β-SnSb for Sodium Ion Battery Anodes: Phase Transformations

Jun 19, 2018 - β-SnSb is known to be a highly stable anode for sodium ion batteries during cycling, but its sodiation–desodiation alloying reaction...
0 downloads 0 Views 15MB Size
Subscriber access provided by Uppsala universitetsbibliotek

Letter

#-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

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

!-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]

1 ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 2 of 20

Page 3 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

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

3 ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

4 ACS Paragon Plus Environment

Page 4 of 20

Page 5 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

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.

5 ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 6 of 20

Page 7 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

8 ACS Paragon Plus Environment

Page 8 of 20

Page 9 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 10 of 20

Page 11 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

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.

11 ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 12 of 20

Page 13 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

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.

13 ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 14 of 20

Page 15 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

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

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

*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

16 ACS Paragon Plus Environment

Page 16 of 20

Page 17 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

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.

REFERENCES

(1) Palomares, V.; Casas-Cabanas, M.; Castillo-Martínez, E.; Han, M. H.; Rojo, T. Update on Na-Based Battery Materials. A Growing Research Path. Energy Environ. Sci. 2013, 6, 2312– 2337. (2) Nayak, P. K.; Yang, L.; Brehm, W.; Adelhelm, P. From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises. Angew. Chem. Int. Ed. 2017, 57, 102–120. (3) Chevrier, V. L.; Ceder, G. Challenges for Na-Ion Negative Electrodes. J. Electrochem. Soc. 2011, 158, A1011–A1014. (4) Luo, W.; Shen, F.; Bommier, C.; Zhu, H.; Ji, X.; Hu, L. Na-Ion Battery Anodes: Materials and Electrochemistry. Acc. Chem. Res. 2016, 49, 231–240. (5)Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Research Development on Sodium-Ion Batteries. Chem. Rev. 2014, 114, 11636–11682. (6) Sung-Wook, K.; Dong-Hwa, S.; Xiaohua, M.; Gerbrand, C.; Kisuk, K. Electrode Materials for Rechargeable Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries. Adv. Energy Mater. 2012, 2, 710–721. (7) Li, Z.; Ding, J.; Mitlin, D. Tin and Tin Compounds for Sodium Ion Battery Anodes: Phase Transformations and Performance. Acc. Chem. Res. 2015, 48, 1657–1665. (8) Lao, M.; Zhang, Y.; Luo, W.; Yan, Q.; Sun, W.; Dou, S. X. Alloy-Based Anode Materials toward Advanced Sodium-Ion Batteries. Adv. Mater. 2017, 29, 1700622. (9) Bommier, C.; Ji, X. Recent Development on Anodes for Na-Ion Batteries. Isr. J. Chem. 2015, 55, 486–507. (10) Deng, J.; Luo, W.-B.; Chou, S.-L.; Liu, H.-K.; Dou, S.-X. Sodium-Ion Batteries: From Academic Research to Practical Commercialization. Adv. Energy Mater. 2017, 8, 1701428. 17 ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(11) Pan, H.; Hu, Y.-S.; Chen, L. Room-Temperature Stationary Sodium-Ion Batteries for LargeScale Electric Energy Storage. Energy Environ. Sci. 2013, 6, 2338–2360. (12) Palomares, V.; Serras, P.; Villaluenga, I.; Hueso, K. B.; Carretero-González, J.; Rojo, T. NaIon Batteries, Recent Advances and Present Challenges to Become Low Cost Energy Storage Systems. Energy Environ. Sci. 2012, 5, 5884–5901. (13) Slater, M. D.; Kim, D.; Lee, E.; Johnson, C. S. Sodium-Ion Batteries. Adv. Funct. Mater. 2013, 23, 947–958. (14) Dahbi, M.; Yabuuchi, N.; Kubota, K.; Tokiwa, K.; Komaba, S. Negative Electrodes for NaIon Batteries. Phys. Chem. Chem. Phys. 2014, 16, 15007–15028. (15) Allan, P. K.; Griffin, J. M.; Darwiche, A.; Borkiewicz, O. J.; Wiaderek, K. M.; Chapman, K. W.; Morris, A. J.; Chupas, P. J.; Monconduit, L.; Grey, C. P. Tracking Sodium-Antimonide Phase Transformations in Sodium-Ion Anodes: Insights from Operando Pair Distribution Function Analysis and Solid-State NMR Spectroscopy. J. Am. Chem. Soc. 2016, 138, 2352–2365. (16) Farbod, B.; Cui, K.; Kalisvaart, W. P.; Kupsta, M.; Zahiri, B.; Kohandehghan, A.; Lotfabad, E. M.; Li, Z.; Luber, E. J.; Mitlin, D. Anodes for Sodium Ion Batteries Based on Tin– Germanium–Antimony Alloys. ACS Nano 2014, 8, 4415–4429. (17) Darwiche, A.; Marino, C.; Sougrati, M. T.; Fraisse, B.; Stievano, L.; Monconduit, L. Better Cycling Performances of Bulk Sb in Na-Ion Batteries Compared to Li-Ion Systems: An Unexpected Electrochemical Mechanism. J. Am. Chem. Soc. 2012, 134, 20805–20811. (18) Qian, J.; Chen, Y.; Wu, L.; Cao, Y.; Ai, X.; Yang, H. High Capacity Na-Storage and Superior Cyclability of Nanocomposite Sb/C Anode for Na-Ion Batteries. Chem. Commun. 2012, 48, 7070–7072. (19) He, Y.; Piper, D. M.; Gu, M.; Travis, J. J.; George, S. M.; Lee, S.-H.; Genc, A.; Pullan, L.; Liu, J.; Mao, S. X.; et al. In-situ Transmission Electron Microscopy Probing of Native Oxide and Artificial Layers on Silicon Nanoparticles for Lithium Ion Batteries. ACS Nano 2014, 8, 11816– 11823. (20) Hou, H.; Jing, M.; Yang, Y.; Zhang, Y.; Zhu, Y.; Song, W.; Yang, X.; Ji, X. Sb Porous Hollow Microspheres as Advanced Anode Materials for Sodium-Ion Batteries. J. Mater. Chem. A 2015, 3, 2971–2977. (21) Hou, H.; Jing, M.; Yang, Y.; Zhang, Y.; Zhu, Y.; Song, W.; Yang, X.; Ji, X. Sb Porous Hollow Microspheres as Advanced Anode Materials for Sodium-Ion Batteries. J. Mater. Chem. A 2015, 3, 2971–2977. (22) Bodenes, L.; Darwiche, A.; Monconduit, L.; Martinez, H. The Solid Electrolyte Interphase a Key Parameter of the High Performance of Sb in Sodium-Ion Batteries: Comparative X-Ray Photoelectron Spectroscopy Study of Sb/Na-Ion and Sb/Li-Ion Batteries. J. Power Sources 2015, 273, 14–24. (23) Zhao, X.; Vail, S. A.; Lu, Y.; Song, J.; Pan, W.; Evans, D. R.; Lee, J.-J. Antimony/Graphitic Carbon Composite Anode for High-Performance Sodium-Ion Batteries. ACS Appl. Mater. Interfaces 2016, 8, 13871–13878.

18 ACS Paragon Plus Environment

Page 18 of 20

Page 19 of 20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

(24) Li, Z.; Tan, X.; Li, P.; Kalisvaart, P.; Janish, M. T.; Mook, W. M.; Luber, E. J.; Jungjohann, K. L.; Carter, C. B.; Mitlin, D. Coupling In-situ TEM and Ex Situ Analysis to Understand Heterogeneous Sodiation of Antimony. Nano Lett. 2015, 15, 6339–6348. (25) Darwiche, A.; Bodenes, L.; Madec, L.; Monconduit, L.; Martinez, H. Impact of the Salts and Solvents on the SEI Formation in Sb/Na Batteries: An XPS Analysis. Electrochim. Acta 2016, 207, 284–292. (26) Mao, J.; Fan, X.; Luo, C.; Wang, C. Building Self-Healing Alloy Architecture for Stable Sodium-Ion Battery Anodes: A Case Study of Tin Anode Materials. ACS Appl. Mater. Interfaces 2016, 8, 7147–7155. (27) Ramireddy, T.; Sharma, N.; Xing, T.; Chen, Y.; Leforestier, J.; Glushenkov, A. M. Size and Composition Effects in Sb-Carbon Nanocomposites for Sodium-Ion Batteries. ACS Appl. Mater. Interfaces 2016, 8, 30152–30164. (28) Wang, J. W.; Liu, X. H.; Mao, S. X.; Huang, J. Y. Microstructural Evolution of Tin Nanoparticles during In Situ Sodium Insertion and Extraction. Nano Lett. 2012, 12, 5897–5902. (29) Zhu, H.; Jia, Z.; Chen, Y.; Weadock, N.; Wan, J.; Vaaland, O.; Han, X.; Li, T.; Hu, L. Tin Anode for Sodium-Ion Batteries Using Natural Wood Fiber as a Mechanical Buffer and Electrolyte Reservoir. Nano Lett. 2013, 13, 3093–3100. (30) Xie, H.; Kalisvaart, W. P.; Olsen, B. C.; Luber, E. J.; Mitlin, D.; Buriak, J. M. Sn–Bi–Sb Alloys as Anode Materials for Sodium Ion Batteries. J. Mater. Chem. A 2017, 5, 9661–9670. (31) Liang, L.; Xu, Y.; Wang, C.; Wen, L.; Fang, Y.; Mi, Y.; Zhou, M.; Zhao, H.; Lei, Y. LargeScale Highly Ordered Sb Nanorod Array Anodes with High Capacity and Rate Capability for Sodium-Ion Batteries. Energy Environ. Sci. 2015, 8, 2954–2962. (32) Yaru, L.; Wei-Hong, L.; Zongcheng, M.; Shu-Lei, C. Nanocomposite Materials for the Sodium–Ion Battery: A Review. Small 2018, 14, 1702514. (33) Liu, Y.; Xu, Y.; Zhu, Y.; Culver, J. N.; Lundgren, C. A.; Xu, K.; Wang, C. Tin-Coated Viral Nanoforests as Sodium-Ion Battery Anodes. ACS Nano 2013, 7, 3627–3634. (34) Nam, D.-H.; Kim, T.-H.; Hong, K.-S.; Kwon, H.-S. Template-Free Electrochemical Synthesis of Sn Nanofibers as High-Performance Anode Materials for Na-Ion Batteries. ACS Nano 2014, 8, 11824–11835. (35) Zhu, Y.; Han, X.; Xu, Y.; Liu, Y.; Zheng, S.; Xu, K.; Hu, L.; Wang, C. Electrospun Sb/C Fibers for a Stable and Fast Sodium-Ion Battery Anode. ACS Nano 2013, 7, 6378–6386. (36) Sottmann, J.; Herrmann, M.; Vajeeston, P.; Hu, Y.; Ruud, A.; Drathen, C.; Emerich, H.; Fjellvåg, H.; Wragg, D. S. How Crystallite Size Controls the Reaction Path in Nonaqueous Metal Ion Batteries: The Example of Sodium Bismuth Alloying. Chem. Mater. 2016, 28, 2750–2756. (37) Xiao, L.; Cao, Y.; Xiao, J.; Wang, W.; Kovarik, L.; Nie, Z.; Liu, J. High Capacity, Reversible Alloying Reactions in SnSb/C Nanocomposites for Na-Ion Battery Applications. Chem. Commun. 2012, 48, 3321–3323. (38) Darwiche, A.; Sougrati, M. T.; Fraisse, B.; Stievano, L.; Monconduit, L. Facile Synthesis and Long Cycle Life of SnSb as Negative Electrode Material for Na-Ion Batteries. Electrochem. Commun. 2013, 32, 18–21. 19 ACS Paragon Plus Environment

ACS Energy Letters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(39) Baggetto, L.; Hah, H.-Y.; Jumas, J.-C.; Johnson, C. E.; Johnson, J. A.; Keum, J. K.; Bridges, C. A.; Veith, G. M. The Reaction Mechanism of SnSb and Sb Thin Film Anodes for Na-Ion Batteries Studied by X-Ray Diffraction, 119Sn and 121Sb Mössbauer Spectroscopies. J. Power Sources 2014, 267, 329–336. (40) Liwen, J.; Meng, G.; Yuyan, S.; Xiaolin, L.; H, E. M.; W, A. B.; Wei, W.; Zimin, N.; Jie, X.; Chongmin, W.; et al. Controlling SEI Formation on SnSb-Porous Carbon Nanofibers for Improved Na Ion Storage. Adv. Mater. 2014, 26, 2901–2908. (41) Yi, Z.; Han, Q.; Geng, D.; Wu, Y.; Cheng, Y.; Wang, L. One-Pot Chemical Route for Morphology-Controllable Fabrication of Sn-Sb Micro/Nano-Structures: Advanced Anode Materials for Lithium and Sodium Storage. J. Power Sources 2017, 342, 861–871. (42) Chen, S.-W.; Chen, C.-C.; Gierlotka, W.; Zi, A.-R.; Chen, P.-Y.; Wu, H.-J. Phase Equilibria of the Sn-Sb Binary System. J. Electron. Mater. 2008, 37, 992–1002. (43) Okamoto, H. Sb-Sn (Antimony-Tin). J. Phase Equilib. Diffus. 2012, 33, 347–347. (44) Luber, E.; Mohammadi, R.; Ophus, C.; Lee, Z.; Nelson-Fitzpatrick, N.; Westra, K.; Evoy, S.; Dahmen, U.; Radmilovic, V.; Mitlin, D. Tailoring the Microstructure and Surface Morphology of Metal Thin Films for Nano-Electro-Mechanical Systems Applications. Nanotechnology 2008, 19, 125705. (45) Yuan, Y.; Amine, K.; Lu, J.; Shahbazian-Yassar, R. Understanding Materials Challenges for Rechargeable Ion Batteries with in Situ Transmission Electron Microscopy. Nat. Commun. 2017, 8, 15806. (46) Hasti, A.-A.; Wentao, Y.; Yifei, Y.; Anmin, N.; Khalil, A.; Jun, L.; Reza, S.-Y. In Situ TEM Investigation of ZnO Nanowires during Sodiation and Lithiation Cycling. Small Methods 2017, 1, 1700202. (47) Mitlin, D.; Raeder, C. H.; Messler, R. W. Solid Solution Creep Behavior of Sn-xBi Alloys. Metall. Mat. Trans. A 1999, 30, 115–122. (48) Gu, M.; Kushima, A.; Shao, Y.; Zhang, J.-G.; Liu, J.; Browning, N. D.; Li, J.; Wang, C. Probing the Failure Mechanism of SnO2 Nanowires for Sodium-Ion Batteries. Nano Lett. 2013, 13, 5203–5211. (49) Liu, Y.; Fan, F.; Wang, J.; Liu, Y.; Chen, H.; Jungjohann, K. L.; Xu, Y.; Zhu, Y.; Bigio, D.; Zhu, T.; et al. In Situ Transmission Electron Microscopy Study of Electrochemical Sodiation and Potassiation of Carbon Nanofibers. Nano Lett. 2014, 14, 3445–3452. (50) Lu, X.; Adkins, E. R.; He, Y.; Zhong, L.; Luo, L.; Mao, S. X.; Wang, C.-M.; Korgel, B. A. Germanium as a Sodium Ion Battery Material: In Situ TEM Reveals Fast Sodiation Kinetics with High Capacity. Chem. Mater. 2016, 28, 1236–1242.

20 ACS Paragon Plus Environment

Page 20 of 20