Thermally Activated Batteries: Calcium
PC Butler, US Department of Defense, Washington, DC, USA
RA Guidotti, Sierra Nevada Consulting, Minden, NV, USA
PJ Masset, Karl-Winnacker-Institut der Dechema e.V, Frankfurt, Germany
& 2009 Elsevier B.V. All rights reserved.
Introduction
Thermal batteries were conceived and developed by
German scientists during World War II and used in V-2
rockets. These batteries made use of the exhaust heat from
the rocket motor to sustain the high temperature neces-
sary for battery output during the rocket’s mission. Dr G.
O. Erb is credited with originally developing this tech-
nology in Germany. The technology was brought to the
United States in 1946, adapted by the National Bureau of
Standards, Ordnance Development Division, for US
defense applications, and placed in production by Catalyst
Research Corporation. Improvements were made during
the late 1940s and early 1950s, including the use of the
lithium chloride–potassium chloride (LiCl–KCl) eutectic
as the electrolyte. Other organizations became active in
the development and manufacture of these devices at this
time, including Eagle Picher, the largest US manufacturer
of thermal batteries today, and Sandia National Labora-
tories, which continues to develop and produce thermal
batteries for national security applications.
Background
Thermal batteries are thermally activated, primary reserve
power sources, which typically operate between 350 and
550 1C. They use an ionically conducting molten salt in
the layer between the anode and cathode (i.e., electrolyte
separator). Consequently, these batteries lose heat during
operation, and this must be considered during the design
of the battery packaging and interface with the next as-
sembly. The anodes and cathodes (usually mixed with the
electrolyte) are typically solid electroactive species in both
the stored and activated states, and most thermal batteries
also contain a chemical heat source. The electrolytes that
are typically used melt between 319 and 436 1C, with the
LiCl–KCl (mp 352 1C) eutectic being the most common.
Once a battery is activated, the electrolyte becomes liquid
and is held in place by a matrix, which usually includes a
binder to retain the molten phase by capillarity forces.
Necessary thermal battery auxiliary components include
an activation device (igniter or squib), insulation (thermal
and electrical), conductors, leads, connectors, and a con-
tainer. Early cell configurations used cups to contain the
electrodes, but this approach required complex inter-
connection hardware and greatly increased manufacturing
difficulty. Later designs typically utilized pellets or wafers
pressed from powdered mixtures. The pellets are stacked
in a series arrangement to form the battery and the ne-
cessary electrical terminals are welded together. The
battery components are packaged into stainless-steel
containers and hermetically sealed.
Thermal batteries are categorized as reserve batteries,
in that they can be stored for long periods of time (dec-
ades) without degradation, an unusual attribute for elec-
trochemical systems. Once activated and heated above the
melting point of the electrolyte, the batteries can provide
power at extremely high rates because of the high intrinsic
conductivity of the molten salts. Typical activated life-
times (operating time) for calcium-anode thermal bat-
teries are about a minute, although experimental versions
with activated lifetimes of over 60 min were built and
tested. The power densities of thermal batteries tend to be
modest, however, due to the high hardware weight over-
head, especially from the chemical heat source.
Electrochemistry
Ca or Mg/WO3
The Ca/WO3 and Mg/WO3 couples were used primarily
in fuzing applications in the early 1950s. In this tech-
nology, glass tape impregnated with electrolyte was used
as the separator. There is almost no information in the
open literature concerning the electrochemistry of WO3
as used in thermal batteries. This technology was one of
the earliest, but was replaced by the Ca/CaCrO4 system
in the mid-1950s.
Ca or Mg/V2O5
The Ca/V2O5 and Mg/V2O5 couples were also used in
early thermal batteries in the 1950s. The high solubility of
V2O5 – more than 17 wt% – complicated its use, since this
can lead to chloride oxidation in the melt. As with the
WO3 system, very little has been published concerning the
electrochemistry of V2O5 in thermal batteries.
Ca/CaCrO4
From the early 1960s until the 1970s, the Ca/CaCrO4
couple, with an electromotive force of over 3 V, was the
primary technology used for thermal batteries. The
CaCrO4 cathode replaced K2CrO4 that had been used
earlier. However, there is a delicate balance that must be
137
138 Primary Batteries – Reserve Systems | Thermally Activated Batteries: Calcium
maintained between the chemical reactions and electro-
chemistry during discharge for these batteries to function
properly. The discharge reactions are quite complex and
involve many intermediates that are critical for proper
battery operation.
Anode reactions
There is no separator present in the Ca/CaCrO4 battery
as it is typically constructed. Thus, the Ca anode is in
direct physical contact with the CaCrO4 cathode ma-
terial that is dissolved in the LiCl–KCl molten salt
(soluble to 34 wt% at 600 1C).
Upon battery activation, a complex series of chemical
reactions occur. First, Ca reacts with Liþ to form a liquid
alloy in a displacement reaction, as shown in eqn [I]:
2Ca þ 2Liþ -CaLi2 ðliqÞ þ Ca2þ ½I
If left uncontrolled, this reaction can lead to intercell
shorting. The CaLi2 immediately reacts with dissolved
chromate to form a dark green Cr(V) compound, as
shown in eqn [II]:
3CaLi2 ðliqÞ þ 4Cl þ 17Ca2þ
þ 12CrO4 2 -4Ca5 ðCrO4 Þ3 ClðsÞ þ 6Liþ ½II
The Ca5(CrO4)3Cl can react further in the presence of
excess Ca2þ under certain temperature conditions, as
shown in eqn [III], to form a second Cr(V) compound,
Ca2CrO4Cl, which is purple in color:
Ca5 ðCrO4 Þ3 ClðsÞ þ Ca2þ þ 2Cl -3Ca2 CrO4 ClðsÞ ½III
The discharge is complicated by a competing double-salt
reaction between CaCl2 and KCl to form solid KCaCl3.
The Cr(V) compounds constitute the separator layer (re-
action barrier) in the cell to minimize self-discharge. The
unreacted CaLi2 continues to function as an anode and, at
the same time, as a separator layer with ionic conductivity
during the electrochemical discharge. The CaLi2 dis-
charges through several stages as shown in eqn [IV]:
CaLi2 -CaLi þ Liþ þ e -Ca þ Liþ þ e ½IV
This Ca reacts with the bulk Liþ again (eqn [I]) to re-
generate the CaLi2 alloy anode.
Cathode reactions
The chemical reactions that occur at the cathode upon
battery activation involve CaCrO4 dissolved in the mol-
ten LiCl–KCl and an iron current collector to form an
Fe-rich lithium–chromium ferrite (Li0.5(Fe2.5xCrx)O4),
and a Cr-rich lithium–iron chromite (Li(Cr1yFey)O2).
Both of these materials are good electronic conductors at
thermal battery operating temperatures. Consequently,
once a film of material has formed on the iron current
collector, further reaction ceases, due to cathodic pro-
tection of the Fe substrate that these materials provide.
The electrochemical discharge sequence that occurs
at the cathode involves the generation of the same
Ca5(CrO4)3Cl compound that is formed chemically at the
anode, through a Cr(V)–chromate intermediate (eqn
[II]). This material then becomes the active cathode. The
discharge process involves a one-electron reduction first,
followed by a two-electron transfer as shown in eqns [V]–
[VII]:
CrO4 2 þ e -CrO4 3 ½V
3CrO4 3 þ Cl þ 5Ca2þ -Ca5 ðCrO4 Þ3 ClðsÞ ½VI
Ca5 ðCrO4 Þ3 ClðsÞ þ 3Liþ þ 6e -3LiCrO2 ðsÞ
þ 5Ca2þ þ Cl þ 6O2 ½VII
The discharge products form dendrites that extend well
into the electrolyte. Since these materials are elec-
tronically conductive, the Cr(VI) in the vicinity is
gradually depleted, causing the electrolyte color to
change from canary yellow to white. During extended
discharge times, these conductive dendrites can result in
cell shorting.
Battery Configurations
In spite of several intrinsic problems with Ca/CaCrO4
batteries (see the next section), they were successfully
developed, engineered, and produced for a wide variety
of defense applications in a range of sizes for many years.
Early designs used a cup to contain each cell. A single
cup cell is shown in Figure 1. These cells were then
stacked in series to form a battery, but such configur-
ations were complex and difficult to manufacture due to
many parts and intercell connections. A battery using the
cup design is shown in Figure 2.
Later, owing to the complexity of the cup configuration,
cell components were developed as individual pellets or
wafers made from pressed powders, eliminating the need
for cups and associated hardware. The pellets were stacked
in series to form a cell as shown in Figure 3. These cells
could then be further stacked in series to form batteries as
shown in Figure 4.
A good example of this design is the small, so-called
‘mailbox’ thermal battery built using pellets that was
developed at Sandia in the 1960s. This battery contained
two, 500 V parallel stacks in a very small volume, as
shown in Figure 5. Assembly of this battery was a sig-
nificant challenge, but it did provide the required high
voltage output. Thousands of these units were built and
fielded successfully.
 Primary Batteries – Reserve Systems | Thermally Activated Batteries: Calcium 139

Cup cathode (+) Cover

Anode (−)
Depolarizer pad: CaCrO4

Electrolyte pad: LiCl−KCl

Calcium anode on Inconel substrate
Heat pad: pad-Zr, BaCrO4

Figure 1 Single cell, cup technology. Reproduced with permission from Van Domelen BH and Wehrle RD (1974) A review of thermal
battery technology. Proceedings of the Intersociety Energy Conversion Engineering Conference, pp. 24–30.

Heat pads Cell cups Anode End heat pellet

Intercell connectors DEB pellet Buffer pellet
Heat pellet

(+)
(+)
(−) (−)

Insulation
Insulation
Heat paper fuse strip
Electrical match
Heat paper fuse strip
Figure 2 Thermal battery using cup cell technology. Electrical match Single cell
Reproduced with permission from Van Domelen BH and Wehrle
RD (1974) A review of thermal battery technology. Proceedings Figure 4 Thermal battery using stacked pellet cells. DEB
of the Intersociety Energy Conversion Engineering Conference, stands for depolarizer, electrolyte, binder. Reproduced with
pp. 24–30. permission from Van Domelen BH and Wehrle RD (1974) A
review of thermal battery technology. Proceedings of the
Intersociety Energy Conversion Engineering Conference,
pp. 24–30.
Heat pellet: Fe, KCIO4

Detailed study of the chemical and physical properties of

DEB pellet
-Depolarizer, CaCrO4
-Electrolyte, LiCl−KCI eutectic
-Binder, SiO2
Anode: Ca on Fe substrate
Figure 3 Single cell, pellet technology. Reproduced with
permission from Van Domelen BH and Wehrle RD (1974) A
review of thermal battery technology. Proceedings of the
Intersociety Energy Conversion Engineering Conference,
pp. 24–30.
Problem Areas
The performance of the Ca/CaCrO4 electrochemical
system tended to be somewhat unpredictable, with changes
in performance attributed to changes in Ca or CaCrO4.
various sheet Ca materials, for example, showed some
correlation in performance only with the bulk nitrogen
content.
Battery performance was also influenced by the source
of CaCrO4, as well as the methods used for processing of
the various catholyte mixtures. The heat treatment of
CaCrO4 influenced performance as it affected average
particle size. This, in turn, influenced its rate of dis-
solution in the molten LiCl–KCl electrolyte and, con-
sequently, its electrochemical characteristics.
During discharge, the chemical reactions associated
with the self-discharge reactions between the dissolved
CaCrO4 and the anode resulted in the generation of heat
and elevated battery temperatures. There had to be a
delicate balance maintained between the chemical and
electrochemical reactions for the battery to not overheat
and still function as intended.
140 Primary Batteries – Reserve Systems | Thermally Activated Batteries: Calcium
Fe/Ca electrode DEB
Match
Epoxy
Figure 5 A small Ca/CaCrO4 thermal battery with two, 500 V parallel stacks.
Finally, the use of chromates in development and
manufacturing operations became increasingly difficult in
the 1970s–1980s due to the implementation of restrictive
environmental safety and health regulations. The re-
strictions were driven by carcinogenic concerns with
hexavalent chromium. The regulations resulted in in-
creased costs and a reduction in the number of suppliers
for chromates. These issues further motivated the shift to
alternative thermal battery electrochemistries.
Nomenclature
Abbreviations and Acronyms
BEO beryllium monoxide
DEB depolarizer, electrolyte, binder
mp melting point
See also: Primary Batteries – Reserve Systems:
Seawater Activated Batteries: Magnesium; Thermally
Activated Batteries: Lithium; Thermally Activated
Batteries: Overview.
Further Reading
Delnick FM and McCarthy DK (1983) Electrochemical reduction of
calcium chromate. Journal of the Electrochemical Society 130(9):
1875.
BEO tube
Heat block
Fuse strip
Monitor
Goldsmith H and Smith JT (1968) Thermal cells in present use.
Electrochemical Technology 6(1–2): 16--19.
Guidotti RA and Masset P (2006) Thermally activated (‘‘thermal’’)
battery technology. Part I: An overview. Journal of Power Sources
161: 1443--1449.
Guidotti RA and Reinhardt FW (1985a) Anodic reactions in the Ca/
CaCrO4 thermal battery. Sandia Report SAND83-2271. http://
infoserve.sandia.gov; www.ntis.gov
Guidotti RA and Reinhardt FW (1985b) Characterization of DEB
powders and pellets for Ca/CaCrO4 thermal batteries. Sandia
Report SAND83-2270. http://infoserve.sandia.gov; www.ntis.gov
Guidotti RA, Reinhardt FW, and Nelson GC (1985) Characterization of
sheet calcium for Ca/CaCrO4 thermal batteries. Sandia Report
SAND83-2269. http://infoserve.sandia.gov; www.ntis.gov
Guidotti RA, Reinhardt FW, Tallant DR, and Higgins KL (1984)
Dissolution of CaCrO4 in molten LiCl–KCl eutectic. Sandia Report
SAND83-2272. http://infoserve.sandia.gov; www.ntis.gov
Guidotti RA, Reinhardt FW, Venturini EL, Rodgers JW, Jr, and Cathey
WN (1985) Characterization of cathodic reaction products in the Ca/
CaCrO4 thermal battery. Sandia Report SAND84-1098. http://
infoserve.sandia.gov; www.ntis.gov
Klasons V and Lamb C (2002) Thermal batteries. In: Linden D and
Reddy T (eds.) Handbook of Batteries, 3rd edn., pp. 21.1--21.22.
McGraw-Hill.
Kuper WE (1994) A brief history of thermal batteries. Proceedings of the
36th Power Sources Conference, pp. 300–309. 6 June. Cherry Hill,
NJ: Army Research Laboratory.
Masset P and Guidotti RA (2007) Thermal activated (thermal) battery
technology. Part II: Molten salt electrolytes. Journal of Power
Sources 164: 397--414.
Rogers W, Jr, Ward SJ, and Guidotti RA (1984) XPS examination of Cr(V)
compounds. Sandia Report SAND84-0236. http://infoserve.sandia.gov;
www.ntis.gov
Van Domelen BH and Wehrle RD (1974) A review of thermal battery
technology. Proceedings of the Intersociety Energy Conversion
Engineering Conference, pp. 24–30. 26–30 August. San Francisco,
CA.