Nanoscale Elemental Mapping of Intact Solid–Liquid Interfaces and Reactive Materials in Energy Devices Enabled by Cryo-FIB/SEM

Zachman, Michael J.; Tu, Zhengyuan; Archer, Lynden A.; Kourkoutis, Lena F.

doi:10.1021/acsenergylett.0c00202

Nanoscale Elemental Mapping of Intact Solid–Liquid Interfaces and Reactive Materials in Energy Devices Enabled by Cryo-FIB/SEM

Journal Article · Mon Mar 16 00:00:00 EDT 2020 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.0c00202· OSTI ID:1767649

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Cornell Univ., Ithaca, NY (United States); OSTI
Cornell Univ., Ithaca, NY (United States)

Many modern energy devices rely on solid–liquid interfaces, highly reactive materials, or both, for their operation and performance. The difficulty of characterizing such materials means these devices often lack high-resolution characterization in an unaltered state. Here, we demonstrate how cryogenic sample preparation and transfer can extend the capabilities of FIB/SEM techniques to solid–liquid interfaces and reactive materials common to energy devices by preserving their integrity through all stages of preparation and characterization. We additionally show how cryo-FIB/SEM paired with energy dispersive X-ray spectroscopy enables nanoscale elemental mapping of cross-sections produced in these materials and discuss strategies to achieve optimal results. Finally, we consider current limitations of the technique and propose future developments that could enhance its capabilities. Our results illustrate that cryo-FIB/SEM will be a useful technique for fields where solid–liquid interfaces or reactive materials play an important role and could, thus far, not be characterized at high resolution.

View Accepted Manuscript (DOE)

Research Organization:: Cornell Univ., Ithaca, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Alkaline-Based Energy Solutions (CABES)

Sponsoring Organization:: King Abdullah Univ. of Science and Technology (KAUST); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001086; SC0019445

OSTI ID:: 1767649

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 4 Vol. 5; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

Integrated Circuits Comprising Patterned Functional Liquids Prasad, Bhagwati; Pfanzelt, Georg; Fillis-Tsirakis, Evangelos Advanced Materials, Vol. 30, Issue 35 https://doi.org/10.1002/adma.201802598	journal	July 2018
A Review of Solid Electrolyte Interphases on Lithium Metal Anode Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Advanced Science, Vol. 3, Issue 3 https://doi.org/10.1002/advs.201500213	journal	November 2015
Direct Cryogenic-Temperature Transmission Electron Microscopy Imaging of Phospholipid Aggregates in Soybean Oil Danino, Dganit; Gupta, Rajan; Satyavolu, Jagannadh Journal of Colloid and Interface Science, Vol. 249, Issue 1 https://doi.org/10.1006/jcis.2002.8229	journal	May 2002
The Ga-Li (Gallium-Lithium) System Sangster, J.; Pelton, A. D. Journal of Phase Equilibria, Vol. 12, Issue 1 https://doi.org/10.1007/BF02663670	journal	February 1991
Introduction to Focused Ion Beams Giannuzzi, Lucille A.; Stevie, Fred A. Springer New York, NY https://doi.org/10.1007/b101190	book	January 2005
Dual-column (FIB–SEM) wafer applications Krueger, Robert Micron, Vol. 30, Issue 3 https://doi.org/10.1016/S0968-4328(98)00044-4	journal	June 1999
Site-Specific Cryo-focused Ion Beam Sample Preparation Guided by 3D Correlative Microscopy Arnold, Jan; Mahamid, Julia; Lucic, Vladan Biophysical Journal, Vol. 110, Issue 4 https://doi.org/10.1016/j.bpj.2015.10.053	journal	February 2016
In situ characterization of resin–dentin interfaces using conventional vs. cryofocused ion-beam milling Bakhsh, Turki A.; Sadr, Alireza; Mandurah, Mona M. Dental Materials, Vol. 31, Issue 7 https://doi.org/10.1016/j.dental.2015.04.010	journal	July 2015
Designing Artificial Solid-Electrolyte Interphases for Single-Ion and High-Efficiency Transport in Batteries Tu, Zhengyuan; Choudhury, Snehashis; Zachman, Michael J. Joule, Vol. 1, Issue 2 https://doi.org/10.1016/j.joule.2017.06.002	journal	October 2017
Quantification of SOFC anode microstructure based on dual beam FIB-SEM technique Iwai, Hiroshi; Shikazono, Naoki; Matsui, Toshiaki Journal of Power Sources, Vol. 195, Issue 4 https://doi.org/10.1016/j.jpowsour.2009.09.005	journal	February 2010
Site-specific 3D imaging of cells and tissues with a dual beam microscope Heymann, Jurgen A. W.; Hayles, Mike; Gestmann, Ingo Journal of Structural Biology, Vol. 155, Issue 1 https://doi.org/10.1016/j.jsb.2006.03.006	journal	July 2006
A site-specific focused-ion-beam lift-out method for cryo Transmission Electron Microscopy Rubino, Stefano; Akhtar, Sultan; Melin, Petter Journal of Structural Biology, Vol. 180, Issue 3 https://doi.org/10.1016/j.jsb.2012.08.012	journal	December 2012
A focused ion beam milling and lift-out approach for site-specific preparation of frozen-hydrated lamellas from multicellular organisms Mahamid, Julia; Schampers, Ruud; Persoon, Hans Journal of Structural Biology, Vol. 192, Issue 2 https://doi.org/10.1016/j.jsb.2015.07.012	journal	November 2015
Exploring cryogenic focused ion beam milling as a Group III–V device fabrication tool Dolph, Melissa Commisso; Santeufemio, Christopher Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 328 https://doi.org/10.1016/j.nimb.2014.02.126	journal	June 2014
Opening windows into the cell: focused-ion-beam milling for cryo-electron tomography Villa, Elizabeth; Schaffer, Miroslava; Plitzko, Jürgen M. Current Opinion in Structural Biology, Vol. 23, Issue 5 https://doi.org/10.1016/j.sbi.2013.08.006	journal	October 2013
Large volume serial section tomography by Xe Plasma FIB dual beam microscopy Burnett, T. L.; Kelley, R.; Winiarski, B. Ultramicroscopy, Vol. 161 https://doi.org/10.1016/j.ultramic.2015.11.001	journal	February 2016
Cryo-electron microscopy of vitrified specimens Dubochet, Jacques; Adrian, Marc; Chang, Jiin-Ju Quarterly Reviews of Biophysics, Vol. 21, Issue 2 https://doi.org/10.1017/S0033583500004297	journal	May 1988
An Improved Cryogen for Plunge Freezing Tivol, William F.; Briegel, Ariane; Jensen, Grant J. Microscopy and Microanalysis, Vol. 14, Issue 5 https://doi.org/10.1017/S1431927608080781	journal	September 2008
Detection of Lithium X-rays by EDS Xiaobing, L.; Holland, J.; Burgess, S. Microscopy and Microanalysis, Vol. 19, Issue S2 https://doi.org/10.1017/S1431927613007678	journal	August 2013
Site-Specific Preparation of Intact Solid–Liquid Interfaces by Label-Free In Situ Localization and Cryo-Focused Ion Beam Lift-Out Zachman, Michael J.; Asenath-Smith, Emily; Estroff, Lara A. Microscopy and Microanalysis, Vol. 22, Issue 6 https://doi.org/10.1017/S1431927616011892	journal	November 2016
Characterization of Sulfur and Nanostructured Sulfur Battery Cathodes in Electron Microscopy Without Sublimation Artifacts Levin, Barnaby D. A.; Zachman, Michael J.; Werner, Jörg G. Microscopy and Microanalysis, Vol. 23, Issue 1 https://doi.org/10.1017/S1431927617000058	journal	February 2017
Stabilizing Protic and Aprotic Liquid Electrolytes at High-Bandgap Oxide Interphases Tu, Zhengyuan; Zachman, Michael J.; Choudhury, Snehashis Chemistry of Materials, Vol. 30, Issue 16 https://doi.org/10.1021/acs.chemmater.8b01996	journal	July 2018
Revealing Nanoscale Passivation and Corrosion Mechanisms of Reactive Battery Materials in Gas Environments Li, Yuzhang; Li, Yanbin; Sun, Yongming Nano Letters, Vol. 17, Issue 8 https://doi.org/10.1021/acs.nanolett.7b02630	journal	July 2017
New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith Nano Letters, Vol. 17, Issue 12 https://doi.org/10.1021/acs.nanolett.7b03606	journal	November 2017
Grazing Incidence Cross-Sectioning of Thin-Film Solar Cells via Cryogenic Focused Ion Beam: A Case Study on CIGSe Sardashti, Kasra; Haight, Richard; Anderson, Ryan ACS Applied Materials & Interfaces, Vol. 8, Issue 24 https://doi.org/10.1021/acsami.6b04214	journal	June 2016
Cryogenic Focused Ion Beam Characterization of Lithium Metal Anodes Lee, Jungwoo Z.; Wynn, Thomas A.; Schroeder, Marshall A. ACS Energy Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acsenergylett.8b02381	journal	January 2019
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Dye-Sensitized Solar Cells Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr900356p	journal	November 2010
Nanostructure Formation in the Lecithin/Isooctane/Water System Koifman, Naama; Schnabel-Lubovsky, Maya; Talmon, Yeshayahu The Journal of Physical Chemistry B, Vol. 117, Issue 32 https://doi.org/10.1021/jp405490q	journal	July 2013
Cryo-Electron Microscopy of Block Copolymers in an Organic Solvent Oostergetel, G. T.; Esselink, F. J.; Hadziioannou, G. Langmuir, Vol. 11, Issue 10 https://doi.org/10.1021/la00010a022	journal	October 1995
Comparative Cryo-Electron Microscopy of Noncovalent N -Dodecanoyl- ( d - and l -) serine Assemblies in Vitreous Toluene and Water Boettcher, Christoph; Schade, Boris; Fuhrhop, Juergen-Hinrich Langmuir, Vol. 17, Issue 3 https://doi.org/10.1021/la001054p	journal	February 2001
Cryogenic Transmission Electron Microscopy Imaging of Vesicles Formed by a Polystyrene−Polyisoprene Diblock Copolymer Kesselman, Ellina; Talmon, Yeshayahu; Bang, Joona Macromolecules, Vol. 38, Issue 16 https://doi.org/10.1021/ma0510587	journal	August 2005
High Performance Electrolyte Gated Carbon Nanotube Transistors Rosenblatt, Sami; Yaish, Yuval; Park, Jiwoong Nano Letters, Vol. 2, Issue 8, p. 869-872 https://doi.org/10.1021/nl025639a	journal	August 2002
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Li–O₂ and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 1, p. 19-29 https://doi.org/10.1038/nmat3191	journal	January 2012
Origin of additional capacities in metal oxide lithium-ion battery electrodes Hu, Yan-Yan; Liu, Zigeng; Nam, Kyung-Wan Nature Materials, Vol. 12, Issue 12 https://doi.org/10.1038/nmat3784	journal	November 2013
Energy and fuels from electrochemical interfaces Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4738	journal	December 2016
Structural analysis of multicellular organisms with cryo-electron tomography Harapin, Jan; Börmel, Mandy; Sapra, K. Tanuj Nature Methods, Vol. 12, Issue 7 https://doi.org/10.1038/nmeth.3401	journal	May 2015
Focused-ion-beam thinning of frozen-hydrated biological specimens for cryo-electron microscopy Marko, Michael; Hsieh, Chyongere; Schalek, Richard Nature Methods, Vol. 4, Issue 3 https://doi.org/10.1038/nmeth1014	journal	February 2007
Designing solid-liquid interphases for sodium batteries Choudhury, Snehashis; Wei, Shuya; Ozhabes, Yalcin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00742-x	journal	October 2017
Fast ion transport at solid–solid interfaces in hybrid battery anodes Tu, Zhengyuan; Choudhury, Snehashis; Zachman, Michael J. Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0096-1	journal	March 2018
Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries Zachman, Michael J.; Tu, Zhengyuan; Choudhury, Snehashis Nature, Vol. 560, Issue 7718 https://doi.org/10.1038/s41586-018-0397-3	journal	August 2018
Carbon-based materials as supercapacitor electrodes Zhang, Li Li; Zhao, X. S. Chemical Society Reviews, Vol. 38, Issue 9 https://doi.org/10.1039/b813846j	journal	January 2009
A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries Manthiram, Arumugam; Chemelewski, Katharine; Lee, Eun-Sung Energy & Environmental Science, Vol. 7, Issue 4 https://doi.org/10.1039/c3ee42981d	journal	January 2014
Perspective: Oxide molecular-beam epitaxy rocks! Schlom, Darrell G. APL Materials, Vol. 3, Issue 6 https://doi.org/10.1063/1.4919763	journal	June 2015
An electromechanical material testing system for in situ electron microscopy and applications Zhu, Y.; Espinosa, H. D. Proceedings of the National Academy of Sciences, Vol. 102, Issue 41, p. 14503-14508 https://doi.org/10.1073/pnas.0506544102	journal	September 2005
The electron-energy-loss spectrum of lithium metal Lru, Dang-Rong; Williams, David B. Philosophical Magazine B, Vol. 53, Issue 6 https://doi.org/10.1080/13642818608240660	journal	June 1986
Critical Droplet Theory Explains the Glass Formability of Aqueous Solutions Warkentin, Matthew; Sethna, James P.; Thorne, Robert E. Physical Review Letters, Vol. 110, Issue 1 https://doi.org/10.1103/PhysRevLett.110.015703	journal	January 2013
A technique for improved focused ion beam milling of cryo-prepared life science specimens Hayles, M. F.; Stokes, D. J.; Phifer, D. Journal of Microscopy, Vol. 226, Issue 3 https://doi.org/10.1111/j.1365-2818.2007.01775.x	journal	June 2007
Cryogenic vitrification and 3D serial sectioning using high resolution cryo-FIB SEM technology for brine-filled grain boundaries in halite: first results: Cryo-FIB-SEM of grain boundary in halite Desbois, G.; Urai, J. L.; Burkhardt, C. Geofluids, Vol. 8, Issue 1 https://doi.org/10.1111/j.1468-8123.2007.00205.x	journal	January 2008
Ultrastructural features of dentinoenamel junction revealed by focused gallium ion beam milling: ULTRASTRUCTURAL FEATURES OF DENTINOENAMEL JUNCTION Bakhsh, Turki A. Journal of Microscopy, Vol. 264, Issue 1 https://doi.org/10.1111/jmi.12410	journal	May 2016
Connectivity of centermost chromatophores in Rhodobacter sphaeroides bacteria Noble, Jade M.; Lubieniecki, Johann; Savitzky, Benjamin H. Molecular Microbiology, Vol. 109, Issue 6 https://doi.org/10.1111/mmi.14077	journal	September 2018
Focused ion beam techniques for the analysis of biological samples: A revolution in ultramicroscopy? Ballerini, Monica; Milani, Marziale; Batani, Dimitri BiOS 2001 The International Symposium on Biomedical Optics, SPIE Proceedings https://doi.org/10.1117/12.424523	conference	April 2001
Designer interphases for the lithium-oxygen electrochemical cell Choudhury, Snehashis; Wan, Charles Tai-Chieh; Al Sadat, Wajdi I. Science Advances, Vol. 3, Issue 4 https://doi.org/10.1126/sciadv.1602809	journal	April 2017
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy Li, Yuzhang; Li, Yanbin; Pei, Allen Science, Vol. 358, Issue 6362 https://doi.org/10.1126/science.aam6014	journal	October 2017
Nanocrystalline Lithium Manganese Oxide Spinel Cathode for Rechargeable Lithium Batteries Kang, Sun-Ho; Goodenough, John B.; Rabenberg, Llewellyn K. Electrochemical and Solid-State Letters, Vol. 4, Issue 5 https://doi.org/10.1149/1.1357696	journal	January 2001
Ga-Li (Gallium-Lithium) Okamoto, H. Journal of Phase Equilibria & Diffusion, Vol. 27, Issue 2 https://doi.org/10.1361/154770306X97722	journal	April 2006

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