We
report the synthesis of solid polymer electrolytes (SPEs) using
a thermally induced and a lithium salt catalyzed cationic ring-opening
polymerization (CROP) technique. A synergistic approach using two
salts such as lithium tetrafluoroborate-LiBF4 and lithium
bis(trifluoromethane sulfonyl)imide-LiTFSI
has assured a complete monomer to polymer conversion and fast reaction
kinetics during the CROP process. The initiation mechanism of lithium
salt-induced CROP is elucidated using molecular dynamic simulation,
quantum chemical calculation, real-time FT-Raman
spectroscopy, nuclear magnetic resonance spectroscopy, X-ray photoelectron
spectroscopy, and thermogravimetry–mass spectrometry analysis
techniques. The cross-linked 3D network of ethylene oxide based SPE
is prepared without the use of any solvents or external catalysts.
In particular, a mixture of poly(ethylene glycol) diglycidyl
ether, LiBF4, and LiTFSI in appropriate proportions after
a baking process produced a freestanding, flexible, and nontacky film.
The synthesized SPEs exhibit low glass transition temperature (<
−50 °C), high ionic conductivity (>0.1 mS cm–1), and excellent oxidation stability (>5.5 V vs Li/Li+). The SPE is polymerized directly onto a carbon-coated LiFePO4 cathode film and successfully cycled in a lithium metal battery
configuration at 40 and 60 °C. As evidence, the SPE is galvanostatically
cycled against a high-voltage LiNi1/3Mn1/3Co1/3O2 cathode, and the preliminary
results indicated exciting characteristics in terms of specific capacity
and Coulombic efficiency.