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With the ongoing global effort to reduce greenhouse gas emission and dependence on oil, electrical energy storage (EES) devices such as Li-ion batteries and supercapacitors have become ubiquitous. Today, EES devices are entering the broader energy use arena and playing key roles in energy storage, transfer, and delivery within, for example, electric vehicles, large-scale grid storage, and sensors located in harsh environmental conditions, where performance at temperatures greater than 25 °C are required. The safety and high temperature durability are as critical or more so than other essential characteristics (e.g., capacity, energy and power density) for safe power output and long lifespan. Consequently, significant efforts are underway to design, fabricate, and evaluate EES devices along with characterization of device performance limitations such as thermal runaway and aging. Energy storage under extreme conditions is limited by the material properties of electrolytes, electrodes, and their synergetic interactions, and thus significant opportunities exist for chemical advancements and technological improvements. In this review, we present a comprehensive analysis of different applications associated with high temperature use (40–200 °C), recent advances in the development of reformulated or novel materials (including ionic liquids, solid polymer electrolytes, ceramics, and Si, LiFePO4, and LiMn2O4 electrodes) with high thermal stability, and their demonstrative use in EES devices. Finally, we present a critical overview of the limitations of current high temperature systems and evaluate the future outlook of high temperature batteries with well-controlled safety, high energy/power density, and operation over a wide temperature range. [ABSTRACT FROM AUTHOR]