Abstract
Hard carbons are the most investigated materials as negative electrode for Na-ion batteries, although the exact mechanism of sodium storage remains under debate. This work is focused on the study of the sodiation mechanism of non-graphitizing carbons (NGC) prepared in a wide range of pyrolysis temperatures (1000 °C–2500 °C), thus covering the whole range from hard carbons (HC) to glassy carbons (GC). Structural and textural characterizations show that increasing the pyrolysis temperature leads to NGCs with a more ordered structure, containing fewer heteroatoms and structural defects, and particularly leads to a developed closed microporosity. In this work, in situ Raman spectroscopy at different excitation wavelengths is used to clarify the mechanism of electrochemical sodiation: it is revealed that the intercalation of Na+ between the graphene layers occurs mainly during the sloping part of the galvanostatic profile, whereas the plateau at low voltage (below 0.1 V vs. Na+/Na) can be associated with the filling of micropores with sodium.