Electrochemical Kinetics of Degradation of Graphite Anodes in Lithium Ion Batteries
Authors: Das Supratim , Bazant Martin Z. 
Published: May 2020

Growth of the solid electrolyte interphase (SEI) is a major driver of capacity fade in LIBs. Despite its importance, the fundamental mechanisms remain unclear, primarily because of the complicated reaction pathways involved[1–3]. SEI growth can be both electrochemical and chemical in nature[4], and thus, it is a strong function of the potential and degree of lithiation of the electrode. We model the early-stage and long-term growth of SEI by accurately capturing the potential dependence of its formation kinetics as well as long term rate limiting steps, and validating it against the world’s largest open source battery cycling data, generated in-house[5]. This is done using the Multiphase Porous Electrode Theory (MPET) framework[6] on graphite (phase separating) and carbon black (non phase separating) particles.

Lithium plating is another key degradation phenomenon that has been elusive, and it becomes important while trying to fast-charge batteries, i.e., 0% - 80% state-of-charge in 30 mins. We show that lithium plating is a key function of electrode morphology, phase-separation dynamics and potential. Phase-separation in graphite is modeled in the electrode using the Cahn-Hilliard Reaction framework described by Bazant[7]. We understand the electrochemistry of the onset of lithium plating with in-situ measurements connected to real time cell potential in a phase-separating electrode for the first time[8].

Results indicate that the peak SEI-forming currents are higher for higher driving currents. Also, we find that SEI only grows during electrode lithiation, i.e. the battery only degrades while being charged. We also find that onset of lithium plating is correctly captured only when phase separation in active material is accounted for. Further, the onset of plating is delayed on electrodes with a thick SEI layer – understanding SEI/plating coupling is integral to predicting fast charging manufacturing protocols for LIBs. This work holds promise for the predictive design of procedures[9] for manufacture and formation of LIBs.

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[4] Das, S.; Attia, P. M.; Chueh, W. C.; Bazant, M. Z. Electrochemical Kinetics of SEI Growth on Carbon Black: Part II. Modeling. J. Electrochem. Soc. 2019, 166 (4), E107–

E118. https://doi.org/10.1149/2.0241904jes.

[5] Attia, P. M.; Das, S.; Harris, S. J.; Bazant, M. Z.; Chueh, W. C. Electrochemical Kinetics of SEI Growth on Carbon Black: Part I. Experiments. J. Electrochem. Soc. 2019, 166 (4), E97–E106. https://doi.org/10.1149/2.0231904jes.

[6] Smith, R. B.; Bazant, M. Z. Multiphase Porous Electrode Theory, J. Electrochem. Soc. 2017, 164 (11). https://doi.org/10.1149/2.0171711jes.

[7] Bazant, M. Z., Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics, Accounts of Chemical Research, 46(5), 1144–1160. https://doi.org/10.1021/ar300145c

[8] T. Gao, Y. Han, S. Das, T. Zhou, D. Fraggedakis, N. Nadkarni, C. N. Yeh, W. Chueh, J. Li, M.Z. Bazant, Interplay of lithium intercalation and plating on graphite using in-situ optical measurements, submitted.

[9] Huang, W.; Attia, P. M.; Wang, H.; Renfrew, S. E.; Jin, N.; Das, S.; Zhang, Z.; Boyle, D. T.; Li, Y.; Bazant, M. Z.; McCloskey, B. D.; Chueh, W. C. and Cui, Y.; Nano

Letters 2019 19 (8), 5140-5148. DOI: 10.1021/acs.nanolett.9b01515