Lithium plating is the deposition of metallic lithium on the surface of the graphite anode. This is one of the most significant degradation mechanisms:
- reduces charge rate capability
- consumes reversible lithium, thus reducing cell capacity
- reduces anode porosity and hence reduces charge and discharge rate
- lithium dendrite formation can lead to an internal short circuit and thermal runaway
Lu et al [1] show relaxation processes at different state-of-charge (SOC), wherein thermodynamically unstable graphite particles undergo a drastic intra-particle lithium redistribution and inter-particle lithium exchange at intermediate SOCs, whereas the electrode equilibrates much slower at low and high SOCs.
There are two basic types [2] of plating:
- Thermodynamic Plating where the negative electrode surface becoming fully lithiated, in which the Li has nowhere else to go.
- Kinetic Plating occurs during fast charging, where the high electrolyte potential increases the rate of the side reaction relative to the main intercalation reaction.
Study of Lithium Plating in Commercial Cells
A review of the paper by Heinrich Ditler et al [3].
The study went far beyond classical electrical analysis. The team combined real time measurements with autopsies of more than 60 commercial cells. First they identified the signs of plating through relaxation and differential voltage analysis. Then they opened the cells and confirmed that the shiny structures were indeed metallic lithium. And not just any lithium: for the first time in commercial cells they observed a polyhedral morphology, a rhombic dodecahedron, very different from the sharp dendrites that dominate the literature. That observation changes how we understand nucleation and the kinetics of the phenomenon.
References
- Lu, X., Lagnoni, M., Bertei, A. et al. Multiscale dynamics of charging and plating in graphite electrodes coupling operando microscopy and phase-field modelling. Nat Commun 14, 5127 (2023). https://doi.org/10.1038/s41467-023-40574-6
- Jacqueline S. Edge, Simon O’Kane, Ryan Prosser, Niall D. Kirkaldy, Anisha N. Patel, Alastair Hales, Abir Ghosh, Weilong Ai, Jingyi Chen, Jiang Yang, Shen Li, Mei-Chin Pang, Laura Bravo Diaz, Anna Tomaszewska, M. Waseem Marzook, Karthik N. Radhakrishnan, Huizhi Wang, Yatish Patel, Billy Wu and Gregory J. Offer, Lithium ion battery degradation: what you need to know, Phys. Chem. Chem. Phys., 2021, 23, 8200
- Heinrich Ditler, Thorsten Tegetmeyer-Kleine, Gereon Stahl, Christiane Rahe, Dirk Uwe Sauer, Lithium plating in commercial lithium-ion cells: An extensive study combining electrical methods with post-mortem analysis, Journal of Energy Storage, Volume 132, Part C, 2025
Related Reading
- Fast Charging of a Lithium-Ion Battery – the charging conditions that push a cell toward kinetic plating.
- Concentration Polarization: The Hidden Limit on How Fast You Can Charge a Lithium-Ion Cell – another mechanism that constrains safe charge rates.
See also: Temperature Limits of a Battery, Cell Temperature Gradient, Cell to Pack Fast Charging, Knee Point