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Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries

Nature Catalysis volume 1, pages 255–262 (2018)Cite this article

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Abstract

The formation of solid electrolyte interphase on graphite anodes plays a key role in the efficiency of Li-ion batteries. However, to date, fundamental understanding of the formation of LiF as one of the main solid electrolyte interphase components in hexafluorophosphate-based electrolytes remains elusive. Here, we present experimental and theoretical evidence that LiF formation is an electrocatalytic process that is controlled by the electrochemical transformation of HF impurity to LiF and H2. Although the kinetics of HF dissociation and the concomitant production of LiF and H2 is dependent on the structure and nature of surface atoms, the underlying electrochemistry is the same. The morphology, and thus the role, of the LiF formed is strongly dependent on the nature of the substrate and HF inventory, leading to either complete or partial passivation of the interface. Our finding is of general importance and may lead to new opportunities for the improvement of existing, and design of new, Li-ion technologies.

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Fig. 1: Chemical transformation of H2O to HF in 1 M LiPF6.
Fig. 2: Electrocatalytic transformation of HF to LiF and H2 on well-defined metal surfaces.
Fig. 3: Schematic of the proposed reaction mechanism for the electrocatalytic conversion of HF to H2 and LiF.
Fig. 4: Electrocatalytic transformation of HF to LiF and H2 on well-defined carbon surfaces.
Fig. 5: Electrocatalytic transformation of HF to LiF and H2 on a real graphite sample.

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References

  1. Ross, P. N. & Lipkowski, J. Structure of Electrified Interfaces (VCH, New York, 1993).

  2. Stamenkovic, V. R., Strmcnik, D., Lopes, P. P. & Markovic, N. M. Energy and fuels from electrochemical interfaces. Nat. Mater. 16, 57–69 (2017).

    Article  CAS  Google Scholar 

  3. Wieckowski, A. Interfacial Electrochemistry (Marcel Dekker, New York, 1999).

  4. Marković, N. & Ross, P. N. Surface science studies of model fuel cell electrocatalysts. Surf. Sci. Rep. 45, 117–229 (2002).

    Article  Google Scholar 

  5. Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).

    Article  Google Scholar 

  6. An, S. J. et al. The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling. Carbon NY 105, 52–76 (2016).

    Article  CAS  Google Scholar 

  7. Peled, E. & Menkin, S. Review—SEI: past, present and future. J. Electrochem. Soc. 164, A1703–A1719 (2017).

    Article  CAS  Google Scholar 

  8. Verma, P., Maire, P. & Novák, P. A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries. Electrochim. Acta 55, 6332–6341 (2010).

    Article  CAS  Google Scholar 

  9. Nie, M., Abraham, D. P., Chen, Y., Bose, A. & Lucht, B. L. Silicon solid electrolyte interphase (SEI) of lithium ion battery characterized by microscopy and spectroscopy. J. Phys. Chem. C 117, 13403–13412 (2013).

    Article  CAS  Google Scholar 

  10. Owejan, J. E., Owejan, J. P., Decaluwe, S. C. & Dura, J. A. Solid electrolyte interphase in Li-ion batteries: evolving structures measured in situ by neutron reflectometry. Chem. Mater. 24, 2133–2140 (2012).

    Article  CAS  Google Scholar 

  11. Soto, F. A., Ma, Y., Martinez De La Hoz, J. M., Seminario, J. M. & Balbuena, P. B. Formation and growth mechanisms of solid-electrolyte interphase layers in rechargeable batteries. Chem. Mater. 27, 7990–8000 (2015).

    Article  CAS  Google Scholar 

  12. Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4417 (2004).

    Article  CAS  Google Scholar 

  13. Aurbach, D. Review of selected electrode—solution interactions which determine the performance of Li and Li ion batteries. J. Power Sources 89, 206–218 (2000).

    Article  CAS  Google Scholar 

  14. Edström, K., Herstedt, M. & Abraham, D. P. A new look at the solid electrolyte interphase on graphite anodes in Li-ion batteries. J. Power Sources 153, 380–384 (2006).

    Article  Google Scholar 

  15. Zhang, B. et al. Role of 1,3-propane sultone and vinylene carbonate in solid electrolyte interface formation and gas generation. J. Phys. Chem. C 119, 11337–11348 (2015).

    Article  CAS  Google Scholar 

  16. Leroy, S., Martinez, H., Dedryvère, R., Lemordant, D. & Gonbeau, D. Influence of the lithium salt nature over the surface film formation on a graphite electrode in Li-ion batteries: an XPS study. Appl. Surf. Sci. 253, 4895–4905 (2007).

    Article  CAS  Google Scholar 

  17. Leroy, S. et al. Surface film formation on a graphite electrode in Li-ion batteries: AFM and XPS study. Surf. Interface Anal. 37, 773–781 (2005).

    Article  CAS  Google Scholar 

  18. Aurbach, D., Zinigrad, E., Cohen, Y. & Teller, H. A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ion. 148, 405–416 (2002).

    Article  CAS  Google Scholar 

  19. Aurbach, D., Markovsky, B., Shechter, A., Ein-Eli, Y. & Cohen, H. A comparative study of synthetic graphite and Li electrodes in electrolyte solutions based on ethylene carbonate–dimethyl carbonate mixtures. J. Electrochem. Soc. 143, 3809–3820 (1996).

    Article  CAS  Google Scholar 

  20. Lee, H., Cho, J.-J., Kim, J. & Kim, H.-J. Comparison of voltammetric responses over the cathodic region in LiPF6 and LiBETI with and without HF. J. Electrochem. Soc. 152, A1193–A1198 (2005).

    Article  CAS  Google Scholar 

  21. Terborg, L. et al. Investigation of thermal aging and hydrolysis mechanisms in commercial lithium ion battery electrolyte. J. Power Sources 242, 832–837 (2013).

    Article  CAS  Google Scholar 

  22. Kawamura, T., Okada, S. & Yamaki, J. Decomposition reaction of LiPF6-based electrolytes for lithium ion cells. J. Power Sources 156, 547–554 (2006).

    Article  CAS  Google Scholar 

  23. Aurbach, D. et al. Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems. J. Power Sources 68, 91–98 (1997).

    Article  CAS  Google Scholar 

  24. Plakhotnyk, A. V., Ernst, L. & Schmutzler, R. Hydrolysis in the system LiPF6—propylene carbonate—dimethyl carbonate—H2O. J. Fluor. Chem. 126, 27–31 (2005).

    Article  CAS  Google Scholar 

  25. Nakajima, T. & Groult, H. Fluorinated Materials for Energy Conversion (Elsevier, Oxford, 2005).

  26. Lux, S. F. et al. The mechanism of HF formation in LiPF6 based organic carbonate electrolytes. Electrochem. Commun. 14, 47–50 (2012).

    Article  CAS  Google Scholar 

  27. Aurbach, D. Electrode–solution interactions in Li-ion batteries: a short summary and new insights. J. Power Sources 119–121, 497–503 (2003).

    Article  Google Scholar 

  28. Zhang, Z. & Zhang, S. S. Rechargeable Batteries: Materials, Technologies and New Trends (Springer, New York, 2015).

  29. Wang, R., Li, X., Wang, Z. & Guo, H. Manganese dissolution from LiMn2O4 cathodes at elevated temperature: methylene methanedisulfonate as electrolyte additive. J. Solid State Electrochem. 20, 19–28 (2016).

    Article  CAS  Google Scholar 

  30. Pieczonka, N. P. W. et al. Understanding transition-metal dissolution behavior in LiNi0.5Mn1.5O4 high-voltage spinel for lithium ion batteries. J. Phys. Chem. C 117, 15947–15957 (2013).

    Article  CAS  Google Scholar 

  31. Kang, S. J., Yu, S., Lee, C., Yang, D. & Lee, H. Effects of electrolyte-volume-to-electrode-area ratio on redox behaviors of graphite anodes for lithium-ion batteries. Electrochim. Acta 141, 367–373 (2014).

    Article  CAS  Google Scholar 

  32. Strmcnik, D. et al. When small is big: the role of impurities in electrocatalysis. Top. Catal. 58, 1174–1180 (2015).

    Article  CAS  Google Scholar 

  33. Marković, N., Gasteiger, H., Grgur, B. & Ross, P. Oxygen reduction reaction on Pt(111): effects of bromide. J. Electroanal. Chem. 467, 157–163 (1999).

    Article  Google Scholar 

  34. Strmcnik, D. S. et al. Unique activity of platinum adislands in the CO electrooxidation reaction. J. Am. Chem. Soc. 130, 15332–15339 (2008).

    Article  CAS  Google Scholar 

  35. Subbaraman, R. et al. Origin of anomalous activities for electrocatalysts in alkaline electrolytes. J. Phys. Chem. C 116, 22231–22237 (2012).

    Article  CAS  Google Scholar 

  36. Vetter, K. J. Electrochemical Kinetics: Theoretical and Experimental Aspects (Academic, New York, 1967).

  37. Thiel, P. A., Madey, T. E. & Sloan, A. P. The interaction of water with solid surfaces: fundamental aspects. Surf. Sci. Rep. 7, 211–385 (1987).

    Article  CAS  Google Scholar 

  38. Henderson, M. A. The interaction of water with solid surfaces: fundamental aspects revisited. Surf. Sci. Rep. 46, 1–308 (2002).

    Article  CAS  Google Scholar 

  39. Trasatti, S. Work function, electronegativity, and electrochemical behaviour of metals: III. Electrolytic hydrogen evolution in acid solutions. Electroanal. Chem. Interfac. Electrochem. 39, 163–184 (1972).

    Article  CAS  Google Scholar 

  40. Greeley, J., Jaramillo, T. F., Bonde, J., Chorkendorff, I. & Nørskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 5, 909–913 (2006).

    Article  CAS  Google Scholar 

  41. Strmcnik, D., Lopes, P. P., Genorio, B., Stamenkovic, V. R. & Markovic, N. M. Design principles for hydrogen evolution reaction catalyst materials. Nano Energy 29, 29–36 (2016).

    Article  CAS  Google Scholar 

  42. Staszak-Jirkovský, J. et al. Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media. ACS Catal. 5, 6600–6607 (2015).

    Article  Google Scholar 

  43. Maibach, J., Lindgren, F., Eriksson, H., Edström, K. & Hahlin, M. Electric potential gradient at the buried interface between lithium-ion battery electrodes and the SEI observed using photoelectron spectroscopy. J. Phys. Chem. Lett. 7, 1775–1780 (2016).

    Article  CAS  Google Scholar 

  44. Matsuoka, O. et al. Ultra-thin passivating film induced by vinylene carbonate on highly oriented pyrolytic graphite negative electrode in lithium-ion cell. J. Power Sources 108, 128–138 (2002).

    Article  CAS  Google Scholar 

  45. Alliata, D., Kötz, R., Novák, P. & Siegenthaler, H. Electrochemical SPM investigation of the solid electrolyte interphase film formed on HOPG electrodes. Electrochem. Commun. 2, 436–440 (2000).

    Article  CAS  Google Scholar 

  46. Jeong, S.-K., Inaba, M., Abe, T. & Ogumi, Z. Surface film formation on graphite negative electrode in lithium-ion batteries: AFM study in an ethylene carbonate-based solution. J. Electrochem. Soc. 148, A989–A993 (2001).

    Article  CAS  Google Scholar 

  47. Domi, Y. et al. Electrochemical AFM observation of the HOPG edge plane in ethylene carbonate-based electrolytes containing film-forming additives. J. Electrochem. Soc. 159, A1292–A1297 (2012).

    Article  CAS  Google Scholar 

  48. Domi, Y. et al. In situ AFM study of surface film formation on the edge plane of HOPG for lithium-ion batteries. J. Phys. Chem. C 115, 25484–25489 (2011).

    Article  CAS  Google Scholar 

  49. Peled, E. et al. Composition, depth profiles and lateral distribution of materials in the SEI built on HOPG-TOF SIMS and XPS studies. J. Power Sources 97–98, 52–57 (2001).

    Article  Google Scholar 

  50. Metzger, M., Strehle, B., Solchenbach, S. & Gasteiger, H. A. Origin of H2 evolution in LIBs: H2O reduction vs. electrolyte oxidation. J. Electrochem. Soc. 163, A798–A809 (2016).

    Article  CAS  Google Scholar 

  51. Mortensen, J. J., Hansen, L. B. & Jacobsen, K. W. Real-space grid implementation of the projector augmented wave method. Phys. Rev. B Condens. Matter Mater. Phys. 71, 1–11 (2005).

    Article  Google Scholar 

  52. Enkovaara, J. et al. Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method. J. Phys. Condens. Matter 22, 253202 (2010).

    Article  CAS  Google Scholar 

  53. Hjorth Larsen, A. et al. The atomic simulation environment—a Python library for working with atoms. J. Phys. Condens. Matter 29, 273002 (2017).

    Article  Google Scholar 

  54. Hammer, B., Hansen, L. & Nørskov, J. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).

    Article  Google Scholar 

  55. Hansen, M. H. & Rossmeisl, J. pH in grand canonical statistics of an electrochemical interface. J. Phys. Chem. C 120, 29135–29143 (2016).

    Article  CAS  Google Scholar 

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Acknowledgements

This research was sponsored by BMW Technology Corporation. The research was conducted at Argonne National Laboratory—a US Department of Energy Office of Science laboratory operated by UChicago Argonne under contract number DE-AC02-06CH11357 and in part at the Technische Universität, München. We acknowledge support from the Office of Science, Office of Basic Energy Sciences and Materials Sciences and Engineering Division. We also thank C. Thompson and H. You for help with the AFM and crystal truncation rod measurements.

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Authors and Affiliations

  1. Materials Science Division, Argonne National Laboratory, Argonne, IL, USA

    Dusan Strmcnik, Justin G. Connell, Milena Zorko, Pedro Martins, Pietro P. Lopes, Bostjan Genorio, Vojislav R. Stamenkovic & Nenad M. Markovic

  2. Nano-Science Center, Department of Chemistry, University of Copenhagen, Copenhagen, Denmark

    Ivano E. Castelli, Thomas Østergaard & Jan Rossmeisl

  3. Chair of Technical Electrochemistry, Department of Chemistry and Catalysis Research Center, Technische Universität München, Garching, Germany

    Dominik Haering & Hubert A. Gasteiger

  4. Battery Cell Technology, BMW Group, München, Germany

    Filippo Maglia & Byron K. Antonopoulos

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Contributions

D.S., J.G.C., H.A.G. and N.M.M. conceived and designed the experiments. D.S., J.G.C., D.H., M.Z., P.M., P.P.L. and B.G. performed the experiments. I.E.C., T.Ø. and J.R. performed the calculations. D.S., J.G.C., I.E.C., F.M., B.K.A., J.R., H.A.G., V.R.S. and N.M.M. discussed the results and wrote the paper.

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Correspondence to Dusan Strmcnik or Jan Rossmeisl.

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Supplementary Methods, Supplementary Figures 1–16, Supplementary Tables 1–3, Supplementary References.

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Strmcnik, D., Castelli, I.E., Connell, J.G. et al. Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries. Nat Catal 1, 255–262 (2018). https://doi.org/10.1038/s41929-018-0047-z

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