Anti-corrosion Behavior and Electrochemical Performance of Zinc Electrodes in Citrulline/ZnSO4 Electrolyte

doi:10.11902/1005.4537.2025.101

Journal of Chinese Society for Corrosion and protection

2026, Vol. 46

Issue (1): 241-251 DOI: 10.11902/1005.4537.2025.101

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Anti-corrosion Behavior and Electrochemical Performance of Zinc Electrodes in Citrulline/ZnSO₄ Electrolyte

LI Caixia, ZHANG Yunhe, LIU Li(

), DONG Lijin, HUANG Yun(

)

School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China

Cite this article:

LI Caixia, ZHANG Yunhe, LIU Li, DONG Lijin, HUANG Yun. Anti-corrosion Behavior and Electrochemical Performance of Zinc Electrodes in Citrulline/ZnSO₄ Electrolyte. Journal of Chinese Society for Corrosion and protection, 2026, 46(1): 241-251.

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Abstract

Zwitterionic citrulline (Cit) was introduced as an additive into a 2 mol/L ZnSO₄ electrolyte. Cit molecules preferentially adsorb onto the Zn²⁺ surface, displacing reactive water molecules within the Zn²⁺ solvation sheath, thereby optimizing the Zn²⁺ solvation structure. Simultaneously, Cit coordinates with Zn²⁺ to form a dynamic electrostatic shielding layer, which suppresses the uncontrolled growth of Zn dendrites caused by localized high current density. The synergistic effect of Cit not only effectively reduces and suppresses the hydrogen evolution reaction (HER) rate but also significantly enhances the electrochemical performance of aqueous zinc-ion batteries (ZIBs). Test results show that batteries assembled with Cit/ZnSO₄ electrolyte exhibit superior electrochemical properties compared to those using pristine 2 mol/L ZnSO₄. Specifically, the Zn||Cu asymmetric cell with Cit/ZnSO₄ electrolyte achieves a cycle life exceeding 500 cycles at 0.5 mA·cm^-2 and 0.5 mAh·cm^-2. The Zn||Zn symmetric cell maintains stable operation for over 5,000 hours at 1.0 mA·cm^-2 and 1.0 mAh·cm^-2, and even under harsh conditions of 5.0 mA·cm^-2 and 5.0 mAh·cm^-2, it sustains 2,500 h of cycling. Furthermore, the Zn||V₂O₅ full cell retains high-capacity retention after 1,000 cycles by 1.0 A·g^-1. This work provides novel insights into the development of efficient electrolyte additives and highlights the practical potential of Cit for high-performance ZIBs.

Key words: aqueous zinc-ion batteries (ZIBs) zwitterionic citrulline (Cit) solvation structure deposition morphology HER reaction

Received: 26 March 2025 32134.14.1005.4537.2025.101

ZTFLH:

TG172

Fund: National Natural Science Foundation of China(52170140);Key R&D Project of Sichuan Province(2025YFHZ0057)

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	LI Caixia
	ZHANG Yunhe
	LIU Li
	DONG Lijin
	HUANG Yun

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https://www.jcscp.org/EN/10.11902/1005.4537.2025.101 OR https://www.jcscp.org/EN/Y2026/V46/I1/241

Fig.1 FTIR spectrum (a) and electrostatic potential diagram (b) of Cit

Fig.2 Electrochemical performances of Zn||Zn cells at 4.0 and 4.0 mA·cm^-2 (a1-a4), rate performance at different current densities (b), and cyclic performance at 0.5 and 1.0 mA·cm^-2 after the rate performance test (c)

Fig.3 HOMO-LUMO orbital energy levels of Cit and H₂O (a) and binding energies of Zn²⁺ with Cit and H₂O (b)

Fig.4 NMR spectra (a), FTIR spectra (b), ionic conductivities (c) and contact angles (d) of Cit/ZnSO₄ electrolyte and 2 mol/L ZnSO₄ electrolyte

Fig.5 LSV curves (a, b), pH values (c) and Tafel curves (d) of Zn||Ti cells

Fig.6 SEM images of Zn anodes of Zn||Zn cells after 120 h cycling at 1.0 mA·cm^-2 with 1.0 mAh·cm^-2 (a, b), XRD patterns (c), and CA curves (d)

Fig.7 In situ optical microscopy images showing the deposition of Cit/ZnSO₄ (a) and ZnSO₄ (b) at 5.0 mA·cm^-2

Fig.8 Low-magnification (a, b) and high-magnification (c, d) SEM images of ZnSO₄ (a, c) and Cit/ZnSO₄ (b, d) electroplating at 10.0 mA·cm^-2

Fig.9 Voltage vs. capacity curves (a, b), voltage vs. cycle number curves (c) and coulombic efficiency plots (d) of Zn||Cu cells

Fig.10 Cycling performances of Zn||Zn cells at 5.0 mA·cm^-2 and 5.0 mAh·cm^-2 (a, b) and at 1.0 mA·cm^-2 and 1.0 mAh·cm^-2 (c), and cycle life comparison plot (d)

Table 1 Comparison of cycle lifes of Zn||Zn cells

Fig.11 Self-discharge curves of Zn||V₂O₅ full cells with Cit/ZnSO₄ electrolyte (a) and 2 mol/L ZnSO₄ electrolyte (b)

Fig.12 CV curves (a), rate performance (b), and long-cycle performance (c) of Zn||V₂O₅ full cells

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