To address the volume-change-induced pulverization problems of electrode materials, we propose a "silica reinforcement" concept, following which silica-reinforced carbon nanofibers with encapsulated Sb nanoparticles (denoted as SiO/Sb@CNFs) are fabricated via an electrospinning method. In this composite structure, insulating silica fillers not only reinforce the overall structure but also contribute to additional lithium storage capacity; encapsulation of Sb nanoparticles into the carbon-silica matrices efficiently buffers the volume changes during Li-Sb alloying-dealloying processes upon cycling and alleviates the mechanical stress; the porous carbon nanofiber framework allows for fast charge transfer and electrolyte diffusion. These advantageous characteristics synergistically contribute to the superior lithium storage performance of SiO/Sb@CNF electrodes, which demonstrate excellent cycling stability and rate capability, delivering reversible discharge capacities of 700 mA h/g at 200 mA/g, 572 mA h/g at 500 mA/g, and 468 mA h/g at 1000 mA/g each after 400 cycles. Ex situ as well as in situ TEM measurements confirm that the structural integrity of silica-reinforced Sb@CNF electrodes can efficiently withstand the mechanical stress induced by the volume changes. Notably, the SiO/Sb@CNF//LiCoO full cell delivers high reversible capacities of ∼400 mA h/g after 800 cycles at 500 mA/g and ∼336 mA h/g after 500 cycles at 1000 mA/g.

The design of tin-based anode materials (SnO2 or Sn) has become a major concern for lithium ion batteries (LIBs) owing to their different inherent characteristics. Herein, particulate SnO2 or Sn crystals coupled with porous N-doped carbon nanofibers (denoted as SnO2/PCNFs and Sn/PCNFs, respectively) are fabricated via the electrospinning method. The electrochemical behaviors of both SnO2/PCNFs and Sn/PCNFs are systematically investigated as anodes for LIBs. When coupled with porous carbon nanofibers, both SnO2 nanoparticles and Sn micro/nanoparticles display superior cycling and rate performances. SnO2/PCNFs and Sn/PCNFs deliver discharge capacities of 998 and 710 mA h g(-1) after 140 cycles (at 100, 200, 500 and 1000 mA g(-1) each for 10 cycles and then 100 cycles at 100 mA g(-1)), respectively. However, the Sn/PCNF electrodes show better cycling stability at higher current densities, delivering higher discharge capacities of 700 and 550 mA h g(-1) than that of SnO2/PCNFs (685 and 424 mA h g(-1)) after 160 cycles at 200 and 500 mA g(-1), respectively. The different superior electrochemical performance is attributed to the introduction of porous N-doped carbon nanofibers and their self-constructed networks, which, on the one hand, greatly decrease the charge-transfer resistance due to the high conductivity of N-doped carbon fibers; on the other hand, the porous carbon nanofibers with numerous voids and flexible one-dimensional (1D) structures efficiently alleviate the volume changes of SnO2 and Sn during the Li-Sn alloying-dealloying processes. Moreover, the discussion of the electrochemical behaviors of SnO2vs. Sn would provide new insights into the design of tin-based anode materials for practical applications, and the current strategy demonstrates great potential in the rational design of metallic tin-based anode materials.

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