Lithium-metal anodes offer unparalleled theoretical capacities of 3,860 mAh/g but suffer from severe dendrite growth and low Coulombic efficiency (<80%). Advanced electrolyte additives like fluoroethylene carbonate (FEC) and lithium nitrate (LiNO3) have been shown to improve Coulombic efficiency to >99% by forming stable solid-electrolyte interphases (SEIs). For instance, FEC reduces SEI resistance by ~50%, enabling stable cycling at current densities of up to 3 mA/cm². Recent studies have also demonstrated that dual-additive systems combining FEC and LiNO3 synergistically enhance SEI stability and suppress dendrite formation.
Nanostructured additives such as graphene oxide (GO) nanosheets have been incorporated into electrolytes to create mechanically robust SEIs that resist dendrite penetration. GO-modified electrolytes have shown dendrite-free cycling for over 500 hours at current densities of 1 mA/cm² while maintaining high Coulombic efficiencies (>98%). Additionally, these additives improve thermal stability, reducing the risk of thermal runaway at temperatures above 150°C. The incorporation of GO also enhances electrolyte wettability on lithium surfaces, reducing interfacial resistance by ~30%.
Electrolyte additives like vinylene carbonate (VC) and succinonitrile (SN) have been explored for their ability to form uniform SEIs on lithium-metal anodes. VC has been shown to increase cycle life by >200 cycles in NMC811||Li cells while maintaining capacity retention >90%. SN acts as a plasticizer in gel polymer electrolytes (GPEs), improving ionic conductivity to ~2 mS/cm at room temperature and enabling flexible battery designs. These additives also reduce gas evolution during cycling by >70%, enhancing safety and longevity.
Recent research has focused on multifunctional additives that simultaneously address multiple challenges in lithium-metal batteries. For example, cesium hexafluorophosphate (CsPF6) has been shown to suppress dendrite growth while improving electrolyte conductivity by ~20%. Prototype cells using CsPF6-modified electrolytes have demonstrated energy densities of ~400 Wh/kg with cycle lives exceeding 800 cycles at C/2 rates.
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