Lithium-Sulfur Batteries with Multi-Electron Redox Chemistry

Lithium-sulfur (Li-S) batteries leverage the multi-electron redox chemistry of sulfur to achieve theoretical energy densities of 2,600 Wh/kg, nearly five times that of LIBs. Recent advancements in cathode design using porous carbon-sulfur composites have increased sulfur utilization to >80%, achieving practical capacities of ~1,200 mAh/g. However, the notorious polysulfide shuttle effect remains a challenge. Advanced separators coated with metal-organic frameworks (MOFs) have reduced polysulfide diffusion by >90%, extending cycle life to over 500 cycles at C/2 rates.

Electrolyte engineering is another frontier in Li-S batteries. Ether-based electrolytes with high donor numbers (>20 kcal/mol) enhance polysulfide solubility and redox kinetics. Additives like LiNO3 form stable solid-electrolyte interphases (SEIs) on lithium anodes, reducing dendrite growth and improving Coulombic efficiency to >99%. Recent studies have also explored ionic liquid electrolytes that suppress polysulfide shuttling while maintaining ionic conductivities >5 mS/cm at room temperature.

Anode protection strategies are critical for Li-S batteries due to lithium’s high reactivity and dendrite formation. Novel approaches include lithiophilic coatings like ZnO or Al2O3 deposited via ALD, which homogenize lithium deposition and reduce dendrite growth rates by ~70%. Composite anodes incorporating graphene or carbon nanotubes have further improved mechanical stability and cycling performance under high current densities (>3 mA/cm²).

Scaling up Li-S batteries for commercial applications requires addressing volumetric energy density challenges caused by sulfur’s low density (~2 g/cm³). Compressed sulfur cathodes combined with lightweight current collectors have achieved volumetric energy densities >700 Wh/L. Prototype pouch cells are being tested for EV applications, demonstrating specific energies >400 Wh/kg and cycle lives exceeding 300 cycles.

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