Co-doping strategy enhanced the ionic conductivity and excellent lithium stability of garnet-type Li7La3Zr2O12 electrolyte in all solid-state lithium batteries

• Published in: Journal of Materiomics Vol. 9; no. 4; pp. 651 - 660
• Main Authors: Xu, Ziqiang, Hu, Xin, Fu, Bowen, Khan, Kashif, Wu, Jintian, Li, Teng, Zhou, Haiping, Fang, Zixuan, Wu, Mengqiang
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.07.2023; Elsevier
• Subjects: Bottleneck size; Co-doping; Garnet-type; Ionic conductivity; Lithium stability; Solid-state electrolytes; Bottleneck size; Solid-state electrolytes; Lithium stability; Garnet-type; Co-doping; Ionic conductivity
• ISSN: 2352-8478
• DOI: 10.1016/j.jmat.2023.01.007

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 × 10−3 S/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 6 000 h at a current density of 0.1 mA/cm2 without 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 0.5C. This new co-doping method presents a practical solution for the realization of high-performance ASSLBs. [Display omitted] •The Ce4+ substitute for Zr4+ site is demonstrated, leading to the solution of a controversy over the doping site of Ce4+.•The ionic conductivity of the LLZTCO electrolyte at the optimal doping ratio can reach 1.05 × 10−3 S/cm.•Li||LLZTCO||Li symmetric cells can cycle stably for more than 6 000 h without any surface modifications.•LFP||LLZTCO||Li cells with a capacity retention rate of 98% after 100 cycles at 0.5C (LFP with mass loading of 3 mg/cm2).