Alkali Hydride-Borohydride Solutions for the Application to Thermally Regenerative Electrochemical Systems
Aubin, Ryan Nicholas
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This thesis was concerned with the proof of concept for mid-grade, 250-500oC, industrial waste heat recovery using a thermally regenerative electrochemical system. Proposed thermally regenerative electrochemical systems are limited to high operating temperatures (> 900oC) and suffer from poor conversion efficiencies (< 20%). As such, a single chamber design that is free of moving parts was presented in this work. The concept for this novel regenerative system relies on gravity and a liquid medium to convey dissolved sodium hydride in a hydride-borohydride solution from cold to hot regions in a continuous circuit. Such a liquid transport medium could allow for operation below 500oC while stabilizing the hydride from thermal decomposition. Investigations on this system were carried out using a custom pressure differential thermal analyzer that was able to operate above temperatures of 700oC and pressures of 2.2MPa. The results of the experiments provided valuable information concerning the phase diagrams of various hydride-borohydride mixtures. The eutectic composition of the NaH-KBH4 system was found to be 43 mole% NaH. The corresponding eutectic temperature (503oC) was determined using the differential cooling curves. Appreciable NaH decomposition was noticed in mixtures above 59.0 mole% NaH. Mixtures up to 42.5 mole% KH in KBH4 were also investigated. The eutectic composition of the KH-KBH4 binary system was determined by extrapolating the liquidus curve to intersect the solidus curve. The KH-KBH4 eutectic temperature was found to be 390oC at 66 mole% KH. The experimental work successfully demonstrates that thermally unstable hydrides can be obtained in the liquid phase below their melting points, under moderate pressures, when mixed with alkali borohydrides. This significantly lowers the achievable operating temperature of the thermally regenerative electrochemical systems currently proposed. The use of the single chamber design with a hydride-borohydride liquid medium offers numerous advantages including: reduced maintenance, reduced operating temperature, reduced system weight, reduced parasitic losses, increased voltage, and increased reliability. The viability for mid-grade industrial waste heat recovery requires construction of a prototype which optimizes power outputs and explores the hydrodynamic transport of material.