The urgent need for safer batteries is leading research to all-solid-state lithium-based cells. To achieve energy density comparable to liquid electrolyte-based cells, ultrathin and lightweight solid electrolytes with high ionic conductivity are desired. However, solid electrolytes with comparable thicknesses to commercial polymer electrolyte separators (~10 μm) used in liquid electrolytes remain challenging to make because of the increased risk of short-circuiting the battery. Here, we report on a polymer–polymer solid-state electrolyte design, demonstrated with an 8.6-μm-thick nanoporous polyimide (PI) film filled with polyethylene oxide/lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI) that can be used as a safe solid polymer electrolyte. The PI film is nonflammable and mechanically strong, preventing batteries from short-circuiting even after more than 1,000 h of cycling, and the vertical channels enhance the ionic conductivity (2.3 × 10−4 S cm−1 at 30 °C) of the infused polymer electrolyte. All-solid-state lithium-ion batteries fabricated with PI/PEO/LiTFSI solid electrolyte show good cycling performance (200 cycles at C/2 rate) at 60 °C and withstand abuse tests such as bending, cutting and nail penetration.
Subscribe to Journal
Get full journal access for 1 year
only $14.08 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.
Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).
Whittingham, M. S. Lithium batteries and cathode materials. Chem. Rev. 104, 4271–4301 (2004).
Goodenough, J. B. & Park, K. S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).
Sun, Y., Liu, N. & Cui, Y. Promises and challenges of nanomaterials for lithium-based rechargeable batteries. Nat. Energy 1, 16071 (2016).
Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).
Suo, L. et al. ‘Water-in-salt’ electrolyte enables high-voltage aqueous lithium-ion chemistries. Science 350, 938–943 (2015).
Tan, G. et al. Burning lithium in CS2 for high-performing compact Li2S–graphene nanocapsules for Li–S batteries. Nat. Energy 2, 17090 (2017).
Sun, Y. K. et al. High-energy cathode material for long-life and safe lithium batteries. Nat. Mater. 8, 320–324 (2009).
Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).
Lu, Y., Tu, Z. & Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 13, 961–969 (2014).
Zheng, Q., Ma, L., Khurana, R., Archer, L. A. & Coates, G. W. Structure–property study of cross-linked hydrocarbon/poly(ethylene oxide) electrolytes with superior conductivity and dendrite resistance. Chem. Sci. 7, 6832–6838 (2016).
Ji, X. et al. Spatially heterogeneous carbon-fiber papers as surface dendrite-free current collectors for lithium deposition. Nano Today 7, 10–20 (2012).
Bachman, J. C. et al. Inorganic solid-state electrolytes for lithium batteries: mechanisms and properties governing ion conduction. Chem. Rev. 116, 140–162 (2016).
Miller, T. F., Wang, Z. G., Coates, G. W. & Balsara, N. P. Designing polymer electrolytes for safe and high capacity rechargeable lithium batteries. Acc. Chem. Res. 50, 590–593 (2017).
Manthiram, A., Yu, X. & Wang, S. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017).
Wang, Y. et al. Design principles for solid-state lithium superionic conductors. Nat. Mater. 14, 1026–1031 (2015).
Fan, L., Wei, S., Li, S., Li, Q. & Lu, Y. Recent progress of the solid-state electrolytes for high-energy metal-based batteries. Adv. Energy Mater. 8, 1702657 (2018).
Han, X. et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572–579 (2017).
Han, F., Gao, T., Zhu, Y., Gaskell, K. J. & Wang, C. A battery made from a single material. Adv. Mater. 27, 3473–3483 (2015).
Kato, Y. et al. High-power all-solid-state batteries using sulfide superionic conductors. Nat. Energy 1, 16030 (2016).
Christie, A. M., Lilley, S. J., Staunton, E., Andreev, Y. G. & Bruce, P. G. Increasing the conductivity of crystalline polymer electrolytes. Nature 433, 50–53 (2005).
Zhang, J. et al. Safety-reinforced poly(propylene carbonate)-based all-solid-state polymer electrolyte for ambient-temperature solid polymer lithium batteries. Adv. Energy Mater. 5, 1501082 (2015).
Lin, D. et al. High ionic conductivity of composite solid polymer electrolyte via in situ synthesis of monodispersed SiO2 nanospheres in poly(ethylene oxide). Nano Lett. 16, 459–465 (2016).
Liu, W. et al. Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires. Nat. Energy 2, 17035 (2017).
Li, Y. et al. Mastering the interface for advanced all-solid-state lithium rechargeable batteries. Proc. Natl Acad. Sci. USA 113, 13313–13317 (2016).
Han, F. et al. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nat. Energy 4, 187–196 (2019).
Tian, H. K., Xu, B. & Qi, Y. Computational study of lithium nucleation tendency in Li7La3Zr2O12 (LLZO) and rational design of interlayer materials to prevent lithium dendrites. J. Power Sources 392, 79–86 (2018).
Fu, K. et al. Three-dimensional bilayer garnet solid electrolyte based high energy density lithium metal-sulfur batteries. Energy Environ. Sci. 10, 1568–1575 (2017).
Harry, K. J., Hallinan, D. T., Parkinson, D. Y., MacDowell, A. A. & Balsara, N. P. Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes. Nat. Mater. 13, 69–73 (2014).
Xue, Z., He, D. & Xie, X. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries. J. Mater. Chem. A 3, 19218–19253 (2015).
Croce, F., Appetecchi, G. B., Persi, L. & Scrosati, B. Nanocomposite polymer electrolytes for lithium batteries. Nature 394, 456–458 (1998).
Wang, C., Zhang, X.-W. & Appleby, A. J. Solvent-free composite peo-ceramic fiber/mat electrolytes for lithium secondary cells. J. Electrochem. Soc. 152, A205–A209 (2005).
Fu, K. et al. Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries. Proc. Natl Acad. Sci. USA 113, 7094–7099 (2016).
Zhao, C.-Z. et al. An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes. Proc. Natl Acad. Sci. USA 114, 11069–11074 (2017).
Villaluenga, I. H. et al. Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries. Proc. Natl Acad. Sci. USA 113, 52–57 (2016).
Zhai, H. et al. A flexible solid composite electrolyte with vertically aligned and connected ion-conducting nanoparticles for lithium batteries. Nano Lett. 17, 3182–3187 (2017).
Zheng, J., Tang, M. & Hu, Y. Y. Lithium ion pathway within Li7La3Zr2O12–polyethylene oxide composite electrolytes. Angew. Chem. Int. Ed. 55, 12538–12542 (2016).
Singh, V. et al. High thermal conductivity of chain-oriented amorphous polythiophene. Nat. Nanotechnol. 9, 384–390 (2014).
Jo, G., Ahn, H. & Park, M. J. Simple route for tuning the morphology and conductivity of polymer electrolytes: one end functional group is enough. ACS Macro Lett. 2, 990–995 (2013).
Webb, M. A. et al. Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes. ACS Cent. Sci. 1, 198–205 (2015).
Sethuraman, V., Mogurampelly, S. & Ganesan, V. Ion transport mechanisms in lamellar phases of salt-doped PS–PEO block copolymer electrolytes. Soft Matter 13, 7793–7803 (2017).
Golodnitsky, D., Livshits, E. & Peled, E. Highly conductive oriented PEO-based polymer electrolytes. Macromol. Symp. 203, 27–45 (2003).
Toney, M. F. et al. Near-surface alignment of polymers in rubbed films. Nature 374, 709–711 (1995).
Wang, C. et al. In situ neutron depth profiling of lithium metal–garnet interfaces for solid state batteries. J. Am. Chem. Soc. 139, 14257–14264 (2017).
Jorgensen, W. L., Maxwell, D. S. & Tirado-Rives, J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).
Frisch, M. J. et al. Gaussian 09 (Gaussian, Inc., 2009).
Van Der Spoel, D. et al. GROMACS: fast, flexible, and free. J. Comput. Chem. 26, 1701–1718 (2005).
The work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research (BMR) programme and Battery 500 Consortium programme. Z.L. and L.-Q.C. also acknowledge the support from the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), under the Award (DE-EE0007803).
The authors declare no competing interests.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Methods, Supplementary Figs. 1–24 and Supplementary Table 1
Flame test of PP/PE/PP separator
Flame test of PEO/LiTFSI SPE
Flame test of PI film
Nail penetration test of LFP/PI/PEO/LiTFSI/Li pouch cell
Phase evolution of Li deposition with PI/PEO/LiTFSI/PEO/Al2O3
About this article
Cite this article
Wan, J., Xie, J., Kong, X. et al. Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries. Nat. Nanotechnol. 14, 705–711 (2019). https://doi.org/10.1038/s41565-019-0465-3
Incorporating multifunctional LiAlSiO4 into polyethylene oxide for high-performance solid-state lithium batteries
Journal of Energy Chemistry (2021)
A flexible, ion-conducting solid electrolyte with vertically bicontinuous transfer channels toward high performance all-solid-state lithium batteries
Chemical Engineering Journal (2021)
Enhancing interfacial stability in solid-state lithium batteries with polymer/garnet solid electrolyte and composite cathode framework
Journal of Energy Chemistry (2021)
Energy Storage Materials (2021)
Journal of Power Sources (2021)