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• A three-dimensional Ni,Co-embedded CNT-coated N-doped hollow porous carbon (Ni/Co-CNT/NHPC) cathode has been designed and prepared for lithium-sulfur battery. • The Ni/Co-CNT/NHPC-S cathode possesses a high specific capacity of 1352 mA h g-1 and an excellent cycle stability at 1 C with low capacity decay of 0.094% per cycle over 500 cycles. • The mechanism of suppressing the shuttle effect on the cathode materials is discussed by analyzing adsorption experiments and density functional theory（DFT）calculation. Lithium-sulfur (Li-S) batteries have attracted great attentions due to their high specific capacity. However, the poor cycle stability caused by polysulfide shuttles, volume expansion and formation of lithium dendrites limit their practical applications. In the present work, to tackle the poor stability and unstable rate capability, a MOF-doping strategy is developed to construct a hollow porous carbon framework，which consists of Ni, Co particles and CNT on a N-doped shell surface (Ni/Co-CNT/NHPC). This hollow framework increases the load of S, slows down the volume changes, and can physically entrap soluble polysulfide. It is found that the CNT-coated network structure is beneficial for optimizing the conductivity and wettability of the material, which accelerates the reaction kinetics. Moreover, synergistic effect of abundant defects and Ni, Co nanoparticles strengthens the chemisorption of polysulfides, which suppresses the shuttle effect. As a consequence, the Ni/Co-CNT/NHPC-S cathode harvests a high specific capacity (1352 mA h g-1), and shows an excellent cycling stability at 1 C with low capacity decay of 0.094% over 500 cycles. [ABSTRACT FROM AUTHOR]

[Display omitted] • A double carbon encapsulated porous composite with compact interface was designed. • The P-Si@rGO@C electrode exhibited inspiring rate-capability and long-cycling life. • The storage mechanism was explored via reaction kinetics, Ex-situ tests, and DFT. • A Li x Si prelithiation suspension was provided to enhance the ICE of the full cell. Developing high-performance composites with fast charging and superior cycle life is paramount for lithium-ion batteries (LIBs). Herein, we synthesized a double-shell carbon-coated porous structure composite with a compact surface (P-Si@rGO@C) using low-cost commercial micron-sized silicon (Si) instead of nanoscale silicon. Results reveal that the unique P-Si@rGO@C features high adaptability to volume expansion, accelerates electron/ion transmission rate, and forms a stable solid electrolyte interphase (SEI) film. This phenomenon arises from the synergistic effect of abundant internal voids and an external double-layer carbon shell with a dense surface. Specifically, the P-Si@rGO@C anode exhibits a high initial coulombic efficiency (ICE) (88.0 %), impressive rate-capability (612.1 mAh/g at 2C), and exceptional long-term cyclability (972.2 mAh/g over 500 cycles at 0.5C). Further kinetic studies elucidate the diffusion-capacitance hybrid energy storage mechanism and reveal an improved Li+ diffusion coefficient (from 3.47 × 10-11 to 2.85 × 10-9 cm2 s-1). Ex-situ characterization confirms the crystal phase change of micron-sized Si and the formation of a stable LiF-rich SEI. Theoretical calculations support these findings by demonstrating an enhancement in the adsorption ability of Si to Li+ (from -0.89 to -0.97 eV) and a reduction in the energy migration barrier (from 0.35 to 0.18 eV). Additionally, practical Li x Si powder is shown to increase the ICE of full cells from 67.4 % to 87.9 %. Furthermore, a pouch cell utilizing the prelithiated P-Si@rGO@C anode paired with LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM111) cathode delivers a high initial reversible capacity of 7.2 mAh and 76.8 % capacity retention after 100 cycles. This work provides insights into the application of commercial silicon-aluminum alloy powder in the anode of high-energy LIBs. [ABSTRACT FROM AUTHOR]