复合型添加剂对全钒液流电池电解液影响的研究

王熙俊; 李朔; 马晓涵; 董靖; 吴华成; 范永哲; 李世杰; 杜安; 王志华

doi:10.19799/j.cnki.2095-4239.2026.0277

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复合型添加剂对全钒液流电池电解液影响的研究

储能材料与器件 | 更新时间：2026-08-26

- 复合型添加剂对全钒液流电池电解液影响的研究
- Study on the effects of composite additives on the electrolyte of all-vanadium redox flow batteries
- 储能科学与技术 2026年15卷第8期页码：3018-3032
- 作者机构：
  
  1.国网冀北电力有限公司电力科学研究院（华北电力科学研究院有限责任公司），北京 100045
  2.国网冀北张家口风光储输新能源有限公司，河北张家口 075000
  3.河北工业大学材料科学与工程学院，天津 300401
  4.河北工业大学大学生创新创业中心，天津 300401
  5.智能配用电装备与系统全国重点实验室（河北工业大学），天津 300401
- 作者简介：
  
  王熙俊（1989—），男，高级工程师，研究方向为电化学储能与电网腐蚀防护，E-mail：wangxijun80@163.com；
  范永哲，教授，研究方向为金属腐蚀防护与电化学储能，E-mail：fyz@hebut.edu.cn。
- 基金信息：
  
  国网冀北电力有限公司科技项目(52018K25000Q)
- DOI：10.19799/j.cnki.2095-4239.2026.0277
  中图分类号： TM 911
- 收稿：2026-03-31，
  
  修回：2026-05-19，
  
  网络首发：2026-08-26，
  
  纸质出版：2026-08-28
- 稿件说明：
移动端阅览
王熙俊, 李朔, 马晓涵, 等. 复合型添加剂对全钒液流电池电解液影响的研究[J]. 储能科学与技术, 2026, 15(8): 3018-3032.

WANG Xijun, LI Shuo, MA Xiaohan, et al. Study on the effects of composite additives on the electrolyte of all-vanadium redox flow batteries[J]. Energy Storage Science and Technology, 2026, 15(8): 3018-3032.
王熙俊, 李朔, 马晓涵, 等. 复合型添加剂对全钒液流电池电解液影响的研究[J]. 储能科学与技术, 2026, 15(8): 3018-3032. DOI： 10.19799/j.cnki.2095-4239.2026.0277.

WANG Xijun, LI Shuo, MA Xiaohan, et al. Study on the effects of composite additives on the electrolyte of all-vanadium redox flow batteries[J]. Energy Storage Science and Technology, 2026, 15(8): 3018-3032. DOI： 10.19799/j.cnki.2095-4239.2026.0277.

摘要

随着清洁能源在发电结构中所占比例持续提升，电网侧与发电侧亟需匹配一个合适的储能方式进行电能的储存与调配，以保障系统的稳定运行。全钒液流电池（VRFB）以其长时、安全等本征特性成为了研究的热点。其中电解液在VRFB中占比巨大，其稳定性直接决定着电池性能的好坏。本研究采用复合添加剂策略，旨在改善电解液在高温条件下的稳定性。通过正交试验设计，系统考察了MgCl

、(NH

)

、MSA三种添加剂的复合配比对电解液性能的影响。以容量保持率为标准进行评判，复合添加剂的最优成分及含量为MgCl

0.1 mol/L+(NH

)

0.2 mol/L+MSA 1.0 mol/L。电池测试结果表明，在120 mA/cm²电流密度下，含复合添加剂的电解液经25次循环后，能量效率由75%提升至79%，放电容量由0.69 Ah提升至0.76 Ah，容量保持率由83%提升至90%，分别提升5.33%、10.14%与8.43%；在230次长循环中，其能量效率仍稳定在约82%，较对照组相对提升约9.33%，放电容量与容量保持率均显著优于未添加体系。同时，50℃高温静置一周后，电解液沉淀体积由11.31 cm

降至7.72 cm

，降幅达34.39%；离子色谱（IC）结果证实，添加剂可在电解液中长期稳定存在，未发生显著跨膜迁移行为。综上，该复合添加剂可同时提升电解液的热稳定性与电池充放电性能，为全钒液流电池的高效稳定运行提供了可行的技术方案。

Abstract

As the share of clean energy in the electricity generation mix continues to rise

grid-side and generation-side stakeholders must urgently deploy energy storage technologies to suitably manage power demand and ensure stable system operation. In this context

vanadium redox flow batteries (VRFBs)

with advantages such as long-duration energy storage capability and intrinsic safety

have attracted significant research interest. The electrolyte is a major cost component of VRFBs

and its stability directly governs the battery electrochemical performance. This study adopts a composite additive strategy to improve electrolyte thermal stability and suppress vanadium precipitation under elevated temperatures. The effects of the composite ratios of MgCl

(NH

)

and methanesulfonic acid (MSA) on electrolyte performance were systematically investigated using an orthogonal experimental design. Based on capacity retention rate

the optimal additive formulation was determined to be 0.1 mol/L MgCl

+ 0.2 mol/L (NH

)

+ 1.0 mol/L MSA. Battery testing showed that

at 120 mA/cm

current density

the electrolyte with the composite additive increased energy efficiency from 75% to 79%

discharge capacity from 0.69 Ah to 0.76 Ah

and capacity retention from 83% to 90% after 25 cycles

respectively corresponding to relative improvements of 5.33%

10.14%

and 8.

43%. During 230 long-term cycles

the energy efficiency remained stable at 82%

representing a relative improvement of about 9.33% over the control group

while both discharge capacity and capacity retention were significantly higher than those of the additive-free system. After static storage at 50℃ for one week

the electrolyte precipitate volume decreased from 11.31 cm

to 7.72 cm

(a 34.39% reduction). Ion chromatography confirmed that the additive remained stable in the electrolyte over an extended period without significant cross-membrane migration. In summary

this composite additive improves both the electrolyte thermal stability and the battery charge-discharge performance

providing a feasible technical solution for the efficient and stable operation of all-vanadium redox flow batteries.

关键词

Keywords

references

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