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. 2024 Dec 10;121(50):e2415388121.
doi: 10.1073/pnas.2415388121. Epub 2024 Dec 6.

High-temperature high-k polyolefin by rational molecular design

Jing Hao #  1 , Irene Mutegi #  2 , Madhubanti Mukherjee  3 , Harikrishna Sahu  3 , Ashish Khomane  2 , Omer Yassin  2 , Rampi Ramprasad  3 , Gregory A Sotzing  2 , Yang Cao  1   4
Affiliations

High-temperature high-k polyolefin by rational molecular design

Jing Hao et al. Proc Natl Acad Sci U S A. .

Abstract

Polymer film dielectrics are highly favored for capacitive energy storage due to the inherent advantages of high breakdown strength, low dielectric loss, and ease of processing. High-density renewables conversion and harsh-condition electrification further emphasize the need for high-temperature, high-k polymers. A unique design strategy is developed to augment high-temperature polyolefins with improved dielectric constant, via the integration of phenyl pendants hanging off the rigid bicyclic backbone. The impacts of the pendant polarizability and steric positioning on dielectric constant, bandgap, glass-transition temperature (Tg), and high-field, high-temperature dielectric characteristics have been investigated. The orientational polarization of the polar phenyl pendants with rotational degree of freedom imparts cyclic olefins with enhanced dielectric constants, while maintaining the large bandgap, and high glass-transition temperature (Tg > 170 °C). Among these synthesized polymers, m-PNB-BP stands out with a remarkable dielectric constant of 4 at a high sub-Tg temperature of 150 °C, and a high discharged density of 8.6 J/m3 at 660 MV/m. This study unveils a different path for designing high-temperature polymers with enhanced dielectric constants, particularly beneficial for capacitive energy storage.

Keywords: dielectric; energy storage; high dielectric constant; high temperature; polymer.

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Conflict of interest statement

Competing interests statement:The authors declare no competing interest.

Figures

Fig. 1.
Fig. 1.
The relationships between bandgap and Tg/dielectric constant for commonly used commercial capacitive polymers in comparison with m-PNB-BP, p-PNB-BP, and p-PNB-BA. (A) Relationship between bandgap and Tg. (B) Relationship between dielectric constant and bandgap.
Fig. 2.
Fig. 2.
Synthesis and structure characterization of p-PNB-BP, m-PNB-BP, and p-PNB-BA. (A) Synthesis process of monomers. (B) Polymerization process. (C) Comparisons of 1H NMR. (D) WAXS results.
Fig. 3.
Fig. 3.
Impacts of the polar group in the pendant and the position of the pendant attached to the backbone on the dielectric constants. Temperature-dependent dielectric spectroscopy of (A) p-PNB-BA, (B) p-PNB-BP, and (C) m-PNB-BP. (D) Temperature-dependent dielectric constant and dissipation factor of p-PNB-BA, p-PNB-BP, and m-PNB-BP at 1 kHz. (E) Calculated electrostatic potential of p-PNB-BP, m-PNB-BP, and p-PNB-BA. (F) Molecule energy of p-PNB-BA, p-PNB-BP, and m-PNB-BP with different dihedral angles between the pendant and the backbone.
Fig. 4.
Fig. 4.
Impacts of the polar group in the pendant and the position of the pendant attached to the backbone on the bandgap. (A) UV-vis spectra of p-PNB-BP, m-PNB-BP, and p-PNB-BA. (B) Calculated DOS of p-PNB-BP, m-PNB-BP, and p-PNB-BA. The dashed lines are tangents to obtain the onset wavelengths of absorption (C) DSC curves of p-PNB-BP, m-PNB-BP, and p-PNB-BA.
Fig. 5.
Fig. 5.
Capacitive performance of p-PNB-BP, p-PNB-BA, and m-PNB-BP. (A–C) DE loops of (A) p-PNB-BP, (B) p-PNB-BA, and (C) m-PNB-BP at RT. (D–F) DE loops of (D) p-PNB-BP, (E) p-PNB-BA, and (F) m-PNB-BP at 150 °C. (G and H) Discharged energy density and charge-discharge efficiency of p-PNB-BP, p-PNB-BA, and m-PNB-BP at (G) RT and (H)150 °C. (I) Field-dependent current density of p-PNB-BP, m-PNB-BP, p-PNB-BA, and Kapton at 150 °C.
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