How lithium-ion cells age

Lithium-ion degradation on one page: where a cell ages, the SEI and cracking on graphite, lithium plating, the degrading cathode, manganese crossing to the anode and the gas that swells a pouch cell. Every caption and number is quoted from the cited papers.

1. Where a cell ages: Degradation is separated into three levels: the mechanisms, the observable consequences at cell level called modes, and operational effects such as capacity or power fade (Edge 2021). As a cell ages the binder and electrolyte decompose, the current collector corrodes, the separator melts and corrodes, and the cathode undergoes structural disorder and metal dissolution (Agubra 2013). 2. Anode ageing: The surface film on graphite is the predominant source of lithium-ion loss during storage: it raises the charge-transfer resistance and impedance and clogs pores. It cracks as the graphite lattice expands and contracts, and further reaction at the cracks may eventually isolate graphite particles (Agubra 2013); SEI cracks let the electrolyte reach the lithiated graphite, which can promote solvent co-intercalation and exfoliation (Yang 2026). 3. Lithium plating: High-EC electrolytes, a low anode/cathode capacity ratio, low temperature (−20 °C) and high charge rates make lithium plate on the graphite surface rather than intercalate; plating shows up as a voltage plateau on discharge and a low coulombic efficiency, and the anode is made larger than the cathode to prevent plating at its ends (Agubra 2013). In transparent full cells lithium plating can occur well before 70% state of charge, even at a low C-rate and at room temperature (Ma 2022). Lithium plated during fast charging becomes dead lithium or penetrates the separator and shorts the cell (Gopal 2026). 4. Cathode ageing: Phase transitions and lattice oxygen release lead to side reactions with the electrolyte, lattice collapse and transition-metal dissolution at the cathode surface (Yang 2026); in cells stored above 3.6 V electrolyte oxidation deposits insulating films over the active area (Agubra 2013); the formation, reformation and growth of the SEI and the CEI increase the active lithium lost during cycling (Nowak 2018). 5. Crosstalk: Manganese dissolved from the cathode deposits on the outer surface of the innermost SEI layer on graphite, where it speeds up electrolyte reduction and removes lithium from the cell’s operation (Vissers 2016); manganese and nickel ions taken into the graphite’s surface layer lead to continuous SEI formation, gas and capacity fade (Michalak 2015); manganese triggered lithium deposition on graphite from an early stage (< 200 cycles), which about 1 mol % Al in the cathode inhibited (Li 2017). In NMC cells the HF mechanism was disproven, and migrated metals accounted for capacity fade only in the per-mille range (Nowak 2018). 6. Gassing: During the first charge gas forms at a high rate as the SEI forms on graphite; pressed between the electrodes it moves to the pouch edges, and bubbles were never seen between the electrodes in cells that cycled well (Michalak 2015). The main formation gases were C₂H₄ and CO, mainly from ethylene carbonate (Schmidt 2025); with an NCM622 cathode O₂ and CO₂ evolved with both liquid and solid electrolytes (Strauss 2020).

Edge et al., “Lithium ion battery degradation: what you need to know”, Phys. Chem. Chem. Phys. 2021 (doi:10.1039/d1cp00359c); Agubra & Fergus, “Lithium Ion Battery Anode Aging Mechanisms”, Materials 2013 (doi:10.3390/ma6041310); Yang et al., “A Review of Failure Modes and Safety Strategies of Lithium-Ion Batteries from Materials to Systems”, Adv. Sci. 2026 (doi:10.1002/advs.76228); Ma et al., “Microscopy Diagnosis of the Onset of Lithium Plating in Transparent Lithium-Ion Full Cells”, ACS Appl. Mater. Interfaces 2022 (doi:10.1021/acsami.2c16090); Gopal et al., “Mapping Out Fast Charging Safe Limits for High-Loading Lithium-Ion Cells by High-Fidelity Operando Microscopy”, Small 2026 (doi:10.1002/smll.202514619); Nowak & Winter, “The Role of Cations on the Performance of Lithium Ion Batteries: A Quantitative Analytical Approach”, Acc. Chem. Res. 2018 (doi:10.1021/acs.accounts.7b00523); Vissers et al., “Role of Manganese Deposition on Graphite in the Capacity Fading of Lithium Ion Batteries”, ACS Appl. Mater. Interfaces 2016 (doi:10.1021/acsami.6b02061); Michalak et al., “Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging”, Sci. Rep. 2015 (doi:10.1038/srep15627); Li et al., “Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover”, ACS Nano 2017 (doi:10.1021/acsnano.7b01494); Schmidt et al., “High temperature in situ gas analysis for identifying degradation mechanisms of lithium-ion batteries”, Chem. Sci. 2025 (doi:10.1039/d4sc08105f); Strauss et al., “Gas Evolution in Lithium-Ion Batteries: Solid versus Liquid Electrolyte”, ACS Appl. Mater. Interfaces 2020 (doi:10.1021/acsami.0c02872); Gu et al., “A Lithium Dendrite Inhibitor in Graphite Anodes Enabling Fast-Charging and Low-Temperature Lithium-Ion Pouch Cells”, Adv. Mater. 2025 (doi:10.1002/adma.202501448); Herrán et al., “Advanced Electrochemical Diagnostics Validation for Early Detection of Lithium Plating in Lithium-Ion Batteries”, ACS Omega 2026 (doi:10.1021/acsomega.5c06081); Daigle et al., “Schiff Base as Additive for Preventing Gas Evolution in Li₄Ti₅O₁₂-Based Lithium-Ion Battery”, ACS Appl. Mater. Interfaces 2017 (doi:10.1021/acsami.7b15112).

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