硫-磷混合酸全钒电解液设计及电化学性能研究
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作者单位:

1.武汉科技大学 资源与环境工程学院, 湖北 武汉 430081 ; 2.国家环境保护矿冶资源利用与污染控制重点实验室, 湖北 武汉 430081 ;3.战略钒资源利用省部共建协同创新中心, 湖北 武汉 430081 ; 4.湖北省页岩钒资源高效清洁利用工程技术研究中心, 湖北 武汉 430081

作者简介:

葛灵(1994—),女,山东泰安人,博士研究生,主要研究方向为钒电池性能提升与机理。

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中图分类号:

TF841.3

基金项目:

国家自然科学基金资助项目(51774216);湖北省科技创新专项资助项目(2017ACA185)


Investigations on electrochemical performance of sulfuric-phosphoric mixed acid full vanadium electrolyte
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1.School of Resources and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081 , China ;2.State Environmental Protection Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control, Wuhan 430081 , China ;3.Collaborative Innovation Center of Strategic Vanadium Resources Utilization, Wuhan 430081 , China ;4.Hubei Provincial Engineering Technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium Resource, Wuhan 430081 , China

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    摘要:

    全钒氧化还原液流电池(简称钒电池)作为一种大型储能技术,因其具有安全性高、稳定性好、使用寿命长、设计灵活、对环境影响小等优点而受到广泛关注。然而,钒电池因为钒化合物溶解度和钒离子的稳定性,使其发展和商业化应用受到一定程度限制。本文为提高钒电池的容量、能量密度和高温稳定性,对硫磷混合酸体系钒电解液的主要成分与其性能影响进行研究。通过电解液的稳定性、电化学性能和电池性能测试与分析,研究表明硫磷混酸体系可明显改善五价钒电解液高温稳定性,在50℃时,稳定时间较同浓度硫酸体系延长68h。但当磷酸浓度超过0.2mol/L,会产生新的磷酸氧钒沉淀,并且原有的五氧化钒沉淀逐渐消失。当硫磷混合酸电解液浓度组成为钒离子浓度为2.0mol/L、硫酸浓度3.0mol/L、磷酸浓度0.15mol/L时,可以在50℃稳定运行,经100次充放电,硫磷混酸电解液无任何沉淀产生,其比容量为16.9Ah/L,能量密度21.5Wh/L,库伦效率可达94.0%。

    Abstract:

    As a large-scale energy storage technology, all-vanadium redox flow batteries (vanadium batteries) have received widespread attention because of their high safety, stability, long service life, design flexibility and low environmental impact. However, vanadium batteries are limited in their development and commercial application because of solubility of vanadium compounds and stability of vanadium ions. In this paper, to improve the capacity, energy density and high-temperature stability of vanadium batteries, the main components of the vanadium electrolyte of the sulfuric-phosphoric mixed acid system and their performance effects were investigated. Through stability, electrochemical performance and battery performance of the electrolyte testing and analysis, the study shows that the sulfuric-phosphoric mixed acid system significantly improves the high-temperature stability of V(V) electrolyte, and the stabilization time is extended by 68h at 50℃. However, when the phosphoric acid concentration exceeds 0.2mol/L, a new precipitate of VOPO4 is formed, and the original V2O5 gradually disappears. When the sulfuric-phosphoric mixed acid electrolyte concentration composition is vanadium ion concentration of 2.0mol/L, sulfuric acid concentration of 3.0mol/L, phosphoric acid concentration of 0.15mol/L keeping stable after 100 times charge and discharge at 50℃, and without any precipitation, its capacity is 16.9Ah/L, energy density is 21.5Wh/L, coulomb efficiency is 94.0%.

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葛灵,刘涛,张一敏,等.硫-磷混合酸全钒电解液设计及电化学性能研究[J]. 中国有色冶金, 2023, 52(5): 68-75.

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  • 收稿日期:2023-03-14
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  • 在线发布日期: 2025-12-23
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