Porous TiO_2–x/C Nanofibers with Axially Aligned Tunnel Pores as Effective Sulfur Hosts for Stabilized Lithium–Sulfur Batteries

Hierarchically porous TiO2–x/C nanofibers (NFs) with axially aligned cylindrical tunnel pore channels were synthesized as a sulfur (S) host for lithium–sulfur batteries (LSBs) by a microemulsion electrospinning method. We explored a synergistic chemical trapping reinforced by coordinatively unsaturated Ti3+ nuclei with oxygen deficiency (or more broadly via polar O–Ti–O units) in combination with physical trapping in both narrow pores (<5 nm) and larger ordered pore tunnels (20–100 nm) separated by thin walls to allow for a large volume of active material and rapid diffusion within the channels while effectively blocking out the diffusion of soluble lithium polysulfides. Due to this unique architecture and enhanced conductivity, the prepared materials enabled a high S loading (∼72 wt %) and significantly reduced the shuttle effect. Hence, the composite TiO2–x/C@S cathodes exhibited a high utilization of active materials, excellent rate performance, and promising cycling stability (retention of up to ∼1010 mAh g–1 after 150 cycles for the aerial capacity of 1.5 mAh cm–2, with very stable performance even for the high S loading of 2.5 mg cm–2). By designing control nanomaterials that lack either the pore tunnels or the desired chemical compositions, we elucidated the importance of the synergistic effect of both factors. This work demonstrates a successful exploration of oxide NFs with tunnel pores via a simple single-needle microemulsion electrospinning method, which should pave the way for similar nanomaterials engineering with other chemistries for improved LSB performance.