Calendering battery electrodes improves electronic transport
and
energy density while increasing the ionic resistance in the pore space.
In hierarchically structured electrodes, the open porosity of the
active material particles offers additional ionic transport paths.
However, there is a lack of knowledge about the interaction between
these pores and the porosity surrounding the particles. Considering
both inter- and intragranular pore space, we combine a Doyle–Fuller–Newman
cell model with experimental discharge curves to show that ionic transport
paths in hierarchically structured electrodes change with compaction
and the discharge rate. If the intergranular porosity is high, it
carries most of the ionic current from the separator to the current
collector. The intragranular porosity ensures ionic transport into
the porous particles. High compaction of a hierarchically structured
electrode leads to an increasing contribution of the intragranular
pores to ionic transport across the electrode with a rising discharge
rate. This study offers a modeling approach to explore the optimum
calendering process for different types of hierarchically structured
electrode materials.