Morphology-Dependent Stability of Complex Metal Hydrides and Their Intermediates Using First-Principles Calculations

Kang, ShinYoung; Heo, Tae Wook; Allendorf, Mark D.; Wood, Brandon C.

doi:10.1002/cphc.201801132

Title: Morphology-Dependent Stability of Complex Metal Hydrides and Their Intermediates Using First-Principles Calculations

Journal Article · Mon Mar 18 00:00:00 EDT 2019 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.201801132· OSTI ID:1543076

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Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Complex light metal hydrides are promising candidates for efficient, compact solid-state hydrogen storage. (De)hydrogenation of these materials often proceeds via multiple reaction intermediates, the energetics of which determine reversibility and kinetics. At the solid-state reaction front, molecular-level chemistry eventually drives the formation of bulk product phases. Therefore, a better understanding of realistic (de)hydrogenation behavior requires considering possible reaction products along all stages of morphological evolution, from molecular to bulk crystalline. Here, we use first-principles calculations to explore the interplay between intermediate morphology and reaction pathways. Employing representative complex metal hydride systems, we investigate the relative energetics of three distinct morphological stages that can be expressed by intermediates during solid-state reactions: i) dispersed molecules; ii) clustered molecular chains; and iii) condensed-phase crystals. Our results verify that the effective reaction energy landscape strongly depends on the morphological features and associated chemical environment, offering a possible explanation for observed discrepancies between X-ray diffraction and nuclear magnetic resonance measurements. Our theoretical understanding also provides physical and chemical insight into phase nucleation kinetics upon (de)hydrogenation of complex metal hydrides.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office

Grant/Contract Number:: AC52-07NA27344; AC04-94AL85000

OSTI ID:: 1543076

Alternate ID(s):: OSTI ID: 1502451; OSTI ID: 1503912

Report Number(s):: LLNL-JRNL-763501; SAND-2018-13649J; 953193

Journal Information:: ChemPhysChem, Vol. 20, Issue 10; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Complex metal hydrides
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Title: Morphology-Dependent Stability of Complex Metal Hydrides and Their Intermediates Using First-Principles Calculations

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