Garnet-Based Solid-State Li Batteries with High-Surface-Area Porous LLZO Membranes

Abstract

Rechargeable garnet-based solid-state Li batteries hold immense promise as nonflammable, nontoxic, and high energy density energy storage systems, employing Li₇La₃Zr₂O₁₂ (LLZO) with a garnet-type structure as the solid-state electrolyte. Despite substantial progress in this field, the advancement and eventual commercialization of garnet-based solid-state Li batteries are impeded by void formation at the LLZO/Li interface at practical current densities and areal capacities beyond 1 mA cm^-2 and 1 mAh cm^-2, respectively, resulting in limited cycling stability and the emergence of Li dendrites. Additionally, developing a fabrication approach for thin LLZO electrolytes to achieve high energy density remains paramount. To address these critical challenges, herein, we present a facile methodology for fabricating self-standing, 50 μm thick, porous LLZO membranes with a small pore size of ca. 2.3 μm and an average porosity of 51%, resulting in a specific surface area of 1.3 μm^-1, the highest reported to date. The use of such LLZO membranes significantly increases the Li/LLZO contact area, effectively mitigating void formation. This methodology combines two key elements: (i) the use of small pore formers of ca. 1.5 μm and (ii) the use of ultrafast sintering, which circumvents ceramics overdensification using rapid heating/cooling rates of ca. 50 °C per second. The fabricated porous LLZO membranes demonstrate exceptional cycling stability in a symmetrical Li/LLZO/Li cell configuration, exceeding 600 h of continuous operation at a current density of 0.1 mA cm^-2.