Copper inks are provided that include a plurality of core-shell nanostructures, with each nanostructure including a copper core and a barrier metal shell, a diameter of less than about 500 nm, and a distinct boundary between the copper core and the barrier metal shell. Methods of forming a copper ink are further provided and include an initial step of synthesizing an amount of copper nanoparticles in an aqueous solution. An amount of a barrier metal is then added to the copper nanoparticles to form a dispersion of the barrier metal and the copper nanoparticles, and a reducing agent is subsequently added to the dispersion to produce a copper ink comprising core-shell nanostructures having a copper core and a barrier metal shell. Copper films are then formed by applying that copper ink to a substrate and sintering the copper ink.