Xianghe Ma, Fei Shao, Weiping Li, Yuxin Zhang, Jingying Yan, Ju Qian, Jun Lin, Xinrong Lin
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引用次数: 0
摘要
高电压锂金属电池(LMB)在储能应用方面前景广阔,但由于固体聚合物电解质(SPE)的电化学窗口较差,很难通过单一聚合物功能实现。本文报告了一种以硅/氟为基础的混合聚合物三维网络,该网络以聚硅氧烷为骨架,并带有含氟垂饰,可调节最高占位分子轨道(HOMO)/最低未占位分子轨道(LUMO)能量,从而在热力学上扩展固体聚合物电解质(SPE)的固有电化学窗口。同时,具有高氟丰度的混合硅/氟官能团在阳极和阴极界面具有双重界面动力学稳定性,分别具有稳定的固体电解质界面(SEI)和阴极电解质界面(CEI)。此外,研究还表明,将 Si/F SPE 与共晶电解质 (EE) 原位混合以形成不易燃的凝胶聚合物电解质,可减轻 EE 对金属锂阳极的寄生反应,并在 25 °C 下实现 4.2 至 4.8 V 的高度可逆充放电循环。
In Situ Hybrid Si/F Polymeric Network Electrolyte with Dual Interfacial Stability for High-Voltage Lithium Metal Batteries
High-voltage lithium-metal batteries (LMBs) are promising for energy storage applications but suffer from poor electrochemical window of solid polymer electrolytes (SPEs), which are difficult to achieve via a single polymeric functionality. Herein, a hybrid Si/F-based polymeric 3D network is reported bearing polysiloxane backbone with fluorinated pendants to tune the highest occupied molecular orbital (HOMO)/the lowest unoccupied molecular orbital LUMO energies, thermodynamically expanding intrinsic electrochemical window of solid polymer electrolyte (SPE). Meanwhile, the hybrid Si/F functionalities with high fluorine abundance is identified to furnish dual interfacial kinetic stability at both anode and cathode interfaces with stabilized solid electrolyte interface (SEI) and cathode electrolyte interface (CEI), respectively. As a result, stable cycling in solid-state high-voltage LMBs is achieved up to an ultrahigh operating voltage of 4.9 V. Furthermore, it shows that in situ blending the Si/F SPE with eutectic electrolytes (EE) to form a non-flammable gel polymer electrolyte can mitigate parasitic reactions of EE against metallic Li anode and achieve highly reversible charge–discharge cycling from 4.2 to 4.8 V at 25 °C.
期刊介绍:
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