Manipulating Cis-Trans Copolymer Chain Conformation to Simultaneously Improve Permittivity and DC Breakdown Strength in Polythiourea.

Polythioureas (PTUs) show great potentials for applications in the new generation of film capacitors due to their excellent dielectric properties. Herein, the cis-trans copolymer chain of PTU is successfully tailored by employing cis and trans cyclohexyl spacers. The relationship between the copolymer chain conformation, microstructure, and dielectric properties is carefully explored by a series of analysis. Compared with cis conformation, the trans with less steric hindrance can promote the formation of H-bonds. The enhanced H-bonding interactions not only reduce the molecular inter-chain spacing, but also drive the self-assembly of molecular chains to form cylindrical and droplet nano-morphologies. The phase separation between cis and trans PTUs is confirmed by combining the experimental results of TEM and DSC, and the CT64-PTU with the most two-phase interface thus obtains the highest permittivity of 5.5 (@10 Hz). The reduced molecular inter-chain spacing is accompanied by a decreased hopping distance of charges, which improves breakdown strength by 17% from 498 MV/m to 580 MV/m. Therefore, the cis-trans copolymer chain conformation in PTU provides a simultaneous high permittivity and breakdown strength. This research offers a strategy to further design high-performance dielectrics via regulation of copolymer chain conformation.

Interfacial Effect on Dielectric Properties of Self-Assembled Polythiourea-Based Copolymers for Ultrahigh Energy Storage.

Polymer dielectrics are highly desirable in capacitor applications due to their low cost, high stability, and reliability. However, there still remains a lack of feasible methods to prepare polymer dielectrics with high energy density and low dielectric loss, which severely hampers the development of compact and efficient power electronics. Here, an amphiphilic block copolymer, polythiourea-b-polydimethylsiloxane (PTU-b-PDMS), with an extraordinarily high energy density of 29.8 J cm-3 and a low loss is synthesized via polyaddition polymerization. This is highly relevant to the block molecule conformation in the interfacial region of the self-assembled PTU-b-PDMS. The block molecule in the interface adopts an extended conformation when the PTU forms nanodots, whereas the block molecule adopts a coiled conformation when the PTU forms nanostrands. The observation and characterization have proved that the coiled block molecule in the interfacial region can simultaneously induce extra strong charge trapping sites and dipolar polarization. It substantially improves the breakdown strength from 652 to 1166 MV m-1 , while maintaining a high dielectric constant of 5 and a low loss of <0.01. This work offers unprecedented structural insights into the conformation-induced interfacial effect and enables rational design of self-assembled copolymers to boost their dielectric properties and energy density.

Optimizing the Interdomain Spacing in Alicyclic Polythiourea toward High-Energy-Storable Dielectric Material.

Organic dielectric materials have been widely developed and investigated for energy storage capacitors. However, challenges remain in terms of the relatively low dielectric constant and energy density. Enhancing the dipolar polarization to increase the dielectric constant is considered to be an effective way to improve the energy density of polymer dielectrics. Herein, enlightened by the chain-packing structure that affects the dipolar relaxation behavior, a simple and low-cost approach is proposed to tailor the interdomain spacing in an alicyclic polythiourea (PTU) by changing quenching temperatures and further facilitate the dipolar polarization. It is found that the large interdomain spacing is beneficial to promote the localized motion of segmental chains in amorphous regions, but at the same time inevitably reduces the dipole density. Therefore, in order to achieve the highest dielectric constant in the PTU, there is an optimal value for the interdomain spacing. It is worth noting that the dielectric constant of PTU increases from 5.7 to 10, and thus the energy density increases by 53% to 16.3 J cm-3 . It proposes a simple and feasible strategy to further improve the energy density through optimizing the interdomain spacing toward high-energy-storable dielectric material.

How to Install TEMPO in Dielectric Polymers-Their Rational Design toward Energy-Storable Materials.

Polar groups and the charge-transport capability play significant roles in the dielectric properties of organic polymers, and thus influence the electric energy density upon application as a capacitor material. Here, the dielectric properties and electric conductivity of a series of polymers containing 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radicals are investigated. The neat radical polymer poly(TEMPO methacrylate) (PTMA) has a high dielectric constant but poor breakdown strength. Poly(methyl methacrylate) (PMMA) is introduced as an insulating polymer with high resistivity on breakdown, along with molecular design of PTMA. Copolymers of TEMPO methacrylate and methyl methacrylate, P(TMA-r-MMA), exhibit high breakdown strengths but low dielectric constants. PMMA blended with TEMPO exhibits the highest electric energy density of 7.4 J cm-3 (that of PTMA is 0.48 J cm-3 as a control), with both a high dielectric constant (≈6.8) and a high breakdown strength (≈500 MV m-1 ). It benefits from long-range but not bulk charge transport in the blends, which is different from the bulk charge transport in PTMA and the short-range charge transport in P(TMA-r-MMA). These results indicate that the TEMPO moiety located in the high breakdown matrix leads to a high energy-storage density in the capacitor.