First-principles calculated decomposition pathways for LiBH4 nanoclusters
Abstract
Here, we analyze thermodynamic stability and decomposition pathways of LiBH4 nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH4)n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li)n, (B)n, (LiB)n, (LiH)n, and Li2BnHn; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathways markedly differ from those in bulk LiBH4. While experiments have found that the bulk material decomposes into LiH and B, with Li2B12H12 as a kinetically inhibited intermediate phase, (LiBH4)n nanoclusters with n ≤ 12 are predicted to decompose into mixed LinBn clusters via a series of intermediate clusters of LinBnHm (m ≤ 4n). The calculated pressure-composition isotherms and temperature-pressure isobars exhibit sloping plateaus due to finite size effects on reaction thermodynamics. Generally, decomposition temperatures of free-standing clusters are found to increase with decreasing cluster size due to thermodynamic destabilization of reaction products.
- Authors:
-
- National Sun Yat-Sen Univ., Kaohsiung (Taiwan). Dept. of Physics
- Univ. of Missouri-St. Louis, St. Louis, MO (United States). Center for Nanoscience and Dept. of Physics and Astronomy
- Univ. of California Los Angeles, Los Angeles, CA (United States). Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- National Sun Yat-Sen Univ., Kaohsiung (Taiwan)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1283014
- Grant/Contract Number:
- FG02-07ER46433; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 6; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; reversible hydrogen storage; nanoporous carbon; lithium clusters; b-n; destabilization; release; dehydrogenation; nanoparticles; desorption; stability
Citation Formats
Huang, Zhi -Quan, Chen, Wei -Chih, Chuang, Feng -Chuan, Majzoub, Eric H., and Ozolins, Vidvuds. First-principles calculated decomposition pathways for LiBH4 nanoclusters. United States: N. p., 2016.
Web. doi:10.1038/srep26056.
Huang, Zhi -Quan, Chen, Wei -Chih, Chuang, Feng -Chuan, Majzoub, Eric H., & Ozolins, Vidvuds. First-principles calculated decomposition pathways for LiBH4 nanoclusters. United States. https://doi.org/10.1038/srep26056
Huang, Zhi -Quan, Chen, Wei -Chih, Chuang, Feng -Chuan, Majzoub, Eric H., and Ozolins, Vidvuds. Wed .
"First-principles calculated decomposition pathways for LiBH4 nanoclusters". United States. https://doi.org/10.1038/srep26056. https://www.osti.gov/servlets/purl/1283014.
@article{osti_1283014,
title = {First-principles calculated decomposition pathways for LiBH4 nanoclusters},
author = {Huang, Zhi -Quan and Chen, Wei -Chih and Chuang, Feng -Chuan and Majzoub, Eric H. and Ozolins, Vidvuds},
abstractNote = {Here, we analyze thermodynamic stability and decomposition pathways of LiBH4 nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH4)n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li)n, (B)n, (LiB)n, (LiH)n, and Li2BnHn; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathways markedly differ from those in bulk LiBH4. While experiments have found that the bulk material decomposes into LiH and B, with Li2B12H12 as a kinetically inhibited intermediate phase, (LiBH4)n nanoclusters with n ≤ 12 are predicted to decompose into mixed LinBn clusters via a series of intermediate clusters of LinBnHm (m ≤ 4n). The calculated pressure-composition isotherms and temperature-pressure isobars exhibit sloping plateaus due to finite size effects on reaction thermodynamics. Generally, decomposition temperatures of free-standing clusters are found to increase with decreasing cluster size due to thermodynamic destabilization of reaction products.},
doi = {10.1038/srep26056},
journal = {Scientific Reports},
number = ,
volume = 6,
place = {United States},
year = {Wed May 18 00:00:00 EDT 2016},
month = {Wed May 18 00:00:00 EDT 2016}
}
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Works referenced in this record:
Improvement of the LiBH4 hydrogen desorption by inclusion into mesoporous carbons
journal, April 2009
- Cahen, S.; Eymery, J. -B.; Janot, R.
- Journal of Power Sources, Vol. 189, Issue 2
Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions
journal, March 2009
- Nguyen, Minh Tho; Matus, Myrna H.; Ngan, Vu Thi
- The Journal of Physical Chemistry A, Vol. 113, Issue 17
Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials
journal, May 1997
- Bogdanović, Borislav; Schwickardi, Manfred
- Journal of Alloys and Compounds, Vol. 253-254, p. 1-9
Reversible Storage of Hydrogen in Destabilized LiBH 4
journal, March 2005
- Vajo, John J.; Skeith, Sky L.; Mertens, Florian
- The Journal of Physical Chemistry B, Vol. 109, Issue 9
Molecular geometry optimization with a genetic algorithm
text, January 1995
- Deaven, D. M.; Ho, K. M.
- arXiv
Nanoconfinement of lithium borohydride in Cu-MOFs towards low temperature dehydrogenation
journal, January 2011
- Sun, Weiwei; Li, Shaofeng; Mao, Jianfeng
- Dalton Transactions, Vol. 40, Issue 21
Hydrogen-storage materials for mobile applications
journal, November 2001
- Schlapbach, Louis; Züttel, Andreas
- Nature, Vol. 414, Issue 6861
First-Principles Study of LiBH 4 Nanoclusters and Their Hydrogen Storage Properties
journal, August 2012
- Hazrati, Ebrahim; Brocks, Geert; de Wijs, Gilles A.
- The Journal of Physical Chemistry C, Vol. 116, Issue 34
Systematic ab initio investigation of bare boron clusters:mDetermination of the geometryand electronic structures of (n=2–14)
journal, June 1997
- Boustani, Ihsan
- Physical Review B, Vol. 55, Issue 24
Thermochemistry and Electronic Structure of Small Boron Clusters (B n , n = 5−13) and Their Anions
journal, January 2010
- Tai, Truong Ba; Grant, Daniel J.; Nguyen, Minh Tho
- The Journal of Physical Chemistry A, Vol. 114, Issue 2
Effect of Particle Size on Hydrogen Release from Sodium Alanate Nanoparticles
journal, September 2010
- Mueller, Tim; Ceder, Gerbrand
- ACS Nano, Vol. 4, Issue 10
Hydrogen-storage materials for mobile applications
journal, November 2001
- Schlapbach, Louis; Züttel, Andreas
- Nature, Vol. 414, Issue 6861
LiBH4 a new hydrogen storage material
journal, May 2003
- Züttel, A.; Wenger, P.; Rentsch, S.
- Journal of Power Sources, Vol. 118, Issue 1-2
Dehydriding and rehydriding reactions of
journal, December 2005
- Orimo, S.; Nakamori, Y.; Kitahara, G.
- Journal of Alloys and Compounds, Vol. 404-406
Stability and Reversibility of LiBH 4
journal, January 2008
- Mauron, Philippe; Buchter, Florian; Friedrichs, Oliver
- The Journal of Physical Chemistry B, Vol. 112, Issue 3
Diborane Release from LiBH 4 /Silica-Gel Mixtures and the Effect of Additives
journal, August 2007
- Kostka, J.; Lohstroh, W.; Fichtner, M.
- The Journal of Physical Chemistry C, Vol. 111, Issue 37
Stability and Reversibility of Lithium Borohydrides Doped by Metal Halides and Hydrides
journal, October 2008
- Au, Ming; Jurgensen, Arthur R.; Spencer, William A.
- The Journal of Physical Chemistry C, Vol. 112, Issue 47
Remarkable irreversible and reversible dehydrogenation of LiBH4 by doping with nanosized cobalt metalloid compounds
journal, March 2013
- Cai, Weitong; Wang, Hui; Jiao, Lifang
- International Journal of Hydrogen Energy, Vol. 38, Issue 8
Nanoconfinement of lithium borohydride in Cu-MOFs towards low temperature dehydrogenation
journal, January 2011
- Sun, Weiwei; Li, Shaofeng; Mao, Jianfeng
- Dalton Transactions, Vol. 40, Issue 21
Metals (Ni, Fe)-Incorporated Titanate Nanotubes Induced Destabilization of LiBH4
journal, April 2011
- Si, Xiaoliang; Li, Fen; Sun, Lixian
- The Journal of Physical Chemistry C, Vol. 115, Issue 19
Reaction of hydrogen with alloys of magnesium and copper
journal, December 1967
- Reilly, James J.; Wiswall, Richard H.
- Inorganic Chemistry, Vol. 6, Issue 12
Reaction of hydrogen with alloys of magnesium and nickel and the formation of Mg2NiH4
journal, November 1968
- Reilly, James J.; Wiswall, Richard H.
- Inorganic Chemistry, Vol. 7, Issue 11
Reaction energetics and crystal structure of from first principles
journal, January 2007
- Siegel, Donald J.; Wolverton, C.; Ozoliņš, V.
- Physical Review B, Vol. 75, Issue 1
Reversible Storage of Hydrogen in Destabilized LiBH 4
journal, March 2005
- Vajo, John J.; Skeith, Sky L.; Mertens, Florian
- The Journal of Physical Chemistry B, Vol. 109, Issue 9
Confined LiBH4: Enabling fast hydrogen release at ∼100 °C
journal, December 2012
- Sun, Tai; Liu, Jian; Jia, Yi
- International Journal of Hydrogen Energy, Vol. 37, Issue 24
Enhanced desorption properties of LiBH4 incorporated into mesoporous TiO2
journal, January 2013
- Guo, Lijing; Jiao, Lifang; Li, Li
- International Journal of Hydrogen Energy, Vol. 38, Issue 1
LiBH4LiBH4 nanoparticles supported by disordered mesoporous carbon: Hydrogen storage performances and destabilization mechanisms
journal, November 2007
- Zhang, Y.; Zhang, W.; Wang, A.
- International Journal of Hydrogen Energy, Vol. 32, Issue 16
Enhanced Hydrogen Storage Kinetics of LiBH4 in Nanoporous Carbon Scaffolds
journal, March 2008
- Gross, Adam F.; Vajo, John J.; Van Atta, Sky L.
- The Journal of Physical Chemistry C, Vol. 112, Issue 14, p. 5651-5657
Kinetic- and thermodynamic-based improvements of lithium borohydride incorporated into activated carbon
journal, December 2008
- Fang, Z. Z.; Wang, P.; Rufford, T. E.
- Acta Materialia, Vol. 56, Issue 20
Improvement of the LiBH4 hydrogen desorption by inclusion into mesoporous carbons
journal, April 2009
- Cahen, S.; Eymery, J. -B.; Janot, R.
- Journal of Power Sources, Vol. 189, Issue 2
Destabilization of LiBH4 by nanoconfinement in PMMA–co–BM polymer matrix for reversible hydrogen storage
journal, March 2014
- Gosalawit-Utke, Rapee; Meethom, Sukanya; Pistidda, Claudio
- International Journal of Hydrogen Energy, Vol. 39, Issue 10
Superior dehydrogenation performance of nanoscale lithium borohydride modified with fluorographite
journal, January 2014
- Zhang, Liuting; Chen, Lixin; Xiao, Xuezhang
- International Journal of Hydrogen Energy, Vol. 39, Issue 2
Reversibility of the hydrogen desorption from LiBH4: a synergetic effect of nanoconfinement and Ni addition
journal, January 2009
- Ngene, Peter; van Zwienen, M. (Rien); de Jongh, Petra E.
- Chemical Communications, Vol. 46, Issue 43
Research progress in LiBH4 for hydrogen storage: A review
journal, November 2011
- Li, C.; Peng, P.; Zhou, D. W.
- International Journal of Hydrogen Energy, Vol. 36, Issue 22
Controlling the Decomposition Pathway of LiBH 4 via Confinement in Highly Ordered Nanoporous Carbon
journal, July 2010
- Liu, Xiangfeng; Peaslee, David; Jost, C. Z.
- The Journal of Physical Chemistry C, Vol. 114, Issue 33
Systematic Pore-Size Effects of Nanoconfinement of LiBH 4 : Elimination of Diborane Release and Tunable Behavior for Hydrogen Storage Applications
journal, March 2011
- Liu, Xiangfeng; Peaslee, David; Jost, Christopher Z.
- Chemistry of Materials, Vol. 23, Issue 5
First-Principles Study of LiBH 4 Nanoclusters and Their Hydrogen Storage Properties
journal, August 2012
- Hazrati, Ebrahim; Brocks, Geert; de Wijs, Gilles A.
- The Journal of Physical Chemistry C, Vol. 116, Issue 34
Effects of a Carbon Surface Environment on the Decomposition Properties of Nanoparticle LiBH 4 : A First-Principles Study
journal, April 2014
- Mason, Tim; Majzoub, E. H.
- The Journal of Physical Chemistry C, Vol. 118, Issue 17
First-Principles Calculated Phase Diagram for Nanoclusters in the Na−Al−H System: A Single-Step Decomposition Pathway for NaAlH 4
journal, January 2011
- Majzoub, E. H.; Zhou, Fei; Ozoliņš, V.
- The Journal of Physical Chemistry C, Vol. 115, Issue 6
First-Principles Prediction of Thermodynamically Reversible Hydrogen Storage Reactions in the Li-Mg-Ca-B-H System
journal, January 2009
- Ozolins, V.; Majzoub, E. H.; Wolverton, C.
- Journal of the American Chemical Society, Vol. 131, Issue 1
Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions
journal, March 2009
- Nguyen, Minh Tho; Matus, Myrna H.; Ngan, Vu Thi
- The Journal of Physical Chemistry A, Vol. 113, Issue 17
Thermochemistry and Electronic Structure of Small Boron Clusters (B n , n = 5−13) and Their Anions
journal, January 2010
- Tai, Truong Ba; Grant, Daniel J.; Nguyen, Minh Tho
- The Journal of Physical Chemistry A, Vol. 114, Issue 2
Density functional theory study of some structural and energetic properties of small lithium clusters
journal, December 1996
- Gardet, Georges; Rogemond, François; Chermette, Henry
- The Journal of Chemical Physics, Vol. 105, Issue 22
Theoretical study of the structure of lithium clusters
journal, November 2003
- Fournier, René; Bo Yi Cheng, Joey; Wong, Anna
- The Journal of Chemical Physics, Vol. 119, Issue 18
First-principles insight into the degeneracy of ground-state LiBH structures
journal, September 2012
- Zhang, Yongsheng; Wang, Yongli; Michel, Kyle
- Physical Review B, Vol. 86, Issue 9
Lithium boro-hydride LiBH4
journal, November 2002
- Soulié, J-Ph; Renaudin, G.; Černý, R.
- Journal of Alloys and Compounds, Vol. 346, Issue 1-2
Crystal structure and morphology of a new compound, LiB
journal, October 2000
- Liu, Zhijian; Qu, Xuanhui; Huang, Baiyun
- Journal of Alloys and Compounds, Vol. 311, Issue 2
Effect of Particle Size on Hydrogen Release from Sodium Alanate Nanoparticles
journal, September 2010
- Mueller, Tim; Ceder, Gerbrand
- ACS Nano, Vol. 4, Issue 10
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Molecular Geometry Optimization with a Genetic Algorithm
journal, July 1995
- Deaven, D. M.; Ho, K. M.
- Physical Review Letters, Vol. 75, Issue 2
Structures of medium-sized silicon clusters
journal, April 1998
- Ho, Kai-Ming; Shvartsburg, Alexandre A.; Pan, Bicai
- Nature, Vol. 392, Issue 6676
Structure of neutral aluminum clusters : Genetic algorithm tight-binding calculations
journal, March 2006
- Chuang, Feng-Chuan; Wang, C. Z.; Ho, K. H.
- Physical Review B, Vol. 73, Issue 12
Prototype electrostatic ground state approach to predicting crystal structures of ionic compounds: Application to hydrogen storage materials
journal, March 2008
- Majzoub, E. H.; Ozoliņš, V.
- Physical Review B, Vol. 77, Issue 10