Boosting Polysulfide Redox Kinetics by Temperature-Induced Metal-Insulator Transition Effect of Tungsten-Doped Vanadium Dioxide for High-Temperature Lithium-Sulfur Batteries.

The practical application of Li-S batteries is still severely restricted by poor cyclic performance caused by the intrinsic polysulfides shuttle effect, which is even more severe under the high-temperature condition owing to the inevitable increase of polysulfides' solubility and diffusion rate. Herein, tungsten-doped vanadium dioxide (W-VO2) micro-flowers are employed with first-order metal-insulator phase transition (MIT) property as a robust and multifunctional modification layer to hamper the shuttle effect and simultaneously improve the thermotolerance of the common separator. Tungsten doping significantly reduces the transition temperature from 68 to 35 °C of vanadium dioxide, which renders the W-VO2 easier to turn from the insulating monoclinic phase into the metallic rutile phase. The systematic experiments and theoretical analysis demonstrate that the temperature-induced in-suit MIT property endows the W-VO2 catalyst with strong chemisorption against polysulfides, low energy barrier for liquid-to-solid conversion, and outstanding diffusion kinetics of Li-ion under high temperatures. Benefiting from these advantages, the Li-S batteries with W-VO2 modified separator exhibit significantly improved rate and long-term cyclic performance under 50 °C. Remarkably, even at an elevated temperature (80 °C), they still exhibit superior electrochemical performance. This work opens a rewarding avenue to use phase-changing materials for high-temperature Li-S batteries.

Manipulating Sulfur Conversion Kinetics through Interfacial Built-In Electric Field Enhanced Bidirectional Mott-Schottky Electrocatalysts in Lithium-Sulfur Batteries.

Efficient electrocatalysts and catalytic mechanisms remain a pressing need in Li-S electrochemistry to address lithium polysulfide (LiPS) shuttling and enhance conversion kinetics. This study presents the development of multifunctional VO2@rGO heterostructures, incorporating interfacial built-in electric field (BIEF) enhancement, as a Mott-Schottky electrocatalyst for Li-S batteries. Electrochemical experiments and theoretical analysis demonstrate that the interfacial BIEF between VO2 and rGO induces self-driven charge redistribution, resulting in accelerated charge transport rates, enhanced LiPS chemisorption, reduced energy barriers for Li2S nucleation/decomposition, and improved Li-ion diffusion behavior. The Mott-Schottky electrocatalyst, combining the strengths of VO2's anchoring ability, rGO's metallic conductivity, and BIEF's optimized charge transport, exhibits an outstanding "trapping-conversion" effect. The modified Li-S battery with a VO2@rGO-modified separator achieves a highly reversible capacity of 558.0 mAh g-1 at 2 C over 600 cycles, with an average decay rate of 0.048% per cycle. This research offers valuable insights into the design of Mott-Schottky electrocatalysts and their catalytic mechanisms, advancing high-efficiency Li-S batteries and other multielectron energy storage and conversion devices.