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Electrode microstructure directly affects ion and electron transport and, in turn, has a strong correlation to battery performance. Understanding the separate yet complementary effects of ionic and electronic transport in cell behavior is a challenge. This work provides through a combination of experiments and modeling a better understanding of the relationship between three aspects of the cell: ion transport within the electrode, electrode uniformity, and cell degradation. The first part of this work compares two experimental methods that determine ion transport in terms of tortuosity, a dimensionless geometric factor. The polarization-interrupt and blocking-electrolyte methods measure effective diffusivity and conductivity, respectively. The tortuosity of several commercial-quality electrodes was measured using both methods, producing reasonable agreement between the two methods in most cases. Next, the effect of cell cycling on ionic and electronic transport of electrodes was investigated. Using the blocking electrolyte method, the tortuosity of electrode films at varying extents of cycling was determined. Variations in electronic resistivity were quantified by micro-scale measurements using a previously developed micro-four-line probe. The changes in tortuosity and electronic resistivity were investigated for a graphite anode and several cathode chemistries including LiCoO2, LiNixCoyMnzO2, LiFePO4, and blends of transition metal oxides. Clear evidence of changes in tortuosity and electronic resistivity was observed during cell formation and cycling. The magnitude of the changes strongly depended on the chemistry of electrodes and cycling conditions. The results indicate that, under normal cycling conditions, electronic resistivity increases while tortuosity unexpectedly decreases. However, accelerated cycling conditions (i.e. elevated temperature) can lead to both electronic resistivity and tortuosity increase. Finally, the interplay of electrode tortuosity heterogeneity and Li-plating was investigated. The Li-plating reaction was incorporated into a Newman-type model and validated using the voltage profile and capacity-loss data from experiments. The simulation result shows that a heterogeneous anode can cause non-uniform Li plating while cathode heterogeneity did not have a significant effect. The Li-plating profile across the thickness of the anode with cell cycling showed that Li tends to plate at the high tortuosity region near the separator. Unexpectedly, Li plating tends to shift to the current collector side upon a sufficient increase in porosity close to the separator. Simulated capacity loss vs. cycling data indicates that there is a feedback mechanism with cycling: as cycling continues the rate of Li plating for the high-tortuosity region decreases at the separator side and the other two regions will eventually catch up in terms of plating.