Co-doping strategy enhanced the ionic conductivity and excellent lithium stability of garnet-type Li7La3Zr2O12electrolyte in all solid-state lithium batteries

Garnet-type Li7La3Zr2O12(LLZO) is one of the most promising solid-state electrolytes (SSEs). However, the application of LLZO is limited by structural instability, low ionic conductivity, and poor lithium stability. To obtain a garnet-type solid electrolyte with a stable structure and high ionic conductivity, a series of TaCe co-doping cubic Li6.4La3Zr1.4-xTa0.6CexO12(LLZTCO, x = 0, 0.02, 0.04, 0.06, 0.08, 0.10, 0.20, 0.30) electrolytes were successfully synthesized through conventional solid-phase method. The Ta5+doping can introduce more lithium vacancies and effectively maintain the stability of the cubic phase. The Ce4+with a larger ionic radius is introduced into the lattice to widen the Li+migration bottleneck size, which significantly increased the ionic conductivity to 1.05 × 10−3S/cm. It also shows excellent stability to lithium metal by the optimization of Li+transport channel. Li||LLZTCO||Li symmetric cells can cycle stably for more than 6000 h at a current density of 0.1 mA/cm2without any surface modifications. The commercialization potential of LLZTCO samples in all solid-state lithium batteries (ASSLBs) is confirmed by the prepared LiFePO4||LLZTCO||Li cells with a capacity retention rate of 98 % after 100 cycles at 0.5 C. This new co-doping method presents a practical solution for the realization of high-performance ASSLBs.