Mixed Metal Oxide Systems Applied to Thermochemical Storage of Solar Energy: Benefits of Secondary Metal Addition in Co and Mn Oxides and Contribution of Thermodynamics

Thermochemical energy storage is promising for the long-term storage of solar energy via chemical bonds using reversible redox reactions. The development of thermally-stable and redox-active materials is needed, as single metal oxides (mainly Co and Mn oxides) show important shortcomings that may delay their large-scale implementation in solar power plants. Drawbacks associated with Co oxide concern chiefly cost and toxicity issues while Mn oxide suffers from slow oxidation kinetics and poor reversibility. Mixed metal oxide systems could alleviate the above-mentioned issues, thereby achieving improved materials characteristics. All binary oxide mixtures of the Mn-Co-Fe-Cu-O system are considered in this study, and their properties are evaluated by experimental measurements and/or thermodynamic calculations. The addition of Fe, Cu or Mn to cobalt oxide decreased both the oxygen storage capacity and energy storage density, thus adversely affecting the performance of Co3O4/CoO. Conversely, the addition of Fe, Co or Cu (with added amounts above 15, 40 and 30 mol%, respectively) improved the reversibility, re-oxidation rate and energy storage capacity of manganese oxide. Computational thermodynamics was applied to unravel the governing mechanisms and phase transitions responsible for the materials behavior, which represents a powerful tool for predicting the suitability of mixed oxide systems applied to thermochemical energy storage.