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Lithiation–delithiation reactions in Li-ion batteries do exhibit a huge electrochemically driven volume change of the anode material between the lithium-free and lithiated-host states, which results in a gradually fading capacity. Minimizing this volume change of the electrode during cycling is essential to achieve stable electrochemical behavior and thus for innovating design of electrode materials for Li storage. Here, ordered mesoporous CoSn intermetallic anode materials with various Co/Sn atomic ratios are developed. A dual-buffer effect is discovered that accommodates the volume changes in the electrode material by not only repeatedly generating void nanospaces but also by incorporating electrochemically inactive elements. Novel insights into the nanostructural changes of electrode materials during the lithiation–delithiation process are obtained by in operando small angle X-ray scattering. The degrees of volume change and nanoscopic order are found to be highly dependent on the Co contents in the mesoporous CoSn intermetallic anode materials, being possible to achieve a durable nanostructured electrode upon prolonged cycling.

We report on a facile synthesis of the ordered mesoporous carbon (OMC) materials with systematically controlled microporosity and mesoporosity simultaneously through the nano-replication route using phosphoric acid as the acid catalyst and activation agent. The use of phosphoric acid affects the pore structures of OMC materials, such as the formation of numerous micropores by activation of the carbon framework and the enlargement of mesopores by spontaneous phase separation during the carbonization. The mesopore sizes, surface areas, total pore volumes, and micropore volumes of the OMC materials are highly dependent on the phosphoric acid content and can be systematically controlled in the range 3.7–7.5 nm, 1027–2782 m2 g–1, 1.12–3.53 cm3 g–1 and 0.34–0.95 cm3 g–1, respectively. OMC materials with systematically controlled pore structures were successfully synthesized using phosphoric acid as the carbonization catalyst and mesoporous silica materials with cubic Ia3d and 2-D hexagonal mesostructures as the templates. The phosphoric acid in the synthesis of ordered mesoporous carbon materials acts as the chemical activating agent for micropore generation of the carbon framework and pore-expanding agent for controlling of mesopore size, in addition to functioning as the acid catalyst. The present synthesis pathway is very useful for preparing OMC materials with tunable mesopore sizes and well-developed microporosities at the same time.