Ceria Quantum Dot Filler-Modified Polymer Electrolytes for Three-Dimensional-Printed Sodium Solid-State Batteries

Solid polymer electrolytes have been considered as promising candidates for solid-state batteries (SSBs), owing to their excellent interfacial compatibility and high mechanical toughness; however, they suffer from intrinsic low ionic conductivity (lower than 10^-6 S/cm) and large thickness (usually surpassed over 100 μm or even 500 μm), which has a negative influence on the interface resistance and ionic migration. In this work, ceria quantum dot (CQD)-modified composite polymer electrolyte (CPE) membranes with a thickness of 20 μm were successfully manufactured via 3D printing technology. The CQD fillers can reduce the crystallinity of the polymer, and the oxygen vacancies on CQDs can facilitate the dissociation of ion pairs in the NaTFSI salt to release more free Na⁺, improving the ionic conductivity. Meanwhile, tailoring the thickness of the CPE-CQDs membrane via 3D printing can further promote the migration and transport of Na⁺. Furthermore, the printed NNM//CPE-CQDs//Na SSB exhibited outstanding rate capability and cycling stability. The combination of CQD modification and thickness tailoring through 3D printing paves a new avenue for achieving high performance solid electrolyte membranes for practical application in Na SSBs.