Composite polymer electrolytes based on LLZO in a cross-linked PEO matrix for all solid state Li metal batteries

Possible concerns about the safety of rechargeable lithium metal batteries has postponed their introduction into the smart electronics or automotive industries and have promoted advances in the field of non-flammable solid electrolytes. Among the oxide ceramic super lithium ion conductors, garnet-type Li7La3Zr2O12 (LLZO) has recently attracted much attention because of its relatively high ionic conductivity at room temperature (>10-4 S cm–1), negligible electronic conductivity and absence of harmful decomposition products upon contact with atmospheric moisture. Anyway, processing LLZO in pellets by sintering, results in brittle and more or less porous electrolytes, which often display poor interfacial contact with Li metal electrodes. Moreover, there are some reports of lithium dendrite growth and instability towards the cathode material - especially while processing of the electrode at high temperature - referred to cells assembled with this electrolyte family. To circumvent these problems, recent efforts have been dedicated to the formulation of composite hybrid polymer electrolytes (CPEs), where the ceramic material is embedded in a polymeric matrix. As compared to the pristine components, CPEs are stiff while preserving flexibility, are easily processed, and can be conceived to attain improved ionic conductivity and interfacial contact with the electrodes. In this work, a polymer based matrix containing poly(ethylene oxide) (PEO), lithium bis (trifluoromethylsulphonyl)imide (LiTFSI), tetra(ethylene glycol dimethyl ether) (G4) and a photoinitiator was added with LLZO particles, thoroughly mixed, formed into a film and cross-linked under UV radiation to obtain a composite hybrid electrolyte. This easy procedure allows obtaining self-standing CPEs with desirable properties of flexibility, shape retention upon thermal stress, improved interfacial contact with the electrodes and ionic conductivity suitable for practical application. Lab-scale lithium metal cells assembled with the CPEs and lithium iron phosphate (LFP) cathodes demonstrated specific capacities up to 125 mAh g1 at 1C rate and could work for hundreds of cycles at ambient temperature.