This work relates to a rigorous study of the correlation among surface chemistry FIR, XPS), 3D structure (X-ray and neutron scattering), morphology (SEM, AFM), and electrochemical and impedance behavior of lithiated carbon electrodes in commonly used liquid electrolyte solutions, Four different types of carbons were explored in a single study. These included, for comparison, two types of disordered carbons, single-wall carbon nanotubes (SWNT), and synthetic graphite powder as a reference system. All four types of carbons develop a similar surface chemistry in alkyl carbonate solutions which is dominated by solvent reduction. The differences in the 3D structure of these carbons leads to pronounced. differences in the mechanisms of Li-insertion into them. The effect of the carbons' 3D structure on the solid-state diffusion of Li-ions is demonstrated and discussed.