全钒液流电池电解液容量衰减及草酸恢复研究

doi:10.19799/j.cnki.2095-4239.2024.0838

摘要/Abstract

摘要：

全钒液流电池因其易于规模化、环境友好和高安全性等优势，被视为一种适合大规模商业化应用的储能技术。然而，长期循环使用中出现的容量衰减问题限制了其在储能领域的广泛应用。本文通过深入分析电池循环前后的电化学特性变化曲线，并结合高锰酸钾滴定的结果，确定了电池容量衰减的主要因素，即电解液失衡和电极退化导致的负极活性物质减少和极化加剧。此外，采用草酸还原的方法将电解液的放电比容量恢复至初始的92.7%，并通过互换正负电极缓解了电池的极化加剧，证实了通过电极交换可以有效恢复并稳定电极的电化学活性。最后，采用恒压充电的方法解决了草酸残留问题，并制定了一种草酸恢复电解液的工艺路线，成功将已用电解液的平均价态从3.580价恢复至3.508价。该研究全面分析了全钒液流电池容量衰减的深层次原因，为电解液的恢复发挥了重要的指导作用，同时针对草酸恢复过程中的残留问题提出了简便有效的技术解决方案，为电解液的恢复和再利用提供了新的可能性。

关键词: 全钒液流电池, 电解液恢复, 草酸还原, 化学滴定

Abstract:

The vanadium flow battery (VFB) is considered a promising energy storage technology for large-scale commercial applications due to its easy scalability, environmental friendliness, and high safety. However, capacity fade during long-term cycling limits its widespread use in energy storage. This study analyzed changes in the electrochemical characteristics of the VFB before and after cycling and, based on potassium permanganate titration results, identified electrolyte imbalance and electrode degradation — which led to a reduction in anode active material and increased polarization — as the main factors contributing to capacity fade. Furthermore, the specific discharge capacity of the electrolyte was restored to 92.7% of its initial value using oxalic acid reduction, and battery polarization was alleviated by swapping the anode and cathode, confirming that electrode exchange effectively restores and stabilizes the electrodes' electrochemical activity. Finally, the oxalic acid residue problem was resolved using a constant-voltage charging method, and a process route for oxalic acid recovery was established, successfully restoring the average oxidation state of the spent electrolyte from 3.580 to 3.508. This research comprehensively analyzed the underlying causes of VFB capacity fade, providing significant guidance for electrolyte recovery, and proposed a simple, effective technical solution for the residue issue during the oxalic acid recovery process, thereby offering new possibilities for the recovery and reuse of the electrolyte.

Key words: vanadium redox flow batteries, electrolyte recovery, oxalic acid reduction, chemical titration

中图分类号:

TM 911

叶涛, 王怡君, 唐子龙, 潘国梁. 全钒液流电池电解液容量衰减及草酸恢复研究[J]. 储能科学与技术, 2025, 14(3): 1177-1186.

Tao YE, Yijun WANG, Zilong TANG, Guoliang PAN. Investigation of capacity fading in vanadium flow battery electrolytes and recovery via oxalic acid[J]. Energy Storage Science and Technology, 2025, 14(3): 1177-1186.

图/表 3

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