Topic 16 - Unveiling the Complexity of Advanced Li-ion Cell Chemistry

Degradation Mechanisms and the SEI · Battery Shortcut

Section 5 · Topic 16

Degradation Mechanisms and the SEI

Cell aging is the sum of chemical and mechanical processes that share two endpoints — they consume cyclable lithium and they raise internal resistance.

Three mechanisms drain the cell’s finite lithium inventory and stiffen its impedance, each through a different driver. Telling them apart matters: each leaves a distinct field signature, developed in Section 7.

SEI GROWTH SEI (thickening) consumes cyclable Li internal resistance ↑ LITHIUM PLATING dendrite dead lithium dendrite → short risk MECHANICAL FADE current collector cracked particle cracking severs contact; delamination = dead zones
Fig. 5.16 — Three mechanisms, two endpoints. SEI growth thickens the passivating film and consumes lithium chemically. Plating deposits metallic lithium and dead lithium on the surface. Mechanical fade cracks particles and delaminates the coating from the collector — severing contact rather than consuming lithium.

SEI growth

Formed on the first charge when the carbonate electrolyte reduces at the graphite surface, a stable SEI is electronically insulating — which stops further electrolyte reduction — and ionically conductive, which admits desolvated lithium. The film does not stay fixed: high temperature and high electrode potential drive it to thicken, each increment consuming more lithium and adding resistance, producing the calendar-clock fade of Section 3.

Lithium plating

Plating is a kinetic failure, not a thermodynamic one. When charging at low temperature or excessive rate pushes lithium toward the anode faster than it can intercalate, the lithium deposits as metal instead of inserting. Some re-intercalates on rest — the basis of the diagnostic signature in Section 3 — but much remains as electrically isolated dead lithium, and the deposits can grow as separator-threatening dendrites.

Mechanical fade

Each cycle expands and contracts the electrode lattices, and over thousands of cycles that breathing fractures active-material particles — severing the electronic path to the current collector — and delaminates the active coating from the foils, leaving dead zones that no longer store charge.

Diagnostic distinction

Particle cracking and SEI consumption are different failures: cracking severs contact and strands capacity mechanically, while SEI growth consumes lithium and raises resistance chemically. A post-mortem that conflates them misreads the dominant failure — Section 7 separates the signatures.

Section 5 · Advanced ElectrochemistryTopic 16 / 23

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