Spontaneous Molecule Aggregation for Nearly Single‐Ion Conducting Sol Electrolyte to Advanced Aqueous Zinc Metal Batteries: The Case of Tetraphenylporphyrin

Zn metal as a promising anode of aqueous batteries faces the severe challenges from dendrite growth and side reactions. Here, tetraphenylporphyrin tetrasulfonic acid (TPPS) is explored as an electrolyte additive for advanced Zn anodes. It is interesting to note that TPPS spontaneously assembles into unique aggregates. As they adsorb on the Zn anode, the aggregates enhance the resistance to electrolyte percolation and dendrite growth compared to the reported single molecules. Meanwhile, TPPS facilitates anion association in the solvation sheath of Zn2+, and boosts the transference number of Zn2+ up to 0.95. Therefore, anion-related side reactions and anion-induced electrode overpotentials are reduced accordingly. In this context, the electrolyte containing TPPS exhibits the excellent electrochemical performance. Even under a high loading of MnO2 (25 mg cm-2), a limited Zn supply (N/P ratio=1.7), and a lean electrolyte (15 uL mAh-1), the full cells still represent a higher cumulative capacity compared to the reported data. The advantages of this electrolyte are also adapted to other cathode materials. The pouch cells of Zn|| NaV3O8·1.5H2O realize a capacity of ~0.35 Ah at 0.4 C under harsh conditions.