Advancements in Asymmetric Supercapacitors: From Historical Milestones to Challenges and Future Directions

Abstract Numerous challenges, like the uninterrupted supply of electricity, stable and reliable power, and energy storage during non‐operational hours, arise across various industries due to the absence of advanced energy storage technologies. With the continual technological advancements in portable electronics, green energy, and transportation, there are inherent limitations in their innovative production. Thus, ongoing research is focused on pursuing sustainable energy storage technologies. An emerging solution lies in the development of asymmetric supercapacitors (ASCs), which offer the potential to extend their operational voltage limit beyond the thermodynamic breakdown voltage range of electrolytes. This is achieved by employing two distinct electrode materials, presenting an effective solution to the energy storage limitations faced by ASCs. The current review concentrates on the progression of working materials to develop authentic pseudocapacitive energy storage systems (ESS). Also, evaluates their ability to exceed energy storage constraints. It provides insights into fundamental energy storage mechanisms, performance evaluation methodologies, and recent advancements in electrode material strategies. The review approaches developing high‐performance electrode materials and achieving efficient ASC types. It delves into critical aspects for enhancing the energy density of ASCs, presenting debates and prospects, thereby offering a comprehensive understanding and design principles for next‐generation ASCs in diverse applications.