Exploring the Versatility of Membrane-Free Battery Concept Using Different Combinations of Immiscible Redox Electrolytes.

Lately, the field of redox flow batteries is flourishing because of the emergence of new redox chemistries, including organic compounds, new electrolytes, and innovative designs. Recently, we reported an original membrane-free battery concept based on the mutual immiscibility of an aqueous catholyte containing hydroquinone and an ionic liquid anolyte containing para-benzoquinone as redox species. Here, we investigate the versatility of this concept exploring the electrochemical performance of 10 redox electrolytes based on different solvents, such as propylene carbonate, 2-butanone, or neutral-pH media, and containing different redox organic molecules, such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine1-oxyl (OH-TEMPO), or substituted anthraquinones. The most representative electrolytes were paired and used as immiscible anolyte-catholyte in 5 different membrane-free batteries. Those batteries with substituted anthraquinones in the anolyte exhibited up to 50% improved open-circuit voltage (2.1 V), an operating voltage of 1.75 V, and 62% higher power density compared with our previous work. On the other hand, the partition coefficient of redox molecules between the two immiscible phases and the inherent self-discharge occurring at the interphase are revealed as intrinsic features affecting the performance of this type of membrane-free battery. It was successfully demonstrated that the functionalization of redox molecules is an interesting strategy to tune the partition coefficients mitigating the crossover that provokes low battery efficiency. As a result, the cycling life of a battery having OH-TEMPO as active species in the catholyte and containing propylene carbonate-based anolyte was evaluated over 300 cycles, achieving 85% capacity retention. These results demonstrated the huge versatility and countless possibilities of this new membrane-free battery concept.