Thermal stability of FeS2 cathode material in thermal batteries: Effect of dissolved oxides and hydroxides in molten salt electrolytes
Patrick Masset* TU Bergakademie Freiberg, Department of Energy Process Engineering and Chemical Engineering Fuchsmhlenweg 9, Haus 1 - Reiche Zeche 09596 Freiberg, Germany *E-mail: [Link]@[Link] Thermally activated batteries (thermal batteries) are used for military applications as power sources for guided missiles and proximity fuses in ordnance devices [1]. The electrolyte is a molten salt mixture which is solid at room temperature. Once thermally activated (pyrotechnics combustion), the molten salt mixture melts and exhibits an ionic conductivity high enough to be utilised as an electrolyte. Recently, the properties of molten salt electrolytes have been thoroughly reviewed [2]. Usually, the molten salts are moisture sensitive. They should be prepared under controlled atmospheres in order to avoid contamination with moisture and oxygen, which may lead to the formation of oxides and hydroxides in the electrolyte at high temperature. In addition, it is known that the presence of oxides modifies the retention properties of the molten electrolyte with magnesia. However, only few studies deal with the thermal stability of the cathode material FeS2 in oxide and/or hydroxide containing molten electrolytes. Under an inert atmosphere the pyrite progressively decomposes into pyrrhotite FeS1.14 and sulphur gas according to Eq. 1. [3]. This leads to the formation of pyrrhotite at the outer surface of the pyrite particle as shown in Figure 1. (Eq. 1) FeS2 FeS1.14 + 0.43 S2
The situation differs in the presence of dissolved of either oxides or hydroxides in the molten electrolyte. For the eutectic compositions LiCl-KCl and LiF-LiCl-LiI, thermogravimetric measurements were conducted for oxide and hydroxide contents up to 10 at.% in the electrolyte (Figure 3).
Figure 3. TGA traces for FeS2+electrolyte mixtures.
Using the TGA, it was shown that the decomposition temperature of the pyrite decreases as the amount of oxide or hydroxide in the electrolyte increases. This effect was found to be significantly more pronounced in the presence of hydroxides. The addition of LiOH to the electrolyte leads to a decrease in the electrolyte melting point. This was evidenced using DTA carried out on the remaining salt mixture (285 C instead of 352C for the LiCl-KCl eutectic). At intermediate temperatures lithium hydroxide may decompose according to Eq. 2. (Eq. 2) 2LiOH Li2O + H2O The decomposition of LiOH leads to dissolved Li2O and H2O evolution, which may react with the pyrite. At elevated temperatures the dissolved oxides could possibly react with the pyrite and this would lead to the production of sulphide in the electrolyte (Eq. 3). 1 (Eq. 3) 2S + O 2 2 O 2 + 2S 2
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<-- endo DTA signal exo -->
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Figure 1. SEM image of a thermally decomposed pyrite particle under helium gas.
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Once the pyrite grains are embedded in the molten salt phase the situation differs as sulphur gas is trapped in the freshly produced porous layer of pyrrhotite until it reaches a critical partial pressure. In the case of the LiCl-KCl eutectic, the decomposition temperature of the pyrite increases by approximately 75 C (Figure 2). The decomposition temperature is shifted towards higher temperatures but the decomposition mechanism remains unchanged in the absence of oxides.
0 -5 Mass variation / % under helium LiCl-KCl eutectic
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Figure 4. DTA trace of a LiCl-KCl (5 at% LiOH) during the cooling pass.
This work shows that the presence of either dissolved oxide or hydroxide species in the electrolyte for thermal batteries decreases the thermal stability of the cathode material FeS2 and may significantly deteriorate the performance of such systems. References [1] R.A. Guidotti, P.J. Masset, J. Power Sources, 161(2) (2006) 1443-1449. [2] P.J. Masset, R.A. Guidotti, J. Power Sources, 164(1) (2007) 397-414. [3] P.J. Masset, R.A. Guidotti, J. Power Sources, 177 (2008) 595-609.
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Figure 2. TGA traces of pyrite samples under helium atmosphere (blue) and in the LiCl-KCl eutectic (red).