Precision-Engineered Nanocatalysts Via Lattice Tailoring and d-Band Center Modulation for High-Performance Lithium-Sulfur Batteries

Abstract

Lithium-sulfur (Li-S) batteries are promising for high-energy-density storage, but their performance is limited by sluggish lithium polysulfide (LiPS) conversion kinetics. Here, we tackle this issue by synthesizing ultrafine truncated octahedral TiO₂ nanocrystals (P-O_v-TiO₂), featuring specific {101} facets and dual defects—phosphorus doping and oxygen vacancies. Acting as an efficient electrocatalyst in the separator, P-O_v-TiO₂ exhibits superior catalytic properties, where oxygen vacancies modulate the electronic structure, enhancing electron enrichment and charge transfer; phosphorus doping tailors the d-band center of the catalyst, strengthening Ti-S interactions between the {101} facets and LiPSs. As a result, Li-S coin cells modified with P-O_v-TiO₂ achieve a high specific capacity of 895 mAh g⁻¹ at 5 C and exhibit a minimal decay rate of 0.14% per cycle over 200 cycles. Furthermore, Li-S pouch cells deliver a high capacity of 1004 mAh g⁻¹ at 0.1 C under lean electrolyte conditions. This study elucidates the mechanisms of charge states on specific crystal planes and deepens our understanding of dual-defect engineering in Li-S electrochemistry, offering a promising approach for developing efficient and cost-effective catalysts for Li-S battery applications.

Keywords

catalyst / lithium-sulfur batteries / oxygen-deficient TiO₂ / phosphorus-doping / specific facet

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