While lithium metal represents the ultimate high-energy-density battery anode material, its use is limited by dendrite formation and associated safety risks, motivating studies of the solid-electrolyte interphase layer that forms on the lithium, which is key in controlling lithium metal deposition. Dynamic nuclear polarisation enhanced NMR can provide important structural information; however, typical exogenous dynamic nuclear polarisation experiments, in which organic radicals are added to the sample, require cryogenic sample cooling and are not selective for the interface between the metal and the solid-electrolyte interphase. Here we instead exploit the conduction electrons of lithium metal to achieve an order of magnitude hyperpolarisation at room temperature. We enhance the 7Li, 1H and 19F NMR spectra of solid-electrolyte interphase species selectively, revealing their chemical nature and spatial distribution. These experiments pave the way for more ambitious room temperature in situ dynamic nuclear polarisation studies of batteries and the selective enhancement of metal-solid interfaces in a wider range of systems.