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Analytical and Bioanalytical Chemistry

, Volume 411, Issue 3, pp 581–589 | Cite as

Adaptation and improvement of an elemental mapping method for lithium ion battery electrodes and separators by means of laser ablation-inductively coupled plasma-mass spectrometry

  • Patrick Harte
  • Marco Evertz
  • Timo Schwieters
  • Marcel Diehl
  • Martin Winter
  • Sascha NowakEmail author
Research Paper
Part of the following topical collections:
  1. Elemental and Molecular Imaging by LA-ICP-MS

Abstract

In this study, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was applied to previously aged carbonaceous anodes from lithium ion batteries (LIBs). The electrodes were treated by cyclic aging in a lithium ion cell set-up with LiNi0.5Mn1,5O4 (LNMO) cathodes and hard carbon (HC)/mesocarbon microbead (MCMB) anodes. An inhomogeneous transition metal deposition pattern could be induced by replacing the spacer in a standard coin cell set-up with a washer. The inhomogeneity pattern matched the dimension of the washer depicted by the hole in the center. These transition metal (TM) patterns were used to optimize higher lateral scanning speeds and frequencies on the spatial resolution of the mapping experiments using LA-ICP-MS. Higher scanning speeds had an observable influence on the resolution of the obtained image and an overall saving of 60% with regard to time and gas consumption could be achieved. Additionally, the optimized method was applied to the cathode and separator in order to visualize the distribution and deposition pattern, respectively.

Keywords

Lithium ion battery LA-ICP-MS Metal migration Lithium distribution 

Notes

Funding information

The authors wish to thank the German Federal Ministry of Education and Research (BMBF) for funding this work in the project “Elektrolytlabor-4E” (03X4632) and the Ministry of Economic Affairs in North Rhine-Westphalia for funding the project “GrEEn” (W044A).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Nagaura T. Progress in batteries and solar cells, vol. 10. Brunswick, OH: JEC Press Inc; 1991.Google Scholar
  2. 2.
    Wagner R, Preschitschek N, Passerini S, Leker J, Winter M. Current research trends and prospects among the various materials and designs used in lithium-based batteries. J Appl Electrochem. 2013;43:481–96.  https://doi.org/10.1007/s10800-013-0533-6.CrossRefGoogle Scholar
  3. 3.
    Schmuch R, Wagner R, Hörpel G, Placke T, Winter M. Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat Energy. 2018;3:267–78.  https://doi.org/10.1038/s41560-018-0107-2.CrossRefGoogle Scholar
  4. 4.
    Patry G, Romagny A, Martinet S, Froelich D. Cost modeling of lithium-ion battery cells for automotive applications. Energy Sci Eng. 2015;3:71–82.  https://doi.org/10.1002/ese3.47.CrossRefGoogle Scholar
  5. 5.
    Armand M, Tarascon JM. Building better batteries. Nature. 2008;451:652–7.  https://doi.org/10.1038/451652a.CrossRefGoogle Scholar
  6. 6.
    Winter M, Brodd RJ. What are batteries, fuel cells, and supercapacitors? Chem Rev. 2004;104:4245–69.  https://doi.org/10.1021/cr020730k.CrossRefGoogle Scholar
  7. 7.
    Placke T, Kloepsch R, Dühnen S, Winter M. Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density. J Solid State Electrochem. 2017;21:1939–64.  https://doi.org/10.1007/s10008-017-3610-7.CrossRefGoogle Scholar
  8. 8.
    Fichtner M. Komplexhydride, Metallfluoride: Konversionsmaterialien für die Energiespeicherung. Chemie Unserer Zeit. 2013;47:230–8.  https://doi.org/10.1002/ciuz.201300604.CrossRefGoogle Scholar
  9. 9.
    He P, Yu H, Li D, Zhou H. Layered lithium transition metal oxide cathodes towards high energy lithium-ion batteries. J Mater Chem. 2012;22:3680.  https://doi.org/10.1039/c2jm14305d.CrossRefGoogle Scholar
  10. 10.
    Meister P, Jia H, Li J, Kloepsch R, Winter M, Placke T. Best practice: performance and cost evaluation of lithium ion battery active materials with special emphasis on energy efficiency. Chem Mater. 2016;28:7203–17.  https://doi.org/10.1021/acs.chemmater.6b02895.CrossRefGoogle Scholar
  11. 11.
    Zhang SS, Jow TR, Amine K, Henriksen GL. LiPF6–EC–EMC electrolyte for li-ion battery. J Power Sources. 2002;107:18–23.  https://doi.org/10.1016/S0378-7753(01)00968-5.CrossRefGoogle Scholar
  12. 12.
    Schmitz RW, Murmann P, Schmitz R, Müller R, Krämer L, Kasnatscheew J, et al. Investigations on novel electrolytes, solvents and SEI additives for use in lithium-ion batteries: systematic electrochemical characterization and detailed analysis by spectroscopic methods. Prog Solid State Chem. 2014;42:65–84.  https://doi.org/10.1016/j.progsolidstchem.2014.04.003.CrossRefGoogle Scholar
  13. 13.
    Xu K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem Rev. 2004;104:4303–417.  https://doi.org/10.1021/cr030203g.CrossRefGoogle Scholar
  14. 14.
    Amereller M, Schedlbauer T, Moosbauer D, Schreiner C, Stock C, Wudy F, et al. Electrolytes for lithium and lithium ion batteries: from synthesis of novel lithium borates and ionic liquids to development of novel measurement methods. Prog Solid State Chem. 2014;42:39–56.  https://doi.org/10.1016/j.progsolidstchem.2014.04.001.Google Scholar
  15. 15.
    Nowak S, Winter M. Elemental analysis of lithium ion batteries. J Anal At Spectrom. 2017;32:1833–47.  https://doi.org/10.1039/C7JA00073A.CrossRefGoogle Scholar
  16. 16.
    Kohs W, Santner HJ, Hofer F, Schröttner H, Doninger J, Barsukov I, et al. A study on electrolyte interactions with graphite anodes exhibiting structures with various amounts of rhombohedral phase. J Power Sources. 2003;119–121:528–37.  https://doi.org/10.1016/S0378-7753(03)00278-7.CrossRefGoogle Scholar
  17. 17.
    Agubra V, Fergus J. Lithium ion battery anode aging mechanisms. Materials (Basel). 2013;6:1310–25.  https://doi.org/10.3390/ma6041310.CrossRefGoogle Scholar
  18. 18.
    Winter M. The solid electrolyte interphase—the most important and the least understood solid electrolyte in rechargeable li batteries. Z Phys Chem. 2009;223:1395–406.  https://doi.org/10.1524/zpch.2009.6086.CrossRefGoogle Scholar
  19. 19.
    Grützke M, Kraft V, Hoffmann B, Klamor S, Diekmann J, Kwade A, et al. Aging investigations of a lithium-ion battery electrolyte from a field-tested hybrid electric vehicle. J Power Sources. 2015;273:83–8.  https://doi.org/10.1016/j.jpowsour.2014.09.064.CrossRefGoogle Scholar
  20. 20.
    Shin H, Park J, Sastry AM, Lu W. Degradation of the solid electrolyte interphase induced by the deposition of manganese ions. J Power Sources. 2015;284:416–27.  https://doi.org/10.1016/j.jpowsour.2015.03.039.CrossRefGoogle Scholar
  21. 21.
    Vetter J, Novák P, Wagner MR, Veit C, Möller KC, Besenhard JO, et al. Ageing mechanisms in lithium-ion batteries. J Power Sources. 2005;147:269–81.  https://doi.org/10.1016/j.jpowsour.2005.01.006.CrossRefGoogle Scholar
  22. 22.
    Evertz M, Horsthemke F, Kasnatscheew J, Börner M, Winter M, Nowak S. Unraveling transition metal dissolution of Li1.04Ni1/3Co1/3Mn1/3O2 (NCM 111) in lithium ion full cells by using the total reflection X-ray fluorescence technique. J Power Sources. 2016;329:364–71.  https://doi.org/10.1016/j.jpowsour.2016.08.099.CrossRefGoogle Scholar
  23. 23.
    Pieczonka NPW, Liu Z, Lu P, Olson KL, Moote J, Powell BR, et al. Understanding transition-metal dissolution behavior in LiNi0.5Mn1.5O4 high-voltage spinel for lithium ion batteries. J Phys Chem C. 2013;117:15947–57.  https://doi.org/10.1021/jp405158m.CrossRefGoogle Scholar
  24. 24.
    Dong HJ, Shin YJ, Oh SM. Dissolution of spinel oxides and capacity losses in 4 V. J Electrochem Soc. 1996;143:2204–11.  https://doi.org/10.1149/1.1836981.CrossRefGoogle Scholar
  25. 25.
    Schwieters T, Evertz M, Mense M, Winter M, Nowak S. Lithium loss in the solid electrolyte interphase: Lithium quantification of aged lithium ion battery graphite electrodes by means of laser ablation-inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectroscopy. J Power Sources. 2017;356:47–55.  https://doi.org/10.1016/j.jpowsour.2017.04.078.CrossRefGoogle Scholar
  26. 26.
    Schwieters T, Evertz M, Fengler A, Börner M, Dagger T, Stenzel Y, et al. Visualizing elemental deposition patterns on carbonaceous anodes from lithium ion batteries: a laser ablation-inductively coupled plasma-mass spectrometry study on factors influencing the deposition of lithium, nickel, manganese and cobalt after dissolution. J Power Sources. 2018;380:194–201.  https://doi.org/10.1016/j.jpowsour.2018.01.088.CrossRefGoogle Scholar
  27. 27.
    Evertz M, Schwieters T, Börner M, Winter M, Nowak S. Matrix-matched standards for the quantification of elemental lithium ion battery degradation products deposited on carbonaceous negative electrodes using pulsed-glow discharge-sector field-mass spectrometry. J Anal At Spectrom. 2017;32:1862–7.  https://doi.org/10.1039/c7ja00129k.CrossRefGoogle Scholar
  28. 28.
    Russo RE, Mao X, Mao SS. Peer reviewed: the physics of laser ablation in microchemical analysis. Anal Chem. 2002;74:70A–7A.  https://doi.org/10.1021/ac0219445.CrossRefGoogle Scholar
  29. 29.
    Börner M, Horsthemke F, Kollmer F, Haseloff S, Friesen A, Niehoff P, et al. Degradation effects on the surface of commercial LiNi0.5Co0.2Mn0.3O2 electrodes. J Power Sources. 2016;335:45–55.  https://doi.org/10.1016/j.jpowsour.2016.09.071.CrossRefGoogle Scholar
  30. 30.
    Kominato A, Yasukawa E, Sato N, Ijuuin T, Asahina H, Mori S. Analysis of surface films on lithium in various organic electrolytes. J Power Sources. 1997;68:471–5.  https://doi.org/10.1016/S0378-7753(97)02592-5.CrossRefGoogle Scholar
  31. 31.
    Peled E, Bar Tow D, Merson A, Gladkich A, Burstein L, Golodnitsky D. Composition, depth profiles and lateral distribution of materials in the SEI built on HOPG-TOF SIMS and XPS studies. J Power Sources. 2001;97–98:52–7.  https://doi.org/10.1016/S0378-7753(01)00505-5.CrossRefGoogle Scholar
  32. 32.
    Pozebon D, Scheffler GL, Dressler VL, Nunes MAG. Review of the applications of laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) to the analysis of biological samples. J Anal At Spectrom. 2014;29:2204–28.  https://doi.org/10.1039/C4JA00250D.CrossRefGoogle Scholar
  33. 33.
    Koch J, Günther D. Review of the state-of-the-art of laser ablation-inductively coupled plasma mass spectrometry. Appl Spectrosc. 2011;65:155–62.  https://doi.org/10.1366/11-06255.CrossRefGoogle Scholar
  34. 34.
    Chen L, Liu Y, Hu Z, Gao S, Zong K, Chen H. Accurate determinations of fifty-four major and trace elements in carbonate by LA-ICP-MS using normalization strategy of bulk components as 100%. Chem Geol. 2011;284:283–95.  https://doi.org/10.1016/j.chemgeo.2011.03.007.CrossRefGoogle Scholar
  35. 35.
    Günther D, Hattendorf B. Solid sample analysis using laser ablation-inductively coupled plasma mass spectrometry. TrAC Trends Anal Chem. 2005;24:255–65.  https://doi.org/10.1016/j.trac.2004.11.017.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Patrick Harte
    • 1
  • Marco Evertz
    • 1
  • Timo Schwieters
    • 1
  • Marcel Diehl
    • 1
  • Martin Winter
    • 1
    • 2
  • Sascha Nowak
    • 1
    Email author
  1. 1.MEET Battery Research Center, Institute of Physical ChemistryUniversity of MünsterMünsterGermany
  2. 2.Helmholtz-Institute Münster, IEK-12Forschungszentrum Jülich GmbHMünsterGermany

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