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 difficulty. Later designs typically utilized pellets or wafers

pressed from powdered mixtures. The pellets are stacked
Thermal batteries were conceived and developed by in a series arrangement to form the battery and the ne-
German scientists during World War II and used in V-2 cessary electrical terminals are welded together. The
rockets. These batteries made use of the exhaust heat from battery components are packaged into stainless-steel
the rocket motor to sustain the high temperature neces- containers and hermetically sealed.
sary for battery output during the rocket’s mission. Dr G. Thermal batteries are categorized as reserve batteries,
O. Erb is credited with originally developing this tech- in that they can be stored for long periods of time (dec-
nology in Germany. The technology was brought to the ades) without degradation, an unusual attribute for elec-
United States in 1946, adapted by the National Bureau of trochemical systems. Once activated and heated above the
Standards, Ordnance Development Division, for US melting point of the electrolyte, the batteries can provide
defense applications, and placed in production by Catalyst power at extremely high rates because of the high intrinsic
Research Corporation. Improvements were made during conductivity of the molten salts. Typical activated life-
the late 1940s and early 1950s, including the use of the times (operating time) for calcium-anode thermal bat-
lithium chloride–potassium chloride (LiCl–KCl) eutectic teries are about a minute, although experimental versions
as the electrolyte. Other organizations became active in with activated lifetimes of over 60 min were built and
the development and manufacture of these devices at this tested. The power densities of thermal batteries tend to be
time, including Eagle Picher, the largest US manufacturer modest, however, due to the high hardware weight over-
of thermal batteries today, and Sandia National Labora- head, especially from the chemical heat source.
tories, which continues to develop and produce thermal
batteries for national security applications.
Electrochemistry
Ca or Mg/WO3
Background The Ca/WO3 and Mg/WO3 couples were used primarily
in fuzing applications in the early 1950s. In this tech-
Thermal batteries are thermally activated, primary reserve nology, glass tape impregnated with electrolyte was used
power sources, which typically operate between 350 and as the separator. There is almost no information in the
550 1C. They use an ionically conducting molten salt in open literature concerning the electrochemistry of WO3
the layer between the anode and cathode (i.e., electrolyte as used in thermal batteries. This technology was one of
separator). Consequently, these batteries lose heat during the earliest, but was replaced by the Ca/CaCrO4 system
operation, and this must be considered during the design in the mid-1950s.
of the battery packaging and interface with the next as-
sembly. The anodes and cathodes (usually mixed with the Ca or Mg/V2O5
electrolyte) are typically solid electroactive species in both
the stored and activated states, and most thermal batteries The Ca/V2O5 and Mg/V2O5 couples were also used in
also contain a chemical heat source. The electrolytes that early thermal batteries in the 1950s. The high solubility of
are typically used melt between 319 and 436 1C, with the V2O5 – more than 17 wt% – complicated its use, since this
LiCl–KCl (mp 352 1C) eutectic being the most common. can lead to chloride oxidation in the melt. As with the
Once a battery is activated, the electrolyte becomes liquid WO3 system, very little has been published concerning the
and is held in place by a matrix, which usually includes a electrochemistry of V2O5 in thermal batteries.
binder to retain the molten phase by capillarity forces.
Ca/CaCrO4
Necessary thermal battery auxiliary components include
an activation device (igniter or squib), insulation (thermal From the early 1960s until the 1970s, the Ca/CaCrO4
and electrical), conductors, leads, connectors, and a con- couple, with an electromotive force of over 3 V, was the
tainer. Early cell configurations used cups to contain the primary technology used for thermal batteries. The
electrodes, but this approach required complex inter- CaCrO4 cathode replaced K2CrO4 that had been used
connection hardware and greatly increased manufacturing 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- once a film of material has formed on the iron current
chemistry during discharge for these batteries to function collector, further reaction ceases, due to cathodic pro-
properly. The discharge reactions are quite complex and tection of the Fe substrate that these materials provide.
involve many intermediates that are critical for proper The electrochemical discharge sequence that occurs
battery operation. 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
Anode reactions
[II]). This material then becomes the active cathode. The
There is no separator present in the Ca/CaCrO4 battery
discharge process involves a one-electron reduction first,
as it is typically constructed. Thus, the Ca anode is in
followed by a two-electron transfer as shown in eqns [V]–
direct physical contact with the CaCrO4 cathode ma-
[VII]:
terial that is dissolved in the LiCl–KCl molten salt
(soluble to 34 wt% at 600 1C). CrO4 2 þ e -CrO4 3 ½V
Upon battery activation, a complex series of chemical
reactions occur. First, Ca reacts with Liþ to form a liquid
3CrO4 3 þ Cl þ 5Ca2þ -Ca5 ðCrO4 Þ3 ClðsÞ ½VI
alloy in a displacement reaction, as shown in eqn [I]:

2Ca þ 2Liþ -CaLi2 ðliqÞ þ Ca2þ ½I Ca5 ðCrO4 Þ3 ClðsÞ þ 3Liþ þ 6e -3LiCrO2 ðsÞ
þ 5Ca2þ þ Cl þ 6O2 ½VII
If left uncontrolled, this reaction can lead to intercell
shorting. The CaLi2 immediately reacts with dissolved The discharge products form dendrites that extend well
chromate to form a dark green Cr(V) compound, as into the electrolyte. Since these materials are elec-
shown in eqn [II]: tronically conductive, the Cr(VI) in the vicinity is
gradually depleted, causing the electrolyte color to
3CaLi2 ðliqÞ þ 4Cl þ 17Ca2þ change from canary yellow to white. During extended
þ 12CrO4 2 -4Ca5 ðCrO4 Þ3 ClðsÞ þ 6Liþ ½II discharge times, these conductive dendrites can result in
cell shorting.
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, Battery Configurations
Ca2CrO4Cl, which is purple in color:
In spite of several intrinsic problems with Ca/CaCrO4
Ca5 ðCrO4 Þ3 ClðsÞ þ Ca2þ þ 2Cl -3Ca2 CrO4 ClðsÞ ½III batteries (see the next section), they were successfully
developed, engineered, and produced for a wide variety
The discharge is complicated by a competing double-salt of defense applications in a range of sizes for many years.
reaction between CaCl2 and KCl to form solid KCaCl3. Early designs used a cup to contain each cell. A single
The Cr(V) compounds constitute the separator layer (re- cup cell is shown in Figure 1. These cells were then
action barrier) in the cell to minimize self-discharge. The stacked in series to form a battery, but such configur-
unreacted CaLi2 continues to function as an anode and, at ations were complex and difficult to manufacture due to
the same time, as a separator layer with ionic conductivity many parts and intercell connections. A battery using the
during the electrochemical discharge. The CaLi2 dis- cup design is shown in Figure 2.
charges through several stages as shown in eqn [IV]: Later, owing to the complexity of the cup configuration,
cell components were developed as individual pellets or
CaLi2 -CaLi þ Liþ þ e -Ca þ Liþ þ e ½IV wafers made from pressed powders, eliminating the need
for cups and associated hardware. The pellets were stacked
This Ca reacts with the bulk Liþ again (eqn [I]) to re-
in series to form a cell as shown in Figure 3. These cells
generate the CaLi2 alloy anode.
could then be further stacked in series to form batteries as
shown in Figure 4.
Cathode reactions A good example of this design is the small, so-called
The chemical reactions that occur at the cathode upon ‘mailbox’ thermal battery built using pellets that was
battery activation involve CaCrO4 dissolved in the mol- developed at Sandia in the 1960s. This battery contained
ten LiCl–KCl and an iron current collector to form an two, 500 V parallel stacks in a very small volume, as
Fe-rich lithium–chromium ferrite (Li0.5(Fe2.5xCrx)O4), shown in Figure 5. Assembly of this battery was a sig-
and a Cr-rich lithium–iron chromite (Li(Cr1yFey)O2). nificant challenge, but it did provide the required high
Both of these materials are good electronic conductors at voltage output. Thousands of these units were built and
thermal battery operating temperatures. Consequently, 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 various sheet Ca materials, for example, showed some
-Depolarizer, CaCrO4 correlation in performance only with the bulk nitrogen
-Electrolyte, LiCl−KCI eutectic
-Binder, SiO2
content.
Battery performance was also influenced by the source
Anode: Ca on Fe substrate of CaCrO4, as well as the methods used for processing of
the various catholyte mixtures. The heat treatment of
Figure 3 Single cell, pellet technology. Reproduced with CaCrO4 influenced performance as it affected average
permission from Van Domelen BH and Wehrle RD (1974) A particle size. This, in turn, influenced its rate of dis-
review of thermal battery technology. Proceedings of the solution in the molten LiCl–KCl electrolyte and, con-
Intersociety Energy Conversion Engineering Conference,
pp. 24–30.
sequently, its electrochemical characteristics.
During discharge, the chemical reactions associated
with the self-discharge reactions between the dissolved
Problem Areas CaCrO4 and the anode resulted in the generation of heat
and elevated battery temperatures. There had to be a
The performance of the Ca/CaCrO4 electrochemical delicate balance maintained between the chemical and
system tended to be somewhat unpredictable, with changes electrochemical reactions for the battery to not overheat
in performance attributed to changes in Ca or CaCrO4. and still function as intended.
140 Primary Batteries – Reserve Systems | Thermally Activated Batteries: Calcium

Fe/Ca electrode DEB

BEO tube
Heat block
Fuse strip
Monitor
Match
Epoxy

Figure 5 A small Ca/CaCrO4 thermal battery with two, 500 V parallel stacks.

Finally, the use of chromates in development and Goldsmith H and Smith JT (1968) Thermal cells in present use.
manufacturing operations became increasingly difficult in Electrochemical Technology 6(1–2): 16--19.
Guidotti RA and Masset P (2006) Thermally activated (‘‘thermal’’)
the 1970s–1980s due to the implementation of restrictive battery technology. Part I: An overview. Journal of Power Sources
environmental safety and health regulations. The re- 161: 1443--1449.
strictions were driven by carcinogenic concerns with Guidotti RA and Reinhardt FW (1985a) Anodic reactions in the Ca/
CaCrO4 thermal battery. Sandia Report SAND83-2271. http://
hexavalent chromium. The regulations resulted in in- infoserve.sandia.gov; www.ntis.gov
creased costs and a reduction in the number of suppliers Guidotti RA and Reinhardt FW (1985b) Characterization of DEB
for chromates. These issues further motivated the shift to powders and pellets for Ca/CaCrO4 thermal batteries. Sandia
Report SAND83-2270. http://infoserve.sandia.gov; www.ntis.gov
alternative thermal battery electrochemistries. 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
Nomenclature Guidotti RA, Reinhardt FW, Tallant DR, and Higgins KL (1984)
Dissolution of CaCrO4 in molten LiCl–KCl eutectic. Sandia Report
Abbreviations and Acronyms SAND83-2272. http://infoserve.sandia.gov; www.ntis.gov
BEO beryllium monoxide Guidotti RA, Reinhardt FW, Venturini EL, Rodgers JW, Jr, and Cathey
WN (1985) Characterization of cathodic reaction products in the Ca/
DEB depolarizer, electrolyte, binder
CaCrO4 thermal battery. Sandia Report SAND84-1098. http://
mp melting point 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
See also: Primary Batteries – Reserve Systems: 36th Power Sources Conference, pp. 300–309. 6 June. Cherry Hill,
NJ: Army Research Laboratory.
Seawater Activated Batteries: Magnesium; Thermally
Masset P and Guidotti RA (2007) Thermal activated (thermal) battery
Activated Batteries: Lithium; Thermally Activated technology. Part II: Molten salt electrolytes. Journal of Power
Batteries: Overview. 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
Further Reading 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,
Delnick FM and McCarthy DK (1983) Electrochemical reduction of
CA.
calcium chromate. Journal of the Electrochemical Society 130(9):
1875.