There are several questions and controversies regarding the Na storage mechanism in hard carbon. This springs from the difficulty of probing the vast diversity of possible configurational environments for Na storage, including surface and defect sites, edges, pores, and intercalation morphologies. In the effort to explain the observed voltage profile, typically existing of a voltage slope section and a low-voltage plateau, several experimental and computational studies have provided a variety of contradicting results. This work employs density functional theory to thoroughly examine Na storage in hard carbon in combination with electrochemical experiments. Our calculation scheme disentangles the possible interactions by evaluating the enthalpies of formation, shedding light on the storage mechanisms. Parallel evaluation of the Li and K storage, and comparison with experiments, put forward a unified reaction mechanism for the three alkali metals. The results underline the importance of exposed metal surfaces and metal-carbon interfaces for the stability of the pore-filling mechanism responsible for the low-voltage plateau, in excellent agreement with the experimental voltage profiles. This generalized understanding provides insights into hard carbons as negative electrodes and their optimized properties.

Pyrolysis is an effective way to convert biomass into biofuel while obtaining highly porous active carbon materials. In this study, a facile approach, involving hydrothermal and pyrolysis steps, is described for preparing hybrid metal oxide nanoparticle-embedded porous hard carbon matrices (MnO/C) from the biowaste rice husk and organometallic precursors. It was found that the pyrolysis/calcination temperature had a strong influence over the microstructure, especially over the porosity, but also over the carbon content and crystallinity of the nanocomposites; hence, the electrical properties can be controlled. Galvanostatic measurements showed that the nanocomposite obtained at 600 °C exhibited the highest charge/discharge capacity and best stability, delivering an initial discharge capacity of 1104 mA·h·g^-1 at a current density of 200 mA·g^-1, and retaining a value of 830 mA·h·g^-1 after 200 cycles, suggesting excellent cycle stability. A discharge capacity of 581 mA·h·g^-1 was obtained even at a current density as high as 2400 mA·g^-1, demonstrating superb rate capability. This outstanding electrochemical performance, ascribed to high electrochemical activity of the embedded MnO nanoparticles enhanced by electrical conductivity provided through the high surface area of the active porous carbon support, is discussed in relation to the microstructure of the nanocomposite.