The Local Atomic Structure and Chemical Bonding in Sodium Tin Phases
Abstract
To understand these electrochemically-derived materials we have reinvestigated the formation of Na-Sn alloys to identify all the phases which form when x ≥ 1 (NaxSn) and characterized the local bonding around the Sn atoms with X-ray diffraction, 119Sn M ssbauer spectroscopy, and X-ray absorption spectroscopies. The results from the well-defined crystallographic materials were compared to the spectroscopic measurements of the local Sn structures in the electrochemically prepared materials. The reinvestigation of the Na-Sn compounds yields a number of new results: (i) Na7Sn3 is a new thermodynamically-stable phase with a rhombohedral structure and R-3m space group; (ii) orthorhombic Na9Sn4 (Cmcm) has relatively slow formation kinetics suggesting why it does not form at room temperature during the electrochemical reaction; (iii) orthorhombic Na14.78Sn4 (Pnma), better described as Na16-xSn4, is Na-richer than cubic Na15Sn4 (I-43d). Characterization of electrochemically prepared Na-Sn alloys indicate that, at the exception of Na7Sn3 and Na15Sn4, different crystal structures than similar Na-Sn compositions prepared via classic solid state reactions are formed. These phases are composed of disordered structures characteristic of kinetic-driven solid-state amorphization reactions. In these structures, Sn coordinates in asymmetric environments, which differ significantly from the environments present in Na-Sn model compounds.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. Montpellier II (France)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1185716
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 44; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Baggetto, Loic, Bridges, Craig A., Jumas, Dr. Jean-Claude, Mullins, David R., Carroll, Kyler J., Meisner, Roberta, Crumlin, Ethan, Liu, Xiason, Yang, Wanli, and Veith, Gabriel M. The Local Atomic Structure and Chemical Bonding in Sodium Tin Phases. United States: N. p., 2014.
Web. doi:10.1039/C4TA04356A.
Baggetto, Loic, Bridges, Craig A., Jumas, Dr. Jean-Claude, Mullins, David R., Carroll, Kyler J., Meisner, Roberta, Crumlin, Ethan, Liu, Xiason, Yang, Wanli, & Veith, Gabriel M. The Local Atomic Structure and Chemical Bonding in Sodium Tin Phases. United States. https://doi.org/10.1039/C4TA04356A
Baggetto, Loic, Bridges, Craig A., Jumas, Dr. Jean-Claude, Mullins, David R., Carroll, Kyler J., Meisner, Roberta, Crumlin, Ethan, Liu, Xiason, Yang, Wanli, and Veith, Gabriel M. Thu .
"The Local Atomic Structure and Chemical Bonding in Sodium Tin Phases". United States. https://doi.org/10.1039/C4TA04356A. https://www.osti.gov/servlets/purl/1185716.
@article{osti_1185716,
title = {The Local Atomic Structure and Chemical Bonding in Sodium Tin Phases},
author = {Baggetto, Loic and Bridges, Craig A. and Jumas, Dr. Jean-Claude and Mullins, David R. and Carroll, Kyler J. and Meisner, Roberta and Crumlin, Ethan and Liu, Xiason and Yang, Wanli and Veith, Gabriel M.},
abstractNote = {To understand these electrochemically-derived materials we have reinvestigated the formation of Na-Sn alloys to identify all the phases which form when x ≥ 1 (NaxSn) and characterized the local bonding around the Sn atoms with X-ray diffraction, 119Sn M ssbauer spectroscopy, and X-ray absorption spectroscopies. The results from the well-defined crystallographic materials were compared to the spectroscopic measurements of the local Sn structures in the electrochemically prepared materials. The reinvestigation of the Na-Sn compounds yields a number of new results: (i) Na7Sn3 is a new thermodynamically-stable phase with a rhombohedral structure and R-3m space group; (ii) orthorhombic Na9Sn4 (Cmcm) has relatively slow formation kinetics suggesting why it does not form at room temperature during the electrochemical reaction; (iii) orthorhombic Na14.78Sn4 (Pnma), better described as Na16-xSn4, is Na-richer than cubic Na15Sn4 (I-43d). Characterization of electrochemically prepared Na-Sn alloys indicate that, at the exception of Na7Sn3 and Na15Sn4, different crystal structures than similar Na-Sn compositions prepared via classic solid state reactions are formed. These phases are composed of disordered structures characteristic of kinetic-driven solid-state amorphization reactions. In these structures, Sn coordinates in asymmetric environments, which differ significantly from the environments present in Na-Sn model compounds.},
doi = {10.1039/C4TA04356A},
journal = {Journal of Materials Chemistry. A},
number = 44,
volume = 2,
place = {United States},
year = {Thu Sep 25 00:00:00 EDT 2014},
month = {Thu Sep 25 00:00:00 EDT 2014}
}
Web of Science
Works referenced in this record:
Na 5 Sn 13 : A New Zintl Phase with a Complex Network Structure Constructed from Tin Pentagons
journal, September 1997
- Vaughey, J. T.; Corbett, John D.
- Inorganic Chemistry, Vol. 36, Issue 20
Toward Na-ion Batteries—Synthesis and Characterization of a Novel High Capacity Na Ion Intercalation Material
journal, January 2013
- Buchholz, Daniel; Moretti, Arianna; Kloepsch, Richard
- Chemistry of Materials, Vol. 25, Issue 2
Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard-Carbon Electrodes and Application to Na-Ion Batteries
journal, August 2011
- Komaba, Shinichi; Murata, Wataru; Ishikawa, Toru
- Advanced Functional Materials, Vol. 21, Issue 20
Thermodynamic studies on Sn–Na alloy in an intermediate temperature ionic liquid NaFSA–KFSA at 363 K
journal, September 2013
- Yamamoto, Takayuki; Nohira, Toshiyuki; Hagiwara, Rika
- Journal of Power Sources, Vol. 237
Mössbauer spectra as a “fingerprint” in tin–lithium compounds: Applications to Li-ion batteries
journal, January 2007
- Robert, F.; Lippens, P. E.; Olivier-Fourcade, J.
- Journal of Solid State Chemistry, Vol. 180, Issue 1
Reversible Insertion of Sodium in Tin
journal, January 2012
- Ellis, L. D.; Hatchard, T. D.; Obrovac, M. N.
- Journal of The Electrochemical Society, Vol. 159, Issue 11
EXPGUI , a graphical user interface for GSAS
journal, April 2001
- Toby, Brian H.
- Journal of Applied Crystallography, Vol. 34, Issue 2
Better Cycling Performances of Bulk Sb in Na-Ion Batteries Compared to Li-Ion Systems: An Unexpected Electrochemical Mechanism
journal, December 2012
- Darwiche, Ali; Marino, Cyril; Sougrati, Moulay T.
- Journal of the American Chemical Society, Vol. 134, Issue 51
Cu2Sb thin films as anode for Na-ion batteries
journal, February 2013
- Baggetto, Loïc; Allcorn, Eric; Manthiram, Arumugam
- Electrochemistry Communications, Vol. 27
Na 7 Sn 12 : A Binary Zintl Phase with a Two-Dimensional Covalently Bonded Tin Framework
journal, September 2003
- Fässler, Thomas F.; Hoffmann, Stefan
- Inorganic Chemistry, Vol. 42, Issue 18
Mo3Sb7 as a very fast anode material for lithium-ion and sodium-ion batteries
journal, January 2013
- Baggetto, Loïc; Allcorn, Eric; Unocic, Raymond R.
- Journal of Materials Chemistry A, Vol. 1, Issue 37
Challenges for Na-ion Negative Electrodes
journal, January 2011
- Chevrier, V. L.; Ceder, G.
- Journal of The Electrochemical Society, Vol. 158, Issue 9
Redox reaction of Sn-polyacrylate electrodes in aprotic Na cell
journal, July 2012
- Komaba, Shinichi; Matsuura, Yuta; Ishikawa, Toru
- Electrochemistry Communications, Vol. 21
In situ X-ray absorption spectroscopy of germanium evaporated thin film electrodes
journal, September 2010
- Baggetto, Loïc; Hensen, Emiel J. M.; Notten, Peter H. L.
- Electrochimica Acta, Vol. 55, Issue 23
Intrinsic thermodynamic and kinetic properties of Sb electrodes for Li-ion and Na-ion batteries: experiment and theory
journal, January 2013
- Baggetto, Loïc; Ganesh, P.; Sun, Che-Nan
- Journal of Materials Chemistry A, Vol. 1, Issue 27
Na-ion batteries, recent advances and present challenges to become low cost energy storage systems
journal, January 2012
- Palomares, Verónica; Serras, Paula; Villaluenga, Irune
- Energy & Environmental Science, Vol. 5, Issue 3
Facile synthesis and long cycle life of SnSb as negative electrode material for Na-ion batteries
journal, July 2013
- Darwiche, Ali; Sougrati, Moulay T.; Fraisse, Bernard
- Electrochemistry Communications, Vol. 32
Probing the Mechanism of Sodium Ion Insertion into Copper Antimony Cu 2 Sb Anodes
journal, April 2014
- Baggetto, Loïc; Carroll, Kyler J.; Hah, Hien-Yoong
- The Journal of Physical Chemistry C, Vol. 118, Issue 15
Sodium Insertion into Tin Cobalt Carbon Active/Inactive Nanocomposite
journal, January 2013
- Ellis, L. D.; Ferguson, P. P.; Obrovac, M. N.
- Journal of The Electrochemical Society, Vol. 160, Issue 6
Spinel lithium titanate (Li 4 Ti 5 O 12 ) as novel anode material for room-temperature sodium-ion battery
journal, February 2012
- Zhao, Liang; Pan, Hui-Lin; Hu, Yong-Sheng
- Chinese Physics B, Vol. 21, Issue 2
Electrodeposited CoSn2 on nickel open-cell foam: advancing towards high power lithium ion and sodium ion batteries
journal, January 2013
- González, José R.; Nacimiento, Francisco; Alcántara, Ricardo
- CrystEngComm, Vol. 15, Issue 44
Synthesis and reactivity of a new intermetallic compound: Na 4 Sn
journal, January 1994
- Guérin, Frédéric; Richeson, Darrin
- J. Chem. Soc., Chem. Commun., Issue 19
Sodium-Ion Batteries
journal, May 2012
- Slater, Michael D.; Kim, Donghan; Lee, Eungje
- Advanced Functional Materials, Vol. 23, Issue 8, p. 947-958
Real-Time NMR Investigations of Structural Changes in Silicon Electrodes for Lithium-Ion Batteries
journal, July 2009
- Key, Baris; Bhattacharyya, Rangeet; Morcrette, Mathieu
- Journal of the American Chemical Society, Vol. 131, Issue 26
A profile refinement method for nuclear and magnetic structures
journal, June 1969
- Rietveld, H. M.
- Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71
Lithium-Ion (De)Insertion Reaction of Germanium Thin-Film Electrodes: An Electrochemical and In Situ XRD Study
journal, January 2009
- Baggetto, Loïc; Notten, Peter H. L.
- Journal of The Electrochemical Society, Vol. 156, Issue 3
Predictions of particle size and lattice diffusion pathway requirements for sodium-ion anodes using η-Cu6Sn5 thin films as a model system
journal, January 2013
- Baggetto, Loïc; Jumas, Jean-Claude; Górka, Joanna
- Physical Chemistry Chemical Physics, Vol. 15, Issue 26
(Cu6Sn5)1−xCx active/inactive nanocomposite negative electrodes for Na-ion batteries
journal, December 2013
- Thorne, J. S.; Dunlap, R. A.; Obrovac, M. N.
- Electrochimica Acta, Vol. 112
Performance of a four-element Si drift detector for X-ray absorption fine-structure spectroscopy: resolution, maximum count rate, and dead-time correction with incorporation into the ATHENA data analysis software
journal, April 2010
- Woicik, J. C.; Ravel, B.; Fischer, D. A.
- Journal of Synchrotron Radiation, Vol. 17, Issue 3
Na 2 Ti 3 O 7 : Lowest Voltage Ever Reported Oxide Insertion Electrode for Sodium Ion Batteries
journal, September 2011
- Senguttuvan, Premkumar; Rousse, Gwenaëlle; Seznec, Vincent
- Chemistry of Materials, Vol. 23, Issue 18
119Sn Mössbauer parameters as predictive tool for future Sn-based negative electrode materials
journal, April 2009
- Naille, S.; Jumas, J. -C.; Lippens, P. -E.
- Journal of Power Sources, Vol. 189, Issue 1
Characterization of sodium ion electrochemical reaction with tin anodes: Experiment and theory
journal, July 2013
- Baggetto, Loïc; Ganesh, P.; Meisner, Roberta P.
- Journal of Power Sources, Vol. 234
Reaction mechanism of tin nitride (de)lithiation reaction studied by means of 119Sn Mössbauer spectroscopy
journal, September 2010
- Baggetto, Loïc; Jumas, Jean-Claude; Hintzen, H. T. (Bert)
- Electrochimica Acta, Vol. 55, Issue 22
The Na-Sn (Sodium-Tin) System
journal, January 1998
- Sangster, J.; Bale, C. W.
- Journal of Phase Equilibria, Vol. 19, Issue 1
Die Struktur der Phase Na3.7Sn (≈Na15Sn4) / The Crystal Structure of Na3,7Sn (≈Na15Sn4)
journal, August 1975
- Müller, Wiking; Volk, Klaus
- Zeitschrift für Naturforschung B, Vol. 30, Issue 7-8
Die Strukturen der Phasen Na9Sn4 und Na15Sn4 / The Structures of the Phases Na9Sn4 and Na15Sn4
journal, March 1978
- Midler, Wiking; Volk, Klaus
- Zeitschrift für Naturforschung B, Vol. 33, Issue 3
Notizen: Die Struktur des β-NaSn / The Crystal Structure of β-NaSn
journal, June 1977
- Müller, Wiking; Volk, Klaus
- Zeitschrift für Naturforschung B, Vol. 32, Issue 6
Redetermination of the crystal structure of tetrasodium tetrahedrotetrastannide, Na4Sn4 and tetrapotassium tetrahedro-tetrastannide, K4Sn4
journal, December 1999
- Grin, Yu.; Baitinger, M.; Kniep, R.
- Zeitschrift für Kristallographie - New Crystal Structures, Vol. 214, Issue 4
Works referencing / citing this record:
Ultrafast and Highly Reversible Sodium Storage in Zinc-Antimony Intermetallic Nanomaterials
journal, December 2015
- Nie, Anmin; Gan, Li-yong; Cheng, Yingchun
- Advanced Functional Materials, Vol. 26, Issue 4
Peering into Alloy Anodes for Sodium‐Ion Batteries: Current Trends, Challenges, and Opportunities
journal, February 2019
- Tan, Huiteng; Chen, Dong; Rui, Xianhong
- Advanced Functional Materials, Vol. 29, Issue 14