Gradient Fabrication of Cu-Zn Alloy Coating and Synergistic Anti-Corrosion Mechanism of Carbon Layer

Abstract

Due to their dense microstructure and excellent thickness controllability, copper films are widely utilized in flexible electronics and energy storage device systems. Their interfacial stability in electrochemical environments becomes the critical factor limiting device cycle life and safety. However, in fluorine-containing electrolyte environments, copper is susceptible to severe HF-induced corrosion, generating unstable products such as CuF₂, which can lead to structural degradation and functional failure. The results indicated that the film with a low Zn content (Cu-Zn (9.5:0.5 wt%)) exhibited deteriorated corrosion resistance due to a significant micro-galvanic effect. Its corrosion current was as high as 6.87 × 10⁻⁵ mAꞏcm⁻². By contrast, the high-Zn-content film (Cu-Zn (9:1 wt%)) formed a composite passivation film that increased charge transfer resistance to 1.22 × 10⁴ Ωꞏcm² and reduced the corrosion current to 2.08 × 10⁻⁵ mAꞏcm⁻². The introduction of an additional carbon layer resulted in optimal stability of the Cu-Zn (9:1 wt%)@C composite film, with the corrosion current decreasing to 6.14 × 10⁻⁶ mAꞏcm⁻² and the structure remaining intact after corrosion. Multi-scale characterization revealed that the addition of zinc to the alloy enhanced the film’s intrinsic passivation capability, while the carbon layer provided an external barrier effect through physical isolation, charge regulation, and stress relief. This synergy effectively suppressed the formation of by-products. In summary, the Cu-Zn (9:1 wt%)@C composite film demonstrated the greatest corrosion resistance, establishing a theoretical foundation and engineering approach for the design of highly stable metallic films for use in intricate electrochemical environments.

Keywords

Cu-Zn alloy composite passivation layer / Alloy proportion control / Interfacial stability / Electrochemical corrosion mechanism

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