CMN 2026

On the Role of Crack Electrolyte Infiltration in the Degradation and Performance of Battery Active Particles

  • Luza-Vega, Sebastián (University of Oxford)
  • Zhao, Ying (Tongji University)
  • Martínez-Pañeda, Emilio (University of Oxford)

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Cathode particle fracture is widely recognised as a major degradation pathway in lithium-ion batteries; repeated chemo-mechanical strains during cycling generate internal stresses that promote intergranular cracking, increase impedance, and accelerate capacity fade. However, fracture can permit electrolyte wetting of newly exposed internal surfaces, potentially altering local reaction pathways and thus introducing some performance benefits. While electrolyte infiltration into cracks increases the electrochemically active surface area, its role in the spatial redistribution of interfacial electrochemical reactions remains unclear. We present a modelling study that isolates the effect of electrolyte wetting on interfacial reaction redistribution in cracked cathode particles using a controlled modelling comparison. We employ a fully coupled electro-chemo-mechanical framework that explicitly resolves lithium concentration, electrostatic potential, and stress fields in both the active material and the electrolyte inside and outside cracks, and we compare it with a single-particle chemo-mechanical model with uniform flux conditions, as commonly assumed in the literature. The coupled model predicts strong spatial heterogeneity in interfacial reaction rates along crack surfaces, with pronounced amplification near crack tips. This redistribution is governed predominantly by solid-state lithium concentration variations, while electrolyte primarily acts as a geometric and electrochemical enabler of additional reaction pathways. Consequently, local concentration limits are reached later, and stresses near the delithiation–lithiation transition are amplified, indicating that uniform flux single-particle models primarily underestimate local utilisation limits and stress histories relevant to fatigue-driven crack propagation.