Enhanced Electrochemical Properties and Optimized Li⁺ Transmission Pathways of PEO/LLZTO-Based Composite Electrolytes Modified by Supramolecular Combination

Abstract

Poly(ethylene oxide) (PEO) and Li_6.75La₃Zr_1.75Ta_0.25O₁₂ (LLZTO)-based composite polymer electrolytes (CPEs) are considered one of the most promising solid electrolyte systems. However, agglomeration of LLZTO within PEO and lack of Li⁺ channels result in poor electrochemical properties. Herein, a functional supramolecular combination (CD-TFSI) consisting of active β-cyclodextrin (CD) supramolecular with self-assembled LiTFSI salt is selected as an interface modifier to coat LLZTO fillers. Benefiting from vast H-bonds formed between β-CD and PEO matrix and/or LLZTO, homogeneous dispersion and tight interface contact are obtained. Moreover, ⁶Li NMR spectra confirm a new Li⁺ transmission pathway from PEO matrix to LLZTO ceramic then to PEO matrix in the as-prepared PEO/LLZTO@CD-TFSI CPEs due to the typical cavity structure of β-CD. As a proof, the conductivity is increased from 5.3 × 10^-4 S cm^-1 to 8.7 × 10^-4 S cm^-1 at 60 ℃, the Li⁺ transference number is enhanced from 0.38 to 0.48, and the electrochemical stability window is extended to 5.1 V versus Li/Li⁺. Li‖LiFePO₄ CR2032 coin full cells and pouch cells prove the practical application of the as-prepared PEO/LLZTO@CD-TFSI CPEs. This work offers a new strategy of interface modifying LLZTO fillers with functional supramolecular combination to optimize PEO/LLZTO CPEs for solid lithium batteries.

Keywords

conductivity / interfacial stability / LLZTO fillers / modification / PEO matrix

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2022 The Authors. Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.