Thermochimica Acta, Vol.673, 105-118, 2019
Calorimetric method for determining the thermochemical energy storage capacities of redox metal oxides
Transition metal oxide compounds have been demonstrated to be promising candidates for thermochemical processes, particularly energy storage. A calorimetric method for measuring enthalpy of these materials is developed in this work. A combination of drop calorimetry and acid-solution calorimetry is used to measure the total enthalpy and standard enthalpy of formation of these materials for compounds that form at high temperatures ( >= 1000 degrees C) after undergoing thermal reduction. These measurements are used to compute the energy storage potential of these materials for a specified set of redox cycle operating temperatures. The construction and calibration of appropriate calorimeter devices are described. A novel approach to performing acid-solution calorimetry is introduced by including tin (II) chloride as a reducing agent for enhancing the dissolution rate of these compounds sufficiently so that acid-solution calorimetry can be implemented accurately. The general procedure is presented and applied to three variations of magnesium-manganese oxide materials for a redox cycle operating under an oxygen partial pressure of 0.2 atm between 1000 and 1500 degrees C. Using this method, the total energies stored by magnesium-manganese oxides of molar ratios Mn/Mg of 2/1, 1/1, and 2/3 were found to be 924 +/- 56.7, 1029 +/- 57.0, and 1070 +/- 64.2 kJ kg(-1), respectively.