Abstract Li-ion batteries are commonly used in portable electronic devices due to their outstanding energy and power density. A remaining issue which hinders the breakthrough e.g. in the automotive sector is the high production cost. For low power applications, such as stationary storage, batteries with electrodes thicker than 300 μm were suggested. High energy densities can be attained with only a few electrode layers which reduces production time and cost. However, mass and charge transport limitations can be severe at already small C-rates due to long transport pathways. In this article we use a detailed 3D micro-structure resolved model to investigate limiting factors for battery performance. The model is parametrized with data from the literature and dedicated experiments and shows good qualitative agreement with experimental discharge curves of thick NMC-graphite Li-ion batteries. The model is used to assess the effect of inhomogeneities in carbon black distribution and gives answers to the possible occurrence of lithium plating during battery charge. Based on our simulations we can predict optimal operation strategies and improved design concepts for future Li-ion batteries employing thick electrodes.