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TiH2-modified MgH2 was prepared by high energy reactive ball milling (HRBM) of Mg and Ti in hydrogen and showed high weight H storage capacity and fast hydrogenation/dehydrogenation kinetics. However, a decrease in the reversible H storage capacity on cycling at high temperatures takes place and is a major obstacle for its use in hydrogen and heat storage applications. Reversible hydrogen absorption/desorption cycling of the materials requires use of the working temperature ≥330 °C and results in a partial step-by-step loss of the recoverable hydrogen storage capacity, with less significant changes in the rates of hydrogenation/dehydrogenation. After hydrogen desorption at 330–350 °C, hydrogen absorption can proceed at much lower temperatures, down to 24 °C. However, a significant decay in the reversible hydrogen capacity takes place with increasing number of cycles. The observed deterioration is caused by cycling-induced drastic morphological changes in the studied composite material leading to a segregation of TiH2 particles in the cycled samples instead of their initial homogeneous distribution. However, the introduction of 5 wt% of graphite into the MgH2–TiH2 composite system prepared by HRBM leads to an outstanding improvement of the hydrogen storage performance. Indeed, hydrogen absorption and desorption characteristics remain stable through 100 hydrogen absorption/desorption cycles and are related to an effect of the added graphite. The TEM study showed that carbon is uniformly distributed between the MgH2 grains covering segregated TiH2, preventing the grain growth and thus keeping the reversible storage capacity and the rates of hydrogen charge and discharge unchanged. Modelling of the kinetics of hydrogen absorption and desorption in the Mg–Ti and Mg–Ti–C composites showed that the reaction mechanisms significantly change depending on the presence or absence of graphite, the number of absorption–desorption cycles and the operating temperature.

In order to uncover the inner working mechanism and performance of solid oxide fuel cell (SOFC) with biomass gasification syngas as fuel, a two dimensional SOFC multi-physical field model is established. This study makes up for the deficiency that the previous studies of coupling biomass gasification unit and SOFC stack mostly stay at the system level. The results show that the SOFC fueled by the syngas produced from gasification of biomass with steam as the agent has the best performance. The peak power density could achieve approximately 10240 W m−2. With the improvement of operating temperature, the peak power density of SOFC will be increased. At the temperature of 1123 K, the peak power density could achieve about 15128 W m−2. The average reaction rate of water gas shift (WGS) reaction is −29.73 mol m−3 s−1 when the operating temperature is 1123 K. This indicates that the WGS reaction will proceed in reverse direction at high temperatures, thereby reducing the hydrogen concentration. In addition, increase in the anode flux and decrease in the cell length lead to the increase of SOFC current density. In general, this work could provide guidance for the optimization and practical application of SOFC using biomass syngas as fuel.

International Symposium On Materials for Energy Storage & Conversion, Akyaka, Mugla / Turkey, September 11-13, 2019 (oral); mESC-IS2019, Abstracts, p. 127

Two-tank metal hydride pairs have gained tremendous interest in thermal energy storage systems for concentrating solar power plants or industrial waste heat recovery. Generally, the system’s performance depends on selecting and matching the metal hydride pairs and the thermal management adopted. In this study, the 2D mathematical modeling used to investigate the heat storage system’s performance under different thermal management techniques, including active and passive heat transfer techniques, is analyzed and discussed in detail. The change in the energy storage density, the specific power output, and the energy storage efficiency is studied under different heat transfer measures applied to the two tanks. The results showed that there is a trade-off between the energy storage density and the energy storage efficiency. The adoption of active heat transfer enhancement (convective heat transfer enhancement) leads to a high energy storage density of 670 MJ m−3 (close to the maximum theoretical value of 755.3 MJ m−3). In contrast, the energy storage efficiency decreases dramatically due to the increase in the pumping power. On the other hand, passive heat transfer techniques using the bed’s thermal conductivity enhancers provide a balance between the energy storage density (578 MJ m−3) and the energy efficiency (74%). The utilization of phase change material as an internal heat recovery medium leads to a further reduction in the heat storage performance indicators (142 MJ m−3 and 49%). Nevertheless, such a system combining thermochemical and latent heat storage, if properly optimized, can be promising for thermal energy storage applications.

Thermo-chemical energy storage based on metal hydrides has gained tremendous interest in solar heat storage applications such as concentrated solar power systems (CSP) and parabolic troughs. In such systems, two metal hydride beds are connected and operating in an alternative way as energy storage or hydrogen storage. However, the selection of metal hydrides is essential for a smooth operation of these CSP systems in terms of energy storage efficiency and density. In this study, thermal energy storage systems using metal hydrides are modeled and analyzed in detail using first law of thermodynamics. For these purpose, four conventional metal hydrides are selected namely LaNi5, Mg, Mg2Ni and Mg2FeH6. The comparison of performance is made in terms of volumetric energy storage and energy storage efficiency. The effects of operating conditions (temperature, hydrogen pressure and heat transfer fluid mass flow rates) and reactor design on the aforementioned performance metrics are studied and discussed in detail. The preliminary results showed that Mg-based hydrides store energy ranging from 1.3 to 2.4 GJ m−3 while the energy storage can be as low as 30% due to their slow intrinsic kinetics. On the other hand, coupling Mg-based hydrides with LaNi5 allow us to recover heat at a useful temperature above 330 K with low energy density ca.500 MJ m−3 provided suitable operating conditions are selected. The results of this study will be helpful to screen out all potentially viable hydrides materials for heat storage applications.

Heat storage systems based on two-tank thermochemical heat storage are gaining momentum for their utilization in solar power plants or industrial waste heat recovery since they can efficiently store heat for future usage. However, their performance is generally limited by reactor configuration, design, and optimization on the one hand and most importantly on the selection of appropriate thermochemical materials. Metal hydrides, although at the early stage of research and development (in heat storage applications), can offer several advantages over other thermochemical materials (salt hydrates, metal hydroxides, oxide, and carbonates) such as high energy storage density and power density. This study presents a system that combines latent heat and thermochemical heat storage based on two-tank metal hydrides. The systems consist of two metal hydrides tanks coupled and equipped with a phase change material (PCM) jacket. During the heat charging process, the high-temperature metal hydride (HTMH) desorbs hydrogen, which is stored in the low-temperature metal hydride (LTMH). In the meantime, the heat generated from hydrogen absorption in the LTMH tank is stored as latent heat in a phase change material (PCM) jacket surrounding the LTMH tank, to be reused during the heat discharging. A 2D axis-symmetric mathematical model was developed to investigate the heat and mass transfer phenomena inside the beds and the PCM jacket. The effects of the thermo-physical properties of the PCM and the PCM jacket size on the performance indicators (energy density, power output, and energy recovery efficiency) of the heat storage system are analyzed and discussed. The results showed that the PCM melting point, the latent heat of fusion, the density and the thermal conductivity had significant impacts on these performance indicators.

The effects of a small amount of nonmetal elements (N, F and Cl) with high electronegativity interstitially doping on improving the hydrogen storage characteristics of Mg-based metal hydrides were systematically investigated by first-principle calculations in this paper. The interstitial positions which the doping elements easily occupied were firstly determined. The calculation results showed that these elements are most likely to hold the center position of octahedral sites with two Ni and four Mg atoms. Based on this, the crystal structures, thermal stability, dehydrogenation energy and electronic structures of all the crystals, including Mg2Ni, Mg2NiN0.5, Mg2NiF0.5, Mg2NiCl0.5 and their hydrides, were further investigated. The nonmetals with high electronegativity exhibit the favorable effects on the characteristics of Mg-based metal hydrides. Doping F significantly reduces the dehydrogenation energy of Mg2NiH4 by about 25%, because of the strong hybridization between F and H atoms. When doping Cl into Mg2Ni and Mg2NiH4, the formation enthalpies decrease respectively by 0.047 and 0.024 eV atom−1, due to the reduction of integral intensity of the bonding electron. Among the three elements, N has the best effects on improving both kinetics and thermodynamics. Doping N not only causes the formation enthalpies of Mg2Ni and its hydride to decrease by 0.215 and 0.141 eV atom−1 respectively, but also reduces the dehydrogenation energy of Mg2NiH4.

The integration of thermal energy storage systems (TES) in waste-heat recovery applications shows great potential for energy efficiency improvement. In this study, a 2D mathematical model is formulated to analyze the performance of a two-tank thermochemical heat storage system using metal hydrides pair (Mg2Ni/LaNi5), for high-temperature waste heat recovery. Moreover, the system integrates a phase change material (PCM) to store and restore the heat of reaction of LaNi5. The effects of key properties of the PCM on the dynamics of the heat storage system were analyzed. Then, the TES was optimized using a genetic algorithm-based multi-objective optimization tool (NSGA-II), to maximize the power density, the energy density and storage efficiency simultaneously. The results indicate that the melting point Tm and the effective thermal conductivity of the PCM greatly affect the energy storage density and power output. For the range of melting point Tm = 30&ndash, 50 &deg, C used in this study, it was shown that a PCM with Tm = 47&ndash, 49 &deg, C leads to a maximum heat storage performance. Indeed, at that melting point narrow range, the thermodynamic driving force of reaction between metal hydrides during the heat charging and discharging processes is almost equal. The increase in the effective thermal conductivity by the addition of graphite brings about a tradeoff between increasing power output and decreasing the energy storage density. Finally, the hysteresis behavior (the difference between the melting and freezing point) only negatively impacts energy storage and power density during the heat discharging process by up to 9%. This study paves the way for the selection of PCMs for such combined thermochemical-latent heat storage systems.