A Multifunctional Conductive Polymer: Synthesis Strategies, Molecular Engineering, and Applications in Energy Storage Systems

ConspectusPolyoxadiazole (POD), a rigid-chain conductive polymer featuring alternating aromatic and electron-deficient oxadiazole rings, has emerged as a versatile platform for advanced energy technologies. Due to its intrinsic n-type conductivity, exceptional thermal stability (>440 °C), and dual ion-electron transport capabilities, it overcomes critical limitations in lithium-ion batteries (LIBs), lithium metal anodes (LMAs), pseudocapacitors, and fuel cells. While conventional conductive polymers prioritize flexibility, POD excels in harsh electrochemical environments. One-step acid-mediated polymerization using oleum enables near-quantitative cyclization (DC ≈ 100%) and in situ sulfonation, bypassing structural defects of traditional two-step methods. Nevertheless, the reliance on corrosive solvents presents scalability challenges, driving innovations in molecular engineering.In this Account, we detail molecular design strategies that address performance trade-offs across energy storage systems through tailored POD-based materials. (1) LIB electrodes: Sulfonated POD binders enable stable dual conduction in Si anodes, with recent advances showing that optimized binder networks facilitate efficient energy dissipation and maintain structural integrity over extended cycling. For graphite anodes, π–π interactions enhance electron transfer and rate capability, retaining significant capacity at high C-rates. (2) Lithium metal systems: Gel polymer electrolytes with high Li+ transference numbers and robust artificial SEI layers effectively suppress dendrite growth, enabling stable long-term cycling under high current densities. (3) Pseudocapacitors: Conjugation-engineered POD anodes achieve high specific capacitance with exceptional cycling stability and Coulombic efficiency, benefiting from molecular optimization and electrolyte engineering. (4) Fuel cells: Sulfonated POD derivatives leverage oxadiazole N-sites for efficient proton transport, demonstrating performance competitive with that of commercial benchmarks.We further examine how (i) backbone functionalization tunes electronic structure for specific redox activity; (ii) cross-linking architectures balance mechanical resilience with ionic conduction; and (iii) controlled carbonization creates doped conductive networks for binder-free electrodes. These strategic approaches highlight the versatility of POD in bridging molecular design with macroscopic performance in advanced energy technologies. Finally, we outline key challenges and future priorities: replacing corrosive solvents with sustainable synthesis, decoding interfacial degradation via machine learning, and expanding into solid-state photovoltaics/bioelectronics. Integration with 2D materials (MXenes and COFs) represents a promising frontier for next-generation hybrid devices.