Lithium Ion Pathway within Li7La3Zr2O12‐Polyethylene Oxide Composite Electrolytes

Abstract Polymer–ceramic composite electrolytes are emerging as a promising solution to deliver high ionic conductivity, optimal mechanical properties, and good safety for developing high‐performance all‐solid‐state rechargeable batteries. Composite electrolytes have been prepared with cubic‐phase Li 7 La 3 Zr 2 O 12 (LLZO) garnet and polyethylene oxide (PEO) and employed in symmetric lithium battery cells. By combining selective isotope labeling and high‐resolution solid‐state Li NMR, we are able to track Li ion pathways within LLZO‐PEO composite electrolytes by monitoring the replacement of 7 Li in the composite electrolyte by 6 Li from the 6 Li metal electrodes during battery cycling. We have provided the first experimental evidence to show that Li ions favor the pathway through the LLZO ceramic phase instead of the PEO‐LLZO interface or PEO. This approach can be widely applied to study ion pathways in ionic conductors and to provide useful insights for developing composite materials for energy storage and harvesting.