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To address the volume change-induced pulverization problem of tin-based anodes, a concept using hollow carbon nanoballs (HCNBs) as buffering supports is herein proposed. HCNBs with hollow interior, flexibility and graphitic crystallization are first prepared by a combined method of chemical vapor deposition (CVD) and template-synthesis using CH4 as the carbon source and CaCO3 as the conformal template. The ultrafine SnO2 nanoparticles are loaded onto the HCNBs (denoted as SnO2@HCNBs) via pyrolysis of tin(II) 2-ethylhexanoate at 300 °C in air. On further annealing SnO2@HCNBs in Ar, SnO2 is partially reduced to SnOx by consuming a part of carbon of HCNBs as the reducing agent, and thus SnOx@HCNBs are obtained (note that SnOx represents a composite consisting of SnO2, SnO and Sn phases). When applied as anode materials for lithium ion batteries (LIBs), HCNBs deliver high reversible capacities of 841 mA h g−1 after 125 cycles at 200 mA g−1, and 726 mA h g−1 after 400 cycles even at 1000 mA g−1, while SnO2@HCNBs and SnOx@HCNBs exhibit discharge capacities of 1042 and 1299 mA h g−1 after 400 cycles at 200 mA g−1, respectively. Notably, all of them display gradually increased capacity with retention over 100% even after long-term cycling, which is attributed to the novel robust characteristic of the HCNBs as revealed by the ex situ TEM analysis. The flexible hollow HCNBs with high graphitic crystallization not only efficiently tolerate the volume changes of the Li–Sn alloying–dealloying but also facilitate the electrolyte/charge transfer owing to the hollow structure and high conductivity of the HCNBs.

To address the volume change-induced pulverization problem of tin-based anodes, a concept using hollow carbon nanoballs (HCNBs) as buffering supports is herein proposed. HCNBs with hollow interior, flexibility and graphitic crystallization are first prepared by a combined method of chemical vapor deposition (CVD) and template-synthesis using CH4 as the carbon source and CaCO3 as the conformal template. The ultrafine SnO2 nanoparticles are loaded onto the HCNBs (denoted as SnO2@HCNBs) via pyrolysis of tin(ii) 2-ethylhexanoate at 300 °C in air. On further annealing SnO2@HCNBs in Ar, SnO2 is partially reduced to SnOx by consuming a part of carbon of HCNBs as the reducing agent, and thus SnOx@HCNBs are obtained (note that SnOx represents a composite consisting of SnO2, SnO and Sn phases). When applied as anode materials for lithium ion batteries (LIBs), HCNBs deliver high reversible capacities of 841 mA h g-1 after 125 cycles at 200 mA g-1, and 726 mA h g-1 after 400 cycles even at 1000 mA g-1, while SnO2@HCNBs and SnOx@HCNBs exhibit discharge capacities of 1042 and 1299 mA h g-1 after 400 cycles at 200 mA g-1, respectively. Notably, all of them display gradually increased capacity with retention over 100% even after long-term cycling, which is attributed to the novel robust characteristic of the HCNBs as revealed by the ex situ TEM analysis. The flexible hollow HCNBs with high graphitic crystallization not only efficiently tolerate the volume changes of the Li-Sn alloying-dealloying but also facilitate the electrolyte/charge transfer owing to the hollow structure and high conductivity of the HCNBs.