Elucidating the role of dopants in the critical current density for dendrite formation in garnet electrolytes

Abstract

Garnet-type solid electrolytes have attracted great interest in solid state battery research thanks to their high ionic conductivity at room temperature (10⁻³ S cm⁻¹) and their electrochemical stability against lithium metal anodes. However, the formation of lithium dendrites following charge/discharge limits their applicability and commercialisation. Although widely investigated, no clear explanation of dendrite formation has been previously reported. In this work, we employ cubic Al- and Ga-doped Li₇La₃Zr₂O₁₂, which represent two of the solid electrolytes with higher technological importance, to investigate the formation and chemical composition of dendrites. For the first time, this study elucidates the role that the dopants play in determining the critical current density for dendrite formation and highlights the importance of controlling the dopant distribution in the garnet structure. We use a combination of techniques including Secondary Electron Microscopy and Secondary Ion Mass Spectrometry in order to analyse the microstructure and chemical composition of dendrites in Li₇La₃Zr₂O₁₂. We show that, following electrochemical cycling, Li_6.55Ga_0.15La₃Zr₂O₁₂ systematically displays a critical current density 60% higher than Li_6.55Al_0.15La₃Zr₂O₁₂. Chemical analysis revealed that in Li_6.55Al_0.15La₃Zr₂O₁₂ the dendritic features are composed of a mixture of Al and Li species, whereas in Li_6.55Ga_0.15La₃Zr₂O₁₂ they are uniquely composed of Li. We also show that only in pristine Li_6.55Al_0.15La₃Zr₂O₁₂, the dopant segregates at the grain boundaries suggesting that local chemical inhomogeneity can have a fundamental role in the nucleation and propagation of dendrites.