High-temperature energy storage polyimide dielectric materials: polymer multiple-structure design

High-temperature energy storage with a new tri-layers polymer composites via hybrid assembly engineering

Polymer films are ideal dielectric materials for energy storage capacitors due to their light weight and flexibility, but lower energy density and poor heat resistance greatly limit their application in high-temperature energy storage. Unlike the traditional method of solely adding wide-bandgap inorganic fillers to enhance energy density, in this study we constructed trap-rich hybrid covalently cross-linked networks in polyetherimide (PEI) via reactive polyhedral oligomeric silsesquioxane (POSS)-functionalized boron nitride nanosheets (BNNS@POSS), which not only serve as interfacial layers for dielectric transitions and insulating barriers but also create deeper traps and higher energy barriers in the region of cross-linked chains. This strategy based on the co-modulation of interfaces and traps achieved the compatibility of high polarization and high breakdown strength and improved energy storage performance. Therefore, the composite film BNNS@POSS/PEI with the addition of 5 wt% BNNS@POSS achieved a maximum discharge energy density and charge-discharge efficiency at 150 °C of 6.16 J cm-3 and 89.92%, and maintained high values at 200 °C of 4.12 J cm-3 and 88.38%, respectively. Moreover, the glass transition temperature (Tg) of the composite dielectrics increased by 20.2 °C. This work provides a promising candidate material and development directions for research in the field of high-temperature energy storage capacitors.

11 - Dielectric Polymer Materials with High Thermal Stability

Global demand for lithium-ion secondary batteries have been increasing due to new market growth from electric vehicles and power storage systems. Lithium-ion batteries possess high power density, energy density and long cycle life without memory effect and little self-discharge, and have been primary energy storage system for commercial electronics. However, recent accidents regarding battery safety, such as Samsung Note 7 issue, has raised doubt among public about lithium-ion batteries as option for energy storage. Separator is one of the primary component for lithium-ion battery safety. Commercial separators like PE or PP not only possess outstanding mechanical and electrochemical performance, but also have thermal shutdown function that provide safety measure by pore—blocking with melted polyolefin materials. Nevertheless, polyolefin materials suffered serious shrinkage at elevated temperature, which cause internal short-circuited of batteries ; also, polyolefin materials have relatively low electrolyte uptake, and could be major obstacle for future lithium-ion battery application. Hence it’s necessary to design new type of separator that guarantee battery safety and demonstrate better electrochemical performance In this study, we proposed a brand-new method to design composite separator with high thermal stability, electrolyte uptake ability and thermal shutdown function. Polyimide(PI) nanofiber film was used as substrate and produced by electrospinning technique, and ultra-thin Low-Density-Polyethylene(LDPE) layer was laid upon PI by simple spin-coating method. Spin-coating method provided unique advantages such as ultra thin coating layer (less than 1 micron), uniform coating structure and simple process, and was yet been applied for construction of composite film as lithium-ion battery separator. Coating parameter was tuned to obtain the optimized composite separator. Field-emission scanning electron microscope (FE-SEM) was used to investigate morphologies of separators ; Contact angle measurement was conducted to verify electrolyte affinity of different separators ; A.C. impedance method was used to measure conductivities and verify thermal shutdown of separators, and electrolyte uptake of different separators were measured by electrolyte soaking method in an argon-filled glovebox. The composite film had sub-micron average pore size, and possessed excellent physical properties, for instance, high porosity(73%), electrolyte uptake(1300%), ion conductivity(4.3*10-4 S/cm), air permeability(gurley value=0), and thermal stability(no shrink up to 150。C). Thermal shutdown function of composite film was also confirmed by impedance measurement at elevated temperature. It was noticed that physical properties between pristine PI and composite film were similar owning to ultra-thin coating layer, which mitigate performance loss from LDPE coating. Afterward, full cell battery tests were conducted with CR2032 type coin cell (Cathode : LFP, anode : MCMB, electrolyte : 1 M LiPF6 in EC/EMC/DMC=1:1:1+1%VC, 1C=2.4mAh/g). The first cycle charge-discharge curves, rate capability and cyclic performance were conducted. The composite film showed flatter first cycle charge-discharge plateau, better capacity retention at higher C-rate (Composite film :102 mAh/g at 1C, 79% retention, Celgard 2500 : 73 mAh/g, 51% retention , w.r.t. 0.1C), and higher discharge capacity at 0.5C 50th cyclic test. The higher porosity and electrolyte uptake of composite film facilitated ion conduction and were the main cause for enhanced battery performance. With enhanced thermal stability and electrochemical performance, we expected this type of composite separator to be promising for future lithium-ion battery application. Figure 1

The availability of high-temperature dielectrics is key to develop advanced electronics and power systems that operate under extreme environmental conditions. In the past few years, many improvements have been made and many exciting developments have taken place. However, currently available candidate materials and methods still do not meet the applicable standards. Polyimide (PI) was found to be the preferred choice for high-temperature dielectric films development due to its thermal stability, dielectric properties, and flexibility. However, it has disadvantages such as a relatively low dielectric permittivity. This chapter presents an overview of recent progress on PI dielectric materials for high-temperature capacitive energy storage applications. In this way, a new molecular design of the skeleton structure of PI should be performed to balance size and thermal stability and to optimize energy storage property for high-temperature application. The improved performance can be generated via incorporation of inorganic units into polymers to form organic-inorganic hybrid and composite structures.

Increased reliance on solar energy conversion technologies will necessarily constitute a major plank of any forward global energy supply strategy. It is possible that solar photovoltaic (PV) technology and concentrating solar thermal (CST) power technology will play roughly equal, but complementary roles by 2050. The ability to increase reliance on CST power technology during this period, however, will be constrained by a number of factors: the large plant sizes dictated by economies of scale, the high associated transmission infrastructure investment cost, and the limitations of current thermal energy storage technologies. Thus, solar technology's main midterm role is seen to be as hybrid solar thermal power plant. The development of low-cost, high-temperature, high-energy density thermal energy storage systems is needed to enable CST plants to be dispatchable and accelerate the deployment of this technology. Thermochemical storage has the best potential to achieve these energy storage requirements and a brief overview of thermochemical energy storage options for CST plants points to high-temperature metal-hydride thermochemical heat energy storage systems. Hydrogen storage systems offer the highest energy storage capacity per volume and are therefore the most likely candidates for achieving the goal of fully dispatchable CST plants. A number of high-temperature metal-hydride thermochemical solar energy storage systems have been proposed and a small number of these systems are currently being investigated and developed. A key component of this work is matching the thermochemical metal-hydride system with a suitable “low-temperature” hydrogen storage material to produce systems that are self-regulating. A summary of the development status of these systems suggests that, despite the technical challenges associated with high-temperature thermochemical energy storage systems, their potential advantages are now seeing development occurring. Although in the early stages, their commercialisation could be fast tracked.

High-temperature capacitive energy storage demands that dielectric materials maintain low electrical conduction loss and high discharged energy density under thermal extremes. The temperature capability of dielectric polymers is limited to below 200 °C, lagging behind requirements for high-power and harsh-condition electronics. Here we report a molecular topology design for dielectric polymers with mechanical bonds that overcomes this obstacle, where cyclic polyethers are threaded onto the axles of various polyimides. From density functional theory and molecular dynamics calculations, we found that the local vibrations of the encircled polymer chains were damped by the cyclic molecules through mechanical bonding, substantially inhibiting the phonon-assisted interchain charge transport that dominates conduction loss when approaching the thermal extremes. At 250 °C, we experimentally observed a d.c. electrical resistivity four orders of magnitude greater than that of commercial polyimides, with the discharged energy density reaching 4.1 J cm-3 with 90% charge-discharge efficiency, exceeding conventional dielectric polymers and polymer composites. These findings open up opportunities for substantially promoting the temperature capability of dielectric polymers given the rich diversity of existing molecular topologies modified with mechanical bonds.

Polymer dielectrics need to operate at high temperatures to meet the demand of electrostatic energy storage in modern electronic and electrical systems. The polymer nanocomposite approach, an extensively proved strategy for the performance improvement, encounters the bottleneck of reduced energy density and poor discharge efficiency beyond 150°C. Here, we report a polymer/metal oxide cluster composite prepared based on the "site isolation" strategy. Capitalizing on the quantum size effect, the bandgap and surface defect states of the ultra-small inorganic clusters (2.2nm diameter) are modulated to markedly differ from the regular-sized nanoparticles. Experimental results in conjunction with computational simulation demonstrate that, the presence of ultra-small inorganic clusters can introduce more abundant, deeper traps in the composite dielectric with respect to the conventional polymer/nanoparticle blends. Unprecedented high-temperature capacitive performance including colossal energy density (6.8 Jcm-3 ), ultra-high discharge efficiency (95%) and superior stability at different electric field frequencies, are achieved in these polymer/cluster composites up to 200°C. Along with the advantages in material preparation (inexpensive precursors and one-pot synthesis), such polymer/inorganic cluster composite approach is promising for high-temperature dielectric energy storage in practical power apparatus and electronic devices. This article is protected by copyright. All rights reserved.

Largely improved dielectric properties of polyimide composites by tuning content and formation of CsPbBr3 nanocrystals

Horizontally-oriented barium titanate@polydomine/polyimide nanocomposite films for high-temperature energy storage

High-temperature resistant polymer dielectrics present large application potentials in harsh-environment electrostatic capacitors. However, the widely used polymer films including polyimide often suffer poor mechanical strength or energy storage level especially at superimposed bending, electrical and thermal stresses during practical operation, owing to the inherent contradiction in synergistically strengthening both sides, which is a challenging problem that urgently needs to be solved. Here an all-organic synthesis route is exploited to synergistically realize high mechanical strength (378.3 MPa), breakdown strength (682 MV/m), energy density/efficiency (6.06 J/cm3 at η = 90%, the peak value reaches 10.29 J/cm3) at 150 °C in fabricated crystalline polyamide film, which respectively has an enhancement (81%, 88%, 2231%) than that of polyimide film, whose comprehensive performances present definite preponderance among existed polymer dielectrics. It is further demonstrated that, different from traditionally disadvantageous π–π and charge-transfer interactions, the particular coexistence of abundant and strong hydrogen bonds constraining large energy gap synergistically strengthens the anticorrelated mechanical and energy-storage performances, and the matched high film crystallinity establishing by Lewis acid and high temperature-assisted chain arrangement further strengthens both sides. Compared with nanocomposite strategy, such all-organic structure also endows it with large potential to match current production process toward large-scale fabrication of high-quality polymer dielectrics.

Scalable polyolefin-based all-organic dielectrics with superior high-temperature capacitive energy storage performance

The rapid development of renewable energy systems, electric vehicles, and pulsed equipment requires energy storage media to have a high energy storage density and efficiency in a wide temperature range. The state-of-the-art biaxially oriented polypropylene (BOPP) film is insufficient to meet the growing demand for energy storage devices due to its low energy storage density and working temperature, which make it a research hotspot for developing dielectric energy storage materials. In this manuscript, based on the epoxy materials that have been shown as a potential energy storage medium, we aim to reduce the influence of the benzene ring delocalization structure on the energy storage losses and enhance the efficiency by gradually replacing them with cyclohexane structures to adjust the segment unsaturation of epoxy materials. The results show that by partially reducing the unsaturation of the curing agent, the epoxy material achieves an excellent high-temperature energy storage density of 2.21 J/cm3 at 150 °C and 300 MV/m while maintaining an extremely high energy storage efficiency of 99.2%. Leakage current density and high-voltage dielectric spectroscopy tests confirm that a moderate reduction of the segment unsaturation of epoxy materials can greatly inhibit polarization loss at high temperatures, which may explain their high energy storage efficiency.

A review on high-temperature thermochemical energy storage based on metal oxides redox cycle

Polyimide (PI) film is widely used in aerospace, microelectronics, and other fields because of its excellent thermal stability and mechanical strength. However, there are very few reports about its application in the direction of optical imaging. To use PI film for imaging, the requirements for the optical homogeneity of the PI film are extremely demanding. The optical homogeneity of the stretch-resistant PI film proposed in this paper with 100 mm diameter and low thermal expansion coefficient meets the Rayleigh criterion, which has the potential for applications in the imaging field. In addition, the tensile strength of this PI is 285 MPa, which is ~2.6 times that of the PMDA-ODA type PI; the coefficient of thermal expansion is about 3.2 ppmK-1, which is comparable to that of the Novastrat®905 type PI and is one order of magnitude lower than that of the commercial PI films. These excellent basic properties reserve more space to further improve the space adaptability of the PI film. The solution of the optical homogeneity of the PI film will lay the foundation for its application in thin film diffractive optical elements.