journal article·2025-07

Enhanced energy storage in high-entropy ferroelectric polymers

Chenyi Li, Yang Liu, Bo Li, Ze Yuan, Tiannan Yang, Yuquan Liu, Hanxiao Gao, Linxiao Xu, Xiang Yu, Quan Luo, Shengfei Tang, Minghai Yao, Yutie Gong, Zekai Fei, Long-Qing Chen, Haibo Zhang, Huamin Zhou, Qing Wang

Nature Materials· Volume 24· Issue 7
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Abstract

Relaxor ferroelectrics have been intensively studied during the past two decades for capacitive energy storage in modern electronics and electrical power systems. However, the energy density of relaxor ferroelectrics is fundamentally limited by early polarization saturation and largely reduced polarization despite high dielectric constants. To overcome this challenge, here we report the formation of a high-entropy superparaelectric phase in relaxor ferroelectric polymers induced by low-dose proton irradiation, which exhibits delayed polarization saturation, reduced ferroelectric loss and markedly improved polarizability. Our combined theoretical and experimental results reveal that new chemical bonds generated by the irradiation-induced chemical reactions are essential to the formation of the high-entropy state in ferroelectric polymers. The high-entropy superparaelectric phase endows the polymer with a substantially enhanced intrinsic energy density of 45.7 J cm-3 at room temperature, outperforming the current ferroelectric polymers and nanocomposites under the same electric field. Our work widens the high-entropy concept in ferroelectrics and lays the foundation for the future exploration of high-performance ferroelectric polymers.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Ferroelectric and Piezoelectric Materials · Dielectric materials and actuators · Polymer Nanocomposite Synthesis and Irradiation

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (65)

Show source-provided references
1. Chu, B. et al. A dielectric polymer with high electric energy density and fast discharge speed. Science 313, 334–336 (2006).10.1126/science.1127798 ↗
2. Kim, J. et al. Ultrahigh capacitive energy density in ion-bombarded relaxor ferroelectric films. Science 369, 81–84 (2020).10.1126/science.abb0631 ↗
3. Pan, H. et al. Ultrahigh energy storage in superparaelectric relaxor ferroelectrics. Science 374, 100–104 (2021).10.1126/science.abi7687 ↗
4. Yang, B. B. et al. Engineering relaxors by entropy for high energy storage performance. Nat. Energy 8, 956–964 (2023).10.1038/s41560-023-01300-0 ↗
5. Li, Q. et al. Flexible high-temperature dielectric materials from polymer nanocomposites. Nature 523, 576–579 (2015).10.1038/nature14647 ↗
6. Chen, J. et al. Ladderphane copolymers for high-temperature capacitive energy storage. Nature 615, 62–66 (2023).10.1038/s41586-022-05671-4 ↗
7. Liu, Y. et al. Relaxor ferroelectric polymers: insight into high electrical energy storage properties from a molecular perspective. Small Sci. 1, 2000061 (2021).10.1002/smsc.202000061 ↗
8. Zhang, X. et al. Achieving high energy density in PVDF-based polymer blends: suppression of early polarization saturation and enhancement of breakdown strength. ACS Appl. Mater. Interfaces 8, 27236–27242 (2016).10.1021/acsami.6b10016 ↗
9. Li, Q. et al. Solution-processed ferroelectric terpolymer nanocomposites with high breakdown strength and energy density utilizing boron nitride nanosheets. Energy Environ. Sci. 8, 922–931 (2015).10.1039/C4EE02962C ↗
10. Li, Q., Han, K., Gadinski, M. R., Zhang, G. & Wang, Q. High energy and power density capacitors from solution-processed ternary ferroelectric polymer nanocomposites. Adv. Mater. 26, 6244–6249 (2014).10.1002/adma.201402106 ↗
11. Wang, G., Huang, X. & Jiang, P. Mussel-inspired fluoro-polydopamine functionalization of titanium dioxide nanowires for polymer nanocomposites with significantly enhanced energy storage capability. Sci. Rep. 7, 43071 (2017).
12. Zhang, X. et al. Giant energy density and improved discharge efficiency of solution‐processed polymer nanocomposites for dielectric energy storage. Adv. Mater. 28, 2055–2061 (2016).10.1002/adma.201503881 ↗
13. Chen, L. et al. Giant energy-storage density with ultrahigh efficiency in lead-free relaxors via high-entropy design. Nat. Commun. 13, 3089 (2022).
14. Yang, B. et al. High-entropy enhanced capacitive energy storage. Nat. Mater. 21, 1074–1080 (2022).10.1038/s41563-022-01274-6 ↗
15. Huang, Y. Jr, Yeh, J.-W. & Yang, A. C.-M. ‘High-entropy polymers’: a new route of polymer mixing with suppressed phase separation. Materialia 15, 100978 (2021).10.1016/j.mtla.2020.100978 ↗
16. Yeh, J. W. et al. Nanostructured high-entropy alloys with multiple principal elements: novel alloy design concepts and outcomes. Adv. Eng. Mater. 6, 299–303 (2004).10.1002/adem.200300567 ↗
17. Rost, C. M. et al. Entropy-stabilized oxides. Nat. Commun. 6, 8485 (2015).
18. Hirai, T. et al. High-entropy polymer blends utilizing in situ exchange reaction. Polymer 240, 124483 (2022).10.1016/j.polymer.2021.124483 ↗
19. Qian, X. et al. High-entropy polymer produces a giant electrocaloric effect at low fields. Nature 600, 664–669 (2021).10.1038/s41586-021-04189-5 ↗
20. Qi, H., Chen, L., Deng, S. & Chen, J. High-entropy ferroelectric materials. Nat. Rev. Mater. 8, 355–356 (2023).10.1038/s41578-023-00544-2 ↗
21. Zhang, Q. M., Bharti, V. & Zhao, X. Giant electrostriction and relaxor ferroelectric behavior in electron-irradiated poly(vinylidene fluoride-trifluoroethylene) copolymer. Science 280, 2101–2104 (1998).10.1126/science.280.5372.2101 ↗
22. Lau, S. T., Chan, H. L. W. & Choy, C. L. Structural and property changes in poly (vinylidene fluoride-trifluoroethylene) 70/30 mol% copolymer induced by proton irradiation. Appl. Phys. A 80, 289–294 (2005).10.1007/s00339-003-2108-6 ↗
23. Lau, S. T. et al. Effects of proton irradiation on the structure and properties of poly(vinylidene fluoride-trifluoroethylene) 80/20 mol.% copolymer. Ferroelectrics 273, 9–14 (2002).10.1080/713716354 ↗
24. Xu, H., Shanthi, G., Bharti, V., Zhang, Q. M. & Ramotowski, T. Structural, conformational, and polarization changes of poly(vinylidene fluoride-trifluoroethylene) copolymer induced by high-energy electron irradiation. Macromolecules 33, 4125–4131 (2000).10.1021/ma9919561 ↗
25. Han, Z., Liu, Y., Chen, X., Xu, W. & Wang, Q. Enhanced piezoelectricity in poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene) random terpolymers with mixed ferroelectric phases. Macromolecules 55, 2703–2713 (2022).10.1021/acs.macromol.1c02302 ↗
26. Bargain, F., Thuau, D., Hadziioannou, G., Domingues Dos Santos, F. & Tencé-Girault, S. Phase diagram of poly(VDF-ter-TrFE-ter-CTFE) copolymers: relationship between crystalline structure and material properties. Polymer 213, 123203 (2021).10.1016/j.polymer.2020.123203 ↗
27. Zhang, Z., Meng, Q. & Chung, T. C. M. Energy storage study of ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) terpolymers. Polymer 50, 707–715 (2009).10.1016/j.polymer.2008.11.005 ↗
28. Zhang, Z. & Chung, T. C. M. The structure-property relationship of poly(vinylidene difluoride)-based polymers with energy storage and loss under applied electric fields. Macromolecules 40, 9391–9397 (2007).10.1021/ma071561e ↗
29. Liu, Y. et al. Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary. Nature 562, 96–100 (2018).10.1038/s41586-018-0550-z ↗
30. Liu, Y. et al. Chirality-induced relaxor properties in ferroelectric polymers. Nat. Mater. 19, 1169–1174 (2020).10.1038/s41563-020-0724-6 ↗
31. Li, F., Zhang, S., Damjanovic, D., Chen, L.-Q. & Shrout, T. R. Local structural heterogeneity and electromechanical responses of ferroelectrics: learning from relaxor ferroelectrics. Adv. Funct. Mater. 28, 1801504 (2018).10.1002/adfm.201801504 ↗
32. Taguet, A., Ameduri, B. & Boutevin, B. Crosslinking of vinylidene fluoride-containing fluoropolymers. Adv. Polym. Sci. 184, 127–211 (2005).10.1007/b136245 ↗
33. Shu, L. et al. Partitioning polar-slush strategy in relaxors leads to large energy-storage capability. Science 385, 204–209 (2024).10.1126/science.adn8721 ↗
34. Liu, H. X. et al. Concurrent enhancement of breakdown strength and dielectric constant in poly(vinylidene fluoride) film with high energy storage density by ultraviolet irradiation. ACS Omega 7, 25999–26004 (2022).10.1021/acsomega.1c07373 ↗
35. Li, H. et al. Crosslinked fluoropolymers exhibiting superior high-temperature energy density and charge-discharge efficiency. Energy Environ. Sci. 13, 1279–1286 (2020).10.1039/C9EE03603B ↗
36. Guan, F., Pan, J., Wang, J., Wang, Q. & Zhu, L. Crystal orientation effect on electric energy storage in poly(vinylidene fluoride-co-hexafluoropropylene) copolymers. Macromolecules 43, 384–392 (2010).10.1021/ma901921h ↗
37. Meng, N. et al. Ultrahigh β-phase content poly(vinylidene fluoride) with relaxor-like ferroelectricity for high energy density capacitors. Nat. Commun. 10, 4535 (2019).
38. Ren, X. et al. Giant energy storage density in PVDF with internal stress engineered polar nanostructures. Nano Energy 72, 104662 (2020).10.1016/j.nanoen.2020.104662 ↗
39. Ren, X. et al. Ultra-high energy density integrated polymer dielectric capacitors. J. Mater. Chem. A 10, 10171 (2022).10.1039/D1TA09045C ↗
40. Scott, J. F. Ferroelectrics go bananas. J. Phys. Condens. Matter 20, 021001 (2008).10.1088/0953-8984/20/02/021001 ↗
41. Khanchaitit, P., Han, K., Gadinski, M. R., Li, Q. & Wang, Q. Ferroelectric polymer networks with high energy density and improved discharged efficiency for dielectric energy storage. Nat. Commun. 4, 2845 (2013).10.1038/ncomms3845 ↗
42. Yang, M. Z. et al. Polymer nanocomposite dielectrics for capacitive energy storage. Nat. Nanotechnol. 19, 588–603 (2024).10.1038/s41565-023-01541-w ↗
43. Zhou, Y. et al. A scalable, high-throughput, and environmentally benign approach to polymer dielectrics exhibiting significantly improved capacitive performance at high temperatures. Adv. Mater. 30, 1805672 (2018).10.1002/adma.201805672 ↗
44. Colla, E. V., Chao, L. K., Weissman, M. B. & Viehland, D. D. Aging in a relaxor ferroelectric: scaling and memory effects. Phys. Rev. Lett. 85, 3033–3036 (2000).10.1103/PhysRevLett.85.3033 ↗
45. Han, D. L. et al. Self-oscillating polymeric refrigerator with high energy efficiency. Nature 629, 1041–1046 (2024).10.1038/s41586-024-07375-3 ↗
46. Ducharme, S. et al. Intrinsic ferroelectric coercive field. Phys. Rev. Lett. 84, 175–178 (2000).10.1103/PhysRevLett.84.175 ↗
47. Li, T., Chen, C. & Zhou, J. Three dimensional phase field study on the thickness effect of ferroelectric polymer thin film. Theor. Appl. Mech. Lett. 1, 011008 (2011).10.1063/2.1101108 ↗
48. Guo, M. et al. Toroidal polar topology in strained ferroelectric polymer. Science 371, 1050–1056 (2021).10.1126/science.abc4727 ↗
49. Su, Y. et al. High-performance piezoelectric composites via β phase programming. Nat. Commun. 13, 4867 (2022).
50. Ahluwalia, R., Sullivan, M. B., Srolovitz, D. J., Zheng, J. W. & Huan, A. C. H. Multiscale kinetic model for polarization switching in ferroelectric polymer thin films. Phys. Rev. B 78, 054110 (2008).10.1103/PhysRevB.78.054110 ↗
51. Arce-Gamboa, J. R. & Guzmán-Verri, G. G. Random electric field instabilities of relaxor ferroelectrics. npj Quantum Mater. 2, 28 (2017).
52. Guzmán-Verri, G. G., Littlewood, P. B. & Varma, C. M. Paraelectric and ferroelectric states in a model for relaxor ferroelectrics. Phys. Rev. B 88, 134106 (2013).10.1103/PhysRevB.88.134106 ↗
53. Wang, S., Yi, M. & Xu, B.-X. A phase-field model of relaxor ferroelectrics based on random field theory. Int. J. Solids Struct. 83, 142–153 (2016).10.1016/j.ijsolstr.2016.01.007 ↗
54. Westphal, V., Kleemann, W. & Glinchuk, M. D. Diffuse phase transitions and random-field-induced domain states of the ‘relaxor’ ferroelectric PbMg1/3Nb2/3O3. Phys. Rev. Lett. 68, 847 (1992).10.1103/PhysRevLett.68.847 ↗
55. Pirc, R. & Blinc, R. Spherical random-bond-random-field model of relaxor ferroelectrics. Phys. Rev. B 60, 13470 (1999).10.1103/PhysRevB.60.13470 ↗
56. Bokov, A. & Ye, Z.-G. Recent progress in relaxor ferroelectrics with perovskite structure. J. Mater. Sci. 41, 31–52 (2006).10.1007/s10853-005-5915-7 ↗
57. Wang, J. & Zhang, T. Y. Size effect in epitaxial ferroelectric islands and thin films. Phys. Rev. B 73, 144107 (2006).10.1103/PhysRevB.73.144107 ↗
58. Li, Y. L., Hu, S. Y., Liu, Z. K. & Chen, L. Q. Effect of substrate constraint on the stability and evolution of ferroelectric domain structures in thin films. Acta Mater. 50, 395–411 (2002).10.1016/S1359-6454(01)00360-3 ↗
59. Noheda, B., Cox, D. E., Shirane, G., Guo, J. & Ye, Z.-G. Phase diagram of the ferroelectric relaxor (1–x)Pb(Mg1/3Nb2/3)-xPbTiO3. Phys. Rev. B 66, 054104 (2002).10.1103/PhysRevB.66.054104 ↗
60. Frisch, M. J. et al. Gaussian (Wallingford CT, 2009).
61. Becke, A. D. Density‐functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993).10.1063/1.464913 ↗
62. Lee, C., Yang, W. T. & Robert, G. P. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988).10.1103/PhysRevB.37.785 ↗
63. Miehlich, B., Savin, A., Stoll, H. & Heinzwerner, P. Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr. Chem. Phys. Lett. 157, 200–206 (1989).10.1016/0009-2614(89)87234-3 ↗
64. Lu, T. & Chen, F. W. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).10.1002/jcc.22885 ↗
65. Hirshfeld, F. L. Bonded-atom fragments for describing molecular charge densities. Theor. Chim. Acta 44, 129–138 (1977).10.1007/BF00549096 ↗