Thermal batteries are specialized as primary reserve batteries that operate when the internal heat source is ignited and the produced heat (450~550oC) melts the initially insulating salt into highly conductive eutectic electrolyte. The heat source is composed of Fe powder and KClO4 with different mass ratios and is inserted in-between the cells (stacks) to allow homogeneous heat transfer and ensure complete melting of the electrolyte. An ideal heat source has following criteria to satisfy: sufficient mechanical durability for stacking, appropriate heat calories, ease of combustion by an igniter, stable combustion rate, and modest peak temperature. To satisfy the aforementioned requirements, Fe powder must have high surface area and porosity to increase the reaction rate. Herein, the hydrothermal and spray drying synthesis techniques for Fe powder samples are employed to investigate the physicochemical properties of Fe powder samples and their applicability as a heat source constituent. The direct comparison with the state-of-the-art Fe powder is made to confirm the validity of synthesized products. Finally, the actual batteries were made with the synthesized iron powder samples to examine their performances during the battery operation.

Lithium anodes (13, 15, 17, and 20 wt% Li) were fabricated by mixing molten lithium and iron powder, which was used as a binder to hold the molten lithium, at about 500℃ (discharge temp.). In this study, the effect of applied pressure and lithium content on the discharge properties of a thermal battery’s single cell was investigated. A single cell using a Li anode with a lithium content of less than 15 wt% presented reliable performance without any abrupt voltage drop resulting from molten lithium leakage under an applied pressure of less than 6 kgf/㎠. Furthermore, it was confirmed that even when the solid electrolyte is thinner, the Li anode of the single cell normally discharges well without a deterioration in performance. The Li anode of the single cell presented a significantly improved open-circuit voltage of 2.06 V, compared to that of a Li-Si anode (1.93 V). The cut-off voltage and specific capacity were 1.83 V and 1,380 As g^-1 (Li anode), and 1.72 V and 1,364 As g^-1 (Li-Si anode). Additionally, the Li anode exhibited a stable and flat discharge curve until 1.83 V because of the absence of phase change phenomena of Li metal and a subsequent rapid voltage drop below 1.83 V due to the complete depletion of Li at the end state of discharge. On the other hand, the voltage of the Li-Si anode cell decreased in steps, 1.93 V → 1.72 V (Li₁₃Si₄ → Li₇Si₃) → 1.65 V (Li₇Si₃→ Li₁₂Si₇), according to the Li-Si phase changes during the discharge reaction. The energy density of the Li anode cell was 807.1 Wh l^-1, which was about 50% higher than that of the Li-Si cell (522.2 Wh l^-1).