Coral reef-inspired hierarchical channel electrolyte: LATP framework-ZrO₂ triggering activation of amorphous fast-ion
Zihao Dang1, Ao Li1, Lin Wu2
1Key Laboratory of Hubei Province for Coal Conversion and New Carbon Materials, School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, China.
Abstract:
To cope with the demand for high-safe lithium-ion batteries, this study developed a new PVDF-HFP/LiTFSI/LATP/ZrO₂ (PHLZ) composite solid electrolyte with coral reef-type hierarchical channel structure. This electrolyte integrates the advantages of the NASICON fast ion conductor Li₁.₃Al₀.₃Ti₁.₇(PO₄)₃ (LATP) framework and the multifunctional inducer ZrO₂ through a dual-filler synergistic strategy. LATP large particles construct a continuous three-dimensional lithium ion rapid transmission main channel and promote LiTFSI dissociation through the surface Lewis acid site. ZrO₂ nanoparticles effectively passivate the LATP surface to inhibit reduction and improve their dispersion, and form hydrogen bonds with the -CF₂-group of PVDF-HFP through the surface hydroxyl group, trigger activation of the fast ion channel in the amorphous region of the polymer and inhibit crystallization. The PHLZ-2 electrolyte with an optimized ratio (LATP:ZrO₂ = 2:1) exhibits excellent comprehensive performance, with ion conductivity up to 1.76 × 10-3 S cm-1 at 60 °C, lithium ion migration number up to 0.76, wide electrochemical window (>4.74 V vs. Li+/Li), significantly improved thermal stability and flame retardant (3 s self-extinguishing), and excellent lithium deposition/peel stability. When applied to Fe₃O₄/phosphorus doped graphene oxide (FPG) anode system, the FPG//PHLZ-2//Li half-cell showed high rate performance (1101.65 mAh g-1 at 3 A/g) and long cycle life (1225.19 mAh g-1 after 300 times at 1.10 mA cm-2); the assembled FPG//PHLZ-2//LFP full battery also showed high capacity and excellent cycle stability. This research provides new ideas for designing high-performance and safe composite solid electrolytes.
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