Calendering of battery electrodes during the manufacturing process enhances the volumetric energy density by increasing the electrode density and has a substantial impact on the cell performance of Li-ion and post-Li-ion batteries. Herein, we present a detailed study on the influence of electrode density on the electrochemical performance of sulfurized poly(acrylonitrile) (SPAN) cathodes. A correlation of the density of the SPAN cathodes with electrode properties and cell performance by applying various chemical and electrochemical methods is displayed. Our results showed that while calendering reduces the electrical resistance, compressing the electrodes to densities higher than 1.05 g cm−3 leads to a reduction of the rate capability, which is caused by a compression-induced reduction of active reaction sites and a poor wettability of the electrode with electrolyte, both visible by an increase in the charge-transfer resistance.
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