A new nanostructured γ-Li₃PO₄/GeO₂ composite for all-solid-state Li-ion battery applications

High-temperature sintering is crucial to achieve good crystallinity and fast-ion conduction in oxide-type solid-electrolytes such as lithium garnets, NASICONs and LISICONs, leading to stiff ceramics which are difficult to integrate in all-solid-state batteries. Developing conventional oxide-based solid-electrolytes in deformable forms that maintain good ion transport properties and allow facile formulation of bulk-type solid-state batteries, hence, remains a challenge. Here, a new γ-Li₃PO₄/GeO₂ composite, that adopts a novel nanostructured architecture and retains deformability after calcination at 500 °C, is successfully synthesized and densified by cold-pressing. Cold-pressed pellets of the new composite showed an ion conductivity that is four orders of magnitude higher than that of the parent γ-Li₃PO₄ and comparable to those of high-temperature stiff Li₃₊P_1-GeO₄ ceramics. The γ-Li₃PO₄/GeO₂ composite is stable against high voltages (up to 5 V vs Li⁺/Li), which suggests a safe use in contact with high-voltage cathodes. The new composite can also be modified to serve as an active anode layer in solid-state cells due to the electrochemical activity of GeO₂ at low voltages (<1 V vs. Li⁺/Li). This study emphasizes the potential of using low-temperature synthesis to develop novel oxide-based nanoarchitectures for all-solid-state battery applications.