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Batteries for high temperature applications capable of withstanding over 60 °C are still dominated by primary cells. Conventional rechargeable energy storage technologies which have exceptional performance at ambient temperatures employ volatile electrolytes and soft separators, resulting in catastrophic failure under heat. A composite electrolyte/separator is reported that holds the key to extend the capability of Li-ion batteries to high temperatures. A stoichiometric mixture of hexagonal boron nitride, piperidinium-based ionic liquid, and a lithium salt is formulated, with ionic conductivity reaching 3 mS cm−1, electrochemical stability up to 5 V and extended thermal stability. The composite is used in combination with conventional electrodes and demonstrates to be stable for over 600 cycles at 120 °C, with a total capacity fade of less than 3%. The ease of formulation along with superior thermal and electrochemical stability of this system extends the use of Li-ion chemistries to applications beyond consumer electronics and electric vehicles.