Low-Temperature Fabrication of Bulk-Type All-Solid-State Lithium-Ion Battery Utilizing Nanosized Garnet Solid Electrolytes.

Garnet-type Li7 La3 Zr2 O12 (LLZ) materials are attracting attention as solid electrolytes (SEs) in oxide-based all-solid-state batteries (ASSBs) owing to their high ionic conductivity. Although the electrochemical stability of LLZ against Li metal is demonstrated with possible high energy density, high-temperature sintering above 1000 °C, which is required to achieve high Li-ion conductivity, results in the formation of insulating impurities at the electrode-electrolyte interfaces. Here, nanosized fine-particle samples of Ta-substituted Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZT) are successfully prepared at a remarkably low temperature of 400 °C utilizing an amorphous precursor oxide. The dense LLZT SE sintered by hot pressing at 500 °C shows room-temperature Li-ion conductivity of 1.03 × 10-4 S cm-1 without any additives. In addition, the bulk-type NCM-graphite full battery cell fabricated with the LLZT fine particles through a hot-pressing sintering method at 550 °C exhibits a good charge-discharge performance at room temperature with the bulk-type areal discharge capacity of 0.831 mAh cm-2 . The nanosized garnet SE strategy demonstrated in this study paves the way for the formation of oxide-based ASSBs by low-temperature sintering.

Low-Temperature Sintering of a Garnet-Type Li6.5La3Zr1.5Ta0.5O12 Solid Electrolyte and an All-Solid-State Lithium-Ion Battery.

Garnet-type Ta-substituted Li7La3Zr2O12 materials attract considerable attention as solid electrolytes for use in future oxide-based all-solid-state lithium-ion batteries owing to their superior ionic conductivity and chemical and electrochemical stabilities. However, high-temperature sintering above 1000 °C, which is needed to realize high lithium-ion conductivity, results in the formation of insulating interface impurities at the electrode-electrolyte interface. Herein, the low-temperature sintering of the Li6.5La3Zr1.5Ta0.5O12 (LLZT) solid electrolyte at a remarkably low temperature of 400 °C was demonstrated using the submicrometer-sized garnet-type LLZT fine powder sample prepared at 600 °C through a reaction of Li2O and La2.4Zr1.2Ta0.4O7. The lithium-ion conductivity at 25 °C was 4.54 × 10-5 S cm-1 without any additives through low-temperature sintering at 400 °C. In addition, the preliminary battery performance of the oxide-based all-solid-state LiNi1/3Co1/3Mn1/3O2-Li4Ti5O12 full-battery cell fabricated at 400 °C using the present LLZT fine powder sample as the solid electrolyte was demonstrated.