High‐temperature dielectric polymers are in constant demand for the multitude of high‐power electronic devices employed in hybrid vehicles, grid‐connected photovoltaic and wind power generation, to name a few. There is still a lack, however, of dielectric polymers that can work at high temperature (> 150 °C). Herein, a series of all‐organic dielectric polymer composites have been fabricated by blending the n‐type molecular semiconductor 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTCDA) with polyetherimide (PEI). Electron traps are created by the introduction of trace amounts of n‐type small molecule semiconductor NTCDA into PEI, which effectively reduces the leakage current and improves the breakdown strength and energy storage properties of the composite at high temperature. Especially, excellent energy storage performance is achieved in 0.5 vol.% NTCDA/PEI at the high temperatures of 150 and 200 °C, e.g., ultrahigh discharge energy density of 5.1 J cm−3 at 150 °C and 3.2 J cm−3 at 200 °C with high discharge efficiency of 85–90%, which is superior to its state‐of‐the‐art counterparts. This study provides a facile and effective strategy for the design of high‐temperature dielectric polymers for advanced electronic and electrical systems.

Superior High‐Temperature Energy Density in Molecular Semiconductor/Polymer All‐Organic Composites

The miniaturization of electronic devices and power systems for capacitive energy storage under harsh environments requires scalable high‐quality ultrathin high‐temperature dielectric films. To meet the need, ultrasonic spray‐coating (USC) can be used. Novel polyimides with a dipolar group, CF3 (F‐PI), and all‐organic composites with trace organic semiconductor can serve as models. These scalable high‐quality ultrathin films (≈2.6 and ≈5.2 µm) are successfully fabricated via USC. The high quality of the films is evaluated from the micro‐millimeter scale to the sub‐millimeter and above. The high glass transition temperature Tg (≈340 °C) and concurrent large bandgap Eg (≈3.53 eV) induced by weak conjugation from considerable interchain distance (≈6.2 Å) enable F‐PI to be an excellent matrix delivering a discharge energy density with 90% discharge efficiency Uη90 of 2.85 J cm−3 at 200 °C. Further, the incorporation of a trace organic semiconductor leads to a record Uη90 of ≈4.39 J cm−3 at 200 °C due to the markedly enhanced breakdown strength caused by deep charge traps of ≈2 eV. Also, a USC‐fabricated multilayer F‐PI foil capacitor with ≈85 nF (six layers) has good performance at 150 °C. These results confirm that USC is an excellent technology to fabricate high‐quality ultrathin dielectric films and capacitors.

Scalable Ultrathin All‐Organic Polymer Dielectric Films for High‐Temperature Capacitive Energy Storage

Multi-layered boron nitride/polyimide high temperature capacitor dielectric film

Dielectric polymer nanocomposites are considered as one of the most promising candidates for high-power-density electrical energy storage applications. Inorganic nanofillers with high insulation property are frequently introduced into fluoropolymer to improve its breakdown strength and energy storage capability. Normally, inorganic nanofillers are thought to introducing traps into polymer matrix to suppress leakage current. However, how these nanofillers effect the leakage current is still unclear. Meanwhile, high dopant (> 5 vol%) is prerequisite for distinctly improved energy storage performance, which severely deteriorates the processing and mechanical property of polymer nanocomposites, hence brings high technical complication and cost. Herein, boron nitride nanosheet (BNNS) layers are utilized for substantially improving the electrical energy storage capability of polyvinylidene fluoride (PVDF) nanocomposite. Results reveal that the high conduction band minimum of BNNS produces energy barrier at the interface of adjacent layers, preventing the electron in PVDF from passing through inorganic layers, leading to suppressed leakage current and superior breakdown strength. Accompanied by improved Young's modulus (from 1.2 GPa of PVDF to 1.6 GPa of nanocomposite), significantly boosted discharged energy density (14.3 J cm-3) and charge-discharge efficiency (75%) are realized in multilayered nanocomposites, which are 340 and 300% of PVDF (4.2 J cm-3, 25%). More importantly, thus remarkably boosted energy storage performance is accomplished by marginal BNNS. This work offers a new paradigm for developing dielectric nanocomposites with advanced energy storage performance. 

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High Conduction Band Inorganic Layers for Distinct Enhancement of Electrical Energy Storage in Polymer Nanocomposites

In modern electronic and power systems, it is essential to develop advanced dielectric materials with high energy density. One-dimensional ferroelectric ceramic nanofibers were proved to be a feasible strategy for improving the permittivity and energy density of nanocomposites. In this paper, to overcome the high loss issue of Na0.5Bi0.5TiO3 (NBT), a kind of novel nanofibers 0.93Na0.5Bi0.5TiO3-0.07BaTiO3 (NBT-BT) with large aspect ratio are synthesized by the electrospinning method and used as the dielectric fillers in trilayer structured poly(vinylidene difluoride) (PVDF) nanocomposites for energy storage applications. The finite element analysis is performed to evaluate the electric field distribution in the nanocomposites. The results showed that the trilayer structured nanocomposite loaded with 6 wt % NBT-BT nanofibers in the middle layer achieved the highest discharge energy density of 19.21 J cm-3 at 527 kV mm-1, which is 87.2% higher than that of pure PVDF (10.26 J cm-3 at 420 kV mm-1). Owing to the contribution of the barrier effect and interface polarization between adjacent layers, the energy density of the trilayer structured nanocomposites is significantly higher than that of the single-layer nanocomposites. This work provides a kind of novel one-dimensional ceramic fillers for obviously improving the energy density of polymer-based dielectrics.

Q.M. Zhang

Papers

Advanced dielectric polymers for energy storage