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MgH2-based hydrogen storage materials are promising candidates for solid-state hydrogen storage allowing efficient thermal management in energy systems integrating metal hydride hydrogen store with a solid oxide fuel cell (SOFC) providing dissipated heat at temperatures between 400 and 600 °C. Recently, we have shown that graphite-modified composite of TiH2 and MgH2 prepared by high-energy reactive ball milling in hydrogen (HRBM), demonstrates a high reversible gravimetric H storage capacity exceeding 5 wt % H, fast hydrogenation/dehydrogenation kinetics and excellent cycle stability. In present study, 0.9 MgH2 + 0.1 TiH2 +5 wt %C nanocomposite with a maximum hydrogen storage capacity of 6.3 wt% H was prepared by HRBM preceded by a short homogenizing pre-milling in inert gas. 300 g of the composite was loaded into a storage tank accommodating an air-heated stainless steel metal hydride (MH) container equipped with transversal internal (copper) and external (aluminium) fins. Tests of the tank were carried out in a temperature range from 150 °C (H2 absorption) to 370 °C (H2 desorption) and showed its ability to deliver up to 185 NL H2 corresponding to a reversible H storage capacity of the MH material of appr. 5 wt% H. No significant deterioration of the reversible H storage capacity was observed during 20 heating/cooling H2 discharge/charge cycles. It was found that H2 desorption performance can be tailored by selecting appropriate thermal management conditions and an optimal operational regime has been proposed.

The strong interactions between Mg and Ni/NiH4 are attributed to harsh operating conditions and difficulties for H2 release, restricting the practical applications of the Mg-based hydrides. In this study, a new method of interstitial nonmetals co-doping was proposed to reduce the strong interactions. The calculation results showed that the method of interstitial nonmetals co-doping causes a more significant reduction in the thermal stability of Mg-based hydrides, as compared with the methods of either single transition metal or nonmetal doping. To determine the influence mechanism, a theoretical study was conducted based on the first-principles calculations. The computations demonstrated that the criss-cross action between B–Ni and N–Mg bonds weakens the bonding effects between Mg and Ni/NiH4. Besides, the mutual interactions between nonmetals and H atoms could weaken Ni–H bonding effects and stimulate the breaking of stable NiH4 clusters, thereby facilitating the release of H2 from the hydride.

In energy systems, multi-generation including co-generation and tri-generation has gained tremendous interest in the recent years as an effective way of waste heat recovery. Solid oxide fuel cells are efficient power plants that not only generate electricity with high energy efficiency but also produce high quality waste heat that can be further used for hot and chilled water production. In this work, we present a concept of combined cooling, heating and power (CCHP) energy system which uses solar power as a primary energy source and utilizes a reversible solid oxide fuel cell (R-SOFC) for producing hydrogen and generating electricity in the electrolyser (SOEC) and fuel cell (SOFC) modes, respectively. The system uses “high temperature” metal hydride (MH) for storage of both hydrogen and heat, as well as “low temperature” MH's for the additional heat management, including hot water supply, residential heating during winter time, or cooling/air conditioning during summer time. The work presents evaluation of energy balances of the system components, as well as heat-and-mass transfer modelling of MH beds in metal hydride hydrogen and heat storage system (MHHS; MgH2), MH hydrogen compressor (MHHC; AB5; A = La + Mm, B Ni + Co + Al + Mn) and MH heat pump (MHHP; AB2; A = Ti + Zr, B Mn + Cr + Ni + Fe). A case study of a 3 kWe R-SOFC is analysed and discussed. The results showed that the energy efficiencies are 69.4 and 72.4% in electrolyser and fuel cell modes, respectively. The round-trip COP's of metal hydride heat management system (MHHC + MHHP) are close to 40% for both heating and cooling outputs. Moreover, the tri-generation leads to an improvement of 36% in round-trip energy efficiency as compared to that of a stand-alone R-SOFC.

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 this work, we report about development of computer model of hydrogen Thermal Desorption Spectra (TDS) using a combination of modified Kissinger approach and combined form of differential kinetic equation. For an individual TDS peak, the developed model allows to adequately fit the experimental TDS data using up to 6 parameters, including the activation energy of desorption and the pre-exponent factor. The fitting procedure also allows visualizing the reaction model function using the experimental TDS data. The model was verified for the nanostructured magnesium hydride prepared by high-energy ball milling of magnesium in hydrogen, including its composites with carbon and titanium.

Mg-based materials have become the cornerstone of hydrogen storage applications and have shown recently promises in thermal energy storage applications. However, synthesis of some materials including Mg2FeH6 ternary hydride poses a number of challenges. In spite a variety of reports on various synthesis routes yielding Mg2FeH6, none of them produces a 100% pure Mg2FeH6. In this communication, we have attempted to synthesize Mg2FeH6 by high energy reactive ball milling (HERBM) performed in hydrogen gas. Prior to the ball milling, the starting stoichiometric 2:1 mixture of the initial materials Mg+Fe was heat treated through a judicious temperature program. It was found that the yield of Mg2FeH6 is related to the conditions of heat treatment, time and temperature, and the milling parameters such as ball to powder mass ratio (BPR) and rotation speed of the planetary mill. Moreover, it was found that the synthesis took place in less than 5 hours of milling with a maximum yield of Mg2FeH6 of 84 wt%, which is a noticeable improvement as compared to the reference data.

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.

Mg-based metal hydride is one of the most promising materials for hydrogen energy storage. However, the high thermal stability due to strong bonding effects between the atoms limits its practical application. In order to reduce the thermal stability, a method of doping double nonmetals into Mg-based system was proposed in this study. The density functional theory (DFT) calculation results showed that the thermal stabilities of both the B-N co-doped Mg-based alloy and its hydride are reduced compared with pure Mg-based system. The relative formation enthalpies of the alloy and its hydride are 0.323 and 0.595 eV atom−1, respectively. The values are much higher than those for either singly B- or N-doped Mg-based system. The more significant destabilization by doping double nonmetal elements than single element is mainly attributed to a dual effect in weakening Mg–Ni/NiH4 bonds, caused by criss-cross interactions between B–Ni and N–Mg bonds.

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.