3D Printing of Li₆.₄La₃Zr₁.4Ta₀.₆O₁₂

Li6.4La3Zr1.4Ta0.6O12 (LLZTO), as an element-doped garnet-type solid electrolyte material, has become one of the most promising ceramic solid electrolyte materials with its high ionic conductivity and high stability to lithium metal. However, in terms of processing LLZTO materials, the traditional casting method is still the mainstream processing technology. The lack of shape diversity and structural complexity when manufacturing LLZTO materials by this traditional methods greatly limits the development and progress of solid electrolytes. Here, three LLZTO ink formulations are presented to successfully print complex high-precision (150 μm) 3D structures by direct ink writing, where the structures include hexagonal honeycomb, triangular, and square log-pile structures. Based on the ink's specially tailored rheological properties, such as pronounced shear-thinning behavior, high modulus G' > 105 Pa, and high yield stress σy ≈ 1000 Pa, these rheological properties contribute to the excellent printing performance of the ink. Based on these inks, LLZTO materials can be 3D printed into three-dimensional complex solid electrolytes with controllable precision and free design.