A layered cathode structure for a molten carbonate fuel cell is provided, along with methods of forming a layered cathode and operating a fuel cell including a layered cathode. The layered cathode can include at least a first cathode layer and a second cathode layer. The first cathode layer can correspond to a layer that is adjacent to the molten carbonate electrolyte during operation, while the second cathode layer can correspond to a layer that is adjacent to the cathode collector of the fuel cell. The first cathode layer can be formed by sintering a layer that includes a conventional precursor material for forming a cathode, such as nickel particles. The second cathode layer can be formed by sintering a layer that includes a mixture of particles of a conventional precursor material and 1.0 vol % to 30 vol % of particles of a lithium pore-forming compound. The resulting layered cathode structure can have an increased pore size adjacent to the cathode collector to facilitate diffusion of CO2 into the electrolyte interface, while also having a smaller pore size adjacent to the electrolyte to allow for improved electrical contact and/or reduced polarization at the interface between the electrolyte and the cathode.