
k thermal conductivity (W/(m K))
Lf ®ber length (m)
r radial distance (m)
T temperature (K)
t time (s)
X volume fraction
a thermal di€usivity (m2/s)
e void fraction
f parameter representing contact heat transfer rate between particles
r density (kg/m3)
Z parameter representing contact heat transfer rate between ®bers

Subscripts
c composite
cal calculation
exp experiment
g gas phase
f ®ber
m energy storage media
s solid phase

improved using some techniques. For instance, nucleating agents are added to the PCM
having a poor nucleating property. From a heat transfer point of view, the PCMs are
required to have a high enough thermal conductivity to give the designed heat exchange
rates. Thermal conductivity promoters are frequently used for the PCMs with low thermal
conductivities.
The PCM that has been most often chosen in the studies of thermal conductivity
enhancement is paran. This is probably because, though paran is one of the most useful
materials for thermal energy storage at less than 1008C, its thermal conductivity is
unacceptably low. For paran, many researchers [2±6] examined thermal conductivity
enhancements using ®ns, honeycombs and porous media. The enhancement techniques are also
important in space based power system applications because of the large amount of heat
rejection from a power cycle in a short period of time [7,8]. The same problem is found in the
development of chemical heat pump systems, which utilize endothermic/exothermic reactions
between a solid and a gas. These systems use packed beds of solid particles to increase the
 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556 1545

surface area. Instead, the e€ective thermal conductivities of the packed beds are extremely low.
This problem is a major obstacle in the practical applications of these systems. In this ®eld, the
enhancement techniques using metal ®ns and wires were also examined [9,10].
The thermal conductivity promoter should not only have high thermal conductivity but also
compatibility with the energy storage media. It is also desirable that its density is too low to
give much extra weight to the energy storage equipment. The aforementioned studies employed
promoters made of aluminum, copper, nickel etc. Although these metals have high thermal
conductivities, they are often incompatible with some of the PCMs. For instance, aluminum is
compatible with paran while copper and nickel are incompatible. Aluminum and copper are
incompatible with some salt hydrates. To this end, the substance of the promoter is frequently
limited by its compatibility with the heat storage media rather than the thermal conductivity.
Carbon ®bers are strongly resistant to corrosion and chemical attack. Thus, they are
supposed to be compatible with most PCMs. There are many commercial carbon ®bers whose
thermal conductivities are the same as those of aluminum and copper. The thermal
conductivities of some products are more than 1000 W/(m K). In addition, the densities of
carbon ®bers are theoretically less than 2260 kg/m3, which is lower than those of metals that
are usually used as the promoters. These physical and chemical properties of carbon ®bers
reveal the possibility that they might become excellent promoters.
In this paper, two thermal conductivity enhancement techniques using carbon ®bers are
investigated. In the ®rst technique, the ®bers are randomly distributed in the PCMs. The
second technique employs a ®ber brush such that the directions of the ®bers coincide with
those of the heat ¯ow. The transient temperature response and the e€ective thermal
conductivity of the composites are measured. The second technique is also applied to a packed
bed to enhance its e€ective thermal conductivity.

2. Experimental

Carbon ®bers with a diameter of 10 mm, a density of 2170 kg/m3 and a thermal conductivity
of 220 W/(m K) at room temperature were provided. The phase change temperature and the
thermal conductivity of the paran wax used in this study are 41±438C and 0.26 W/(m K),
respectively, at the solid state. The ®bers and the paran wax were packed into a steel
cylindrical capsule having a 50 mm diameter and 130 mm height. Two types of enhancement
techniques were studied. In the ®rst example, the carbon ®bers, cut to a certain length were
randomly packed in the capsule (Fig. 1(a)). The ®ber lengths were 5 and 200 mm, which are
much shorter and longer than the diameter of the capsule. In another example, a radial brush
made of carbon ®bers was inserted into the capsule (Fig. 1(b)). The diameter of the brush is
the same as that of the capsule. In both samples, molten paran was poured into the capsule
after the promoter was inserted in the capsule. Air was left inside the capsule because of the
volume change in the phase change process. The volume fraction of the composite in the
capsule was about 80%. Thick caps made of an acrylic resin covered the top and bottom of
the capsule to suppress any heat ¯ow in the longitudinal direction as much as possible.
For measurement of the transient temperature response, a thermocouple was placed at the
1546 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556

center of the sample (Fig. 1(b)). The sample at a uniform temperature was heated to melt the
paran wax and cooled to solidify it in a temperature controlled bath.
The e€ective thermal conductivity of the composite was determined through measurement of
the e€ective thermal di€usivity. Four thermocouples were placed at regular intervals in the
radial direction of the sample (Fig. 1(b)). The sample at the uniform temperature of ÿ258C
was heated to 08C in a water bath. The one-dimensional conduction heat transfer equation for
a homogeneous cylindrical body, initial conditions and boundary conditions are written as
 
@T 1@ @T
ˆa r …1†
@t r @r @r

ICs T ˆ f…r† at t ˆ 0 …2†

@T
BCs ˆ0 at r ˆ 0 …3†
@r

T ˆ g…t† at r ˆ b …4†

where f…r† is the initial temperature and g…t† the wall temperature. The thermal di€usivity was
determined by using a nonlinear least square technique:

Fig. 1. Con®gurations of the carbon ®bers within a cylindrical capsule. In Figure (b), the open circle indicates the
location of the thermocouple for the measurement of the transient temperature response. The crosses indicate those
for the measurement of the thermal di€usivity. These thermocouples are also located at the corresponding locations
in the random type.
 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556 1547
X X 2
Tcal …a; ri , tj † ÿ Texp, i, j 4min …5†
j i

where ri is the position of the ith thermocouple, tj the jth sampling instant, Tcal the
temperature numerically calculated by using Eqs. (1)±(4) and Texp the experimental
temperature. The ratio of the thermal di€usivity of the composite to that of the PCM is
approximately equal to the thermal conductivity ratio when the ®ber volume fraction is low.
The composite, including the ®ber brush, is heterogeneous because the ®ber volume fraction
depends on the radial distance (Fig. 1(b)). To this end, the model that accounts for this issue
was developed to estimate the e€ective thermal di€usivity. However, the di€erences between
the results for the two models were negligible (Appendix A).

3. Results and discussion

3.1. Paran

The thermal conductivity of the composite usually increases with the volume fraction of the
thermal conductivity promoter. Instead, the energy storage density accordingly decreases. The
thermal conductivity enhancement should be attempted under an acceptable reduction in the
energy storage density. In this study, the ®ber volume fraction was restricted to approximately
< 2%.
The photographs shown in Fig. 2 are the typical con®gurations of the carbon ®bers packed
into the capsule, which is transparent with the same dimensions as the aforementioned capsule.

Fig. 2. Carbon ®bers packed into a transparent cylindrical capsule. The volume fraction of the carbon ®bers is
0.005.
1548 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556

This ®gure demonstrates that the ®bers are densely and entirely distributed in the capsule even
at Xf ˆ 0:005 (0.5%). There are distinct voids for the brush type because the brush is
handmade. The transparent capsule containing the ®ber/paran composite was repeatedly
frozen and melted in a water bath to investigate the change in the packing states of the ®bers.
As the result, the ®ber state was not changed. That is, the ®bers did not sink toward the
bottom of the capsule. This is an important property for a thermal conductivity promoter.
Fig. 3 shows the transient temperature response for the random type. In both processes, the
slopes of the curves decrease at 41±428C due to the phase change. The thermal response within
the composite must be more sensitive as the ®ber volume fraction increases. Nevertheless, the
melting times for Xf < 0:01 are longer than that for the paran wax …Xf ˆ 0†: This is because
the ®bers suppress natural convection in the liquid phase. However, two percent volume ®bers
provide almost full recovery of the melting time. This fact shows that the loss in the convection
heat transfer rate is fully compensated by the increase in the conduction heat transfer.
Contrary to the melting process, the ®bers essentially decrease the freezing time as the volume
fraction increases. At the early stage of the freezing process, the ®bers must suppress the
natural convection in the liquid phase. This e€ect is slightly observed in the curves for Xf ˆ
0:0054 and 0.01 at T > 428C: However, the convection heat transfer does not play an
important role in the entire freezing process.
Fig. 4 shows the e€ect of the ®ber length on the temperature response. Again, these lengths
are much smaller or larger than the radius of the capsule. Although the thermal responses for
the longer ®ber are slightly sensitive, the ®ber length does not have a signi®cant e€ect on the
response. This fact reveals that for the random type, an arbitrary length of carbon ®bers is

Fig. 3. The time variation of the transient temperature responses at the center of the ®ber/paran composites (the
random type).
 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556 1549

Fig. 4. The e€ect of the ®ber length on the transient temperature response at the center of the ®ber/paran
composites (the random type).

Fig. 5. Transient temperature response at the center of the ®ber/paran composite. Comparison between the
random type and the brush type.
1550 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556

allowed in practical applications as long as the ®bers are densely and entirely distributed in the
energy storage media.
Fig. 5 compares the results for the di€erent con®gurations. The temperature responses for
the brush type are more sensitive than those for the random type. This is because the ®bers for
the former are oriented in the heat ¯ow direction.
Fig. 6 shows the e€ective thermal conductivity of the composites …kc † normalized with the
thermal conductivity of the PCM …km †: In these measurements, four test pieces were provided
for the individual volume of the ®bers. The measurements were performed ®ve times for each
test piece. The errors for these results were within 3%. The average and range of the results for
the four test pieces are indicated in the ®gure. Apparently, the e€ective thermal conductivity of
the composite increases as the ®ber volume fraction increases. It is worthwhile noting that for
paran, two percent ®bers increase the e€ective thermal conductivity by a factor of six.
Although the ®ber length slightly a€ects the e€ective thermal conductivity, this e€ect is not
signi®cant as observed in Fig. 4. The results for the mixture whose main component is
Na2SO4
10H2O [11] are also indicated in the ®gure. The thermal conductivity of this mixture is
0.8 W/(m K). The thermal conductivity ratio for this mixture is lower because of its high
thermal conductivity. However, an enhancement is still observed for this mixture.
Kunii and Smith [12] developed the following heat transfer model for ®ber matrices:
kc ÿ
kf
X ÿ1=3
m ˆ X ÿ1=3
m ÿ X 1=3
m ‡1 …6†
km Zkm
where kf is the thermal conductivity of the ®ber, Xm the volume fraction of the PCM …ˆ
1 ÿ Xf † and Z the empirical parameter. Based on Eq. (6), the experimental results are

Fig. 6. Thermal conductivity enhancement of the phase change materials using the random type.
 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556 1551

Fig. 7. Correlation of the e€ective thermal conductivity.

Fig. 8. Thermal conductivity enhancement of the phase change material using the brush type.
1552 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556

rearranged in Fig. 7. This ®gure demonstrates that a straight line ®ts the experimental results
for each ®ber length. Thus, the values of Z ˆ 1:75 for Lf ˆ 200 mm and Z ˆ 2:19 for Lf ˆ 5
mm were evaluated using a least square technique. It should be noted that the value of Z is
independent of the thermal conductivity of the PCM.
Fig. 8 shows the results for the ®ber brush. The e€ective thermal conductivity for this type is
three times as large as that for the random type. The parallel model, theoretically, gives a
maximum for the e€ective thermal conductivity of the composite media:
kc ˆ …1 ÿ Xf †km ‡ Xf kf …7†
A comparison between the experiment and the theory, in Fig. 8, shows that the brush type has
the greatest enhancement e€ect.
It is dicult to discuss generally the amount of carbon ®ber to be added in the energy
storage unit using paran. If the thermal conductivity is required to increase to that of ice (2.2
W/(m K)), it should be increased by a factor of 10. If the carbon ®ber used in this study is
employed, the ®bers of 3% in volume are needed for the random type while those of 1% are
needed for the brush type. The reductions in the energy storage density corresponding to these
®ber volumes are probably acceptable.

3.2. Packed beds

The ®ber brush was used for a packed bed of glass particles, which are substitutions for the
particles used for chemical heat pump systems. The thermal conductivity of the glass used is

Fig. 9. E€ect of the ®bers on the void fraction of the packed beds.
 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556 1553

0.8 W/(m K). The glass particles were packed, with intermittent vibration, into the cylindrical
capsule into which the brush was inserted.
Fig. 9 shows the e€ect of the ®ber volume fraction on the void fraction of the packed beds.
dp is the mean diameter of the particles. The particle diameters for dp ˆ 0:5 and 1.2 mm range
within 20:15 mm, while the diameter range for dp ˆ 0:1 mm is not known. The ®bers obstruct
the packing of the particles, thus increasing the void fraction. The void fraction does not
proportionally increase at Xf > 0:005, while it rapidly increases at Xf < 0:005: This fact reveals
that the ®bers do not signi®cantly reduce the stored chemical energy density even if the ®ber
volume fraction increases to some degree. The reason that the void fraction for dp ˆ 0:5 mm is
higher than those for the others might be due to the di€erence in the particle size distribution.
Fig. 10 shows the normalized e€ective thermal conductivities. The e€ective thermal
conductivity of the packed bed without the ®bers is 0.20±0.24 W/(m K) (= km). These values
are of the same order as the e€ective thermal conductivities of the packed beds employed in
the studies on the chemical heat pump system (0.1±0.3 W/(m K) [9,13]). The e€ective thermal
conductivity increases as the ®ber volume fraction increases. There is no e€ect of the particle
diameter on the thermal conductivity ratio. Ogura et al. [9] attempted to enhance the e€ective
thermal conductivity of packed calcium hydroxide particles by using coiled copper wires with
an 80 mm diameter. They reported that the wires hardly enhanced the e€ective thermal
conductivity because the wires obstructed the dense packing of the particles. Contrary to their
results, the carbon ®bers essentially enhance the e€ective thermal conductivity of the packed
beds.
The parallel model given by Eq. (7) was also applied for this system. In the model, one

Fig. 10. Thermal conductivity enhancement of the packed beds using the brush type.
1554 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556

phase is the ®ber phase and the other is the packed bed phase. km in Eq. (7) is de®ned as the
e€ective thermal conductivity of the packed bed. Based on the model developed by Kunii and
Smith [12], the e€ective thermal conductivity of the packed bed phase is modeled by
e 1 ÿ e=…1 ÿ Xf †
km ˆ kg ‡ ÿ
kg …8†
1 ÿ Xf f ‡ 2kg =…3ks †

where kg and ks are the thermal conductivities of gas and solid phases, respectively, and f is
the parameter representing the heat transfer rate between particles. In this equation, radiation
heat transfer is neglected because of the low temperature in the present experiments. To this
end, Eqs. (7) and (8) give the theoretical value of this system. Eq. (8), including the f value, is
independent of the particle diameter. At this point, this equation explains no dependence of the
experimental results on the particle diameter. However, the theory is higher than the
experimental results as shown in Fig. 10. The reasons for this di€erence are probably as
follows: Eq. (7) is available when the temperatures in the two phases located nearby are
assumed to be identical. This assumption is usually available for the composite media. In the
packed beds, on the other hand, the contact between a ®ber and a particle occurs at a line or a
point. Therefore, the thermal contact resistance between the two phases is probably too high to
maintain them at the same temperature. The second reason is due to the error estimation of
the parameter f in Eq. (8). This parameter is modeled considering the number of contact
points on the surface of a particle [12]. Though the ®bers must obstruct the contact between
the particles in this system, this e€ect is not considered. Accordingly, the model for this
parameter has error. The former is probably a major reason for the error in the theory while
the latter is minor. This is because the heat transfer between the particles and the ®bers, not
that between the particles, mainly contributes to the thermal conductivity enhancement.

4. Conclusion

Carbon ®bers having a high thermal conductivity are employed to enhance the thermal
conductivity of thermal energy storage media. The random and brush types were examined.
Both types are useful for thermal conductivity enhancement. For the random type, the ®ber
length has a slight e€ect on the enhancement. The brush type signi®cantly enhances the
e€ective thermal conductivity in the direction of the ®ber orientation. Although the brush type
is superior to the random one from the standpoint of the enhancement technique, the choice
between the two types also depends on the structure of the energy storage equipment, the cost
and so on. The experimental results reveal that carbon ®bers are also useful for enhancing the
e€ective thermal conductivity of the packed beds.

Acknowledgements

We thank the Nippon Graphite Fiber Corporation for providing carbon ®bers.
 J. Fukai et al. / Energy Conversion & Management 41 (2000) 1543±1556 1555

Appendix A

The ®bers are assumed to locate in regular intervals in the azimuthal and longitudinal
directions (Fig. 1(b)). In this case, the local volume fraction of the ®bers is modeled by

Xf0 =…2R † at 0 < R < Xf0 =2
Xf …r† ˆ …A1†
1 at Xf0 =2 < R < 1

where R …ˆ r=b† is the nondimensional radial distance and Xf0 is the mean volume fraction of
the ®bers. The local e€ective thermal conductivity of the composite in the radial direction is
written as
kc …r† ˆ kc0 F…r† …A2†
where kc0 is the e€ective thermal conductivity in the radial direction, corresponding to Xf0 : The
thermal conductivities kc …r† and kc0 are given by

kc …r† ˆ 1 ÿ Xf …r† km ‡ Xf …r†kf …A3†

and
kc0 ˆ …1 ÿ Xf0 †km ‡ Xf0 kf …A4†
The substitutions of Eqs. (A3) and (A4) into Eq. (A2) yield

1 ÿ Xf …r† km ‡ Xf …r†kf
F…r† ˆ …A5†
…1 ÿ Xf0 †km ‡ Xf0 kf
On the other hand, the dependence of the heat capacities, CPr , on the radial distance can be
neglected because the di€erence between the heat capacities for the ®bers and paran is about
10%. To this end, the heat conduction equation for the brush system is written as
 
@T 1@ @T
ˆ a0 F…r†r …A6†
@t r @r @r
where a0 is the e€ective thermal di€usivity corresponding to Xf0 : Instead of Eq. (1), Eq. (A6)
was used to estimate a0 for several experiments. The di€erences between the a values from Eq.
(1) and a0 values from Eq. (A6) were less than 3%. Accordingly, Eq. (1) was used for the
brush type as well as the random type.

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