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Sustainable and green manufacturing of hard carbon (HC) material in a low-cost way is the key issue in promoting its industrial applications in Na-ion batteries (SIB). Nowadays, most synthesis ways to prepare HC need the help of chemical reagents to improve its Na-ion storage performance. Herein, we firstly developed a completely green biological fermentation technology to prepare HCs on a large scale using cheap and renewable carbon sources of various biomass starch. Pre-treatment by bio-fermentation can effectively modify the carbon precursor for facile pyrolysis to fabricate starch-based HCs, and make its internal microstructure with larger interlayer spacing, more disordered structure and abundant closed micropores. Finally, a case of cornstarch-based hard carbon exhibits a high reversible capacity of 335 mA h g−1 at a current density of 30 mA h g−1 and high rate performance with a reversible capacity of 140.6 mA h g−1 even at a high current of 5 A g−1 as well as long cycling stability. In-situ Raman spectra, ex-situ SAXS and ex-situ XPS tests during discharge and charge process reveal the pore filling mechanism of quasi-metallic Na in hard carbon anode. Such a "bread-making"strategy is a facile and scalable route to fabricate various starch-based hard carbons with improved performance, demonstrating a very practically promising application for industrial manufacture. • A green biological fermentation technology to prepare HCs is firstly developed. • Renewable carbon sources of various biomass starch derived HCs are achieved. • Bio-fermentation effectively improve interlayer spacing with abundant closed micropores. • HC with a reversible capacity of 335 mA h g−1 and long cycling stability is demonstrated. • Such a "bread-making" strategy is a scalable route to fabricate hard carbons at a kilogram. [ABSTRACT FROM AUTHOR]

Abstract: A new type of CoO nanoparticles encapsulated by graphitable hollow carbon sphere (GHCS) composite material was synthesized. The core–shell structure CoO/GHCS composite shows the improved cyclability as an anodic material in Li-ion battery. The core–shell composite containing 50wt% CoO exhibits a reversible capacity of 584mAhg−1 at a constant current density of 100mAg−1 between 0 and 3.0V (vs. Li+/Li), and remains a capacity retention of 95% after 50th cycle. The improvement could be attributed to that the GHCS with a good electronic conductivity and high surface severs as dispersing medium to prevent CoO nanoparticles from aggregating, and provide the enough space to buffer the volume change during the Li-ion insertion and extraction reactions in CoO nanoparticles. [Copyright &y& Elsevier]

Inspired by the successful application of spinel LiMn 2 O 4 cathode in Li-ion batteries, analogous spinel ZnMn 2 O 4 (ZMO) is regarded as a promising cathode for rechargeable aqueous Zn-ion batteries (ZIBs). Nevertheless, clear Zn2+ storage mechanism and phase transition of spinel ZMO is still scarce. Herein, in the first time, we report an in-situ Raman study in dynamically probing the phase and structure evolution of a spinel ZMO-based cathode during charging-discharging process, in which spinel ZMO nanoparticles are anchored on porous carbon polyhedrons (PCPs). By in-situ investigation, it is demonstrated that the electrochemical mechanism can be attributed to the highly reversible phase transformation between spinel ZMO and λ-type MnO 2 upon Zn2+ insertion/extraction, which is driven by stepwise oxidation and reduction reactions of Mn3+/Mn4+ along with efficient charge carriers. Furthermore, the resultant ZMO@PCPs composite as cathode delivers a large reversible capacity of 125.6 mAh g−1 at a high current density of 1 A g−1 after 2000 cycles, representing superior long-term cyclic stability (capacity retention of 90.3%) and remarkable rate capability in aqueous ZIBs. As a proof of concept, high-performance flexible aqueous ZIBs are fabricated and represent stable electrochemical performance under various deformation states, indicating their potential applications in portable and wearable electronics. • A 3D-confined spinel ZnMn 2 O 4 cathode is proposed for aqueous Zn-ion batteries (ZIBs). • Zn2+ storage mechanism is explored by in-situ Raman investigation in the first time. • Reversible phase change between ZnMn 2 O 4 and λ-MnO 2 upon Zn2+ insertion/extraction. • The resultant cathode represents superior electrochemical behaviors in aqueous ZIBs. • Flexible aqueous ZIBs show stable electrochemical performance at deformation states. [ABSTRACT FROM AUTHOR]