Î²-SnSb for Sodium Ion Battery Anodes: Phase Transformations

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#-SnSb for Sodium Ion Battery Anodes: Phase Transformations Responsible for Enhanced Cycling Stability Revealed by In-situ TEM Hezhen Xie, Xuehai Tan, Erik J. Luber, Brian Olsen, W. Peter Kalisvaart, Katherine L. Jungjohann, David Mitlin, and Jillian M. Buriak ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.8b00762 • Publication Date (Web): 19 Jun 2018 Downloaded from http://pubs.acs.org on June 20, 2018

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!-SnSb for Sodium Ion Battery Anodes: Phase Transformations Responsible for Enhanced Cycling Stability Revealed by In-situ TEM

Hezhen Xie,†,‡,¥ Xuehai Tan,¶, ¥ Erik J. Luber,†,‡ Brian C. Olsen,†,‡ W. Peter Kalisvaart,†,‡ Katherine L. Jungjohann,! David Mitlin,*,§ Jillian M. Buriak,*,†,‡

†

Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton, AB T6G 2G2, Canada ‡

National Institute for Nanotechnology, National Research Council Canada, 11421 Saskatchewan Drive, Edmonton, AB T6G 2M9, Canada ¶

Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4, Canada !

Center for Integrated Nanotechnologies, Sandia National Laboratories, Albuquerque, New Mexico 87185, United States §

Chemical & Biomolecular Engineering, Clarkson University, 8 Clarkson Avenue, Potsdam, New York 13699, United States ¥ Co-first authors *Corresponding authors, David Mitlin: [email protected]; Jillian M. Buriak: [email protected]

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Sodium ion batteries (SIBs) are of great interest due to the much higher abundance of sodium compared to lithium in the earth’s crust. SIBs lag, however, far behind lithium batteries in terms of research and development, and suffer from sluggish kinetics, poor cycling stabilities, and lower theoretical capacities. Sodium ion battery (SIB) alloyed reaction anode materials are being intensively investigated due to the very high specific capacity attained with certain combinations of elements.1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 Compared to non-graphitic carbon, two of the most widely studied anode materials for SIBs, Sn and Sb, possess significantly higher specific capacities of 847 (Na15Sn4) and 660 mAh g-1 (Na3Sb), tin being close to that of sodium metal (1,166 mAh/g). By comparison, Na-active carbons typically struggle to reach even 350 mAh/g. Sn electrodes usually have a coarse microstructure and thus the dramatic volume expansion and contraction (420%) results in rapid pulverization of the active material.16 Antimony is reported to deliver a reversible capacity above 600 mAh/g with sodium ions, close to its theoretical value.17, 18, 19, 20,21 Although the cycling performance of pure Sb as a SIB anode is generally better than pure Sn, there are significant study-to-study variations and the overall capacity retention is still far from adequate for commercial applications.16, 22,23, 24,25 Alloyed materials possessing a nanoscale microstructure may exhibit improved resistance towards the severe problem of mechanical fracture and pulverization induced by internal stress buildup during repeated volume expansion and contraction.26,27,28,29,30 Nanostructured alloyed materials are also expected to possess much better kinetics compared to their coarser counter parts due to shorter diffusion distances,31,32,33,34,35 and in some cases metastable phases.36 In this work, we use in-situ TEM to probe the sodiation and desodiation of the promising !-SnSb alloy, which is composed of two elements that are highly active for sodiation. The !-phase SnSb intermetallic is one of the most interesting binary systems in terms of structural stability and



facile sodiation kinetics.37,38,39,40,41 To date, however, the underlying reasons for the promising cycling stability of the !-SnSb have not been identified, and there is incomplete understanding of the sodiation-desodiation sequence. Per the room temperature binary equilibrium phase diagram of Sb-Sn in the range of 46-48 at.%, there is a cubic rock salt ordered solid solution intermetallic (!-SnSb) with an enthalpy of formation of about -3 kJ/mol.42,43 Reports based on combined XRD and Mössbauer studies highlight the presence of the Na3Sb phase at terminal sodiation, and an amorphous NaSb phase at lower Na content.39 For the !-SnSb alloy, however, XRD alone is difficult to interpret due to the highly broadened peaks of the nanocrystalline/amorphous phases that form.44 In-situ TEM has been shown to be a highly powerful technique for site-specific analysis of sodiation induced phase transformations, even when the phases are truly nanostructured.45,46 Here we analyze the reversible sodiation-desodiation reactions of !-SnSb by this technique, and connect these results to the electrochemical performance of !-SnSb films as anodes for SIBs. To investigate the SnSb system, the following films were prepared via sputtering: cosputtered SnSb (1:1 mole fraction), bilayers of Sn(top)/Sb(bottom) and Sb(top)/Sn(bottom), and the corresponding pure elemental films. The indexed XRD patterns of the as-deposited 100 nm !SnSb alloy film and of the 50 nm/50 nm Sn/Sb and Sb/Sn bilayers are shown in Figure S1. The combination of the thermodynamic driving force and short diffusion distances in the Sn/Sb and Sb/Sn bilayer films causes partial formation of !-SnSb intermetallic even in the as-deposited state. The co-sputtered film is fully converted to the !-SnSb phase, with no evidence of elemental Sn or Sb. As will be demonstrated by TEM and XRD (vide infra), the Sn and Sb bilayers react during desodiation cycles to form !-SnSb in the desodiated state. Figure 1 compares the electrochemical performance of the co-sputtered SnSb film, the Sn/Sb and Sb/Sn bilayers, and


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elemental Sn and Sb films. We also examined a trilayer system containing a very thin silicon inter-diffusion barrier sandwiched between the tin and antimony, Sb(49 nm)/Si(2 nm)/Sn(49 nm). Figures 1a-c show the galvanostatic charge–discharge curves of the co-sputtered SnSb film and of the bilayers at cycles 2, 10 and 50. Galvanostatic data for baseline elemental Sn, Sb, and the trilayer Sn/Si/Sb films are shown in Figure S2. It is evident that the galvanostatic voltage versus capacity plateaus for the bilayers are very similar to that of the co-sputtered SnSb alloy film, especially in later cycles, all the while being distinct from both the elemental Sn and Sb films. The shapes and positions of the plateaus for the co-sputtered SnSb versus the Sn/Sb bilayers only show minor differences in the region of the reaction overpotentials. Figure 1d shows the cycling performance and the associated coulombic efficiency (CE) of all the films tested. It should be noted that the elemental Sn and Sb films degrade rapidly - the Sn immediately, and the Sb after ~40 cycles. The co-sputtered SnSb and Sn/Sb bilayer films exhibit much better capacity retention, with similar cycling stability with 70% capacity retention after 150 cycles. In fact, they demonstrate analogous initial reversible capacity near 700 mAh/g, increasing to 740 mAh/g over the first 20 cycles, and slowly decaying afterward. The Sn/Sb bilayer with a sandwiched 2 nm Si inter-diffusion barrier does not show the same level of extended stability, fading rapidly after fewer than 10 cycles. This result with the trilayer sandwich suggests that the !-SnSb alloy reaction sequence is an essential microstructural feature necessary for the material to withstand repeated cycling.




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shows the image of a co-sputtered SnSb film analyzed at the first cycle of sodiation-desodiation. To sodiate and desodiate the film, a voltage of -0.5 V and +5 V vs. Na was applied, respectively. The bright-field TEM (BF-TEM) micrographs of the pristine SnSb film deposited on Ge/TiN nanowires revealed three distinct layers, from external to internal: the SnSb film, the TiN barrier layer, and the supporting Ge nanowire. The SnSb was not expected to be reactive with the stable TiN underlayer (vide infra). By comparing experimental selected area diffraction (SAED) patterns of pristine SnSb with the simulated pattern shown (Figure 3), it was confirmed that the as-deposited SnSb film is polycrystalline single-phase !- SnSb intermetallic with a rocksalt cubic crystal structure (Fm-3m [225]). As expected, inspection of the BF-TEMs (Figure 3) shows that the diameter of the nanowire increases during sodiation due to Na uptake in the SnSb film. The volume expansion is measured as a function of (de)sodiation time and is shown in Figure S3a (see the Supporting Information and Figures S3b,c for details on how volume expansion was measured). We see that there is a very rapid initial volume expansion of 85% (2 min), followed by a gradual increase to 135% (40 min) and then a final more rapid increase to 210% (60 min). This data suggests that the Sb sodiates first (as is expected from the equilibrium sodiation potentials), while the Sn begins to sodiate much more slowly, and is likely a mixture of amorphous-NaxSny and crystalline-Na15Sn4 phase by the end of 60 min of in-situ sodiation. This hypothesis is validated by analyzing the TEM micrographs for the sodiation of Sn/Sb bilayers (Figure S4), where the Sn particles on the free surface only experience a volume increase of ~100% after 65 min of in-situ sodiation, which is much less than the 420% of fully sodiated Sn. Therefore, if we assume that the Sb is fully sodiated (290%) after 60 min and the Sn has experienced a 100% volume increase, the estimated


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observed. The observed segregation of a small amount of Na15Sn4 during sodiation, converting to elemental Sn upon desodiation, is in agreement with the XRD results (Figure 2). Two peaks at 4.2 and 6.0 nm-1 also appeared after 20 min of desodiation and become more distinct as desodiation time increased. We ascribe these peaks to the (111) and (511) reflections of orthorhombic NaOH (cmcm [63]), which may form when the Na metal is transferred to the TEM column and may migrate quickly on the surface, along the length of the nanowire.24,28,48,49,50 The peak at 6.0 nm-1 also coincides with the (301) reflection of elemental Sn. From 30 to 60 minutes, the overlapping peaks centered at 2.5 nm-1 further decreased and the (200) peak of rocksalt !SnSb and/or (012) peak of rhombohedral Sb (R-3m [166]) near 3.2 nm-1 was observed. As the peak is obviously broadened, this observation suggests that nanocrystalline !-SnSb and/or Sb forms. The assignment of this nanocrystalline feature is further supported by HRTEM micrographs of the desodiated SnSb film, shown in Figure 5. The interplanar distance of 0.31 nm matches the d-spacing of the {200} planes of the cubic SnSb phase. As desodiation progresses, the BF-TEM micrographs show that the sodiated SnSb film gradually shrinks as a result of extraction of Na.




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progresses. During desodiation, Na15Sn4 decomposes first and the (200), (101), (211), (420) peaks of elemental Sn are visible after 30 minutes. Subsequently, Sb or !-SnSb was observed although they are difficult to distinguish from each other. As shown in Figure S7, the simulated peak position of !-SnSb is closer to the observed center of the peak at 3.3 nm-1 and so the formed phase is likely !-SnSb. From the in-situ TEM diffraction data, it appears that both Sn/Sb and Sb/Sn bilayer films followed a very similar sodiation/desodiation reaction sequence as co-sputtered SnSb. The !SnSb pattern is much sharper in the desodiated Sb/Sn film compared to co-sputtered SnSb, showing that it is reformed upon desodiation. Elemental Sn is recognizable in both the SAED patterns of SnSb and Sb/Sn. Elemental Sb, on the other hand, is very hard to discern as the strongest peak in the pristine bilayer overlaps with a broadened !-SnSb peak, as well as that of NaOH. These results suggest that Sn/Sb bilayers mix and form !-SnSb during sodiationdesodiation cycle, and do so every cycle. To summarize, the in-situ TEM analysis results are in accordance with the XRD and the electrochemical results. Based the observations and analyses above, the following overall reaction mechanism is proposed, which is illustrated in Scheme 1. The label "c-" denotes a crystalline phase with a distinctly identifiable diffraction pattern. The label "a-" denotes amorphous or sufficiently nanocrystalline as not to yield indexable TEM SAED or XRD reflections.




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reaction in pure Sb films,36 but, these phases are very difficult to detect by TEM or XRD in a composite electrode such as the one examined here. With increased cycling number, the Sn element does not fully alloy with Sb, and rather precipitates out as a distinct crystalline phase. This process drives the composition of the remaining !-phase to be richer in Sb, which is thermodynamically allowable since at room temperature the !-phase spans 46 at.% to 48 at.% Sb. Moreover beyond these compositions, the !-phase may become supersaturated or precipitate out as minority Sb. To conclude, by connecting the phase diagram of SbSn intermetallics with detailed in-situ TEM, electrochemistry, and ex-situ XRD, a fundamental understanding of the behavior of this interesting compound as an anode for SIBs was realized, enabling optimization in future iterations.

ASSOCIATED CONTENT

Supporting Information Experimental details, figures showing indexed XRD patterns of as-deposited and cycled cosputtered SnSb films, Sn/Sb and Sb/Sn bilayer films, galvanostatic voltage profiles of Sn, Sb and Sn/Si/Sb films, volume change of SnSb films as function of sodiation time, in-situ BF-TEMs and SADs of a single cycle of bilayer Sn/Sb and Sb/Sn and multi-cycled co-sputtered SnSb films, and a table of as-deposited and cycled grain sizes for a co-sputtered SnSb film, and Sn/Sb and Sb/Sn bilayer films.

AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (D.M) 15 ACS Paragon Plus Environment


*E-mail: [email protected] (J.M.B)

Author Contributions These authors (H.X. and X.H.T.) contributed equally.

ORCID Hezhen Xie: 0000-0001-9275-9169 Xuehai Tan: 0000-0002-8571-1586 Erik J. Luber: 0000-0003-1623-0102 Brian C. Olsen: 0000-0001-9758-3641 Katherine L. Jungjohann: 0000-0002-8132-1230 Jillian M. Buriak: 0000-0002-9567-4328

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS H. Xie, E. J. Luber, B. C. Olsen, W. P. Kalisvaart, and J. M. Buriak are supported by grants from the Future Energy Systems of the University of Alberta (https://futureenergysystems.ca; grant number T12-P04), the Natural Sciences and Engineering Research Council (NSERC, grant number RGPIN-2014-05195), Alberta Innovates Technology Futures (grant number AITF iCORE IC50-T1 G2013000198), an AITF graduate fellowship to HX, and the Canada Research Chairs program (CRC 207142). The X-ray diffraction spectra were carried out at NRC-NINT. The TEM


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analysis in this work (K.L. Jungjohann, X. Tan, H. Xie, D. Mitlin) was performed at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. DOE's National Nuclear Security Administration under contract DE-NA-0003525. The views expressed in the article do not necessarily represent the views of the U.S. DOE or the United States Government. D. Mitlin is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award No. DE-SC0018074.

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Î²-SnSb for Sodium Ion Battery Anodes: Phase Transformations

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