Synergistic polarization engineering on BaTiO3 bulk and surface for boosting redox kinetics of polysulfides in lithium–sulfur batteries

The notorious shuttle effect of intermediate lithium polysulfides and the sluggish kinetics of sulfur redox reactions restrict the further development of high-energy-density lithium-sulfur (Li–S) batteries. Herein, a strategy of synergistic polarization engineering on ferroelectric barium titanate (BaTiO ₃) bulk and surface is reported, aiming to collectively improve the adsorption-catalytic ability of ferroelectric BaTiO ₃ to polysulfides. Differential phase contrast-scanning transmission electron microscopy (DPC-STEM) demonstrates that the introduction of ultrathin heteroepitaxial TiO _x surface can give rise to the surface local electric field differing from bulk internal polarization field. Experimental and theoretical results further reveal that synergistic polarization engineering by integrating the enhanced bulk internal polarization field with the surface local electric field can collaboratively realize excellent adsorption-catalytic activity resulting from rapid electrons transfer and optimized active sites. As a result, employing BaTiO ₃@TiO _x modified separator can endow the batteries with favorable rate performance (the discharge specific capacity achieves 710 mAh g ⁻¹ at 4 C) and substantial enhancement on cyclic performance (64.5 % capacity retention at 2 C over 500 cycles). Impressively, even at high sulfur loading of 2.5 mg cm ⁻², the BaTiO ₃@TiO _x-based cell still stabilizes 78 % capacity retention with at 1 C over 150 cycles, showing the practical potential of BaTiO ₃@TiO _x in optimizing catalytic efficiency.