Organic electrolytes based on propylene carbonate for supercapacitors used in power supplies for wearable electronics

The results of a systematic study of propylene carbonate (PC) based organic electrolytes with alkylammonium tetrafluoroborates for use in supercapacitors (SC) designed for wearable electronics and self-charging power supplies are presented. The relevance of the study is due to the requirement to combine high specific energy of SC, electrochemical stability over a wide temperature range and safety during operation, especially as part of miniature autonomous devices. Unlike acetonitrile (AN), which is traditionally used in electrolytes for SC, PC is nontoxic and fireproof, however, its high viscosity limits the electrical conductivity of electrolytes, which makes it critically important to choose the optimal salt. The properties of PC-based electrolytes with tetrafluoroborates of tetraethylammonium (TEA·TFB), methyltriethylammonium (TEMA·TFB), spiro-(1,1')-bipyrrolidinium (SBP·TFB) and 1,1-dimethylpyrrolidinium (DMP·TFB), differing in size and structure of cations (acyclic and cyclic), have been studied. All the salts studied provide similar capacitance characteristics of SC cells, but TEA·TFB exhibits slightly lower values due to the larger size of the cation. Salts with cyclic cations (SBP·TFB and especially DMP·TFB) provide significantly wider operating voltages at temperatures elevated to 85 °C, while electrolytes with TEA·TFB and TEMA·TFB degrade at temperatures above 60 °C. Resource tests (up to 70,000 cycles at temperatures of 50-95 ℃) have confirmed the electrochemical and thermal stability of the DMP·TFB+PC electrolyte: SC cells with this electrolyte retain 80% of their original capacity after 50,000 cycles of galvanostatic charge-discharge and allow the use of an operating voltage up to 3.0 V. The recommended temperature range for the operation of SC with DMP·TFB+PC electrolyte is 0 °C – 85 °C with the possibility of a short-term temperature increase to 95 °C. At temperatures below 0 °C, an increase in viscosity leads to a sharp decrease in capacitance characteristics. Thus, an electrolyte based on PC and DMP·TFB salt is promising for SC in terms of use in wearable electronics devices.

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