Capturing the calendering U-shape in lithium-ion electrode thermal conductivity

Abstract

Calendering is a key manufacturing step in lithium-ion electrode production, increasing volumetric energy density by reducing electrode porosity. Its effect on through-plane effective thermal conductivity, however, can be non-monotonic: measurements of graphite-based anodes show an initial decrease in thermal conductivity during early calendering followed by recovery at higher compaction. Conventional porosity-based effective-medium closures cannot reproduce this U-shaped behaviour. We develop a calendering-aware extension of the Zehner--Bauer--Schl\"under model that combines a Knudsen-corrected porous-medium baseline with a compression-indexed contact contribution. For graphite electrodes, the model represents the competing effects of increasing particle contact and calendering-induced reorientation of anisotropic graphite particles, which initially reduces favourable through-plane heat-transport pathways. For quasi-isotropic NMC cathodes, the observed response is instead captured through process-dependent contact-network evolution. Across 27 calendering states spanning thin and thick graphite anodes and NMC622 and NMC811 cathodes, the proposed closure reduces the mean absolute percentage error from 31.1% for the zero-fit reference model to 4.5%. The result shows that incorporating process-dependent microstructural evolution is necessary to capture the measured conductivity minimum. Validation across additional electrode formulations, thicknesses, and chemistries remains necessary to assess transferability.