Study of Heating and Cooling Rate of Cobalt Oxide-Based TCES System Using Experimental Redox Kinetics Analysis

Cost-effective solar power generation in CSP plants requires the challenging integration of high energy density and high-temperature thermal energy storage with the solar collection equipment and the power plant. Thermochemical energy storage (TCES) is currently a very good option for thermal energy storage, which can meet the industry requirement of large energy density and high storage temperature. TCES specifically exploits reversible chemical reactions wherein heat is absorbed during the forward endothermic reaction and released during the reverse exothermic reaction. The associated enthalpic storage of energy (i.e., the heat of reaction) offers higher density and enhanced stability compared to sensible and latent heat storage. Metal oxide redox reactions are particularly well-suited for TCES given their characteristically high enthalpy of reaction and high reaction temperature. In addition, the air is suitable as both a heat transfer fluid (HTF) and reactant; thus, simplifying process design and eliminating the need for indirect HTF storage and any intermediate heat exchanger. Among the palette of available metal oxides, cobalt oxide is one of the most promising candidates for TCES given its high enthalpy of reaction with high reaction temperature. One of the critical design parameters for TCES reactors is the optimal heating and cooling rates during respective charging and discharging modes of operation. In order to study the effect of heating/cooling rate on cobalt oxide TCES performance, a constant 10°C/min rate was selected for both storage cycle heating and cooling. Considering the intrinsic redox kinetics of cobalt oxide at considered constant heating/cooling rate, we studied milligram scale quantities of cobalt oxide (99.9% purity, 40 μm average particle size) using a dual-mode thermogravimetric (TGA)/differential scanning calorimetry (DSC) system, which simultaneously measures weight change (TGA) and differential heat flow (DSC) as a function of TCES cycling under continuous air purge. In addition, we investigated the cyclic stability of cobalt oxide in the context of the redox kinetics and particle coarsening behavior, employing scanning electron microscopy (SEM). TGA/DSC tests were conducted for 30 successive cycles using pure cobalt oxide. It was shown that pure cobalt oxide in powder form (38μ particle size) could complete both forward and reverse reaction at the selected heating rate with little degradation between cycles. In parallel, SEM was used to examine morphology and particle size changes before and after heating cycles. SEM results proved grain growth occurs even after only five initial cycles.