Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds
Abstract
Abstract The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M I dimeric complexes with M−M bonding, [M 2 (en) 2 ] 2+ , (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor‐type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en) 2 ] 2+ . Here, the facile interconversion between dimeric‐M I and monomeric‐M II intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X‐ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M 2 (en) 2 ] 2+ or [M(en) 2 ] 2+ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M 0 →M 2+ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.
- Authors:
-
- Department of Chemistry Oregon State University Corvallis Oregon 97331-4003 United States
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1631493
- Grant/Contract Number:
- DE SC0010802
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Name: Chemistry - A European Journal Journal Volume: 26 Journal Issue: 36; Journal ID: ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Xu, Wei, Kozma, Karoly, Sha, Tianxiang, Wu, Yi‐Jen, Nyman, May, and Lerner, Michael M. Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds. Germany: N. p., 2020.
Web. doi:10.1002/chem.202000504.
Xu, Wei, Kozma, Karoly, Sha, Tianxiang, Wu, Yi‐Jen, Nyman, May, & Lerner, Michael M. Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds. Germany. https://doi.org/10.1002/chem.202000504
Xu, Wei, Kozma, Karoly, Sha, Tianxiang, Wu, Yi‐Jen, Nyman, May, and Lerner, Michael M. Tue .
"Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds". Germany. https://doi.org/10.1002/chem.202000504.
@article{osti_1631493,
title = {Reversible M−M Bonding by Alkaline Earth Metals (Mg, Ca, Sr, Ba) in Graphite Intercalation Compounds},
author = {Xu, Wei and Kozma, Karoly and Sha, Tianxiang and Wu, Yi‐Jen and Nyman, May and Lerner, Michael M.},
abstractNote = {Abstract The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M I dimeric complexes with M−M bonding, [M 2 (en) 2 ] 2+ , (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor‐type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en) 2 ] 2+ . Here, the facile interconversion between dimeric‐M I and monomeric‐M II intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X‐ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M 2 (en) 2 ] 2+ or [M(en) 2 ] 2+ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M 0 →M 2+ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.},
doi = {10.1002/chem.202000504},
journal = {Chemistry - A European Journal},
number = 36,
volume = 26,
place = {Germany},
year = {Tue Jun 02 00:00:00 EDT 2020},
month = {Tue Jun 02 00:00:00 EDT 2020}
}
https://doi.org/10.1002/chem.202000504
Web of Science
Works referenced in this record:
Stable Adducts of a Dimeric Magnesium(I) Compound
journal, November 2008
- Green, Shaun P.; Jones, Cameron; Stasch, Andreas
- Angewandte Chemie, Vol. 120, Issue 47
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries
journal, September 2000
- Poizot, P.; Laruelle, S.; Grugeon, S.
- Nature, Vol. 407, Issue 6803, p. 496-499
Energy-band structure and charge distribution for BaC6
journal, April 1983
- Holzwarth, N. A. W.; Divincenzo, D. P.; Tatar, R. C.
- International Journal of Quantum Chemistry, Vol. 23, Issue 4
Stable and High‐Power Calcium‐Ion Batteries Enabled by Calcium Intercalation into Graphite
journal, November 2019
- Park, Jooha; Xu, Zheng‐Long; Yoon, Gabin
- Advanced Materials, Vol. 32, Issue 4
Experimental Electron Density Study of the Mg−Mg Bonding Character in a Magnesium(I) Dimer
journal, April 2009
- Overgaard, Jacob; Jones, Cameron; Stasch, Andreas
- Journal of the American Chemical Society, Vol. 131, Issue 12
Electrochemical formation of graphite intercalation compound in magnesium chloride-dimethylsulphoxide solution
journal, May 1988
- Maeda, Y.; Touzain, Ph.; Bonnetain, L.
- Synthetic Metals, Vol. 24, Issue 3
Aqueous Li-ion battery enabled by halogen conversion–intercalation chemistry in graphite
journal, May 2019
- Yang, Chongyin; Chen, Ji; Ji, Xiao
- Nature, Vol. 569, Issue 7755
Graphite as a Long‐Life Ca 2+ ‐Intercalation Anode and its Implementation for Rocking‐Chair Type Calcium‐Ion Batteries
journal, October 2019
- Richard Prabakar, S. J.; Ikhe, Amol Bhairuba; Park, Woon Bae
- Advanced Science, Vol. 6, Issue 24
Cointercalation of Mg 2+ Ions into Graphite for Magnesium-Ion Batteries
journal, May 2018
- Kim, Dong-Min; Jung, Sung Chul; Ha, Seongmin
- Chemistry of Materials, Vol. 30, Issue 10
Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries
journal, January 2018
- Yu, Seung-Ho; Feng, Xinran; Zhang, Na
- Accounts of Chemical Research, Vol. 51, Issue 2
Stable dimeric magnesium(i) compounds: from chemical landmarks to versatile reagents
journal, January 2011
- Stasch, Andreas; Jones, Cameron
- Dalton Transactions, Vol. 40, Issue 21
Ball milling: a new route for the synthesis of superdense lithium GICs
journal, October 2001
- Janot, Raphaël; Conard, Jacques; Guérard, Daniel
- Carbon, Vol. 39, Issue 12
Molecular Magnesium(I) Compounds: From Curiosity to Kudos
journal, March 2008
- Westerhausen, Matthias
- Angewandte Chemie International Edition, Vol. 47, Issue 12
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions
journal, March 2013
- Juhás, P.; Davis, T.; Farrow, C. L.
- Journal of Applied Crystallography, Vol. 46, Issue 2
Lithium ion battery applications of molybdenum disulfide (MoS 2 ) nanocomposites
journal, January 2014
- Stephenson, Tyler; Li, Zhi; Olsen, Brian
- Energy Environ. Sci., Vol. 7, Issue 1
Neutron scattering study of the high-energy graphitic phonons in superconducting
journal, July 2010
- Dean, M. P. M.; Walters, A. C.; Howard, C. A.
- Physical Review B, Vol. 82, Issue 1
Neutron-diffraction studies of : c -axis compressibility, carbon – carbon bond length, and charge transfer
journal, September 1987
- Fischer, J. E.; Kim, H. J.; Cajipe, V. B.
- Physical Review B, Vol. 36, Issue 8
Intercalation behaviour of magnesium into natural graphite using organic electrolyte systems
journal, January 2017
- God, C.; Bitschnau, B.; Kapper, K.
- RSC Advances, Vol. 7, Issue 23
Nonadiabatic phonons within the doped graphene layers of compounds
journal, January 2010
- Dean, Mark P. M.; Howard, Christopher A.; Saxena, Siddharth S.
- Physical Review B, Vol. 81, Issue 4
A Dimeric Magnesium(I) Compound as a Facile Two-Center/Two-Electron Reductant
journal, March 2009
- Bonyhady, Simon J.; Green, Shaun P.; Jones, Cameron
- Angewandte Chemie International Edition, Vol. 48, Issue 16
Solid Lithium-Silicon Electrode
journal, January 1976
- Lai, San-Cheng
- Journal of The Electrochemical Society, Vol. 123, Issue 8
Multi-ion strategies towards emerging rechargeable batteries with high performance
journal, December 2019
- Liu, Qirong; Wang, Haitao; Jiang, Chunlei
- Energy Storage Materials, Vol. 23
Stable Magnesium(I) Compounds with Mg-Mg Bonds
journal, December 2007
- Green, S. P.; Jones, C.; Stasch, A.
- Science, Vol. 318, Issue 5857
Mapping the Challenges of Magnesium Battery
journal, April 2016
- Song, Jaehee; Sahadeo, Emily; Noked, Malachi
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
Barium intra-atomic reconfiguration in
journal, September 1984
- Preil, M. E.; Fischer, J. E.; DiCenzo, S. B.
- Physical Review B, Vol. 30, Issue 6
Reversible Formation and Decomposition of LiF Clusters Using Transition Metal Fluorides as Precursors and Their Application in Rechargeable Li Batteries
journal, May 2003
- Li, H.; Richter, G.; Maier, J.
- Advanced Materials, Vol. 15, Issue 9
Dependence of Lithium-Silicon Electrode Potential and Lithium Utilization on Reference Electrode Location
journal, January 1980
- Seefurth, Randall N.
- Journal of The Electrochemical Society, Vol. 127, Issue 5
Metallic anodes for next generation secondary batteries
journal, January 2013
- Kim, Hansu; Jeong, Goojin; Kim, Young-Ugk
- Chemical Society Reviews, Vol. 42, Issue 23
Electrochemical behavior of superdense ‘LiC2’ prepared by ball-milling
journal, April 2003
- Tossici, R.; Janot, R.; Nobili, F.
- Electrochimica Acta, Vol. 48, Issue 10
Contribution of X-ray Photoelectron Spectroscopy to the Study of the Electrochemical Reactivity of CoO toward Lithium
journal, March 2004
- Dedryvère, R.; Laruelle, S.; Grugeon, S.
- Chemistry of Materials, Vol. 16, Issue 6
New synthesis routes for donor-type graphite intercalation compounds
journal, June 1996
- Hérold, C.; Hérold, A.; Lagrange, P.
- Journal of Physics and Chemistry of Solids, Vol. 57, Issue 6-8
Stable Adducts of a Dimeric Magnesium(I) Compound
journal, November 2008
- Green, Shaun P.; Jones, Cameron; Stasch, Andreas
- Angewandte Chemie International Edition, Vol. 47, Issue 47
A New and Facile Route Using Electride Solutions To Intercalate Alkaline Earth Ions into Graphite
journal, September 2018
- Xu, Wei; Lerner, Michael M.
- Chemistry of Materials, Vol. 30, Issue 19
Investigation of Lithium Utilization from A Lithium-Silicon Electrode
journal, January 1977
- Seefurth, Randall N.
- Journal of The Electrochemical Society, Vol. 124, Issue 8
Effect of the Addition of Bivalent Ions on Electrochemical Lithium-Ion Intercalation at Graphite Electrodes
journal, January 2016
- Takeuchi, Saya; Kokumai, Ryohei; Nagata, Shingo
- Journal of The Electrochemical Society, Vol. 163, Issue 8
Synthesis and XPS investigation of superdense lithium-graphite intercalation compound, LiC2
journal, July 1996
- Mordkovich, V. Z.
- Synthetic Metals, Vol. 80, Issue 3
Confession of a Magnesium Battery
journal, August 2015
- Bucur, Claudiu B.; Gregory, Thomas; Oliver, Allen G.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
A Dimeric Magnesium(I) Compound as a Facile Two-Center/Two-Electron Reductant
journal, March 2009
- Bonyhady, Simon J.; Green, Shaun P.; Jones, Cameron
- Angewandte Chemie, Vol. 121, Issue 16
Molekulare Magnesium(I)-Verbindungen – mehr als nur eine Laborkuriosität
journal, March 2008
- Westerhausen, Matthias
- Angewandte Chemie, Vol. 120, Issue 12