Designing Next-Generation PVDF-HFP Polymer Electrolytes: Insights from Ion Transport, Dielectric Studies, and Ex-Situ Filler Engineering

Nurul Ilham Adam; Nurul Izza  Taib; Nur Liyana Nasrin  Hafiz; Nur Qistina  Karmila; Mohd Sukor  Su’ait

doi:10.36378/internationalconferenceuniks.v4i1.6129

Nurul Ilham Adam Faculty of Applied Sciences, Universiti Teknologi MARA, Perak Branch
Nurul Izza Taib Faculty of Applied Sciences, Universiti Teknologi MARA, Perak Branch
Nur Liyana Nasrin Hafiz 4Advanced Materials for Environmental Research Initiative Group, Universiti Teknologi MARA Perak Branch, Tapah Campus
Nur Qistina Karmila 4Advanced Materials for Environmental Research Initiative Group, Universiti Teknologi MARA Perak Branch, Tapah Campus,
Mohd Sukor Su’ait Solar Energy Research Institute, Universiti Kebangsaan Malasyia, Lingkungan Ilmu, Bangi, Selangor

DOI: https://doi.org/10.36378/internationalconferenceuniks.v4i1.6129

Keywords: PVDF-HFP Polymer Electrolytes, Ion Transport Mechanisms, Dielectric Analysis, Ex-Situ Filler Engineering, Lithium-Ion Conductivity

Abstract

The development of safe, flexible, and high-performance solid polymer electrolytes is essential for next-generation lithium-based energy storage. PVDF-HFP remains a leading polymer system owing to its high dielectric constant, mechanical strength, and compatibility with lithium salts. However, its limited ion mobility and low room-temperature conductivity require targeted material enhancements. This review highlights recent progress in improving PVDF-HFP polymer electrolytes through ex-situ ceramic filler engineering, optimized plasticizer incorporation, and detailed dielectric–impedance analysis. Ex-situ synthesized fillers such as SiO₂ and TiO₂ have been shown to enhance segmental mobility, promote lithium-salt dissociation, and create continuous ion-conduction pathways within the semi-crystalline matrix. Reported dielectric and impedance studies reveal strong relationships between permittivity, relaxation behaviour, charge-carrier density, and ionic conductivity, with optimized systems achieving 10⁻⁴–10⁻⁵ S cm⁻¹. This review consolidates key structure–property correlations and identifies the primary drivers of mobility enhancement, offering valuable guidance for designing next-generation PVDF-HFP-based solid polymer electrolytes for safe and efficient lithium-energy storage applications.

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References

1. Halder, B., Mohamed, M. G., Kuo, S.-W., & Elumalai, P. (2024). Review on composite polymer electrolyte using PVDF-HFP for solid-state lithium-ion battery. Materials Today Chemistry, 36, 101926.
2. Wang, X., et al. (2025). Recent advances and future prospects for PVDF-based solid polymer electrolytes. Journal of Power Sources, 628, 235855.
3. Khan, K. H., Haleem, A., Arwish, S., Shah, A., & Hussain, H. (2025). PVDF-based solid polymer electrolytes for lithium-ion batteries: strategies in composites, blends, dielectric engineering, and machine learning approaches. RSC Advances, 15, 20629–20656.
4. Zhou, D., et al. (2022). Advances and prospects of PVDF based polymer electrolytes.
Journal of Energy Chemistry, 64, 62–84.
5. Stephan, A. M., & Nahm, K. S. (2006). Review on composite polymer electrolytes for lithium batteries. Polymer, 47, 5952–5964.
6. Armand, M. B. (1979). Polymer solid electrolytes—An overview. Solid State Ionics.
7. Bruce, P. G. (1995). Solid State Electrochemistry. Cambridge University Press.
8. Tarascon, J. M., & Armand, M. (2001). Issues and challenges facing rechargeable lithium batteries. Nature, 414, 359–367.
9. Goodenough, J. B., & Kim, Y. (2010). Challenges for rechargeable Li batteries.
Chemistry of Materials, 22, 587–603.
10. Scrosati, B., Garche, J. (2010). Lithium batteries: Status, prospects and future. Journal of Power Sources, 195, 2419–2430.
11. Croce, F., Appetecchi, G. B., Persi, L., & Scrosati, B. (1998). Nanocomposite polymer electrolytes for lithium batteries. Nature, 394, 456–458.
12. Croce, F., Persi, L., Ronci, F., et al. (2001). Role of ceramic fillers in polymer electrolytes. Electrochimica Acta, 46, 2457–2461.
13. Wieczorek, W., et al. (1996). Composite polyether-based solid electrolytes. Solid State Ionics, 85, 67–72.
14. Stolarska, M., Niedzicki, L., Borkowska, R., Zalewska, A., & Wieczorek, W. (2007). Structure, transport properties and interfacial stability of PVDF-HFP electrolytes containing modified inorganic filler. Electrochimica Acta, 53, 1512–1517.
15. Appetecchi, G. B., et al. (1995). PEO-based composite polymer electrolytes.
Electrochimica Acta.
16. Gray, F. M. (1997). Solid Polymer Electrolytes. VCH Publishers.
17. Bruce, P. G., Vincent, C. A. (1993). Polymer electrolytes. Journal of the Chemical Society, Faraday Transactions.
18. Vincent, C. A. (1987). Polymer Electrolyte Reviews. Elsevier.
19. Xue, Z., He, D., & Xie, X. (2015). Polymer electrolytes for lithium batteries. Journal of Materials Chemistry A, 3, 19218–19253.
20. Zhang, H., et al. (2018). Composite polymer electrolytes for solid-state lithium batteries. Advanced Energy Materials.
21. Zheng, F., et al. (2018). Review of solid-state electrolytes for lithium batteries. Journal of Power Sources, 389, 198–213.
22. Zhao, Q., Stalin, S., Zhao, C., & Archer, L. A. (2020). Designing solid-state electrolytes. Nature Reviews Materials, 5, 229–252.
23. Sun, C., Liu, J., Gong, Y., Wilkinson, D. P., & Zhang, J. (2017). Recent advances in all-solid-state rechargeable lithium batteries. Nano Energy, 33, 363–386.
24. Manthiram, A., Yu, X., & Wang, S. (2017). Lithium battery chemistries. Nature Reviews Materials, 2, 16103.
25. Janek, J., & Zeier, W. G. (2016). Solid-state batteries. Nature Energy, 1, 16141.
26. Famprikis, T., et al. (2019). Fundamentals of inorganic solid-state electrolytes. Nature Materials, 18, 1278–1291.
27. Xu, K. (2004). Nonaqueous liquid electrolytes for lithium batteries. Chemical Reviews, 104, 4303–4418.
28. Xu, K. (2014). Electrolytes and interphases in Li-ion batteries. Chemical Reviews, 114, 11503–11618.
29. Bruce, P. G., Freunberger, S. A., Hardwick, L. J., & Tarascon, J. M. (2012). Li–O₂ and Li–S batteries. Nature Materials, 11, 19–29.
30. Zhang, S. S. (2007). A review on electrolyte additives. Journal of Power Sources, 162, 1379–1394.
31. Costa, C. M., Silva, M. M., & Lanceros-Méndez, S. (2013). Battery separators based on PVDF and its copolymers. RSC Advances.
32. Xia, W., et al. (2018). PVDF-based dielectric polymers and their applications in electronic materials. IET Nanodielectrics, 1, 17–31.
33. Long, L., Wang, S., Xiao, M., & Meng, Y. (2016). Polymer electrolytes for lithium polymer batteries. Journal of Materials Chemistry A, 4, 10038–10069.
34. Agrawal, R. C., & Pandey, G. P. (2008). Solid polymer electrolytes: materials designing and applications. Journal of Physics D: Applied Physics, 41, 223001.
35. Fenton, D. E., Parker, J. M., & Wright, P. V. (1973). Complexes of alkali metal ions with poly(ethylene oxide). Polymer, 14, 589.
36. Wright, P. V. (1975). Electrical conductivity in ionic complexes of poly(ethylene oxide). British Polymer Journal, 7, 319–327.
37. Armand, M. (1986). The history of polymer electrolytes. In Fast Ion Transport in Solids.
38. Maier, J. (2004). Nanoionics: ion transport and electrochemical storage. Nature Materials, 4, 805–815.
39. Shao, Y., et al. (2022). Transference number in polymer electrolytes: mind the reference-frame gap. Nature Communications (conceptual work on transport coefficients).
40. Li, Y., et al. (2025). Enabling enhanced ion transport in PVDF-HFP electrolytes by engineering local dielectric microenvironments with dual-functional SrTiO₃/LLZTO fillers. Chemical Engineering Journal.