Note: Times Cited: 875 Reference EPFL-ARTICLE-206025doi:10.1021/cr0501846View record in Web of Science URL: ://WOS:000249839900009 Record created on 2015-03-03, modified on 2017-05-12

Complex Hydrides for Hydrogen Storage

Hydrogen production for energy: An overview

Hydrogen storage in Mg: A most promising material

This paper provides an insight to the feasibility of adopting hydrogen as a key energy carrier and fuel source in the near future. It is shown that hydrogen has several advantages, as well as few drawbacks in using for the above purposes. The research shows that hydrogen will be a key player in storing energy that is wasted at generation stage in large-scale power grids by off-peak diversion to dummy loads. The estimations show that by the year of 2050 there will be a hydrogen demand of over 42 million metric tons or 45 billion gallon gasoline equivalent (GGE) in the United States of America alone which can fuel up 342 million light-duty vehicles for 51 × 1011 miles (82 × 1011 km) travel per year. The production at distributed level has also been discussed. The paper also presents the levels of risk in production, storage and distribution stages and proposes possible techniques to address safety issues. It is shown that the storage in small to medium scale containers is much economical compared to doing the same at large-scale containers. The study concludes that hydrogen has a promising future to be a highly feasible energy carrier and energy source itself at consumer level.

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Hydrogen as an energy carrier: Prospects and challenges

The possibility of using ammonia as a hydrogen carrier is discussed. Compared to other hydrogen storage materials, ammonia has the advantages of a high hydrogen density, a well-developed technology for synthesis and distribution, and easy catalytic decomposition. Compared to hydrocarbons and alcohols, it has the advantage that there is no CO2 emission at the end user. The drawbacks are mainly the toxicity of liquid ammonia and the problems related to trace amounts of ammonia in the hydrogen after decomposition. Storage of ammonia in metal ammine salts is discussed, and it is shown that this maintains the high volumetric hydrogen density while alleviating the problems of handling the ammonia. Some of the remaining challenges for research in ammonia as a hydrogen carrier are outlined.

Ammonia for hydrogen storage: challenges and opportunities

Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy-storage and conversion-related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation-resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano-MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg2 NiH4 single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas-solid reactions. This well-defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas-selective permeability to prevent further oxidation of Mg2 NiH4 meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol-1 ) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents.

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

State of the art multi-strategy improvement of Mg-based hydrides for hydrogen storage

Magnesium hydride is considered as an ideal candidate for effective hydrogen storage due to its high gravimetric hydrogen capacity and accessibility. But its use as a commercial material is hindered by its relatively high operating temperatures and slow release/uptake kinetics. To solve this, we first synthesized Ni decorated graphene nanoplate (Ni/Gn) catalysts with highly dispersed metal nano-particles (NPs) via a facile method, then the as-prepared Ni/Gn catalysts were introduced by using the hydriding combustion synthesis and mechanical milling (HCS + MM) method to obtain Mg-based composites. Remarkable enhancement of hydrogen sorption rates has been found for these composites in the presence of Ni/Gn additives, especially for the Mg@Ni8Gn2 sample: a hydrogen absorption amount of 6.28 wt% within 100 s at 373 K and a hydrogen desorption amount of 5.73 wt% within 1800 s at 523 K. A rather low activation energy (71.8 kJ mol−1) for the dehydrogenation of MgH2 was determined in the same sample, indicating that relatively moderate temperatures are required to absorb/desorb hydrogen. The excellent hydrogen sorption rates of the composites are thought to be associated with the high dispersity of in situ formed nanometric Mg2NiH4 particles during the HCS + MM process. In addition, a microstrain-induced synergetic hydrogen sorption mechanism is proposed, being correlated by the local introduction of a Mg2Ni nano-catalyst into the Mg matrix.

Nickel-decorated graphene nanoplates for enhanced H2 sorption properties of magnesium hydride at moderate temperatures

Metal nanocatalysis is an effective method to enhance the hydrogen storage properties of magnesium hydride (MgH2), and the catalytic effect can be further improved by a matrix material supported nanometal. In this work, carbon supported nano-Ni (Ni@C) was synthesized by calcination of dimethylglyoxime dinickel chelate, and then it was doped into MgH2 to improve the de/rehydrogenation kinetics. This shows that the homogeneously distributed Ni with refined particle size in carbon base leads to superior catalytic effects on hydrogen absorption/desorption of MgH2-5 wt % Ni@C. The MgH2-5 wt % Ni@C starts to desorb hydrogen at 187 °C, which is 113 °C lower than that of as-milled MgH2. Moreover, it takes only 500 s to thoroughly desorb hydrogen at 300 °C, which is 3000 s faster than as-milled MgH2 under the same dehydrogenation conditions. According to the Kissinger’s method, the apparent activation energy for desorption of the MgH2-5 wt % Ni@C is 66.5 ± 1.8 kJ mol–1, which is about 79.9 kJ mol–1 lower than that...

Facile Synthesis of Carbon Supported Nano-Ni Particles with Superior Catalytic Effect on Hydrogen Storage Kinetics of MgH2

Catalysts play an extraordinarily important role in accelerating the hydrogen sorption rates in metal-hydrogen systems. Herein, we report a surprisingly synergetic enhancement of metal-metal oxide cocatalyst on the hydrogen sorption properties of MgH2: only 5 wt % doping of Ni into ultrafine TiO2 enables a significant increase in hydrogen desorption kinetics; it absorbs 4.50 wt % hydrogen even at a low temperature of 50 °C. The striking improvement is partially ascribed to the formation of a particular Ni@TiO2 core-shell structure, thereby forming versatile interfaces. This study provides insights into the way of designing high-efficiency catalysts in hydrogen storage and other energy-related fields.

Liquan Li

Papers

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement.

State of the art multi-strategy improvement of Mg-based hydrides for hydrogen storage

Nickel-decorated graphene nanoplates for enhanced H2 sorption properties of magnesium hydride at moderate temperatures

Facile Synthesis of Carbon Supported Nano-Ni Particles with Superior Catalytic Effect on Hydrogen Storage Kinetics of MgH2

Remarkable Synergistic Catalysis of Ni-Doped Ultrafine TiO2 on Hydrogen Sorption Kinetics of MgH2