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用于室温氟离子电池的Lewis酸碱协同增强实用复合电解质

Lewis Acid-Base Synergistically Enhancing Practical Composite Electrolyte for Fluoride-ion Batteries at Room Temperature.

作者信息

Cui Hong, Gao Xiao, Guo Keyu, Liu Wu, Ouyang Bo, Yi Wenbin

机构信息

The School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China.

The School of Science, Nanjing University of Science and Technology, Nanjing, 210094, China.

出版信息

Adv Sci (Weinh). 2025 Jul;12(27):e2502824. doi: 10.1002/advs.202502824. Epub 2025 Apr 27.

Abstract

Fluoride-ion batteries (FIBs) represent a potential "next-generation" electrochemical storage device, offering high energy density. However, the practical implementation of FIBs at room temperature is impeded by the limitations of currently available ceramic electrolytes. Here, a composite NHHF@PEO@β-PbSnF electrolyte with both high conductivity of 10 S cm and wide electrochemical stability window (4.59 V vs Pb/PbF) at room temperature is fabricated. Field emission transmission electron microscope (FETEM) demonstrates the presence of a space charge region, which enhances the conductivity. Furthermore, F NMR and density functional theory (DFT) calculations elucidate that the interaction between Sn (Lewis acid) and HF (Lewis base) induces significant modifications to the electronic structure, which critically contribute to the enhanced electrochemical stability window of the composite electrolyte. Integrating this promising electrolyte with high-voltage CuF cathodes and Pb/PbF anodes, a reversible coin cell with a discharge capacity of 143 mAh g up to 50 cycles is demonstrated. The rational design of such composite electrolytes offers a pathway toward the practical application of FIBs at room temperature.

摘要

氟离子电池(FIBs)是一种具有潜力的“下一代”电化学储能装置,具备高能量密度。然而,目前可用的陶瓷电解质的局限性阻碍了FIBs在室温下的实际应用。在此,制备了一种复合NHHF@PEO@β-PbSnF电解质,其在室温下具有10 S cm的高电导率和4.59 V(相对于Pb/PbF)的宽电化学稳定窗口。场发射透射电子显微镜(FETEM)证明了空间电荷区的存在,这提高了电导率。此外,氟核磁共振(F NMR)和密度泛函理论(DFT)计算表明,锡(路易斯酸)与氟化氢(路易斯碱)之间的相互作用引起了电子结构的显著变化,这对复合电解质电化学稳定窗口的提高起到了关键作用。将这种有前景的电解质与高压CuF阴极和Pb/PbF阳极相结合,展示了一种可逆扣式电池,其放电容量可达143 mAh g,循环次数高达50次。这种复合电解质的合理设计为FIBs在室温下的实际应用提供了一条途径。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/391b/12279211/5895bae4bf99/ADVS-12-2502824-g004.jpg

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