Aqueous Cold Sintering of Li-Based Compounds

Aqueous cold sintering of two lithium-based compounds, the electrolyte Li_6.25La₃Zr₂Al_0.25O₁₂ (LLZAO) and cathode material LiCoO₂ (LCO), is reported. For LLZAO, a relative density of ∼87% was achieved, whereas LCO was sintered to ∼95% with 20 wt % LLZAO as a flux/binder. As-cold sintered LLZAO exhibited a low total conductivity (10^-8 S/cm) attributed to an insulating grain boundary blocking layer of Li₂CO₃. The blocking layer was reduced with a post-annealing process or, more effectively, by replacing deionized water with 5 M LiCl during cold sintering to achieve a total conductivity of ∼3 × 10^-5 S/cm (similar to the bulk conductivity). For LCO-LLZAO composites, scanning electron microscopy and X-ray computer tomography indicated a continuous LCO matrix with the LLZAO phase evenly distributed but isolated throughout the ceramics. [001] texturing during cold sintering resulted in an order of magnitude difference in electronic conductivity between directions perpendicular and parallel to the c-axis at room temperature. The electronic conductivity (∼10^-2 S/cm) of cold sintered LCO-LLZAO ceramics at room temperature was comparable to that of single crystals and higher than those synthesized via either conventional sintering or hot pressing.