Grain boundary modification of Li₃PO₄ and Li₃BO₃ in garnet-type solid electrolyte for suppressing Li dendrite growth

Abstract

Li ionic conductors that are stable to lithium metal with high ionic conductivity are required as solid electrolytes for all-solid-state lithium metal batteries with high energy density. Lithium dendrite growth leading to short-circuit is one of the major issues to solve for developing practical batteries using lithium metal electrodes. We have introduced Li3PO4 (LPO) and Li3BO3 (LBO) as a grain boundary phase in the garnet-type lithium ionic conductor, Li6.25Ga0.25La3Zr2O12 (LGLZ), by co-sintering. The lattice parameters, sinterability, elemental distribution, particle morphology, and electrochemical properties have been investigated. The sinterability has decreased with the introduction of LPO and LBO, while no significant change in the ionic conductivity is observed. The LGLZ with LPO was unstable to Li metal and did not exhibit the improvement of Li plating/stripping. Meanwhile, the LBO introduction into the grain boundary as a functional core increased the critical current density of the short circuit. Li dendrite growth could be suppressed by modifying the grain boundaries of the sintered body.