Exploration of novel polymer dielectrics exhibiting high electric-field stability and high energy density with high efficiency at elevated temperatures is urgently needed for ever-demanding energy-storage technologies. Conventional high-temperature polymers with conjugated backbone structures cannot fulfill this demand due to their deteriorated performance at elevated electric fields. Here, in search of new polymer structures, we have explored the effect of fluorine groups on the energy-storage properties of polyoxanorbornene imide polymers with simultaneous wide band gap and high glass transition temperature (Tg). The systematic synthesis of polymers with varying amounts of fluorine is carried out and characterized for the energy-storage properties. The incorporation of fluorine imparts flexibility to the polymer structure, and free-standing films can be obtained. An oxanorbornene copolymer with 25% fluorination exhibits a high breakdown strength of 700 MV/m and a discharged energy density of 6.3 J/cm3 with 90% efficiency. The incorporation of fluorine helps to increase the polymer band gap, as observed using UV-vis spectroscopy, but lowers the polymer Tg, as shown by differential scanning calorimetry. Both the displacement-electric field (D-E) hysteresis loop and high-field conduction measurements show increased conduction loss for polymers with higher fluorine content, despite their larger band gap. The presence of excess free volume may play a key role in increasing the conduction current and lowering the efficiency of polymers with high fluorine content. Such an improved understanding of the effect of fluorination on the polymer energy-storage properties, as revealed in this systematic molecular engineering study, broadens the basis of material-informatic proxies to enable a more targeted codesign of scalable and efficient polymer dielectrics.
Keywords: capacitors; energy-storage properties; fluorine; high temperature polymer dielectrics.