Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Improving Li-ion interfacial transport in hybrid solid electrolytes

Abstract

The development of commercial solid-state batteries has to date been hindered by the individual limitations of inorganic and organic solid electrolytes, motivating hybrid concepts. However, the room-temperature conductivity of hybrid solid electrolytes is still insufficient to support the required battery performance. A key challenge is to assess the Li-ion transport over the inorganic and organic interfaces and relate this to surface chemistry. Here we study the interphase structure and the Li-ion transport across the interface of hybrid solid electrolytes using solid-state nuclear magnetic resonance spectroscopy. In a hybrid solid polyethylene oxide polymer–inorganic electrolyte, we introduce two representative types of ionic liquid that have different miscibilities with the polymer. The poorly miscible ionic liquid wets the polymer–inorganic interface and increases the local polarizability. This lowers the diffusional barrier, resulting in an overall room-temperature conductivity of 2.47 × 10−4 S cm−1. A critical current density of 0.25 mA cm−2 versus a Li-metal anode shows improved stability, allowing cycling of a LiFePO4–Li-metal solid-state cell at room temperature with a Coulombic efficiency of 99.9%. Tailoring the local interface environment between the inorganic and organic solid electrolyte components in hybrid solid electrolytes seems to be a viable route towards designing highly conducting hybrid solid electrolytes.

This is a preview of subscription content, access via your institution

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Fig. 1: Li-ion interface diffusion between LiTFSI–PEO and Li6PS5Cl.
Fig. 2: Macroscopic diffusion in HSEs with PP13-TFSI and EMIM-TFSI IL additives.
Fig. 3: Structural characterization of the HSEs with PP13-TFSI and EMIM-TFSI IL additives.
Fig. 4: Locating the positions of PP13-TFSI and EMIM-TFSI IL additives in the HSEs.
Fig. 5: Quantification of Li-ion diffusion across phase boundaries in the HSE with the PP13-TFSI IL.
Fig. 6: Electrochemical characterization of the HSE with PP13-TFSI and EMIM-TFSI IL additives.

Data availability

The data that support the findings of this study are available at the online depository Zenodo (https://doi.org/10.5281/zenodo.6334099).

References

  1. Armand, M. & Tarascon, J.-M. Building better batteries. Nature 451, 652–657 (2008).

    CAS  Article  Google Scholar 

  2. Dunn, B., Kamath, H. & Tarascon, J.-M. Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011).

    CAS  Article  Google Scholar 

  3. Cheng, X. B., Zhao, C. Z., Yao, Y. X., Liu, H. & Zhang, Q. Recent advances in energy chemistry between solid-state electrolyte and safe lithium-metal anodes. Chem 5, 74–96 (2019).

    CAS  Article  Google Scholar 

  4. Zaman, W., Hortance, N., Dixit, M. B., De Andrade, V. & Hatzell, K. B. Visualizing percolation and ion transport in hybrid solid electrolytes for Li-metal batteries. J. Mater. Chem. A 7, 23914–23921 (2019).

    CAS  Article  Google Scholar 

  5. Armand, M. The history of polymer electrolytes. Solid State Ion. 69, 309–319 (1994).

    CAS  Article  Google Scholar 

  6. Bouchet, R. et al. Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries. Nat. Mater. 12, 452–457 (2013).

    CAS  Article  Google Scholar 

  7. Ma, Q. et al. Single lithium‐ion conducting polymer electrolytes based on a super‐delocalized polyanion. Angew. Chem. Int. Ed. 55, 2521–2525 (2016).

    CAS  Article  Google Scholar 

  8. Dixit, M. B. et al. Scalable manufacturing of hybrid solid electrolytes with interface control. ACS Appl. Mater. Interfaces 11, 45087–45097 (2019).

    CAS  Article  Google Scholar 

  9. Osada, I., de Vries, H., Scrosati, B. & Passerini, S. Ionic‐liquid‐based polymer electrolytes for battery applications. Angew. Chem. Int. Ed. 55, 500–513 (2016).

    CAS  Article  Google Scholar 

  10. Liu, M. et al. Tandem interface and bulk Li-ion transport in a hybrid solid electrolyte with microsized active filler. ACS Energy Lett. 4, 2336–2342 (2019).

    CAS  Article  Google Scholar 

  11. Yang, K. et al. Stable interface chemistry and multiple ion transport of composite electrolyte contribute to ultra-long cycling solid-state LiNi0.8Co0.1Mn0.1O2/lithium metal batteries. Angew. Chem. Int. Ed. 60, 24668–24675 (2021).

    CAS  Article  Google Scholar 

  12. Croce, F., Sacchetti, S. & Scrosati, B. Advanced lithium batteries based on high-performance composite polymer electrolytes. J. Power Sources 162, 685–689 (2006).

    CAS  Article  Google Scholar 

  13. Syzdek, J. et al. Ceramic-in-polymer versus polymer-in-ceramic polymeric electrolytes—A novel approach. J. Power Sources 194, 66–72 (2009).

    CAS  Article  Google Scholar 

  14. Hassoun, J. & Scrosati, B. A high‐performance polymer tin sulfur lithium ion battery. Angew. Chem. Int. Ed. 49, 2371–2374 (2010).

    CAS  Article  Google Scholar 

  15. Płcharski, J. & Weiczorek, W. PEO based composite solid electrolyte containing nasicon. Solid State Ion. 28, 979–982 (1988).

    Article  Google Scholar 

  16. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).

    CAS  Article  Google Scholar 

  17. Lei, D. et al. Cross-linked beta alumina nanowires with compact gel polymer electrolyte coating for ultra-stable sodium metal battery. Nat. Commun. 10, 4244 (2019).

    Article  CAS  Google Scholar 

  18. Zheng, J., Tang, M. X. & Hu, Y. Y. Lithium ion pathway within Li7La3Zr2O12-polyethylene oxide composite electrolytes. Angew. Chem. Int. Ed. 55, 12538–12542 (2016).

    CAS  Article  Google Scholar 

  19. Wang, S. et al. A dendrite-suppressed flexible polymer-in-ceramic electrolyte membrane for advanced lithium batteries. Electrochim. Acta 353, 136604 (2020).

    CAS  Article  Google Scholar 

  20. Fergus, J. W. Ceramic and polymeric solid electrolytes for lithium-ion batteries. J. Power Sources 195, 4554–4569 (2010).

    CAS  Article  Google Scholar 

  21. Blanga, R., Burstein, L., Berman, M., Greenbaum, S. & Golodnitsky, D. Solid polymer-in-ceramic electrolyte formed by electrophoretic deposition. J. Electrochem. Soc. 162, D3084–D3089 (2015).

    CAS  Article  Google Scholar 

  22. Chen, L. et al. PEO/garnet composite electrolytes for solid-state lithium batteries: from “ceramic-in-polymer” to “polymer-in-ceramic”. Nano Energy 46, 176–184 (2018).

    CAS  Article  Google Scholar 

  23. Huo, H. Y. et al. Rational design of hierarchical “ceramic-in-polymer” and “polymer-in-ceramic” electrolytes for dendrite-free solid-state batteries. Adv. Energy Mater. 9, 1804004 (2019).

    Article  CAS  Google Scholar 

  24. Bonizzoni, S. et al. NASICON-type polymer-in-ceramic composite electrolytes for lithium batteries. Phys. Chem. Chem. Phys. 21, 6142–6149 (2019).

    CAS  Article  Google Scholar 

  25. Dixit, M. B. et al. Nanoscale mapping of extrinsic interfaces in hybrid solid electrolytes. Joule 4, 207–221 (2020).

    CAS  Article  Google Scholar 

  26. Simon, F. J. et al. Properties of the interphase formed between argyrodite-type Li6PS5Cl and polymer-based PEO10:LiTFSI. ACS Appl. Mater. Interfaces 11, 42186–42196 (2019).

    CAS  Article  Google Scholar 

  27. Simon, F. J., Hanauer, M., Richter, F. H. & Janek, J. Interphase formation of PEO20:LiTFSI–Li6PS5Cl composite electrolytes with lithium metal. ACS Appl. Mater. Interfaces 12, 11713–11723 (2020).

    CAS  Article  Google Scholar 

  28. Zheng, J., Wang, P., Liu, H. & Hu, Y.-Y. Interface-enabled ion conduction in Li10GeP2S12–poly (ethylene oxide) hybrid electrolytes. ACS Appl. Energy Mater. 2, 1452–1459 (2019).

    CAS  Article  Google Scholar 

  29. Yu, C. et al. Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface. Nat. Commun. 8, 1086 (2017).

    Article  CAS  Google Scholar 

  30. Ganapathy, S., Yu, C., van Eck, E. R. H. & Wagemaker, M. Peeking across grain boundaries in a solid-state ionic conductor. ACS Energy Lett. 4, 1092–1097 (2019).

    CAS  Article  Google Scholar 

  31. Schwietert, T. K. et al. Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes. Nat. Mater. 19, 428–435 (2020).

    CAS  Article  Google Scholar 

  32. Hoefling, A. et al. Mechanism for the stable performance of sulfur-copolymer cathode in lithium–sulfur battery studied by solid-state NMR spectroscopy. Chem. Mater. 30, 2915–2923 (2018).

    CAS  Article  Google Scholar 

  33. Rataboul, F. et al. Molecular understanding of the formation of surface zirconium hydrides upon thermal treatment under hydrogen of [(SiO)Zr(CH2tBu)3] by using advanced solid-state NMR techniques. J. Am. Chem. Soc. 126, 12541–12550 (2004).

    CAS  Article  Google Scholar 

  34. Zhu, C., Cheng, H. & Yang, Y. Electrochemical characterization of two types of PEO-based polymer electrolytes with room-temperature ionic liquids. J. Electrochem. Soc. 155, A569 (2008).

    CAS  Article  Google Scholar 

  35. Kodama, K. et al. Structural effects of polyethers and ionic liquids in their binary mixtures on lower critical solution temperature liquid-liquid phase separation. Polym. J. 43, 242–248 (2011).

    CAS  Article  Google Scholar 

  36. Cesare Marincola, F. et al. NMR investigation of imidazolium‐based ionic liquids and their aqueous mixtures. ChemPhysChem 13, 1339–1346 (2012).

    Article  CAS  Google Scholar 

  37. Wang, B.-H., Xia, T., Chen, Q. & Yao, Y.-F. Probing the dynamics of Li+ ions on the crystal surface: a solid-state NMR study. Polymers 12, 391 (2020).

    CAS  Article  Google Scholar 

  38. Zhao, Z. et al. Ionic‐association‐assisted viscoelastic nylon electrolytes enable synchronously coupled interface for solid batteries. Adv. Funct. Mater. 30, 2000347 (2020).

    CAS  Article  Google Scholar 

  39. Ganapathy, S., van Eck, E. R., Kentgens, A. P., Mulder, F. M. & Wagemaker, M. Equilibrium lithium‐ion transport between nanocrystalline lithium‐inserted anatase TiO2 and the electrolyte. Chem. Eur. J. 17, 14811–14816 (2011).

    CAS  Article  Google Scholar 

  40. Kumar, M. & Sekhon, S. S. Role of plasticizer’s dielectric constant on conductivity modification of PEO–NH4F polymer electrolytes. Eur. Polym. J. 38, 1297–1304 (2002).

    CAS  Article  Google Scholar 

  41. Liu, M. et al. Novel gel polymer electrolyte for high-performance lithium–sulfur batteries. Nano Energy 22, 278–289 (2016).

    CAS  Article  Google Scholar 

  42. Fung, B., Khitrin, A. & Ermolaev, K. An improved broadband decoupling sequence for liquid crystals and solids. J. Magn. Reson. 142, 97–101 (2000).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

We thank F. Ooms, F. Zhang and C. Ma for their assistance with experiments. M.L. and M.W. acknowledge the financial support from the Netherlands Organization for Scientific Research (NWO) under the VICI grant nr. 16122. E.R.H.v.E. further acknowledges NWO for their support of the solid-state NMR facility for advanced materials science, which is part of the uNMR-NL grid (NWO grant 184.035.002). M.W. gratefully acknowledges the financial support from the Advanced Dutch Energy Materials (ADEM) programme of the Dutch Ministry of Economic Affairs, Agriculture and Innovation.

Author information

Authors and Affiliations

Authors

Contributions

S.G. and M.W. designed and supervised the research. M.L., S.Z. and C.W. synthesized and characterized the hybrid solid electrolytes. M.L. and S.Z. carried out the electrochemical measurements. M.L., S.G. and E.R.H.v.E. measured and analysed the NMR data. M.L., S.G. and M.W. wrote the manuscript.

Corresponding authors

Correspondence to Swapna Ganapathy or Marnix Wagemaker.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Nanotechnology thanks Ye-Feng Yao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 SEM image of the pristine micron-sized Li6PS5Cl and LiTFSI-PEO-Li6PS5Cl HSE.

(a) SEM image of the pristine micron-sized Li6PS5Cl. (b) SEM image showing the morphology of the HSE where the Li6PS5Cl particles are marked with circles.

Extended Data Fig. 2 1H-6Li CPMAS spectra of the LiTFSI-PEO-Li6PS5Cl HSE.

1H-6Li CPMAS spectra of the LiTFSI-PEO-Li6PS5Cl HSE measured at contact times ranging from 0.2 ms (lightest grey) to 6 ms (black).

Extended Data Fig. 3 1D 6Li magic angle spinning (MAS) spectrum corresponding to the Li6PS5Cl -LiTFSI-PEO HSE.

1D 6Li magic angle spinning (MAS) spectrum corresponding to the Li6PS5Cl -LiTFSI-PEO HSE.

Extended Data Fig. 4 DSC measurements showing the heat flow of the HSE, HSE-EMIM, HSE-PP13.

DSC measurements showing the heat flow of the HSE, HSE-EMIM, HSE-PP13 under heating up from 0 to 65 °C.

Extended Data Fig. 5 1H-1H cross peak intensity buildup of protons in EMIM-TFSI and PP13-TFSI correlated to PEO from the 2D 1H-1H NOESY spectra of HSE-PP13 and HSE-EMIM.

1H-1H cross peak intensity buildup of protons in EMIM-TFSI (a) and PP13-TFSI (b) correlated to PEO from the 2D 1H-1H NOESY spectra of HSE-PP13 and HSE-EMIM given in Fig. 4. All the cross peaks between EMIM-TFSI and LiTFSI-PEO appear at nearly at the same mixing time which means that there is no preferred orientation of the EMIM-TFSI species with respect to PEO. While a sequence of cross peak evolution with mixing time is observed in HSE-PP13. At the shortest mixing times, 1H-1H correlations are first observed between 1H resonances at positions 1.0 ppm and 1.6 ppm on the piperidine ring of PP13-TFSI and the –OCH2- protons from PEO. These ring protons are the furthest away from the bulky propyl and methyl groups attached to the N atom on the piperidine ring.

Extended Data Fig. 6 1D 7Li CPMAS spectra and intensity plots measured of the HSE-EMIM and HSE-PP13, and the full build-up of the peak intensity of the broad component.

1D 7Li CPMAS spectra and intensity plots measured of the (a,c) HSE-EMIM and (b,d) HSE-PP13 at contact times between 200 µs and 12 ms (e) Full build-up of peak intensity at 0.2–0.7 ppm as function of contact time of the spectra given in (a) and (b).

Extended Data Fig. 7 Li+ transport characterization in HSE-EMIM and HSE-PP13 using 6,7Li-6,7Li 2D EXSY NMR.

Li+ transport characterization in HSE with PP13-TFSI and EMIM-TFSI IL additives. 7Li–7Li, 6Li-6Li 2D-EXSY corresponding to the HSE-EMIM (a, b) and HSE-PP13 (c, d) ILs measured under MAS at a spinning speed of 5 kHz mixing time of 1.5 s and 2 s at 328 K.

Extended Data Fig. 8 Plating and stripping curves of a Li metal symmetrical cell with HSE-EMIM and HSE-PP13.

Plating and stripping curves of a Li metal symmetrical cell with LiTFSI-PEO-Li6PS5Cl HSEs with PP13 TFSI and EMIM TFSI ionic liquids. The cell with HSE-EMIM shows quick polarization after 300 h of cycling at a current density of 0.05 mA/cm2. In comparison the cell with HSE-PP13 shows a very stable over-potential (lower than 200 mV) during 800 hours of cycling, indicating a higher ionic conductivity and better interfacial stability against Li-metal.

Extended Data Fig. 9 Electrochemical impedance spectroscopy measurements (EIS) of the cell with LiTFSI-PEO-Li6PS5Cl HSE with both PP13-TFSI and EMIM-TFSI ionic liquids.

Electrochemical impedance spectroscopy measurements (EIS) of cell with LiTFSI-PEO-Li6PS5Cl HSE with both PP13-TFSI and EMIM-TFSI (PP13-TFSI and EMIM-TFSI, 0.25:1 molar ratio IL:Li-ion, HSE—EMIM-PP13) ionic liquids.

Supplementary information

Supplementary Information

Supplementary Figs. 1 and 2, discussion and Tables 1 and 2.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Liu, M., Zhang, S., van Eck, E.R.H. et al. Improving Li-ion interfacial transport in hybrid solid electrolytes. Nat. Nanotechnol. 17, 959–967 (2022). https://doi.org/10.1038/s41565-022-01162-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41565-022-01162-9

Search

Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research