Search

Gel-polymer electrolyte (GPE) is a pragmatic choice for high-safety sodium batteries but still plagued by interfacial compatibility with both cathode and anode simultaneously. Here, salt-in-polymer fibers with NaF salt inlaid in polylactide (PLA) fiber network was fabricated via electrospinning and subsequent in situ forming gel-polymer electrolyte in liquid electrolytes. The obtained PLA-NaF GPE achieves a high ion conductivity (2.50×10 -3  S cm -1 ) and large Na + transference number (0.75) at ambient temperature. Notably, the dissolution of NaF salt occupies solvents leading to concentrated-electrolyte environment, which facilitates aggregates with increased anionic coordination (anion/Na + >1). Aggregates with higher HOMO realize the preferential oxidation on the cathode so that inorganic-rich and stable CEI covers cathode' surface, preventing particles' breakage and showing good compatibility with different cathodes (Na 3 V 2 (PO 4 ) 3 , Na 2+2x Fe 2-x (SO 4 ) 3 , Na 0.72 Ni 0.32 Mn 0.68 O 2 , NaTi 2 (PO 4 ) 3 ). While, passivated Na anode induced by the lower LUMO of aggregates, and the lower surface tension between Na anode and PLA-NaF GPE interface, leading to the dendrites-free Na anode. As a result, the assembled Na || Na 3 V 2 (PO 4 ) 3 cells display excellent electrochemical performance at all-climate conditions., (© 2024 Wiley‐VCH GmbH.)

Polymer electrolytes provide a visible pathway for the construction of high-safety quasi-solid-state batteries due to their high interface compatibility and processability. Nevertheless, sluggish ion transfer at room temperature seriously limits their applications. Herein, a triangular synergy strategy is proposed to accelerate Na-ion conduction via the cooperation of polymer-salt, ionic liquid, and electron-rich additive. Especially, PVDF-HFP and NaTFSI salt acted as the framework to stably accommodate all the ingredients. An ionic liquid (Emim + -FSI - ) softened the polymer chains through a weakening molecule force and offered additional liquid pathways for ion transport. Physicochemical characterizations and theoretical calculations demonstrated that electron-rich Nerolin with π-cation interaction facilitated the dissociation of NaTFSI and effectively restrained the competitive migration of large cations from EmimFSI, thus lowering the energy barrier for ion transport. The strategy resulted in a thin F-rich interphase dominated by NaTFSI salt's decomposition, enabling rapid Na + transmission across the interface. These combined effects resulted in a polymer electrolyte with high ionic conductivity (1.37×10 -3  S cm -1 ) and t Na+ (0.79) at 25 °C. The assembled cells delivered reliable rate capability and stability (200 cycles, 99.2 %, 0.5 C) with a good safety performance., (© 2023 Wiley-VCH GmbH.)

Sodium storage batteries are one of the ever-increasing next-generation large-scale energy storage systems owing to the abundant resources and low cost. However, their viability is severely hampered by dendrite-related hazards on anodes. Herein, a novel ultrathin (8 µm) exterior-nonporous separator composed of honeycomb-structured fibers is prepared for homogeneous Na deposition and suppressed dendrite penetration. The unhindered ion transmission greatly benefits from honeycomb-structured fibers with huge electrolyte uptake (376.7%) and the polymer's inherent transport ability. Additionally, polar polymer chains consisting of polyethersulfone and polyvinylidene customize the highly aggregated solvation structure of electrolytes via substantial solvent immobilization, facilitating ion-conductivity-enhanced inorganic-rich solid-electrolyte interphase with remarkable interface endurance. With the reliable mechanical strength of the separator, the assembled sodium-ion full cell delivers significantly improved energy density and high safety, enabling stable operation under cutting and rolling. The as-prepared separator can further be generalized to lithium-based batteries for which apparent dendrite inhibition and cyclability are accessible and demonstrates its potential for practical application., (© 2023 Wiley-VCH GmbH.)