To accelerate the commercial implementation of high-energy batteries, recent research thrusts have turned to the practicality of Si-based electrodes. Although numerous nanostructured Si-based materials with exceptional performance have been reported in the past 20 years, the practical development of high-energy Si-based batteries has been beset by the bias between industrial application with gravimetrical energy shortages and scientific research with volumetric limits. In this context, the microscale design of Si-based anodes with densified microstructure has been deemed as an impactful solution to tackle these critical issues. However, their large-scale application is plagued by inadequate cycling stability. In this review, we present the challenges in Si-based materials design and draw a realistic picture regarding practical electrode engineering. Critical appraisals of recent advances in microscale design of stable Si-based materials are presented, including interfacial tailoring of Si microscale electrode, surface modification of SiO x microscale electrode, and structural engineering of hierarchical microscale electrode. Thereafter, other practical metrics beyond active material are also explored, such as robust binder design, electrolyte exploration, prelithiation technology, and thick-electrode engineering. Finally, we provide a roadmap starting with material design and ending with the remaining challenges and integrated improvement strategies toward Si-based full cells.

Microsized silicon oxide (SiO) has become a highly potential anode material for practical lithium‐ion batteries (LIBs) in virtue of its low cost and high capacity. However, its commercialization is still impeded by the low inherent conductivity and nonignorable volume expansion of SiO in the lithiation/delithiation processes. Herein, an in situ catalytic growth approach is developed for grafting N‐doped bamboo‐like carbon nanotubes (NCNTs) onto the polydopamine‐coated SiO microparticles, yielding a unique adina rubella‐like SiO@NC‐NCNT composite. The cross‐sectional scanning electron microscopy images reveal that the flexible middle‐carbon layer plays a crucial role in alleviating volume expansions and improving structural stability of SiO@NC‐NCNTs. Theoretical density functional theory simulation results further prove that the rational construction of ternary heterostructure can effectively balance lithium adsorption energies and greatly improve conductivity of SiO@NC‐NCNTs. As a result, the as‐fabricated SiO@NC‐NCNTs LIB anode shows a high reversible specific capacity of 1103.7 mA h g−1 at 0.2 A g−1 after 200 cycles with a high retention of 99.6% and an outstanding rate capability of 569 mA h g−1 at 5000 mA g−1. The strategy developed herein demonstrates a feasible avenue for developing high‐energy SiO‐based anodes for LIBs.

The exploration of high‐efficiency and inexpensive electrocatalysts for oxygen reduction reaction (ORR) is of critical significance for renewable energy conversion. Herein, an in situ catalytic transformation strategy toward a unique hierarchical nanostructure is reported. In the architecture, Co nanoparticles encapsulated at the tip of bamboo‐like N‐doped carbon nanotubes (NCNTs) are grafted on N‐doped polypyrrole‐derived CNTs. Thanks to the smart design of unique 3D architecture, the NPCN@Co‐NCNTs catalyst displays an extraordinary ORR activity in 0.1 m KOH solution (the onset and half‐wave potentials are 0.96 and 0.90 V vs RHE, respectively), which is similar to commercial Pt/C catalyst (0.99 and 0.88 V vs RHE, respectively). Meanwhile, the catalyst shows the low Tafel slope of 78 mV dec−1 and long‐time stability. Experimental and theoretical results verify that the improved ORR performance is mainly related to the existence of Co nanoparticles protected by pyridinic‐N‐doped carbon, which lowers the theoretical overpotential of ORR. Density functional theory calculations reveal that Pyridinic‐NCCo site is the reactive site with the lowest overpotential for ORR (0.57 V). These results unambiguously indicate that the NPCN@Co‐NCNTs represent a low‐cost yet high‐efficiency electrocatalyst for the electrocatalytic ORR.

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