Germanium-Free Dense Lithium Superionic Conductor and Interface Re-Engineering for All-Solid-State Lithium Batteries against High-Voltage Cathode.

Li10GeP2S12 (LGPS) solid electrolyte is not affordable due to the high cost of Ge metal, making it economically unviable despite being a lithium superionic conductor. The synthesis of such solid electrolytes is much more time- and energy-consuming and needs an inert environment. Here, we report Si (silicon)-based composition [Li10SiP2S12 (LSiPS)] to make it cost-effective through microwave heating (MW). The total time for synthesis processes, including ball milling, heating rate, and heating dwell time, is ∼120 min, much less than the previous reports. We have also avoided vacuum sealing/Ar-purging to reduce the synthesis cost further. During MW heating, the densification process dominates over coarsening, resulting in a dense nanoflake morphology with a finer crystallite size. The synthesized LSiPS has a high fraction (∼89%) of more conducting tetragonal phase as identified by NMR analysis. Further, we modified the interface between the Li anode and LSiPS by forming a lithiophobic and lithiophilic kind of gradient interlayer to reduce the reduction of LSiPS and suppress the side reactions. The interface modification resulted in a better Li/LSiPS/Li cyclic performance for 1800 h at 0.2 mA/cm2 and 500 h at 1.0 mA/cm2. All-solid-state lithium-metal batteries (ASSLIB) have been developed against a high-voltage cathode (LCMO-coated LCO) and showed an excellent cycling performance with a reversible capacity of ∼110 mAh/g after 300 cycles.