Endowing the Operability of Supercapacitors at High Temperatures by Regulating the Solvation Structure in Dilute Hybrid Electrolyte with Trimethyl Phosphate Cosolvent

The redox stabilities of different oxygen donor solvents (C═O, P═O and S═O) and lithium salt anions for supercapacitors (SCs) electrolytes have been compared by calculating the frontier molecular orbital energy. Among six lithium difluoro(oxalate)borate (LiDFOB)-based mono-solvent electrolytes, the dilute LiDFOB-1,4-butyrolactone (GBL) electrolyte exhibits the highest operating voltage but suffers from electrolyte breakdown at elevated temperatures. Trimethyl phosphate (TMP) exhibits the highest redox stability and a strongly negative electrostatic potential (ESP), making it suitable for promoting the dissolution of LiDFOB as expected. Therefore, TMP is selected as a co-solvent into LiDFOB-GBL electrolyte to regulate Li+ solvation structure and improve the operability of electrolytes at high temperatures. The electrochemical stable potential window (ESPW) of 0.5 m LiDFOB-G/T(5/5) hybrid electrolyte can reach 5.230 V. The activated carbon (AC)-based symmetric SC using 0.5 m LiDFOB-G/T(5/5) hybrid electrolyte achieves a high energy density of 54.2 Wh kg-1 at 1.35 kW kg-1 and the capacitance retention reaches 89.2% after 10 000 cycles. The operating voltage of SC can be maintained above 2 V when the temperature rises to 60 °C.