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<p>The inherent depletion of metal ions during electroplating with inert anodes poses a significant challenge for long-term process stability and coating quality. To address this issue, a method for real-time replenishment of metal ions based on anion exchange membrane-assisted electrolysis was proposed. This method utilized an anion exchange membrane to hinder the migration of large anionic metal complexes (e.g., [Cu(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]<sup>6−</sup>), preventing their reduction and loss at the electrolytic cathode, while allowing the selective migration of small anions (e.g., NO₃⁻ and OH⁻) to maintain charge balance. When applied to Cu-Sn alloy electroplating in a pyrophosphate bath, this method maintained copper-ion concentration fluctuations within ± 2% at the optimal electrolytic current density (1&#xa0;A dm<sup>−2</sup>). This precise regulation extended the electrolyte service life by approximately 50% and delayed plating defects such as charring (carbonization) and surface irregularities. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction results indicated that even after prolonged operation, the deposits maintained a dense morphology, a relatively stable Sn content, and a refined grain structure, while partially suppressing the crystal orientation shift from (200) to (111). This study provided a method for real-time replenishment of metal ions for inert anode systems, suggesting potential application in precision alloy electrodeposition.</p> Graphical Abstract <p></p>

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Ion equilibrium control in Cu–Sn electroplating via anion exchange membrane-assisted synchronous electrolysis

  • 期刊论文

  • 发表日期：

    2026年3月1日

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  • Junwei Yang,
  • Deqiao Xie,
  • Jinbiao Liao,
  • Yue Zhang,
  • Zhaowei Liu,
  • Shimao Shangguan,
  • Zongjun Tian

摘要

The inherent depletion of metal ions during electroplating with inert anodes poses a significant challenge for long-term process stability and coating quality. To address this issue, a method for real-time replenishment of metal ions based on anion exchange membrane-assisted electrolysis was proposed. This method utilized an anion exchange membrane to hinder the migration of large anionic metal complexes (e.g., [Cu(P2O7)2]6−), preventing their reduction and loss at the electrolytic cathode, while allowing the selective migration of small anions (e.g., NO₃⁻ and OH⁻) to maintain charge balance. When applied to Cu-Sn alloy electroplating in a pyrophosphate bath, this method maintained copper-ion concentration fluctuations within ± 2% at the optimal electrolytic current density (1 A dm−2). This precise regulation extended the electrolyte service life by approximately 50% and delayed plating defects such as charring (carbonization) and surface irregularities. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction results indicated that even after prolonged operation, the deposits maintained a dense morphology, a relatively stable Sn content, and a refined grain structure, while partially suppressing the crystal orientation shift from (200) to (111). This study provided a method for real-time replenishment of metal ions for inert anode systems, suggesting potential application in precision alloy electrodeposition.

Graphical Abstract