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Dense inorganic electrolyte particles as a lever to promote composite electrolyte conductivity

Nature Materials volume 21, pages 1412–1418 (2022)Cite this article

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Abstract

Solid-state batteries are seen as key to the development of safer and higher-energy-density batteries, by limiting flammability and enabling the use of the lithium metal anode, respectively. Composite polymer–ceramic electrolytes are a possible solution for their realization, by benefiting from the combined mechanical properties of the polymer electrolyte and the thermal stability and high conductivity of the ceramic electrolyte. In this study we used different liquid electrolyte chemistries as models for the polymer electrolytes, and evaluated the effect of adding a variety of porous and dense ceramic electrolytes on the conductivity. All the results could be modelled with the effective medium theory, allowing prediction of the conductivity of electrolyte combinations. We unambiguously determined that highly conductive porous particles act as insulators in such systems, whereas dense particles act as conductors, thereby advancing our understanding of composite electrolyte conductivity.

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Fig. 1: Possible factors that can affect the effective conductivity of composite electrolytes.
Fig. 2: Conductivity of composites with porous particles.
Fig. 3: Effective conductivity of porous particles.
Fig. 4: Modelling the conductivity of aggregated CE particles as non-conducting.
Fig. 5: Conductivity of composites containing dense particles.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  1. Armand, M. & Tarascon, J. M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Article  Google Scholar 

  2. Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2016).

    Article  Google Scholar 

  3. Varzi, A., Raccichini, R. & Scrosati, B. Challenges and prospects of the role of solid electrolytes in the revitalization of lithium metal batteries. J. Mater. Chem. A 4, 17251–17259 (2016).

    Article  CAS  Google Scholar 

  4. Tan, D. H. S., Banerjee, A., Chen, Z. & Meng, Y. S. From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries. Nat. Nanotechnol. https://doi.org/10.1038/s41565-020-0657-x (2020).

  5. Chen, R., Li, Q., Yu, X., Chen, L. & Li, H. Approaching practically accessible solid-state batteries: stability issues related to solid electrolytes and interfaces. Chem. Rev. https://doi.org/10.1021/acs.chemrev.9b00268 (2019).

  6. Long, L., Wang, S., Xiao, M. & Meng, Y. Polymer electrolytes for lithium polymer batteries. J. Mater. Chem. A 4, 10038–10069 (2016).

    Article  CAS  Google Scholar 

  7. Zhou, D., Shanmukaraj, D., Tkacheva, A., Armand, M. & Wang, G. Polymer electrolytes for lithium-based batteries: advances and prospects. Chem 5, 2326–2352 (2019).

    Article  CAS  Google Scholar 

  8. Sun, C., Liu, J., Gong, Y., Wilkinson, D. P. & Zhang, J. Recent advances in all-solid-state rechargeable lithium batteries. Nano Energy 33, 363–386 (2017).

    Article  CAS  Google Scholar 

  9. Meesala, Y., Jena, A., Chang, H. & Liu, R. S. Recent advancements in Li-ion conductors for all-solid-state Li-ion batteries. ACS Energy Lett. 2, 2734–2751 (2017).

    Article  CAS  Google Scholar 

  10. Famprikis, T., Canepa, P., Dawson, J. A., Islam, M. S. & Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 18, 1278–1291 (2019).

    Article  CAS  Google Scholar 

  11. Balaish, M. et al. Processing thin but robust electrolytes for solid-state batteries. Nat. Energy https://doi.org/10.1038/s41560-020-00759-5 (2021).

  12. Lewis, J. A. et al. Linking void and interphase evolution to electrochemistry in solid-state batteries using operando X-ray tomography. Nat. Mater. https://doi.org/10.1038/s41563-020-00903-2 (2021).

  13. Kasemchainan, J. et al. Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells. Nat. Mater. 18, 1105–1111 (2019).

    Article  CAS  Google Scholar 

  14. Zhang, J. et al. High-voltage and free-standing poly(propylene carbonate)/Li6.75La3Zr1.75Ta0.25O12 composite solid electrolyte for wide temperature range and flexible solid lithium ion battery. J. Mater. Chem. A 5, 4940–4948 (2017).

    Article  CAS  Google Scholar 

  15. Chen, F. et al. Solid polymer electrolytes incorporating cubic Li7La3Zr2O12 for all-solid-state lithium rechargeable batteries. Electrochim. Acta 258, 1106–1114 (2017).

    Article  CAS  Google Scholar 

  16. Zhang, X. et al. Synergistic coupling between Li6.75La3Zr1.75Ta0.25O12 and poly(vinylidene fluoride) induces high ionic conductivity, mechanical strength, and thermal stability of solid composite electrolytes. J. Am. Chem. Soc. 139, 13779–13785 (2017).

    Article  CAS  Google Scholar 

  17. 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).

    Article  CAS  Google Scholar 

  18. Li, R. et al. Unitized configuration design of thermally stable composite polymer electrolyte for lithium batteries capable of working over a wide range of temperatures. Adv. Eng. Mater. https://doi.org/10.1002/adem.201900055 (2019).

  19. Villa, A., Verduzco, J. C., Libera, J. A. & Marinero, E. E. Ionic conductivity optimization of composite polymer electrolytes through filler particle chemical modification. Ionics 27, 2483–2493 (2021).

    Article  CAS  Google Scholar 

  20. Zha, W., Chen, F., Yang, D., Shen, Q. & Zhang, L. High-performance Li6.4La3Zr1.4Ta0.6O12/poly(ethylene oxide)/succinonitrile composite electrolyte for solid-state lithium batteries. J. Power Sources 397, 87–94 (2018).

    Article  CAS  Google Scholar 

  21. Zhang, J. et al. Flexible and ion-conducting membrane electrolytes for solid-state lithium batteries: dispersion of garnet nanoparticles in insulating polyethylene oxide. Nano Energy 28, 447–454 (2016).

    Article  CAS  Google Scholar 

  22. Zhao, C. Z. et al. An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes. Proc. Natl Acad. Sci. U.S.A. 114, 11069–11074 (2017).

    Article  CAS  Google Scholar 

  23. Cheng, S. H. S. et al. Electrochemical performance of all-solid-state lithium batteries using inorganic lithium garnets particulate reinforced PEO/LiClO4 electrolyte. Electrochim. Acta 253, 430–438 (2017).

    Article  CAS  Google Scholar 

  24. Tao, X. et al. Solid-state lithium–sulfur batteries operated at 37 °C with composites of nanostructured Li7La3Zr2O12/carbon foam and polymer. Nano Lett. 17, 2967–2972 (2017).

    Article  CAS  Google Scholar 

  25. Liang, Y. F. et al. A superior composite gel polymer electrolyte of Li7La3Zr2O12-poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) for rechargeable solid-state lithium ion batteries. Mater. Res. Bull. 102, 412–417 (2018).

    Article  CAS  Google Scholar 

  26. Li, Z. et al. Ionic conduction in composite polymer electrolytes: case of PEO:Ga-LLZO composites. ACS Appl. Mater. Interfaces 11, 784–791 (2019).

    Article  CAS  Google Scholar 

  27. Samsinger, R. F. et al. Influence of the processing on the ionic conductivity of solid-state hybrid electrolytes based on glass-ceramic particles dispersed in PEO with LiTFSI. J. Electrochem. Soc. 167, 120538 (2020).

    Article  CAS  Google Scholar 

  28. Mei, X. et al. A quantitative correlation between macromolecular crystallinity and ionic conductivity in polymer-ceramic composite solid electrolytes. Mater. Today Commun. 24, 101004 (2020).

    Article  CAS  Google Scholar 

  29. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011).

    Article  CAS  Google Scholar 

  30. Kato, M., Hiraoka, K. & Seki, S. Investigation of the ionic conduction mechanism of polyether/Li7La3Zr2O12 composite solid electrolytes by electrochemical impedance spectroscopy. J. Electrochem. Soc. 167, 070559 (2020).

    Article  Google Scholar 

  31. Langer, F., Bardenhagen, I., Glenneberg, J. & Kun, R. Microstructure and temperature dependent lithium ion transport of ceramic–polymer composite electrolyte for solid-state lithium ion batteries based on garnet-type Li7La3Zr2O12. Solid State Ion. 291, 8–13 (2016).

    Article  CAS  Google Scholar 

  32. Wang, Y. J., Pan, Y. & Kim, D. Conductivity studies on ceramic Li1.3Al0.3Ti1.7(PO4)3-filled PEO-based solid composite polymer electrolytes. J. Power Sources 159, 690–701 (2006).

    Article  CAS  Google Scholar 

  33. Zhao, Y. et al. A promising PEO/LAGP hybrid electrolyte prepared by a simple method for all-solid-state lithium batteries. Solid State Ion. 295, 65–71 (2016).

    Article  CAS  Google Scholar 

  34. Xia, Y. et al. A newly designed composite gel polymer electrolyte based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) for enhanced solid-state lithium-sulfur batteries. Chem. Eur. J. 23, 15203–15209 (2017).

    Article  CAS  Google Scholar 

  35. Wang, W., Yi, E., Fici, A. J., Laine, R. M. & Kieffer, J. Lithium ion conducting poly(ethylene oxide)-based solid electrolytes containing active or passive ceramic nanoparticles. J. Phys. Chem. C. 121, 2563–2573 (2017).

    Article  CAS  Google Scholar 

  36. Jung, Y.-C., Lee, S.-M., Choi, J.-H., Jang, S. S. & Kim, D.-W. All solid-state lithium batteries assembled with hybrid solid electrolytes. J. Electrochem. Soc. 162, A704–A710 (2015).

    Article  CAS  Google Scholar 

  37. Park, M. S., Jung, Y. C. & Kim, D. W. Hybrid solid electrolytes composed of poly(1,4-butylene adipate) and lithium aluminum germanium phosphate for all-solid-state Li/LiNi0.6Co0.2Mn0.2O2 cells. Solid State Ion. 315, 65–70 (2018).

    Article  CAS  Google Scholar 

  38. MacFarlane, D. R., Newman, P. J., Nairn, K. M. & Forsyth, M. Lithium-ion conducting ceramic/polyether composites. Electrochim. Acta 43, 1333–1337 (1998).

    Article  CAS  Google Scholar 

  39. Yi, J., Liu, Y., Qiao, Y., He, P. & Zhou, H. Boosting the cycle life of Li–O2 batteries at elevated temperature by employing a hybrid polymer–ceramic solid electrolyte. ACS Energy Lett. 2, 1378–1384 (2017).

    Article  CAS  Google Scholar 

  40. Maxwell, J. C. A Treatise on Electricity and Magnetism Vol. 1 (Clarendon Press, 1873).

  41. Barrande, M., Bouchet, R. & Denoyel, R. Tortuosity of porous particles. Anal. Chem. 79, 9115–9121 (2007).

    Article  CAS  Google Scholar 

  42. Weissberg, H. L. Effective diffusion coefficient in porous media. J. Appl. Phys. 34, 2636–2639 (1963).

    Article  CAS  Google Scholar 

  43. Bouchet, R., Devaux, D., Wernert, V. & Denoyel, R. Separation of bulk, surface, and topological contributions to the conductivity of suspensions of porous particles. J. Phys. Chem. C. 116, 5090–5096 (2012).

    Article  CAS  Google Scholar 

  44. Kubanska, A. et al. Elaboration of controlled size Li1.5Al0.5Ge1.5(PO4)3 crystallites from glass-ceramics. Solid State Ion. 266, 44–50 (2014).

    Article  CAS  Google Scholar 

  45. Hou, M., Liang, F., Chen, K., Dai, Y. & Xue, D. Challenges and perspectives of NASICON-type solid electrolytes for all-solid-state lithium batteries. Nanotechnology 31, 132003 (2020).

    Article  CAS  Google Scholar 

  46. Devaux, D., Bouchet, R., Glé, D. & Denoyel, R. Mechanism of ion transport in PEO/LiTFSI complexes: effect of temperature, molecular weight and end groups. Solid State Ion. 227, 119–127 (2012).

    Article  CAS  Google Scholar 

  47. Pfaffenhuber, C., Göbel, M., Popovic, J. & Maier, J. Soggy-sand electrolytes: status and perspectives. Phys. Chem. Chem. Phys. 15, 18318–18335 (2013).

    Article  CAS  Google Scholar 

  48. Aveyard, R. et al. Solid/Liquid Dispersions (ed. Tadros, T. F.) (Academic Press, 1987).

  49. Weiss, M. et al. From liquid‑ to solid‑state batteries: ion transfer kinetics of heteroionic interfaces. Electrochem. Energy Rev. https://doi.org/10.1007/s41918-020-00062-7 (2020).

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Acknowledgements

We thank B. Simon from the company SAFT for the mercury porosimetry measurements. The Agence de la Transition Ecologique (ADEME) is acknowledged for funding through the project IDOLES (grant no. 1982C0016).

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Authors and Affiliations

  1. Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP, LEPMI, Grenoble, France

    James A. Isaac, Didier Devaux & Renaud Bouchet

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Contributions

R.B. designed the study. J.A.I. collected the experimental data. Data analysis and interpretation were performed by J.A.I. with the help of R.B. and D.D. The manuscript was written by J.A.I., R.B. and D.D. All authors have approved the final version of the manuscript.

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Correspondence to Renaud Bouchet.

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Supplementary Figs. 1–8, Tables 1 and 2, description of the microstructures of CE powders and experimental procedure for measuring the conductivity of LATP.

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Isaac, J.A., Devaux, D. & Bouchet, R. Dense inorganic electrolyte particles as a lever to promote composite electrolyte conductivity. Nat. Mater. 21, 1412–1418 (2022). https://doi.org/10.1038/s41563-022-01343-w

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