Silicon is an attractive material for anodes in energy storage devices, because it has ten times the theoretical capacity of its state-of-the-art carbonaceous counterpart. Silicon anodes can be used both in traditional lithium-ion batteries and in more recent Li-O2 and Li-S batteries as a replacement for the dendrite-forming lithium metal anodes. The main challenges associated with silicon anodes are structural degradation and instability of the solid-electrolyte interphase caused by the large volume change (∼300%) during cycling, the occurrence of side reactions with the electrolyte, and the low volumetric capacity when the material size is reduced to a nanometre scale. Here, we propose a hierarchical structured silicon anode that tackles all three of these problems. Our design is inspired by the structure of a pomegranate, where single silicon nanoparticles are encapsulated by a conductive carbon layer that leaves enough room for expansion and contraction following lithiation and delithiation. An ensemble of these hybrid nanoparticles is then encapsulated by a thicker carbon layer in micrometre-size pouches to act as an electrolyte barrier. As a result of this hierarchical arrangement, the solid-electrolyte interphase remains stable and spatially confined, resulting in superior cyclability (97% capacity retention after 1,000 cycles). In addition, the microstructures lower the electrode-electrolyte contact area, resulting in high Coulombic efficiency (99.87%) and volumetric capacity (1,270 mAh cm(-3)), and the cycling remains stable even when the areal capacity is increased to the level of commercial lithium-ion batteries (3.7 mAh cm(-2)).

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In this work we have carried out systematic studies and identified the critical role of hydrogen peroxide instead of the generally believed citrate in the well-known chemical reduction route to silver nanoplates. This improved understanding allows us to develop consistently reproducible processes for the synthesis of nanoplates with high efficiency and yields. By harnessing the oxidative power of H(2)O(2), various silver sources including silver salts and metallic silver can be directly converted to nanoplates with the assistance of an appropriate capping ligand, thus significantly enhancing the reproducibility of the synthesis. Contrary to the previous conclusion that citrate is the key component, we have determined that the group of ligands with selective adhesion to Ag (111) facets can be expanded to many di- and tricarboxylate compounds whose two nearest carboxylate groups are separated by two or three carbon atoms. We have also found that the widely used secondary ligand polyvinylpyrrolidone can be replaced by many hydroxyl group-containing compounds or even removed entirely while still producing nanoplates of excellent uniformity and stability. In addition to the general understanding of NaBH(4) as a reducing agent, it has also been found to act as a capping agent to stabilize the silver nanoparticles, prolong the initiation time required for nanoplate nucleation, and contribute to the control of the thickness as well as the aspect ratio of silver nanoplates. The improved insight into the specific roles of the reaction components and significantly enhanced reproducibility are expected to help elucidate the formation mechanism of this interesting nanostructure.

Silicon, because of its high specific capacity, is intensively pursued as one of the most promising anode material for next‐generation lithium‐ion batteries. In the past decade, various nanostructures are successfully demonstrated to address major challenges for reversible Si anodes related to pulverization and solid‐electrolyte interphase. However, the electrochemical performance is still limited by challenges that stem from the use of nanomaterials. In this progress report, the focus is on the challenges and recent progress in the development of Si anodes for lithium‐ion battery, including initial Coulombic efficiency, areal capacity, and material cost, which call for more research effort and provide a bright prospect for the widespread applications of silicon anodes in the future lithium‐ion batteries.