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Title: Morphology-dependent stability of complex metal hydrides and their intermediates using first-principles calculations

Abstract

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.

Authors:
 [1];  [1];  [2];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1502451
Alternate Identifier(s):
OSTI ID: 1503912
Report Number(s):
SAND-2018-13649J
Journal ID: ISSN 1439-4235; 670639
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Name: ChemPhysChem; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kang, ShinYoung, Heo, Tae Wook, Allendorf, Mark D., and Wood, Brandon C. Morphology-dependent stability of complex metal hydrides and their intermediates using first-principles calculations. United States: N. p., 2019. Web. doi:10.1002/cphc.201801132.
Kang, ShinYoung, Heo, Tae Wook, Allendorf, Mark D., & Wood, Brandon C. Morphology-dependent stability of complex metal hydrides and their intermediates using first-principles calculations. United States. doi:10.1002/cphc.201801132.
Kang, ShinYoung, Heo, Tae Wook, Allendorf, Mark D., and Wood, Brandon C. Mon . "Morphology-dependent stability of complex metal hydrides and their intermediates using first-principles calculations". United States. doi:10.1002/cphc.201801132.
@article{osti_1502451,
title = {Morphology-dependent stability of complex metal hydrides and their intermediates using first-principles calculations},
author = {Kang, ShinYoung and Heo, Tae Wook and Allendorf, Mark D. and Wood, Brandon C.},
abstractNote = {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.},
doi = {10.1002/cphc.201801132},
journal = {ChemPhysChem},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
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