Chem. Res. Chin. Univ., 2016, 32(4), 665―668 doi: 10.

1007/s40242-016-6030-9

Thermal Transfer During the Activation Process in

LiSi/FeS2 Thermal Batteries

KANG Bo1,2, ZHANG Wenli1, LIN Haibo1*, XING Yonghui2,

ZHAO Jinfeng2 and WANG Yan2
1. College of Chemistry, Jilin University, Changchun 130012, P. R. China;
2. Tianjin Institute of Power Source, Tianjin 300384, P. R. China

Abstract Thermal batteries(TBs) as primary power sources are widely applied in defense and military affairs, and
used in electronic packages and nuclear weapons. The activation time(AT) of TBs restricts the reactive speed of them.
Therefore, it is a remarkably important parameter and needs to be studied in detail. In our previous study, the thermal
transfer model has already been found during the activation process in TBs. In this work, the experimental TBs were
fabricated and tested for validating the model. The error between the average value of test and calculation value from
this model is less than 1%. As a result, the thermal transfer function for the activation process in the given
TBs[FeS2/LiCl-KCl(MgO)/LiSi containing Fe/KClO4 heat pellet] is suggested.
Keywords Thermal battery; Activation time; Thermal transfer model; Thermal transfer function

1 Introduction CoS2), an electrolyte pellet(e.g., LiCl-KCl, LiCl-LiF-LiBr), an

Thermal batteries(TBs) are primary power sources
equipped with an electric or mechanical match for activation
and a molten-salt electrolyte as the ionically conductive
medium. After the ignition, the produced heat could raise the
temperature of the molten salt over its melting point and
activates the battery. The battery ends its operation until the
active components of electrodes are exhausted or until the elec-
trolyte freezes or the solids precipitate at the anode-separator
interface due to high lithium cation concentration gradients that
make the electrolyte composition move off electrolyte[1]. TBs
have several advantages over other primary batteries, such as
high power density(2 kW/kg), fast activation(less than 100 ms),
long storage life(over 15 years), and no self-discharge, and so
on. TBs can work under severe external conditions, require no
maintenance and exhibit high reliability(more than 99.95%).
TBs are widely applied in defense and military affairs in a wide
variety of devices, such as missiles, torpedoes, decoys, and
training targets, and are also employed as power sources of
electronic packages and the radar systems for nuclear wea-
pons[2―4].
The time between energy input to the igniter and the dis-
charge voltage reaching the minimum of the operation voltage
is defined as the activation time(AT), which is concerned with
the electrochemical system, the molten point of the halide elec-
trolyte, the firing time of the match, the burning speed of heat
source pellet and so on. AT restricts the reactive speed of TBs.
Consequently it is a critical parameter for TBs and needs to be
studied in detail.
A unit cell in TBs consists of a cathode pellet(e.g., FeS2,
———————————
*Corresponding author. E-mail: lhb910@jlu.edu.cn
Received January 22, 2016; accepted March 22, 2016.
Supported by the National Natural Science Foundation of China(No.21573093).
© Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH
anode pellet(Li-alloy, e.g., LiSi, LiAl), and a heat source pel-
let(e.g., Fe/KClO4, Zr/BaCrO4), which is widely manufactured
by means of cold press technology at present. The configura-
tion typically consists of two forms; those are pellet with and
without a center hole.
Traditionally, we took a lot of time and cost to enhance the
understanding of thermal aspects and to design new batteries
for given requirements. A valuable thermal transfer model
could be used to resolve the above mentioned problem very
well. Eivind[5] developed and validated the transient tempera-
ture model for TBs, which was currently in the validation phase.
Sandia National Laboratories(SNL, USA)[6] developed an axi-
symmetric finite element code to predict temperature and heat
flux throughout TBs as a function of time. Eagle Picher Tech-
nologies(EPT, USA)[7] have been engaged in igniter activation
measurement and modeling to provide design insight into TBs
with a center hole.
In our previous work, the thermal model for the discharge
process established by finite-element method was found for
TBs without a center hole[8]. In the present study, the electro-
chemical system of FeS2/LiCl-KCl(MgO)/LiSi containing
Fe/KClO4 heat pellet was employed, which was primarily em-
ployed in current TBs technology. We simulated the activated
process of TBs without a center hole and compared the simula-
tion results to the experimental measurements. The calculated
data are consistent with the experimental values. It is concluded
that heat transfer is the dominate factor for AT based on the
results of analyzing the activated process. As a result, the heat
transfer discipline for activation process was concluded for a
given electrochemical system, and the thermal transfer function
666   Chem. Res. Chin. Univ. Vol.32
was found. At the given time, there is a linear-relationship be- humidity.
tween the temperature(T) at different sites of TBs and the dis-
tance of heat transfer (x) in TBs.

2 Experimental
2.1 Model Setup
ANSYS software was employed to compute heat diffusion
model for the activation process. A planar mesh was generated
to represent the configurations of unit cell and cell stack.
The mesh contained different numbers of nodes making up
Fig.1 Section view of experimental TB(A) and
rectangular elements. Each element was assigned on the basis
sketch of the unit cell(B)
of the properties of material included in it. The unit cell and
(A) a. Cell stack; sites A, B and C represent the upper location, the middle
cell stack were computationally simulated and endowed with a location and the lower location of the cell stack; b. case; c. cover; d. insula-
symmetric axis, resulting in an axisymmetric model. Initial tion; e. heat insulator material; f. electronic match, Zr fuse flake; (B) a. heat
condition was that the external was a heat insulator because the source pellet; b. cathode; c. electrolyte-binder; d. anode.
activation time was very short(0.1―1.0 s). Boundary condition
was that the initial internal temperature was 25 °C. 2.4 Measurement
The insulating resistances of unit cell and TBs were mea-
2.2 Materials
sured on an insulating resistance meter. TB test system was
FeS2(the mineral pyrite) powder contained LiSi as a lithia- used to measure AT, temperature and other parameters, which
tion agent to reduce a voltage spike that normally would occur utilized a computer, a USB/GBIP interface, N3300 electronic
at the start of discharge and to enhance the conductivity of the load and 6653A DC power source and a programmable micro-
cathode material. LiSi alloy powder purchased from General controller(Agilent VEE Pro. Version: 7.51.7801.0) to operate
Research Institute for Nonferrous Metals(Beijing, China) was the measurement and activation process(Fig.2)[13]. Data were
used as anode material. The electrolyte-binder material was collected on a portable data recorder(Model: 1-GEN2i-2, Made
prepared by fu- sing a fixed proportion of LiCl-KCl eutectic by HBM in Germany). The thermocouples(SMCJ-K) provided
mixture and MgO powder[9―12], which was non-conductive in by OMEGA Engineering. INC were used to test the tempera-
solid but ionically conductive in melt. The high surface area of ture at the select locations[sites A, B and C, Fig.1(A)].
MgO used as a separator or a binder made the molten salt ar-
rested between the cathode and anode via capillary action. LiCl,
KCl and MgO were of analytical grade and purchased from
Tianjin Chemical Agent Factory(China). Zr heat paper was
fabricated by active metal Zr powder and oxidizing agent by
means of paper fabricated method. Fe/KClO4 heat powder was
purchased from a fixed factory. The case of TBs, the cover of
TBs, the fixed plank of cell stack and the current collector were
all stainless steel. Insulation material was made of mica flake,
and heat insulator material was made of glass and asbestos Fig.2 TB test system
fiber.
3 Results and Discussion
2.3 TB Assembly The parameters of the material employed are density, heat
TB was assembled by electric match, cell stack, insula- capacity and thermal conductivity, which are shown in Table 1.
tion(e.g., mica flake) and heat insulator(e.g., asbestos fiber) The method used to measure the thermal characteristic of
materials, stainless steel cover and case, and so on. The cell asbestos fiber was the pulse method described by Kubicar
stack consisted of 15 unit cells, and two current collectors were et al.[14].
placed in each unit cell. Zr fuse flakes were placed at the top Table 1 Material parameters
and bottom of each cell stack along with the insulation mate- 10–3 Density/ Heat capacity/ Thermal conductivity/
Material
(kg·m–3) (J·kg–1·°C–1) (W·m–1·°C–1)
rials, and a set of fixed planks were used to fix the whole cell Cathode 2.76 530 1.017
stack[Fig.1(A)]. Each unit cell was prepared by pressing ca- Electrolyte-binder 1.93 750 1.220
thode, electrolyte-binder, anode and a heat pellet into a circle Anode 0.80 1830 5.442
pellet with a diameter of 32 mm[Fig.1(B)]. At sites A, B and C Current collector 7.86 480 21.64
were instrumented internal thermocouples respectively to Asbestos fiber 0.86 1600 0.048
measure the temperature of cell stack. All the materials Fixed plank 7.80 460 21.64
in TB were highly hygroscopic and the entire assembling The computational models of the unit cell and the cell
process must be done in a dry room of less than 4% room stack for the activation process are shown in Fig.3 and Fig.4,
No.4 KANG Bo et al. 667
respectively. From the external of the unit cell to the middle of Table 2 Comparison between the data from TB test
it range Fe/KClO4 heat pellet, current collector, elec- and those from model calculation
trode(cathode or anode) pellet and electrolyte-binder pellet. As Temperature/°C
Test No.
expected, Fig.3 describes the temperature varying at different Site A Site B Site C
sites of the unit cell at the time when Fe/KClO4 heat pellet is 1 456.3 448.6 456.2
ignited. However, the redox reaction is not completely at 2 456.2 448.5 456.3
3 456.4 448.5 456.3
t=0.078 s. At that time, the unit cell is not activated, for the
4 456.3 448.7 456.4
temperature of electrolyte-binder is 267.0 °C, which is below
5 456.2 448.7 456.2
its molten point(352 °C)[15]. The maximal temperature is
Average value of test(AV) 456.3 448.6 456.3
593.511 °C of the Fe/KClO4 heat pellet and the minimal tem- Calculation from model(CM) 460.8 452.8 460.6
perature is 267.0 °C of the electrolyte-binder pellet[16―20]. The (CM–AV)/AV(%) 0.99 0.94 0.95
temperature of the unit cell drops from external to internal. The AT values measured from five experimental results
Fig.4 describes the temperature varying at different sites of the were 0.536, 0.540, 0.538, 0.540 and 0.536 s respectively, and
cell stack at time t=0.540 s. At that time, the Fe/KClO4 heat the average AT value was 0.538 s. The AT value calculated
pellet reacts completely and the temperature of all the unit cell from the model was 0.540 s. The difference between AV and
is above 380.0 °C. The discharge voltage reaches the minimum CM for AT was 0.37%(also less than 1%). Consequently, this
of the cut-off voltage(25 V). Consequently, all the unit cells are thermal model is suitable for designing TB. Also, it could be
activated. In other words, the TB is activated. used to simulate the thermal transfer for the activation process
in TBs.
Within AT, the Fe/KClO4 heat pellet reacted completely.
The heat transferred from it, mainly, to the connect components,
such as the electrolyte-binder via current collector and cathode.
Simultaneously, the same diffusion occurred for the other unit
cell in the cell stack. Once the temperature reached the molten
point of the eutectic, the electrolyte started to melt and the vol-
Fig.3 Color-map at t=0.078 s for unit cell tage of TB started to increase. When the discharge voltage
Tmin=267.039 °C; Tmax=593.511 °C.
reached the minimum operation voltage, the TB was activated.
Therefore, the states of all the tested TBs are the same as Fig.4
describes[21―23].
The activation process of TBs is divided into five steps:
(1) activation of igniter; (2) heat pellet reaction; (3) heat trans-
fer; (4) electrolyte melt; (5) electrochemical reaction. The re-
dox reaction, phase changing(the electrolyte changes from solid
to liquid) and electrochemical reaction are instantaneously
completed. In our study, the ignited time of the electric match
was 0.050 s. The redox reaction time and phase changing time
were respectively about 0.050 s. Moreover, according to the AT
of experimental TB(0.538 s), we can conclude that Step 3 is a
rate-determining step for the activation process of TB. In other
words, it takes most of the activation time in the step of heat
transferring in TB.
Fig.4 Color-map at t=0.540 s for cell stack According to the equation of heat transfer in non-steady
Sites A, B and C represent the upper location, the middle location and the state:
lower location of the cell stack, respectively. Tmin=25.004 °C;
∂T k ∂ 2T
Tmax=674.816 °C. = (1)
To validate the computational model, the temperatures of ∂t PCp ∂ 2 x
A, B and C locations and AT were tested on TB test system. where T is the temperature(°C); t is the time(s); k is the coeffi-
The comparison between the data from the test of TBs and cient of heat transfer(J·cm–1·s–1·°C–1); P is the mass density of
those calculations from model calculation is shown in Table 2. material(g/cm3); Cp is the specific heat(J·g–1·°C–1); x is the dis-
The temperatures of A, B and C locations vary slightly for dif- tance of heat transfer. For a given electrochemical system(a
ferent TBs. The differences could be attributed to the TB-to-TB given material of cathode, anode, electrolyte, binder and heat
variability, or could be caused by the TB test system for diffe- source), T is the average temperature value of an area in the
rent time, or owned to the deviation of the data capture instru- unit cell, t is the activation time of TB, P and Cp are the average
ment. The standard deviation of five test values is not more mass density of the 15 unit cells, and average specific heat of
than 10%. The difference between the temperatures obtained them respectively, and the distance of heat transfer x is the dis-
from experiment and those from the model calculation was less tance between half of the heat pellet and the center of the elec-
than 1%. trolyte-binder pellet. Therefore, T is the function of x.
668   Chem. Res. Chin. Univ.
It is hard to accurately measure the temperatures of many
different locations in TBs due to the differences in, such as, the
quality of battery, the deviation of the test system, and so on.
Accordingly, from the color-map of unit cell(Fig.3), we could
conclude the equation of heat transfer in TBs. As shown in
Fig.5, abscissa 1 represents the center part of the unit cell. Si-
milarly, abscissa 10 represents the Fe/KClO4 heat pellet, on the
other hand, which also represents heat transfer in the unit cell at
t=0.078 s. The coefficient of heat transfer k is 151.90
J·cm–1·s–1·°C–1. The initial temperature of 230.8 °C represents
the heat starting to transfer from the Fe/KClO4 heat pellet to
the electrolyte-binder. In our study, T is the function of
x(distance between two sites of the unit cell). Because AT con-
sists of many time nodes, we can also infer that in the
heat transfer process for the activation process in the
FeS2/LiCl-KCl(MgO)/LiSi system containing Fe/KClO4 heat
pellet is a non-steady state, based on the equation of heat
transfer.
Fig.5 Temperatures of different sites in the unit
cell at t=0.078 s
4 Conclusions
The thermal transfer model was developed for the activa-
tion process in LiSi/FeS2 TB[FeS2/LiCl-KCl(MgO)/LiSi con-
taining Fe/KClO4 heat pellet]. The difference between average
value of test and calculation value from model is less than 1%.
Therefore, it is suitable for designing TBs, and could help to
simplify the experiment. Raw material and processing costs
may be reduced by refining material specifications to align with
critical thermal parameters. The activation process in the TBs
was analyzed and divided into five steps. Step 3 was a
rate-determining step for the activation process of TBs, that is,
heat transfer in TBs consumed the most of AT. The study may
be used to help the engineers optimize the thermal design and
management for the activation process. In addition, a thermal
transfer function was found for the activation process in Li-
Si/FeS2 TBs[FeS2/LiCl-KCl(MgO)/LiSi containing Fe/KClO4
heat pellet]. At the given time, there was a linear-relationship
between T at different sites of TB and the distance of heat
Vol.32
transfer x in TB.
References
[1] Guidotti R. A., Masset P., J. Power Sources, 2006, 161, 1443
[2] Masset P. J., Guidotti R. A., J. Power Sources, 2008, 177, 595
[3] Masset P. J., Guidotti R. A., J. Power Sources, 2008, 178, 456
[4] Guidotti R. A., Reinhardt F. W., Deformation Study of Separator
Pellets for Thermal Batteries, Sandia Report SAND90-2318, Albu-
querque, 1995, 1
[5] Eivind L., Development and Validation of Transient Temperature
Model for Thermal Batteries, Proceedings of 42th Power Sources
Conference, Las Vegas, 2006, 389
[6] Nicholas D. S., David I., Dean D., A Thermal Model for Thermal
Batteries, Proceedings of 43th Power Sources Conference, Philadel-
phia, 2008, 421
[7] Joe E., Julie B., Thermal Battery Igniter Activation Measurement and
Flow Modeling, Proceedings of 45th Power Sources Conference, Las
Vegas, 2010, 599
[8] Zhao J. F., Chu D. W., Yang X. Y., Zhang W. H., Kang B., Chinese
Journal of Power Sources, 2008, 32(9), 614
[9] Du F., Bie X. F., Bian X. F., Hu F., Chen G., Wang C. Z., Wei Y. J.,
Chem. Res. Chinese Universities, 2013, 29(2), 210
[10] Liu M., Hu L., Xu P. F., Zhao K., Zong L. B., Yu R. B., Chen J., Xing
X. R., Chem. Res. Chinese Universities, 2015, 31(3), 342
[11] Popescu A., Constantin V., Chem. Res. Chinese Universities, 2015,
31(5), 858
[12] Jiang T., Wang N., Peng S. M., Yan L. M., Chem. Res. Chinese Uni-
versities, 2015, 31(2), 281
[13] Dong C. L., The Development and Application of Automatic Test
System for Thermal Battery, Nankai University, Tianjin, 2008, 32
[14] Kubicar L., Bohač V., Vretanár V., Barta Š., Neuer G., Brandt R., Int.
J. Thermophys., 2005, 26(6), 1949
[15] Masset P. J., Guidotti R. A., J. Power Sources, 2007, 164, 397
[16] Guidotti R. A., Odinek J., Reinhardt F. W., Journal of Energetic Ma-
terials, 2006, 24(4), 271
[17] Kingery A. W., Bowen H. K., Uhlmann D. R., Introduction to Ce-
ramics, 2nd Ed., John Wiley and Sons, Inc., New York, 1976, 177
[18] Cairns E. J., Steunenberg R. K.; Eds.: Rouse C. A., Progress in High
Temperature Physics and Chemistry, Plenum Press, New York, 1973,
Vol. 5, 63
[19] Stull D. R., Prophet H., JANAF Thermochemical Tables, National
Standard Reference Data System, NSRDS-NBS 37, Gaitherburg,
1971, 1
[20] Damle A. S., Argade S. D., Modeling of Thermal Battery Activation,
Proceedings of 37th Power Sources Conference, Cherry Hill, 1996,
271
[21] Serge S., J. Power Sources, 2005, 142, 361
[22] Lee J., Battery Thermal Modeling: The Methodology and Applica-
tions, Sandia Report DE87-004865, Albuquerque, 1987, 1
[23] Giancarlo C. S. F., Fernando C. P., Ardson S. V. Jr., J. Power Sources,
2008, 179, 424