Amphipathic Phenylalanine-Induced Nucleophilic-Hydrophobic Interface Toward Highly Reversible Zn Anode

doi:10.1007/s40820-024-01380-x

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Abstract

Aqueous Zn²⁺-ion batteries (AZIBs), recognized for their high security, reliability, and cost efficiency, have garnered considerable attention. However, the prevalent issues of dendrite growth and parasitic reactions at the Zn electrode interface significantly impede their practical application. In this study, we introduced a ubiquitous biomolecule of phenylalanine (Phe) into the electrolyte as a multifunctional additive to improve the reversibility of the Zn anode. Leveraging its exceptional nucleophilic characteristics, Phe molecules tend to coordinate with Zn²⁺ ions for optimizing the solvation environment. Simultaneously, the distinctive lipophilicity of aromatic amino acids empowers Phe with a higher adsorption energy, enabling the construction of a multifunctional protective interphase. The hydrophobic benzene ring ligands act as cleaners for repelling H₂O molecules, while the hydrophilic hydroxyl and carboxyl groups attract Zn²⁺ ions for homogenizing Zn²⁺ flux. Moreover, the preferential reduction of Phe molecules prior to H₂O facilitates the in situ formation of an organic-inorganic hybrid solid electrolyte interphase, enhancing the interfacial stability of the Zn anode. Consequently, Zn||Zn cells display improved reversibility, achieving an extended cycle life of 5250 h. Additionally, Zn||LMO full cells exhibit enhanced cyclability of retaining 77.3% capacity after 300 cycles, demonstrating substantial potential in advancing the commercialization of AZIBs.

Key words： Zn anode Phenylalanine Adsorption energy Solvation sheath

Received: 31 December 2023 Published: 28 March 2024

Corresponding Authors: Xin Hu, Yongxin Huang, Renjie Chen

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Anbin Zhou and Huirong Wang have contributed equally to this work.

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	Anbin Zhou
	Huirong Wang
	Fengling Zhang
	Xin Hu
	Zhihang Song
	Yi Chen
	Yongxin Huang
	Yanhua Cui
	Yixiu Cui
	Li Li
	Feng Wu
	Renjie Chen

Cite this article:

Anbin Zhou,Huirong Wang,Fengling Zhang, et al. Amphipathic Phenylalanine-Induced Nucleophilic-Hydrophobic Interface Toward Highly Reversible Zn Anode[J]. Nano-Micro Letters, 2024, 16(1): 164-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01380-x OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/164

Fig. 1 Characterization of electrolyte system. a Schematic illustration for various derivatives of amino acids. b LSV curves and c corrosion current density and potential derived from Tafel plots in 20 mmol L−1 Phe/Asp/Ser/Cys additives electrolytes. d Electrostatic potential mapping of Phe molecule. e Images of ZSO/Phe system obtained from molecular dynamics simulations. f Radial distribution functions for Zn2+-O (H2O) and Zn2+-O (Phe) in ZSO/Phe electrolyte. g 2H NMR spectra of H2O from pure D2O, ZSO, and ZSO/Phe system. h Raman spectra and i FTIR spectra for ZSO and ZSO/Phe system with various concentrations

Fig. 2 Characterization of SEI chemistry. a XPS depth profile of C 1s, N 1s, O 1s and S 2p for Zn anode cycled in ZSO/Phe electrolyte for 5 cycles at a current density of 1 mA cm−1. b HOMO − LUMO energy levels of Phe and water molecules. c 3D visualization of TOF-SIMS for CH−, CN−, SO3−, and ZnS− in ZSO/Phe electrolyte. d HAADF image. e-g HRTEM image of the electrode interface and corresponding elemental mapping

Fig. 3 Characterization of interfacial interaction. a In situ Raman spectrum for Zn anode tested in ZSO and ZSO/Phe electrolytes in Zn2+ plating process. b XRD patterns of cycled Zn anodes. c In situ DEMS measurement of H2 evolution rate within Zn||Cu cells. d LSV curves and e Tafel plots of Zn electrodes measured in ZSO and ZSO/Phe electrolytes. f CA curves at an overpotential of − 150 mV within Zn||Zn cells (inset: schematic diagrams of 2D and 3D diffusion process of Zn2+). In situ optical microscopic images of Zn plating process in g ZSO and h ZSO/Phe electrolytes

Fig. 4 Reversible Zn plating/stripping stability characterization. a, b Long-term galvanostatic cycling of Zn||Zn cells at current density of 2, 5, 10, 20, 30, and 50 mA cm−2, respectively. c Comparison of cumulative plated capacity with previously reported. d Rate performances of Zn||Zn cells in different electrolytes. e Galvanostatic cycling of Zn||Zn cells in diluted electrolyte. f CV curves for Zn nucleation of Zn-Ti cells in different electrolytes. g CE of the Zn plating/stripping in Zn||Cu cells. h In situ XRD measurements on Zn||Zn cells during charging/discharging process. i, j AFM images of the cycled Zn in different electrolytes

Fig. 5 Zn||LMO full cell performance. a Long-term cycling performance at a current density of 1 C. The corresponding voltage-capacity profile in b ZSO/Phe and c ZSO electrolytes. SEM images of cycled Zn anode in ZSO/Phe d ZSO e electrolytes. f Rate performance at rates of 1, 2, 3, and 5 C. g, h Digital photo of open-circuit voltage for the pouch Zn||LMO cell and a model airplane in action powered by Zn||LMO cell

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