Study on enhancing cycle stability and suppressing hydrogen evolution in iron-chromium flow batteries using threonine additives

ZHANG Tianying; NIU Zhengrong; CUI Yuanyuan; LI Bo; BIAN Shaoju; DONG Yaping; GAO Yanfeng; XU Naicai; FENG Haitao

doi:10.19799/j.cnki.2095-4239.2025.1136

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Study on enhancing cycle stability and suppressing hydrogen evolution in iron-chromium flow batteries using threonine additives

Energy Storage Materials and Devices | 更新时间：2026-07-13

- Study on enhancing cycle stability and suppressing hydrogen evolution in iron-chromium flow batteries using threonine additives
- Energy Storage Science and Technology Vol. 15, Issue 6, Pages: 2139-2147(2026)
- 作者机构：
  
  1.青海师范大学化学化工学院，青海西宁 810008
  2.青海环境功能材料先进技术与应用重点实验室，青海西宁 810016
  3.中国科学院青海盐湖研究所，盐湖资源绿色高值利用重点实验室，青海西宁 810008
  4.上海大学材料科学与工程学院，上海 200444
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2025.1136
  CLC： O 63;TM 912
- Received：18 December 2025，
  
  Revised：2026-01-08，
  
  Published：28 June 2026
- 稿件说明：
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张天应, 牛峥嵘, 崔苑苑, 等. 苏氨酸提升铁铬液流电池循环稳定性与抑制析氢的研究[J]. 储能科学与技术, 2026, 15(6): 2139-2147.

ZHANG Tianying, NIU Zhengrong, CUI Yuanyuan, et al. Study on enhancing cycle stability and suppressing hydrogen evolution in iron-chromium flow batteries using threonine additives[J]. Energy Storage Science and Technology, 2026, 15(6): 2139-2147.
张天应, 牛峥嵘, 崔苑苑, 等. 苏氨酸提升铁铬液流电池循环稳定性与抑制析氢的研究[J]. 储能科学与技术, 2026, 15(6): 2139-2147. DOI： 10.19799/j.cnki.2095-4239.2025.1136.

ZHANG Tianying, NIU Zhengrong, CUI Yuanyuan, et al. Study on enhancing cycle stability and suppressing hydrogen evolution in iron-chromium flow batteries using threonine additives[J]. Energy Storage Science and Technology, 2026, 15(6): 2139-2147. DOI： 10.19799/j.cnki.2095-4239.2025.1136.

摘要

铁铬液流电池作为一种低成本、长寿命的大规模储能技术，其性能主要受制于电解液中铬电对的可逆性差导致的容量衰减问题。本文提出在电解液中引入苏氨酸（threonine，Thr）利用其对铬离子的络合作用调控溶液中铬的溶剂化结构，从而改善电池的整体电化学性能。密度泛函理论计算表明，Thr可优先与铬离子配位，改变其溶剂化结构并形成较稳定的铬离子络合物。同时，Thr在电极表面竞争吸附氢离子，有效抑制析氢副反应，提高容量保持率。紫外可见光谱与长循环测试结果进一步验证络合物实体系中生成的络合物在循环过程中结构稳定性，对维持电化学稳定性具有关键作用。在相同条件下，原始电解液在仅100次循环后放电能力下降至初始容量的39%，其每次循环平均容量衰减为6.4 mAh，而添加0.03 mol/L Thr的电池在稳定运行200次循环后，放电容量保持率达43.7%，其每次循环平均容量衰减为2.9 mAh，显著优于原始电解液。这一发现也证实了Thr的引入增强了铁铬液流电池的循环稳定性，提高了电池的使用寿命，此策略为设计高稳定性、低容量衰减的铁铬液流电池电解液体系提供了可借鉴的研究思路。

Abstract

Iron-chromium flow batteries

as a low-cost

long-duration

large-scale energy storage technology

suffer from capacity decay primarily owing to the poor reversibility of the chromium electrode in the electrolyte. This study proposes the introduction of threonine (Thr) into the electrolyte to regulate the solvation structure of chromium species through its chelating interaction with chromium ions

thereby enhancing the overall electrochemical performance of the battery. Density functional theory calculations reveal that Thr preferentially coordinates with chromium ions

altering its native solvation shell and leading to the formation of a stable chromium-Thr complex. This structural modification is crucial for enhancing the kinetics and reversibility of the chromium redox reaction. Concurrently

Thr molecules exhibit a competitive adsorption effect toward hydrogen ions on the electrode surface. This behavior effectively suppresses the hydrogen evolution reaction (HER)

a predominant side reaction at the negative electrode during charging and a major contributor to Coulombic efficiency loss and capacity fade. The suppression of the HER directly contributes to improved capacity retention over extended cycling. The formation and stability of the chromium-Thr complex were further validated experimentally. Ultraviolet-visible spectroscopy and long-term cycling tests further confirm that the generated complex maintains structural stability during cycling

playing a crucial role in sustaining electrochemical stability. Under identical conditions

the battery employing the pristine electrolyte (without the Thr additive) suffered rapid performance degradation. Its discharge capacity dropped to merely 39% of its initial value after only 100 cycles

and its average capacity decreased to 6.4 mAh per cycle. By contrast

the battery with an electrolyte containing 0.03 mol/L Thr demonstrated remarkably enhanced cycling stability. It sustained stable operation for 200 cycles

with a discharge capacity retention of 43.7% at the end of this period

and its average capacity decreased to 2.9 mAh per cycle. This performance is notably superior to that of the pristine electrolyte

not only in terms of absolute capacity retention but also in terms of doubled cycle life under identical testing conditions. In conclusion

this study demonstrates that the introduction of Thr as a complexing and surface-modifying additive is an effective and promising strategy to enhance the reversibility of the chromium electrode and suppress detrimental side reactions in iron-chromium flow batteries. The resulting reaction system exhibits excellent cycling stability and improved capacity retention. The insights gained from combined theoretical calculations and experimental characterizations provide a solid theoretical foundation and a novel design for developing high-stability

high-performance electrolyte systems for iron-chromium and potentially other chromium-based redox flow batteries. This study provides a reference approach for designing electrolyte systems with high stability and low capacity decay in iron-chromium flow batteries.

关键词

Keywords

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