Abstract
As one of the most promising next-generation energy storage devices, the lithium-metal battery has been extensively investigated. However, safety issues and undesired lithium dendrite growth hinder its development. The application of solid-state electrolytes has attracted increasing attention as they can solve safety issues and show great potential to inhibit the growth of lithium dendrites. Polyethylene oxide (PEO)-based electrolytes are very promising due to their enhanced safety and excellent flexibility. However, they suffer from low ionic conductivity at room temperature and cannot effectively inhibit lithium dendrites at high temperatures due to the intrinsic semicrystalline properties and poor mechanical strength. In this work, a novel coral-like Li6.25Al0.25La3Zr2-O12 (C-LALZO) is synthesized to serve as an active ceramic filler in PEO. The PEO with LALZO coral (PLC) exhibits increased ionic conductivity and mechanical strength, which leads to uniform deposition/stripping of lithium metal. The Li symmetric cells with PLC do not cause a short circuit after cycling for 1500 h at 60°C. The assembled LiFePO4/PLC/Li batteries display excellent cycling stability at both 60 and 50°C. This work reveals that the electrochemical properties of the composite electrolyte can be effectively improved by tuning the microstructure of the filler, such as the C-LALZO architecture.
摘要
锂金属电池被认为是最有前景的下一代储能设备之一, 但是锂 金属电池的安全性问题以及锂枝晶生长问题严重阻碍了它的实用化进 程. 固态电解质可以有效解决这一安全性问题, 表现出能够抑制锂枝晶 生长的巨大潜力, 并因此受到大家的关注. 其中聚环氧乙烷(PEO)基固 态电解质由于具有较高的安全性以及出色的柔韧性, 被认为是一类非 常有应用前景的固态电解质. 但是, 其固有的半结晶特性以及较差的力 学性能导致它们在室温下的离子电导率较低, 并且在高温下不能有效 地抑制锂枝晶生长. 为改善上述问题, 本文设计并合成了一种新型的珊 瑚状Li6.25Al0.25La3Zr2O12(C-LALZO)活性陶瓷填料来增强PEO聚合物电 解质, 制备得到的复合固态电解质(PLC)表现出更高的离子电导率和机 械强度, 保证了锂金属的均匀沉积/剥离. 采用PLC的锂对称电池在60°C 下循环1500小时不发生短路. 组装得到的LiFePO4/PLC/Li全固态电池 在60和50°C时均有出色的循环稳定性. 这项工作表明, 通过调节填料的 微观结构(如C-LALZO结构), 可以有效地改善复合电解质的电化学性 能.
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Acknowledgements
This work was supported by the School Research Startup Expenses of Harbin Institute of Technology (Shenzhen) (DD29100027), the National Natural Science Foundation of China (52002094), China Postdoctoral Science Foundation (2019M661276), Guangdong Basic and Applied Basic Research Foundation (2019A1515110756), and the High-level Talents Discipline Construction Fund of Shandong University (31370089963078).
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Author contributions Ci L and Li D conceived and supervised this project. Cheng J and Hou G designed the experiments. Cheng J carried out the preparation of electrolyte materials, material characterization, assembly of batteries, electrochemical measurements, and data analysis. Sun Q and Chen Q performed some data analysis and offered helpful suggestions. Li J and Zeng Z assisted in the preparation of electrolyte materials. Cheng J and Li D co-wrote the paper. Li K, Yuan Q, Wang J, and Ci L revised the manuscript. All authors contributed to the general discussion.
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Jun Cheng is currently a doctoral candidate at the School of Materials Science and Engineering, Harbin Institute of Technology (Shenzhen). He received his Master’s degree under the supervision of Prof. Lijie Ci at the Materials Science and Engineering Institute, Shandong University. His current research focuses on solid state batteries.
Deping Li is currently an assistant professor at the School of Materials Science and Engineering, Harbin Institute of Technology (Shenzhen). He received his PhD degree in materials science and engineering from Shandong University under the supervision of Prof. Lijie Ci in 2019. His current research focuses on next-generation energy storage applications like solid-state batteries, potassium-ion batteries, and lithium-air batteries.
Lijie Ci is currently a full professor at the School of Materials Science and Engineering, Harbin Institute of Technology (Shenzhen). He received his PhD degree in mechanical engineering from Tsinghua University. He had been a researcher at the Institute of Physics, Chinese Academy of Sciences, Ecole Central Paris in France, the Max Planck Institute for Metals in Germany, Rensselaer Polytechnic Institute, Rice University and Samsung Cheil Industry (San Jose Lab) in USA. Before he joined Harbin Institute of Technology (Shenzhen), he was a professor at Shandong University. His scientific interest focuses on carbon-based materials and energy storage devices.
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Cheng, J., Hou, G., Sun, Q. et al. A novel coral-like garnet for high-performance PEO-based all solid-state batteries. Sci. China Mater. 65, 364–372 (2022). https://doi.org/10.1007/s40843-021-1748-7
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DOI: https://doi.org/10.1007/s40843-021-1748-7