Bian Juncao, Yuan Huimin, Li Muqing, Ling Sifan, Deng Bei, Luo Wen, Chen Xuedan, Yin Lihong, Li Shuai, Kong Long, Zhao Ruo, Lin Haibin, Xia Wei, Zhao Yusheng, Lu Zhouguang
Shenzhen Key Laboratory of Solid State Batteries, Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology (SUSTech), Shenzhen, China.
Guangdong Provincial Key Laboratory of Energy Materials for Electric Power, Academy for Advanced Interdisciplinary Studies, SUSTech, Shenzhen, China.
Front Chem. 2021 Nov 15;9:744417. doi: 10.3389/fchem.2021.744417. eCollection 2021.
Lithium-rich antiperovskites (LiRAPs) hold great promise to be the choice of solid-state electrolytes (SSEs) owing to their high ionic conductivity, low activation energy, and low cost. However, processing sheet-type solid-state Li metal batteries (SSLiB) with LiRAPs remains challenging due to the lack of robust techniques for battery processing. Herein, we propose a scalable slurry-based procedure to prepare a flexible composite electrolyte (CPE), in which LiRAP (e.g., LiOHClBr, LOCB) and nitrile butadiene rubber (NBR) serve as an active filler and as a polymer scaffold, respectively. The low-polar solvent helps to stabilize the LiRAP phase during slurry processing. It is found that the addition of LOCB into the NBR polymer enhances the Li ion conductivity for 2.3 times at 60°C and reduces the activation energy (max. 0.07 eV). The as-prepared LOCB/NBR CPE film exhibits an improved critical current of 0.4 mA cm and can stably cycle for over 1000 h at 0.04 mA cm under 60°C. In the SSLiB with the sheet-type configuration of LiFePO(LFP)||LOCB/NBR CPE||Li, LFP exhibits a capacity of 137 mAh/g under 60 at 0.1°C. This work delivers an effective strategy for fabrication of LiRAP-based CPE film, advancing the LiRAP-family SSEs toward practical applications.
富锂反钙钛矿（LiRAPs）因其高离子电导率、低活化能和低成本，极有希望成为固态电解质（SSEs）的选择。然而，由于缺乏用于电池加工的可靠技术，用LiRAPs加工片状固态锂金属电池（SSLiB）仍然具有挑战性。在此，我们提出一种可扩展的基于浆料的方法来制备柔性复合电解质（CPE），其中LiRAP（如LiOHClBr，LOCB）和丁腈橡胶（NBR）分别作为活性填料和聚合物支架。低极性溶剂有助于在浆料加工过程中稳定LiRAP相。研究发现，在NBR聚合物中添加LOCB可使60°C时的锂离子电导率提高2.3倍，并降低活化能（最大0.07 eV）。所制备的LOCB/NBR CPE薄膜的临界电流提高到0.4 mA/cm²，在60°C下0.04 mA/cm²的电流密度下可稳定循环超过1000小时。在具有LiFePO（LFP）||LOCB/NBR CPE||Li片状结构的SSLiB中，LFP在60°C、0.1°C的条件下容量为137 mAh/g。这项工作为制备基于LiRAP的CPE薄膜提供了一种有效策略，推动LiRAP系列SSEs走向实际应用。
