Abstract: The present embodiments relate to lithium-based batteries, and particularly to coordinated solvent molecules that can increase the ionic conductivity of the electrolyte without undermining its non-flammability. Some embodiments include a liquid-state polymer electrolyte composed of LiFSI salts, Dimethoxyethane (DME) solvents, and polysiloxane tethered with ion solvating moieties. DME coordinates with both the salt and the polymer, while together with the salt, they synergistically plasticize the polymer to increase the ionic conductivity. The resulting non-flammable polymer electrolyte has a room temperature ionic conductivity of 1.6 mS/cm and a wide operation window of 25-100° C. Benefiting from its liquid nature, the electrolyte can pair with commercially available electrodes without further cell engineering. Embodiments can extend the ionic conductivity range of polymer electrolytes and provide a new design pathway for next generation safe and manufacturable electrolytes.