Recent research advances in charge-conducting materials have enabled the transformation of the naturally-occurring materials into crucial components in many technologies, including renewable energy storage devices or bioelectronics. Among various candidates, eumelanins are promising charge storage materials, exhibiting hybrid electronic ionic conductivity in a hydrated environment. The chemical and electrochemical properties of eumelanins are relatively well studied; however, the structure-property relationship is still elusive up to date. Herein, we reported the mesoscale structure of eumelanins and its impact on the charge transport. X-ray scattering suggests that eumelanin pigments exhibit the semi-crystalline structure with ordered d-spacings. These unique mesoscale structures further influence the charge transport mechanism with the cations of various sizes. Understanding the structures with consequent electrochemical properties suggest that eumelanins can further be tuned to serve as high-performance naturally-occurring charge storage materials.
