Calcium Based All‐Organic Dual‐Ion Batteries with Stable Low Temperature Operability

Abstract In response to the application requirements of secondary batteries at low temperature, an all‐organic dual‐ion battery with calcium perchlorate contained acetonitrile as the electrolyte (CAN‐ODIB) is fabricated in this work. The electrochemical energy is stored in CAN‐ODIB via the association and disassociation of calcium and perchlorate ions in perylene diimide‐ethylene diamine/carbon black composite based anode and polytriphenylamine based cathode with highly reversible redox states. Benefiting from the energy storage mechanism, CAN‐ODIB exhibits excellent electrochemical performances in tests with the temperature ranging from 25 to −50 °C. Especially, CAN‐ODIB at −50 °C reserves ≈61% of the capacity at 25 °C (83.4 mA h g⁻¹) with the current density of 0.2 A g⁻¹. CAN‐ODIB also shows excellent cycling stability at low temperature by retaining 90.3% of the initial capacity at 1.0 A g⁻¹ after 450 charge–discharge cycles at −30 °C. The impedance analysis of CAN‐ODIB at different temperatures indicates that the low temperature performance of CAN‐ODIB depends more on the electrode materials than the electrolyte, which provides the important guidance for the further design of secondary batteries operable at low temperatures.