Ultrafast bulk diffusion of AlHx in high-entropy dehydrogenation intermediates of NaAlH4 [Highly mobile AlHx species and the dehydogenation kinetics of NaAlH4]

Zhang, Feng; Wood, Brandon C.; Wang, Yan; Wang, Cai -Zhuang; Ho, Kai -Ming; Chou, Mei -Yin

doi:10.1021/jp504550m

Title: Ultrafast bulk diffusion of AlH_x in high-entropy dehydrogenation intermediates of NaAlH₄ [Highly mobile AlH_x species and the dehydogenation kinetics of NaAlH₄]

Journal Article · Mon Jul 21 00:00:00 EDT 2014 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp504550m· OSTI ID:1325879

Zhang, Feng ^[1]; Wood, Brandon C. ^[2]; Wang, Yan ^[3]; Wang, Cai -Zhuang ^[4]; Ho, Kai -Ming ^[4]; Chou, Mei -Yin ^[5]

Georgia Inst. of Technology, Atlanta, GA (United States); Ames Lab., Ames, IA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Georgia Inst. of Technology, Atlanta, GA (United States)
Ames Lab., Ames, IA (United States)
Georgia Inst. of Technology, Atlanta, GA (United States); Academia Sinica, Taipei (Taiwan)

Using first-principles molecular dynamics (FPMD) and total-energy calculations, we demonstrate low-barrier bulk diffusion of Al-bearing species in γ-NaAlH₄, a recently proposed high-entropy polymorph of NaAlH₄. For charged AlH₄– and neutral AlH₃ vacancies, the computed barriers for diffusion are <0.1 eV, and we directly observe the predicted diffusive pathways in FPMD simulations at picosecond time scales. In contrast, such diffusion in the α phase is inaccessible to FPMD, consistent with much higher barriers. The transport behavior of γ-NaAlH₄, in addition to key dynamical and structural signatures, is consistent with experimental observations of high-mobility species, strongly supporting the idea that an intermediate transition from the α phase to a high-entropy polymorph facilitates the hydrogen-releasing decomposition of NaAlH4. Lastly, our results provide an answer to longstanding questions regarding the responsible agent for the experimentally observed efficient Al transport during dehydrogenation and suggest that mass transport and phase transformation kinetics are coupled. Implications for understanding the (de)hydrogenation of undoped and catalyzed NaAlH₄ are discussed.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1325879

Report Number(s):: LLNL-JRNL-644033

Journal Information:: Journal of Physical Chemistry. C, Vol. 118, Issue 32; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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Title: Ultrafast bulk diffusion of AlHx in high-entropy dehydrogenation intermediates of NaAlH4 [Highly mobile AlHx species and the dehydogenation kinetics of NaAlH4]

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Title: Ultrafast bulk diffusion of AlH_x in high-entropy dehydrogenation intermediates of NaAlH₄ [Highly mobile AlH_x species and the dehydogenation kinetics of NaAlH₄]