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Flexible, high-voltage, ion-conducting composite membranes with 3D aramid nanofiber frameworks for stable all-solid-state lithium metal batteries

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  • ReceivedNov 28, 2019
  • AcceptedDec 26, 2019
  • PublishedJan 20, 2020

Abstract


Acknowledgment

This work was supported partially by Beijing Natural Science Foundation (L172036), Joint Funds of the Equipment Pre-Research and Ministry of Education (6141A020225), Par-Eu Scholars Program, Science and Technology Beijing 100 Leading Talent Training Project, Beijing Municipal Science and Technology Project (Z161100002616039), China Postdoctoral Science Foundation (2018M631419), and the Fundamental Research Funds for the Central Universities (2017ZZD02 and 2019QN001).


Interest statement

The authors declare no conflict of interest.


Contributions statement

Li M conceived the project and designed the experiments. Liu L, Lyu J, Mo J, Peng P and Li J conducted the material synthesis and measurements. Liu L, Jiang B and Chu L wrote the paper. All authors discussed the results and commented on the manuscript.


Author information

Lehao Liu is a postdoctoral researcher in the North China Electric Power University. He received a PhD degree in 2016 from the Northwestern Polytechnical University. During 2012–2015, he was a joint-training PhD student at the University of Michigan. After obtaining his PhD degree, he began to work as a chief engineer in CITIC Guoan MGL Power Source Technology Company. His research focuses on nano/micro-materials for energy storage.


Meicheng Li is the Director of the Center for New Energy Materials and Photoelectric Technology at the School of Renewable Energy in North China Electric Power University. His current focus is lithium/sodium ion battery, including fundamental understanding, applied research and development, and flexible device design. He also has interest in R&D of perovskite solar cells, battery system and other new energy materials and devices.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


References

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  • Figure 1

    (a) Schematic illustration of the preparation of ANF/PEO-LiTFSI composite electrolyte membranes. (b) The hydrogen bond interaction between the amide groups of the ANFs. (c) The interactions between the ANF, PEO and LiTFSI. (d) The structure of the ANF framework-supported PEO-LiTFSI electrolytes.

  • Figure 2

    Optical images of (a) the ANF/DMSO solution, and (b) the 3D porous ANF film and the ANF/PEO-DF and ANF/PEO-FF composite electrolyte membranes. (c) TEM image of the ANFs. (d) Surficial SEM image of the PEO-LiTFSI electrolyte film. (e, f) Surficial and (g, h) cross-sectional SEM images of the 3D porous ANF film. (i) Top-view, (j) back-view, and (k, l) cross-sectional SEM images of the ANF/PEO-FF CPE membrane. (m) Top-view, (n) back-view, and (o, p) cross-sectional SEM images of the ANF/PEO-DF CPE membrane.

  • Figure 3

    (a) LSV profiles, (b) mechanical tensile stress-strain curves, (c) TGA curves, and optical photographs at 160°C for (d) 0, (e) 0.5, (f) 1.0, (g) 3.0 and (h) 10.0 h in an oven of the films. (i) Optical image of the films at the back side after peeling off from the glass substrate.

  • Figure 4

    (a, b) FTIR spectra, and (c) XRD patterns of the porous ANF film and the electrolyte membranes. (d) Ionic conductivities of the electrolyte membranes.

  • Figure 5

    Galvanostatic cycling curves of the (a, c and e) PEO-LiTFSI and (b, d and f) ANF/PEO-FF electrolyte-based Li/Li cells under (a, b) various current densities of 0.025–0.50 mA cm−2 for 200 h at 60°C, (c, d) 0.10 mA cm−2 with the charge-discharge time of 10 min per cycle for 500 h at 30°C, and (e, f) 0.10 mA cm−2 with the charge-discharge time of 60 min per cycle for 1000 h at 30°C. EIS spectra of the Li/Li cells at 30°C (g) before and after the galvanostatic cycling under (h) 0.10 mA cm−2 for 500 h with the charge-discharge time of 10 min per cycle and then under (i) 0.10 mA cm−2 for 1000 h with the charge-discharge time of 60 min per cycle (an equivalent circuit model was given in Fig. 5g).

  • Figure 6

    (a) Cycling performance of the solid-state LiFePO4/Li cells at 0.1 C under various operation temperatures. Typical charge-discharge profiles of the solid-state cells using (b) PEO-LiTFSI and (c) ANF/PEO-FF electrolytes at 60°C and various current densities, respectively. (d) Rate performance of the solid-state LiFePO4/Li cells at 60°C. The charge-discharge profiles of the solid-state cells using (e) PEO-LiTFSI and (f) ANF/PEO-FF electrolytes at 0.4 C and 60°C, respectively. (g) Cycling performance, (h) Coulombic efficiency and (i) average discharge voltage change of the solid-state LiFePO4/Li cells at 0.4 C and 60°C for 100 cycles.