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Characterization of Lithium Ion Battery Materials with Valence Electron Energy-Loss Spectroscopy

Published online by Cambridge University Press:  07 June 2018

Fernando C. Castro  and
Vinayak P. Dravid
Fernando C. Castro
Affiliation:
Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive, Cook Hall, Room 1137, Evanston, IL 60208, USA
Vinayak P. Dravid*
Affiliation:
Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive, Cook Hall, Room 1137, Evanston, IL 60208, USA NUANCE Center, Northwestern University, 2220 Campus Drive, Cook Hall, Room 2036, Evanston, IL 60208, USA
*
*Author for correspondence: Vinayak P. Dravid, E-mail: [email protected]
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Abstract

Cutting-edge research on materials for lithium ion batteries regularly focuses on nanoscale and atomic-scale phenomena. Electron energy-loss spectroscopy (EELS) is one of the most powerful ways of characterizing composition and aspects of the electronic structure of battery materials, particularly lithium and the transition metal mixed oxides found in the electrodes. However, the characteristic EELS signal from battery materials is challenging to analyze when there is strong overlap of spectral features, poor signal-to-background ratios, or thicker and uneven sample areas. A potential alternative or complementary approach comes from utilizing the valence EELS features (<20 eV loss) of battery materials. For example, the valence EELS features in LiCoO2 maintain higher jump ratios than the Li–K edge, most notably when spectra are collected with minimal acquisition times or from thick sample regions. EELS maps of these valence features give comparable results to the Li–K edge EELS maps of LiCoO2. With some spectral processing, the valence EELS maps more accurately highlight the morphology and distribution of LiCoO2 than the Li–K edge maps, especially in thicker sample regions. This approach is beneficial for cases where sample thickness or beam sensitivity limit EELS analysis, and could be used to minimize electron dosage and sample damage or contamination.

Keywords

electron energy-loss spectroscopylithium ion batteryFourier-log deconvolutionvalence EELS
Type
Materials Science Applications
Information
Microscopy and Microanalysis , Volume 24 , Issue 3 , June 2018 , pp. 214 - 220
Copyright
© Microscopy Society of America 2018 

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Footnotes

Cite this article: Castro FC, Dravid VP (2018) Characterization of Lithium Ion Battery Materials with Valence Electron Energy-Loss Spectroscopy. Microsc Microanal24(3): 214–220. doi: 10.1017/S1431927618000302

References

Abellan, P, Woehl, TJ, Parent, LR, Browning, ND, Evans, JE and Arslan, I (2014) Factors influencing quantitative liquid (scanning) transmission electron microscopy. Chem Commun 50, 4873–4880.CrossRefGoogle ScholarPubMed
Boniface, M, Quazuguel, L, Danet, J, Guyomard, D, Moreau, P and Bayle-Guillemaud, P (2016) Nanoscale chemical evolution of silicon negative electrodes characterized by low-loss STEM-EELS. Nano Lett 16, 7381–7388.CrossRefGoogle ScholarPubMed
Cosandey, F (2010) Analysis of Li-ion battery materials by electron energy loss spectroscopy. In Microscopy: Science, Technology, Applications, and Education, Méndez-Vilas A and Díaz J (Eds.), pp. 1662–1666. Badajoz, Spain: Formatex Research Center.Google Scholar
Ellis, BL, Lee, KT and Nazar, LF (2010) Positive electrode materials for Li-ion and Li-batteries. Chem Mater 22, 691–714.CrossRefGoogle Scholar
Evmenenko, G, Fister, TT, Buchholz, DB, Castro, FC, Li, Q, Wu, J, Dravid, VP, Fenter, P and Bedzyk, MJ (2017) Lithiation of multilayer Ni/NiO electrodes: Criticality of nickel layer thicknesses on conversion reaction kinetics. Phys Chem Chem Phys 19, 20029–20039.CrossRefGoogle ScholarPubMed
Graetz, J, Ahn, CC, Yazami, R and Fultz, B (2003) An electron energy-loss spectrometry study of charge compensation in LiNi0.8 Co0.2O2 . J Phys Chem B 107, 2887–2891.CrossRefGoogle Scholar
Grunes, LA, Leapman, RD, Wilker, CN, Hoffmann, R and Kunz, AB (1982) Oxygen K near-edge fine structure: An electron-energy-loss investigation with comparisons to new theory for selected 3d transition-metal oxides. Phys Rev B 25, 7157–7173.CrossRefGoogle Scholar
Gu, L, Srot, V, Sigle, W, Koch, C, Aken, PV, Scholz, F, Thapa, SB, Kirchner, C, Jetter, M and Rühle, M (2007) Band-gap measurements of direct and indirect semiconductors using monochromated electrons. Phys Rev B 75, 1–8.CrossRefGoogle Scholar
He, K, Xin, HL, Zhao, K, Yu, X, Nordlund, D, Weng, TC, Li, J, Jiang, Y, Cadigan, CA, Richards, RM, Doeff, MM, Yang, XQ, Stach, EA, Li, J, Lin, F and Su, D (2015) Transitions from near-surface to interior redox upon lithiation in conversion electrode materials. Nano Lett 15, 1437–1444.CrossRefGoogle ScholarPubMed
Holtz, ME, Yu, Y, Gunceler, D, Gao, J, Sundararaman, R, Schwarz, KA, Arias, TA, Abruña, HD and Muller, DA (2014) Nanoscale imaging of lithium ion distribution during in situ operation of battery electrode and electrolyte. Nano Lett 14, 1453–1459.CrossRefGoogle ScholarPubMed
Horák, M and Stöger-Pollach, M (2015) The Čerenkov limit of Si, GaAs and GaP in electron energy loss spectrometry. Ultramicroscopy 157, 73–78.CrossRefGoogle ScholarPubMed
Jiang, N Spence, JCH (2004) Core-hole effects on electron energy-loss spectroscopy of Li2O. Phys Rev B 69, 115112.CrossRefGoogle Scholar
Jiang, N and Spence, JCH (2013) Valence electron energy-loss spectroscopy study of ZrSiO4 and ZrO2 . Ultramicroscopy 134, 68–76.CrossRefGoogle ScholarPubMed
Johnson, CS, Li, N, Lefief, C, Vaughey, JT and Thackeray, MM (2008) Synthesis, characterization and electrochemistry of lithium battery electrodes: xLi2MnO3 (1 - x) LiMn0.333Ni0.333Co0.333O2 (0≤x≤0.7). Chem Mater 2, 6095–6106.CrossRefGoogle Scholar
Kikkawa, J and Takeda, S (2007) Enhanced direct interband transitions in silicon nanowires studied by electron energy-loss spectroscopy. Phys Rev B 75, 245317.CrossRefGoogle Scholar
Kikkawa, J, Terada, S, Gunji, A, Nagai, T, Kurashima, K and Kimoto, K (2015) Chemical states of overcharged LiCoO2 particle surfaces and interiors observed using electron energy-loss spectroscopy. J Phys Chem C 119, 15823–15830.CrossRefGoogle Scholar
Kobayashi, H, Tabuchi, M, Shikano, M, Kageyama, H and Kanno, R (2003) Structure, and magnetic and electrochemical properties of layered oxides, Li2IrO3 . J Mater Chem 13, 957–962.CrossRefGoogle Scholar
Kurata, H, Lefevre, E, Colliex, C and Brydson, R (1993) Electron-energy-loss near-edge structures in the oxygen K-edge spectra of transition-metal oxides. Phys Rev B 47, 763–768.CrossRefGoogle ScholarPubMed
Lee, E, Blauwkamp, J, Castro, FC, Wu, J, Dravid, VP, Yan, P, Wang, C, Kim, S, Wolverton, C, Benedek, R, Dogan, F, Park, JS, Croy, JR and Thackeray, MM (2016) Exploring lithium-cobalt-nickel oxide spinel electrodes for >3.5 V Li-ion cells. ACS Appl Mater Interf 8, 27720–27729.CrossRefGoogle ScholarPubMed
Li, Z, Peng, Z, Zhang, H, Hu, T, Hu, M and Zhu, K (2016) [100]-Oriented LiFePO4 nanoflakes toward high rate Li-ion battery cathode. Nano Lett 16, 795–799.CrossRefGoogle Scholar
Lin, D, Liu, Y and Cui, Y (2017) Reviving the lithium metal anode for high-energy batteries. Nat Nanotechnol 12, 194–206.CrossRefGoogle ScholarPubMed
Lu, J, Chen, Z, Ma, Z, Pan, F, Curtiss, LA and Amine, K (2016) The role of nanotechnology in the development of battery materials for electric vehicles. Nat Nanotechnol 11, 1031–1038.CrossRefGoogle ScholarPubMed
Malis, T, Cheng, SC and Egerton, RF (1988) EELS log-ratio technique for specimen-thickness measurement in the TEM. J Electron Microsc Tech 8, 193–200.CrossRefGoogle ScholarPubMed
Martin, JM, Vacher, B, Ponsonnet, L and Dupuis, V (1996) Chemical bond mapping of carbon by image-spectrum EELS in the second derivative mode. Ultramicroscopy 65, 229–238.CrossRefGoogle Scholar
Mauchamp, V, Boucher, F and Moreau, P (2008a) Electron energy-loss spectroscopy in the low-loss region as a characterization tool of electrode materials. Ionics 14, 191–195.CrossRefGoogle Scholar
Mauchamp, V, Moreau, P, Ouvrard, G and Boucher, F (2008b) Local field effects at Li K edges in electron energy-loss spectra of Li, Li2O and LiF. Phys Rev B Condensed Matter Mater Phys 77, 1–9.Google Scholar
Moreau, P and Boucher, F (2012) Revisiting lithium K and iron M2,3 edge superimposition: The case of lithium battery material LiFePO4 . Micron 43, 16–21.CrossRefGoogle ScholarPubMed
Potapov, PL, Zschech, E and Stöger-Pollach, M (2009) Measuring the dielectric constant of materials from valence EELS. Micron 40, 262–268.CrossRefGoogle ScholarPubMed
Sigle, W, Amin, R, Weichert, K, van Aken, PA Maier, J (2009) Delithiation study of LiFePO4 crystals using electron energy-loss spectroscopy. Electrochem Solid State Lett 12, A151–A154.CrossRefGoogle Scholar
Stöger-Pollach, M (2008) Optical properties and bandgaps from low loss EELS: Pitfalls and solutions. Micron 39, 1092–1110.CrossRefGoogle ScholarPubMed
Tarascon, J, Poizot, P, Laruelle, S, Grugeon, S and Dupont, L (2000) Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 407, 496–499.Google Scholar
Wang, F, Graetz, J, Moreno, MS, Ma, C, Wu, L, Volkov, V and Zhu, Y (2011) Chemical distribution and bonding of lithium in intercalated graphite: Identification with optimized electron energy loss spectroscopy. ACS Nano 5, 1190–1197.CrossRefGoogle ScholarPubMed
Wang, YW, Kim, JS, Kim, GH and Kim, KS (2006) Quantum size effects in the volume plasmon excitation of bismuth nanoparticles investigated by electron energy loss spectroscopy. Appl Phys Lett 88, 143106.CrossRefGoogle Scholar
Williams, DB and Carter, CB (2009) Transmission Electron Microscopy: A Textbook for Materials Science, 2nd ed. New York, NY: Springer.CrossRefGoogle Scholar
Wu, JS, Kim, AM, Bleher, R, Myers, BD, Marvin, RG, Inada, H, Nakamura, K, Zhang, XF, Roth, E, Li, SY, Woodruff, TK, Halloran, TVO and Dravid, VP (2013) Imaging and elemental mapping of biological specimens with a dual-EDS dedicated scanning transmission electron microscope. Ultramicroscopy 128, 24–31.CrossRefGoogle ScholarPubMed
Zhu, X, Zhu, Y, Murali, S, Stoller, MD and Ruoff, RS (2011) Nanostructured reduced graphene oxide/Fe2O3 composite as a high-performance anode material for lithium ion batteries. ACS Nano 5, 3333–3338.CrossRefGoogle ScholarPubMed
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