Garnet-Based Composite Cathodes for All Solid-State Li Batteries

Abstract

All-solid-state Li batteries are regarded as a highly promising system for future electrochemical energy storage. Oxide-ceramic based all-solid-state lithium batteries (ASB) can provide high intrinsic safety, extended operational temperature range and high energy density.As the first two are intrinsic to the materials system, one prerequisite to obtain high energy densities with such ASBs is the manufacturing of thick (approx. 150 µm), dual-conducting free-standing composite cathodes, analogous to that of conventional liquid electrolyte-based lithium batteries. However, the preparation of composite cathodes using oxide-ceramic electrolytes is challenging since high temperature sintering steps are necessary during electrode and cell manufacturing to achieve proper mechanical stability, contact between the individual phases and good ionic and electronic conductivity.[1, 2] For oxide-based ceramic electrolyte materials like Li7La3Zr2O12 (LLZ) or Li1+xAlxTi2-x(PO4)3 (LATP) a sintering temperature around 1000 °C is necessary. However, cathode active materials like spinels (e. g. Li2NiMn3O8) or layered materials (e. g. Li[Ni1-x-yCoxMny]O2 (NCM)) show thermal stability only to around 700 °C and the required sintering temperature for the electrolyte exceeds their thermal stability window.To mitigate these materials interactions, advanced sintering techniques like high-pressure Field Assisted Sintering Technique/ Spark Plasma Sintering (FAST/SPS) is required, as it allows low temperature consolidation.[3]Using high-pressure FAST/SPS we have developed a method to prepare thick mixed-conducting composite cathodes and half-cells at sintering temperatures as low as 700 °C. The analysis of these composite cathodes revealed well sintered pure phases and a homogenous distribution of cubic LLZ and cathode active material. Electrochemical tests showed promising electronic and ionic conductivity (0.4 mS cm-1) values and an increased capacity (4 mA cm-2) compared to cathodes with pure active material.FAST/SPS can, therefore, open new processing windows for ceramic-based ASSLBs to alleviate the problem of interphase formation.