Amino Acid‐Induced Interface Charge Engineering Enables Highly Reversible Zn Anode

Abstract

Despite the impressive merits of low-cost and high-safety electrochemical energy storage for aqueous zinc ion batteries, researchers have long struggled against the unresolved issues of dendrite growth and the side reactions of zinc metal anodes. Herein, a new strategy of zinc-electrolyte interface charge engineering induced by amino acid additives is demonstrated for highly reversible zinc plating/stripping. Through electrostatic preferential absorption of positively charged arginine molecules on the surface of the zinc metal anode, a self-adaptive zinc-electrolyte interface is established for the inhibition of water adsorption/hydrogen evolution and the guidance of uniform zinc deposition. Consequently, an ultra-long stable cycling up to 2200 h at a high current density of 5 mA cm −2 is achieved under an areal capacity of 4 mAh cm −2 . Even cycled at an ultra-high current density of 10 mA cm −2 , 900 h-long stable cycling is still demonstrated, demonstrating the reliable self-adaptive feature of the zinc-electrolyte interface. This work provides a new perspective of interface charge engineering in realizing highly reversible bulk zinc anode that can prompt its practical application in aqueous rechargeable zinc batteries.

Strategies of regulating Zn2+solvation structures for dendrite-free and side reaction-suppressed zinc-ion batteries

“…207 Except the anions, positively charged amino acids such as arginine (Arg) are demonstrated to be preferentially adsorbed onto the zinc metal anode due to the higher adsorption energy (Fig. 8e and f), 208 initiating a self-adaptive zinc-electrolyte interface with a strong steric hindrance, thus effectively hindering H 2 O adsorption and guiding uniform zinc deposition. Besides arginine, 208,209 glutamate has been demonstrated to regulate the structure of hydrated zinc ions.…”

“…8e and f), 208 initiating a self-adaptive zinc-electrolyte interface with a strong steric hindrance, thus effectively hindering H 2 O adsorption and guiding uniform zinc deposition. Besides arginine, 208,209 glutamate has been demonstrated to regulate the structure of hydrated zinc ions. 210…”

“…The strategies of zinc-philic additives and the corresponding electrochemical performance are summarized in Table 3. 58,87,101,207–209,211,213,216–225 These zinc-philic additives can adsorb onto the zinc anode surface via physical/chemical adsorption to form a protective layer on the anode surface, which can effectively prevent the contact between H 2 O and zinc and guide the uniform zinc deposition. Besides, the adsorbed additive molecules promote the desolvation of Zn(H 2 O) 6 2+ by removing H 2 O molecules from the solvation sheath of Zn 2+ , which can suppress the HER, corrosion, and formation of by-products and zinc dendrites.…”

Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives

“…Resulting from the suppressed 2D diffusion, the subsequent Zn deposition will grow a dense and smooth Zn layer. In a recent report of amino acids as additives [ 145 ], positively charged amino acids, especially arginine (Arg), will preferentially undergo anodic interface adsorption due to their higher adsorption energy than H 2 O and Zn (Fig. 18 c).…”

“…Inset is absorption energy of Arg and Glu with positively charged, uncharged, and negatively charged on Zn surface, respectively; d CV curve of Zn symmetric cell with 0.1 M Arg solution at 5 mV s −1 . e Schematic illustration of Zn plating behavior with and without Arg additive; surface morphology of Zn electrode at 1st, 10th, and 50th cycle f in bare ZnSO 4 electrolyte and g in ZnSO 4 + Arg electrolyte [ 145 ]. Copyright 2021, Wiley–VCH …”