Electron‐Donating Conjugation Effect Modulated Zn2+ Reduction Reaction for Separator‐Free Aqueous Zinc Batteries

Zinc‐based aqueous batteries (ZABs) are attracting extensive attention due to the low cost, high capacity, and environmental benignity of the zinc anode. However, their application is still hindered by the undesired zinc dendrites. Despite Zn‐surface modification being promising in relieving dendrites, a thick separator (i.e. glass fiber, 250–700 μm) is still required to resist the dendrite puncture, which limits volumetric energy density of battery. Here, we pivot from the traditional interphase plus extra separator categories, proposing an all‐in‐one ligand buffer layer (ca. 20 μm) to effectively modulate the Zn2+ transfer and deposition behaviors proved by in situ electrochemical digital holography. Experimental characterizations and density functional theory simulations further reveal that the catechol groups in the buffer layer can accelerate the Zn2+ reduction reaction (ZRR) through the electron‐donating p‐π conjugation effect, decreasing the negative charge in the coordination environment. Without extra separators, the elaborated system endows low polarization below 28.2 mV, long lifespan of 4950 h at 5 mA cm−2 in symmetric batteries, and an unprecedented volumetric energy density of 99.2 Wh L−1 based on the whole pouch cells. The concomitantly “separator‐free” and “dendrite‐free” conjugation effect with an accelerated ZRR process could foster the progression of metallic anodes and benefit energetic aqueous batteries. Interphase engineering still requires a thick separator (i.e. glass fiber, 250–700 μm) to resist the puncture of inevitable dendrites, which prejudices the energy density of an aqueous battery. We pivot from the traditional interphase plus extra separator categories, proposing an all‐in‐one ligand buffer layer (ca. 20 μm) to modulate the Zn2+ transfer and deposition behaviors effectively. The catechol groups of the buffer layer can also accelerate the Zn2+ reduction reaction based on their electron‐donating p‐π conjugation effect, decreasing the negative charge in the coordination environment.