Customizing H2O‐Poor Electric Double Layer and Boosting Texture Exposure of Zn (101) Plane towards Super‐High Areal Capacity Zinc Metal Batteries

The catastrophic dendrite hyperplasia and parasitic reactions severely impede the future deployment of aqueous Zn‐ion batteries. Controlling zinc orientation growth is considered to be an effective method to overcome the aforementioned concerns, especially for regulating the (002) plane of deposited Zn. Unfortunately, Zn (002) texture is difficult to obtain stable cycling under high deposition capacity resulting from its large lattice distortion and nonuniform distribution in electric field. Herein, different from traditional cognition, a crystallization orientation regulation tactic is proposed to boost Zn (101) texture exposure and inhibit zinc dendrite proliferation during plating/stripping. Experimental results and theoretical calculations demonstrate the malate molecules preferentially adsorb on the Zn (002) facet, leading to the texture exposure of distinctive Zn (101) plane. Meanwhile, the –COOH and –OH groups of malate molecules exhibit strong adsorption on the Zn anode surface and chelate with Zn2+, achieving H2O‐poor electrical double layer. Very impressively, the multifunctional malate additive enlists zinc anode to survive for 600 h under a harsh condition of 15 mAh cm−2/15 mAh cm−2. Moreover, the symmetric cell harvests highly‐reversible cycling life of 6600 h at 5 mA cm−2/1.25 mAh cm−2, remarkably outperforming the ZnSO4 electrolyte. The assembled Zn//MnO2 full cells also demonstrate prominent electrochemical reversibility.