Dendrite Growth—Microstructure—Stress—Interrelations in Garnet Solid‐State Electrolyte

Abstract

This study illustrates how the microstructure of garnet solid‐state electrolytes (SSE) affects the stress‐state and dendrite growth. Tantalum‐doped lithium lanthanum zirconium oxide (LLZTO, Li6.4La3Zr1.4Ta0.6O12) is synthesized by powder processing and sintering (AS), or with the incorporation of intermediate‐stage high‐energy milling (M). The M compact displays higher density (91.5% vs 82.5% of theoretical), and per quantitative stereology, lower average grain size (5.4 ± 2.6 vs 21.3 ± 11.1 µm) and lower AFM‐derived RMS surface roughness contacting the Li metal (45 vs 161 nm). These differences enable symmetric M cells to electrochemically cycle at constant capacity (0.1 mAh cm−2) with enhanced critical current density (CCD) of 1.4 versus 0.3 mA cm−2. It is demonstrated that LLZTO grain size distribution and internal porosity critically affect electrical short‐circuit failure, indicating the importance of electronic properties. Lithium dendrites propagate intergranularly through regions where LLZTO grains are smaller than the bulk average (7.4 ± 3.8 µm for AS in a symmetric cell, 3.1 ± 1.4 µm for M in a half‐cell). Metal also accumulates in the otherwise empty pores of the sintered compact present along the dendrite path. Mechanistic modeling indicates that reaction and stress heterogeneities are interrelated, leading to current focusing and preferential plating at grain boundaries.

Interfacial engineering of suppressing Li dendrite growth in all solid-state Li-metal batteries

“…35 The stress and strain tune the microstructure of the SSEs, especially inducing stress heterogeneity between Li metal and SSE to drive the growth of Li dendrites. 36 Furthermore, temperature variations affect the diffusion rate of ions and the growth rate of crystals in SSEs, impacting the formation and growth of Li dendrites. Typically, higher operating temperatures are required to obtain higher ionic conductivity, but this would accelerate the growth of Li dendrites.…”