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Metal hydrides have been demonstrated as energy storage materials for thermal battery applications. This is due to the high energy density associated with the reversible thermochemical reaction between metals and hydrogen. Magnesium iron hydride (Mg 2 FeH 6) is one such material that has been identified as a thermal energy storage material due to its reversible hydrogenation reaction at temperatures between 400 and 600 °C. This study demonstates an automated thermal battery prototype containing 900 g of Mg 2 FeH 6 as the thermal energy storage material with pressurised water acting as the heat transfer fluid to charge and discharge the battery. The operating conditions of the system were optimised by assessing the ideal operating temperature, flow rate of the heat transfer fluid, and hydrogen pressures. Overall, excellent cyclic energy storage reversibility was demonstrated between 410 and 450 °C with a maximum energy capacity of 1650 kJ which is 87% of the theoretical value (1890 kJ). [Display omitted] • A prototype thermal battery was developed using Mg 2 FeH 6 as the thermal energy storage material. • The automated battery consisted of a heat transfer fluid system to charge and discharge the material. • Complete optimisation of the operating conditions of the system was established. • Excellent cycle reversibility was demonstrated between 410 and 450 °C. [ABSTRACT FROM AUTHOR]

• The SrH 2 and 2Al system was studied for thermochemical energy storage applications. • Thermodynamic destablization was observed compared to pure strontium hydride. • The system reversibly stores H 2 at a temperature of 846 °C at 1 bar H 2 pressure. • After 50 cycles mild degradation in H 2 storage capacity was observed. • The material could be a thermal energy storage material upon further modification. [Display omitted] Thermal batteries are ideal for storing renewable energies or excess electricity from the grid. The most efficient thermal batteries utilize reversible thermochemical reactions where the heat produced during discharge drives a heat engine. Metal hydrides can be used as the thermal energy storage (TES) material in these batteries, since when heated, hydrogen is released in an endothermic process, charging the battery. When this hydrogen is reintroduced to the metal the metal hydride is reformed during the exothermic reaction (discharge). The optimal thermal battery would have a high operating temperature, low operating pressure and low material cost. SrH 2 could meet these demands except its operating temperature is above 1000 °C. Adding aluminum to strontium hydride causes thermal destablization allowing an operating temperature of 1 bar hydrogen at 846 ± 36 °C, providing ideal properties as a TES material. The SrH 2 -2Al system reacts in two stages with the second step exhibiting only a 32% reduction in capacity over 50 cycles. Pressure-composition isotherm analysis of the second step determined the thermodynamics of H 2 desorption to be Δ H des = 132 ± 2 kJ/mol H 2 and Δ S des = 118 ± 2 J/K/mol H 2. Further studies by scanning electron microscopy have determined changes in morphology over cyclic activity, while simultaneous thermal analysis and powder X-ray diffraction have identified the reaction pathways of the process. A cost analysis of the system has shown that a reduction in materials cost would enhance technological application of this material. [ABSTRACT FROM AUTHOR]

Thermochemical energy storage offers a cost-effective and efficient approach for storing thermal energy at high temperature (∼1100 °C) for concentrated solar power and large-scale long duration energy storage. SrCO 3 is a potential candidate as a thermal energy storage material due to its high energy density of 205 kJ/mol of CO 2 during reversible CO 2 release and absorption. However, it loses cyclic capacity rapidly due to sintering. This study determined that the cyclic capacity of SrCO 3 was enhanced by the addition of either reactive SrTiO 3 or inert SrZrO 3 , where the molar ratios of SrCO 3 to SrZrO 3 were varied from 1:0.125 to 1:1. Thermogravimetric analysis over 15 CO 2 sorption cycles demonstrated that both materials retained ∼80 % of their maximum cyclic capacity on the milligram scale. Repeated measurements using gram scale samples revealed a decrease in maximum capacity to 11 % using a sample of SrCO 3 – 0.5 SrZrO 3 over 53 cycles, while the use of SrTiO 3 additives allowed for the retention of 80 % maximum capacity over 55 cycles. These findings highlight the potential of reactive additives in enhancing the performance of thermochemical energy storage systems, while providing valuable insights for the development of cost-effective materials. [Display omitted] • SrCO 3 is a cost-effective thermochemical energy storage material. • TGA shows both SrZrO 3 and SrTiO 3 additives increase cyclic capacity up to ∼80 %. • SrTiO 3 reduces sintering whereas SrZrO 3 does not prevent sintering. [ABSTRACT FROM AUTHOR]

• Carbonation reaction kinetics of limestone-based CaCO 3 /Al 2 O 3 mixture is estimated. • Numerical modelling of CaCO 3 based reactor for thermal storage application is performed. • The influence of operating parameters on the reactor's performance is examined. • The effect of incorporating graphite fin into the CaCO 3 reactor is studied. This study conducts kinetic analyses of the carbonation reaction of CaCO 3 (doped with Al 2 O 3) as well as parametric analyses of the performance of a thermochemical reactor, which can act as a thermal battery. Kinetic measurements of CO 2 release and absorption were carried out using thermogravimetric analysis (TGA) at 815, 830 and 845 °C on a CaCO 3 /Al 2 O 3 sample that had been previously cycled over 500 times. The rapid reaction kinetics revealed that the Avrami nucleation growth model with exponent 3 fits well to explain the carbonation reaction. The numerical study considered a cylindrical reactor with a height and diameter of 100 mm. According to numerical analysis, at an applied CO 2 pressure of 1 bar, increasing the thermal conductivity of the reactor bed from 1.33 to 5 W/m.K increases the rate of carbonation reaction by 74%. When the applied CO 2 pressure is increased from 1 to 2 bar, the performance of the reactor bed with thermal conductivity of 1.33 W/m.K improves by 42%; however, when the applied CO 2 pressure is increased from 2 to 3 bar, the performance improves by only 18%. Additionally, when the boundary temperature of the reactor was lowered by 30 °C, performance was enhanced by 43% at an applied CO 2 pressure of 1 bar. This study also examined the effect of using a graphite fin as a heat extraction system. The graphite fin allowed for more rapid heat extraction and increased the carbonation reaction by 44% in the reactor bed with poor thermal conductivity (1.33 W/m.K) but had no effect in the reactor with modest thermal conductivity of (5 W/m.K) due to its ability to already transfer heat effectively to the reactor shell. [ABSTRACT FROM AUTHOR]

The inherent nature concerning the intermittency of concentrating solar power (CSP) plants can be overcome by the integration of efficient thermal energy storage (TES) systems. Current CSP plants employ molten salts as TES materials although metal hydrides (MH) have proven to be more efficient due to their increased operating temperatures. Nonetheless, the heat exchange between the MH bed and the heat transfer medium used to operate a heat engine is a critical factor in the overall efficiency of the TES system. In this work, a computational study is carried out to investigate the performance of a magnesium hydride TES packed bed using a multiphase (boiling) medium instead of single-phase heat absorption methods. The boiling heat transfer behaviour is simulated by using the Eulerian two-fluid framework. The simulations are conducted at a transient state using SST- k -ω Reynolds-Averaged Navier-Stokes equations. It is observed that, unlike the single-phase heat collection method, the multiphase heat absorption method maintains a constant temperature in the heat transfer fluid throughout the reactor. Consequently, a higher temperature gradient is realised between the MH bed and heat transfer fluid (HTF), leading to improvements in the overall reaction rate of the hydrogenation process. • Performance enhancement of a magnesium hydride reactor due to multiphase heat absorption was studied. • Boiling heat transfer behaviour was simulated using Eulerian two-fluid framework. • The percentage of improvement in reactor performance was variable at different reacted fractions. • Dry out condition was critical in the reactor efficiency. [ABSTRACT FROM AUTHOR]

Metal hydrides are regarded as one of the most attractive options for thermal energy storage (TES) materials for concentrated solar thermal applications. Improved thermal performance of such systems is vitally determined by the effectiveness of heat exchange between the metal hydride and the heat transfer fluid (HTF). This paper presents a numerical study supported by experimental validation on a magnesium hydride reactor fitted with a helical coil heat exchanger for enhanced thermal performance. The model incorporates hydrogen absorption kinetics of ball-milled magnesium hydride, with titanium boride and expanded natural graphite additives obtained by Sievert's apparatus measurements and considers thermal diffusion within the reactor to the heat transfer fluid for a realistic representation of its operation. A detailed parametric analysis is carried out, and the outcomes are discussed, examining the ramifications of hydrogen supply pressure and its flow rate. The study identifies that the enhancement of thermal conductivity in magnesium hydride has an insignificant impact on current reactor performance. • 3-D validation of MgH 2 reactor with a helical coil heat exchanger was performed. • Reaction kinetics was found out by using Sievert's apparatus. • Effect of operating parameters on MH reactor performance was studied. • Addition of 20% ENG into MH reactor, under the study, proved ineffective. [ABSTRACT FROM AUTHOR]

Abstract Thermochemical energy storage materials have advantage of much higher energy densities compared to latent or sensible heat storage materials. Metal hydrides show good reversibility and cycling stability combined with high enthalpies. They can be used for short and long-term heat storage applications and can increase the overall flexibility and efficiency of solar thermal energy production. Metal hydrides with working temperatures less than 500 °C were in the focus of research and development over the last years. For the new generation of solar thermal energy plants new hydrides materials with working temperatures above 600 °C must be developed and characterized. In addition to thorough research on new metal hydrides, the construction and engineering of heat storage systems at these high temperatures are challenging. Corrosion problems, hydrogen embrittlement and selection of heat transfer fluids are significant topics for future research activities. Highlights • Metal hydrides are described concerning their potential for heat storage at different temperatures. • For future thermochemical energy storage useful for the next generation of solar power plants new metal hydrides with working temperatures above 600 °C must be developed. • In this regard challenges of engineering, corrosion, hydrogen embrittlement and heat transfer must be solved. [ABSTRACT FROM AUTHOR]

The thermochemical energy storage properties of calcium hydride (CaH 2) destabilised with either silicon (Si) or Ca x Si y compounds at various molar ratios, were thoroughly studied by a combination of experimental and computer assisted thermodynamic calculations. Particularly, the destabilisation effect of Si on CaH 2 at five different molar ratios (1:1, 1:2, 2:1, 3:4, 5:3 CaH 2 to Si) was extensively investigated. Theoretical calculations predicted a multi-step thermal decomposition reaction between CaH 2 and Si forming Ca x Si y at varying temperatures, which was confirmed by in-situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and mass-spectroscopic measurements. The most suitable destabilisation reactions between CaH 2 and Si or Ca x Si y that meet the criteria of a thermal energy storage system for the next-generation of concentrated solar power (CSP) plants were identified. The CaH 2 and CaSi system (in a 2:3 molar ratio of CaH 2 to CaSi) showed desirable operating conditions with a decomposition temperature of 747 ± 33 °C at a hydrogen pressure of 1 bar. Pressure composition isothermal measurements were conducted on this system to determine its practical enthalpy of decomposition to form Ca 5 Si 3. The calculated value (107.3 kJ mol−1 H 2) was lower compared to the experimentally determined value (154 ± 4 kJ mol−1 H 2). This mismatch was mainly due to the formation of CaO and a CaSi solid solution in addition to the desired Ca 5 Si 3 phase. ga1 • Calcium hydride has been thermodynamically destabilised with silicon. • A multistep decomposition pathway was determined by theoretical calculations. • The experimental thermal decomposition pathway and thermodynamics were established. • The Ca–Si system is a viable thermal energy storage material. [ABSTRACT FROM AUTHOR]