Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates

Cao, Hujun; Richter, Th.; Pistidda, Claudio; Chaudhary, Anna‐Lisa; Santoru, Antonio; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

doi:10.1002/cssc.201500990

Cited by 13 publications

(18 citation statements)

References 37 publications

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“…For some of the investigated systems, outstanding absorption kinetics have been observed. As an example, the product of the decomposition of K 2 [Zn(NH 2 ) 4 ] + 8LiH can be fully hydrogenated within 30 s, as reported in Figure 7, at 230 • C and 50 bar of H 2 [147]. Similar phenomenon was also observed in K 2 [Mn(NH 2 ) 4 ] + 8LiH under the same temperature and hydrogen pressure conditions [148].…”

Section: Ternary Transition Metal Amide-hydride Systemsupporting

confidence: 65%

Recent Progress and New Perspectives on Metal Amide and Imide Systems for Solid-State Hydrogen Storage

et al. 2018

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Hydrogen storage in the solid state represents one of the most attractive and challenging ways to supply hydrogen to a proton exchange membrane (PEM) fuel cell. Although in the last 15 years a large variety of material systems have been identified as possible candidates for storing hydrogen, further efforts have to be made in the development of systems which meet the strict targets of the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) and U.S. Department of Energy (DOE). Recent projections indicate that a system possessing: (i) an ideal enthalpy in the range of 20-50 kJ/mol H 2 , to use the heat produced by PEM fuel cell for providing the energy necessary for desorption; (ii) a gravimetric hydrogen density of 5 wt. % H 2 and (iii) fast sorption kinetics below 110 • C is strongly recommended. Among the known hydrogen storage materials, amide and imide-based mixtures represent the most promising class of compounds for on-board applications; however, some barriers still have to be overcome before considering this class of material mature for real applications. In this review, the most relevant progresses made in the recent years as well as the kinetic and thermodynamic properties, experimentally measured for the most promising systems, are reported and properly discussed.

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Section: Ternary Transition Metal Amide-hydride Systemsupporting

confidence: 65%

Recent Progress and New Perspectives on Metal Amide and Imide Systems for Solid-State Hydrogen Storage

et al. 2018

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“…This particular feature (rehydrogenation rate increases toward the end of the reaction) is 228 preserved upon the following two dehydrogenation/rehydrogenation cycles (Figure 4). Interestingly, 229 the first hydrogenation is faster than the second, which was observed before with a similar system 230 [36]. Usually, hydrogenation of materials are slower at the later stage [47,48].…”

Section: Dehydrogenation/rehydrogenation Properties Upon Cycling 227mentioning

confidence: 64%

“…Also RbH appears to be an excellent additive for enhancing the hydrogen sorption properties of this system [33,34]. Recently, the bimetallic amide-hydride systems K 2 Mn(NH 2 ) 4 + 8LiH and K 2 Zn(NH 2 ) 4 + 8LiH with ultrafast hydrogenation properties were reported by Cao et al [35][36][37]. In these works, extremely fast hydrogenation of as much as 60% of the total H 2 capacity (1.75 wt.%) within 60 seconds was observed.…”

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confidence: 93%

Enhancement Effect of Bimetallic Amide K2Mn(NH2)4 and In-Situ Formed KH and Mn4N on the Dehydrogenation/Hydrogenation Properties of Li–Mg–N–H System

Gizer¹,

Cao

Puszkiel

et al. 2019

Energies

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In this work, we investigated the influence of the K2Mn(NH2)4 additive on the hydrogen sorption properties of the Mg(NH2)2 + 2LiH (Li–Mg–N–H) system. The addition of 5 mol% of K2Mn(NH2)4 to the Li–Mg–N–H system leads to a decrease of the dehydrogenation peak temperature from 200 °C to 172 °C compared to the pristine sample. This sample exhibits a constant hydrogen storage capacity of 4.2 wt.% over 25 dehydrogenation/rehydrogenation cycles. Besides that, the in-situ synchrotron powder X-ray diffraction analysis performed on the as prepared Mg(NH2)2 + 2LiH containing K2Mn(NH2)4 indicates the presence of Mn4N. However, no crystalline K-containing phases were detected. Upon dehydrogenation, the formation of KH is observed. The presence of KH and Mn4N positively influences the hydrogen sorption properties of this system, especially at the later stage of rehydrogenation. Under the applied conditions, hydrogenation of the last 1 wt.% takes place in only 2 min. This feature is preserved in the following three cycles.

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“…The hydrogen absorption of the KZH system starts at about 140 • C. As already reported in ref. [48], the hydrogen absorption of this system is characterized by the presence of an extremely fast absorption step occurring at about 230 • C. In this step, within less than a minute, more than 50% of the overall hydrogen is absorbed. A final absorption step between 230 • C and 300 • C resulted in an overall capacity of 3.0 wt.%.…”

Section: Resultsmentioning

confidence: 99%

“…Zinc possesses chemical properties similar to those of nickel and titanium, which is known to be an effective additive for these systems, therefore the possibility to synthesize ternary amides containing alkali metals and zinc might be considered a good strategy to develop novel amide-based hydrogen storage systems with improved thermodynamic and kinetic properties. In this regard, previous works [47][48][49] on the systems Li 4 Zn(NH 2 ) 6 -12LiH and K 2 Zn(NH 2 ) 4 -8LiH showed extremely promising results, especially for the latter. In fact, the desorbed state of the system K 2 Zn(NH 2 ) 4 -8LiH can be fully rehydrogenated at ca.…”

Section: Introductionmentioning

confidence: 92%

De-hydrogenation/Rehydrogenation Properties and Reaction Mechanism of AmZn(NH2)n-2nLiH Systems (A = Li, K, Na, and Rb)

et al. 2022

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With the aim to find suitable hydrogen storage materials for stationary and mobile applications, multi-cation amide-based systems have attracted considerable attention, due to their unique hydrogenation kinetics. In this work, AmZn(NH2)n (with A = Li, K, Na, and Rb) were synthesized via an ammonothermal method. The synthesized phases were mixed via ball milling with LiH to form the systems AmZn(NH2)n-2nLiH (with m = 2, 4 and n = 4, 6), as well as Na2Zn(NH2)4∙0.5NH3-8LiH. The hydrogen storage properties of the obtained materials were investigated via a combination of calorimetric, spectroscopic, and diffraction methods. As a result of the performed analyses, Rb2Zn(NH2)4-8LiH appears as the most appealing system. This composite, after de-hydrogenation, can be fully rehydrogenated within 30 s at a temperature between 190 °C and 200 °C under a pressure of 50 bar of hydrogen.

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Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates

Cited by 13 publications

References 37 publications

Recent Progress and New Perspectives on Metal Amide and Imide Systems for Solid-State Hydrogen Storage

Recent Progress and New Perspectives on Metal Amide and Imide Systems for Solid-State Hydrogen Storage

Enhancement Effect of Bimetallic Amide K2Mn(NH2)4 and In-Situ Formed KH and Mn4N on the Dehydrogenation/Hydrogenation Properties of Li–Mg–N–H System

De-hydrogenation/Rehydrogenation Properties and Reaction Mechanism of AmZn(NH2)n-2nLiH Systems (A = Li, K, Na, and Rb)

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