Bilayer cathodes comprising two active materials are explored for their ability to improve lithium-ion battery charging performance. Electrodes are manufactured with various arrangements of lithium nickel manganese cobalt oxide Li[Ni0.6Co0.2Mn0.2]O2 (NMC622) and lithium iron phosphate LiFePO4 (LFP) active particles, including in two different discrete sub-layers. We present experimental data on the sensitivity of the electrode C rate performance to the electrode design. To understand the complex bilayer electrode performance, and to identify an optimal design for fast charging, we develop an extension to the Doyle-Fuller-Newman (DFN) model of electrode dynamics that accommodates different active materials in any number of sub-layers, termed the multilayer DFN (M-DFN) model. The M-DFN model is validated against experimental data and then used to explain the performance differences between the electrode arrangements. We show how the different open circuit potential functions of NMC and LFP can be exploited synergistically through electrode design. Manipulating the Li electrolyte concentration increases achievable capacity. Finally the M-DFN model is used to further optimise the best performing bilayer electrode arrangement by adjusting the ratio of the LFP and NMC sub-layer thickness.