Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds

Adam Tornheim, Soroosh Sharifi-Asl, Juan C. Garcia, Javier Bareño, Hakim Iddir, Reza Shahbazian-Yassar, Zhengcheng Zhang

    Research output: Contribution to journalArticle

    Abstract

    Surface degradation of lithium-ion cathodes at high voltages represents a significant barrier to increasing the useable energy of conventional cathodes. Though much work has been focused on mitigating the detrimental effects of such phenomena, the complex and correlated mechanisms involved have made progress difficult. Herein, the effect of electrolyte identity on surface degradation is examined. LiNi0.5Mn0.3Co0.2O2 (NMC532)/Li4Ti5O12 (LTO) full cells were constructed using three different electrolytes: a baseline organic carbonate electrolyte, a baseline organic carbonate electrolyte with an oxidizable additive, and a fluorinated carbonate electrolyte. Each system was subjected to a 60 h potentiostatic hold at 3.05 V (4.6 V vs. Li+/Li) and subsequently deconstructed for characterization via transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Molecular simulations were carried out on each distinct component of the three electrolytes in contact with crystal surfaces of an NMC532 particle. Results indicate an affinity for the additive-containing electrolyte to extract atomic oxygen from the cathode surface, whereas the fluorinated electrolyte components have negligible interactions. Hydrogen abstraction from the baseline electrolyte is facilitated by the NMC532 surface. TEM analysis of cathode surfaces, after the potentiostatic holds, revealed that the NMC532 particles cycled with the additive-containing electrolyte underwent significant surface degradation, including changes to local crystal structure in a region penetrating 20–40 nm from the surface; consistent with oxygen and lithium loss from the cathode material. However, the NMC532 in contact with the fluorinated electrolyte showed a disordered layer of just a few nm in thickness, similar to the depth of crystal disorder observed in pristine NMC532 primary particles. EELS data of the oxygen K-edge also indicated transition metal (TM) reduction, consistent with oxygen loss and changes in crystal structure extending into the cathode surface for each of the electrolytes surveyed. These surface reactions, including oxygen loss, are shown to correlate well with elevated oxidation currents and surface reconstructions of cathode particles.

    LanguageEnglish (US)
    Pages216-225
    Number of pages10
    JournalNano Energy
    Volume55
    DOIs
    StatePublished - Jan 1 2019

    Fingerprint

    Lithium Compounds
    Manganese Compounds
    Manganese compounds
    Lithium compounds
    Titanium compounds
    Nickel compounds
    Carbonation
    Electron scattering
    Electron energy loss spectroscopy
    Surface reactions
    High resolution transmission electron microscopy
    Electron energy levels
    Electrolytes
    Transition metals
    Energy dissipation
    Cathodes
    Salts
    Crystal structure
    Rocks
    Oxygen

    Keywords

    • Cathode/electrolyte interface
    • Electrolytes
    • High voltages
    • Lithium-ion batteries

    ASJC Scopus subject areas

    • Renewable Energy, Sustainability and the Environment
    • Materials Science(all)
    • Electrical and Electronic Engineering

    Cite this

    Tornheim, A., Sharifi-Asl, S., Garcia, J. C., Bareño, J., Iddir, H., Shahbazian-Yassar, R., & Zhang, Z. (2019). Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds. Nano Energy, 55, 216-225. https://doi.org/10.1016/j.nanoen.2018.10.065

    Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds. / Tornheim, Adam; Sharifi-Asl, Soroosh; Garcia, Juan C.; Bareño, Javier; Iddir, Hakim; Shahbazian-Yassar, Reza; Zhang, Zhengcheng.

    In: Nano Energy, Vol. 55, 01.01.2019, p. 216-225.

    Research output: Contribution to journalArticle

    Tornheim, A, Sharifi-Asl, S, Garcia, JC, Bareño, J, Iddir, H, Shahbazian-Yassar, R & Zhang, Z 2019, 'Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds' Nano Energy, vol. 55, pp. 216-225. https://doi.org/10.1016/j.nanoen.2018.10.065
    Tornheim, Adam ; Sharifi-Asl, Soroosh ; Garcia, Juan C. ; Bareño, Javier ; Iddir, Hakim ; Shahbazian-Yassar, Reza ; Zhang, Zhengcheng. / Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds. In: Nano Energy. 2019 ; Vol. 55. pp. 216-225.
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    abstract = "Surface degradation of lithium-ion cathodes at high voltages represents a significant barrier to increasing the useable energy of conventional cathodes. Though much work has been focused on mitigating the detrimental effects of such phenomena, the complex and correlated mechanisms involved have made progress difficult. Herein, the effect of electrolyte identity on surface degradation is examined. LiNi0.5Mn0.3Co0.2O2 (NMC532)/Li4Ti5O12 (LTO) full cells were constructed using three different electrolytes: a baseline organic carbonate electrolyte, a baseline organic carbonate electrolyte with an oxidizable additive, and a fluorinated carbonate electrolyte. Each system was subjected to a 60 h potentiostatic hold at 3.05 V (4.6 V vs. Li+/Li) and subsequently deconstructed for characterization via transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Molecular simulations were carried out on each distinct component of the three electrolytes in contact with crystal surfaces of an NMC532 particle. Results indicate an affinity for the additive-containing electrolyte to extract atomic oxygen from the cathode surface, whereas the fluorinated electrolyte components have negligible interactions. Hydrogen abstraction from the baseline electrolyte is facilitated by the NMC532 surface. TEM analysis of cathode surfaces, after the potentiostatic holds, revealed that the NMC532 particles cycled with the additive-containing electrolyte underwent significant surface degradation, including changes to local crystal structure in a region penetrating 20–40 nm from the surface; consistent with oxygen and lithium loss from the cathode material. However, the NMC532 in contact with the fluorinated electrolyte showed a disordered layer of just a few nm in thickness, similar to the depth of crystal disorder observed in pristine NMC532 primary particles. EELS data of the oxygen K-edge also indicated transition metal (TM) reduction, consistent with oxygen loss and changes in crystal structure extending into the cathode surface for each of the electrolytes surveyed. These surface reactions, including oxygen loss, are shown to correlate well with elevated oxidation currents and surface reconstructions of cathode particles.",
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