浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液

doi:10.11949/0438-1157.20221541

化工学报 ›› 2023, Vol. 74 ›› Issue (S1): 338-345.DOI: 10.11949/0438-1157.20221541

• 材料化学工程与纳米技术 • 上一篇下一篇

浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液

胡超¹^,²^,³(), 董玉明¹^,²(), 张伟³, 张红玲¹^,²^,⁴, 周鹏¹^,², 徐红彬¹^,²^,⁴

^1.中国科学院过程工程研究所，中国科学院绿色过程与工程重点实验室，北京 100190
^2.战略金属资源绿色循环利用国家工程研究中心，中国科学院过程工程研究所，北京 100190
^3.燕山大学环境与化工学院，河北应用化学重点实验室，河北秦皇岛 066004
^4.中国科学院大学，北京 100049

收稿日期:2022-11-30 修回日期:2023-01-19 出版日期:2023-06-05 发布日期:2023-09-27
通讯作者: 董玉明
作者简介:胡超(1993—)，男，硕士研究生，huchao2206@163.com
基金资助:
国家自然科学基金项目(52174282)

Preparation of high-concentration positive electrolyte of vanadium redox flow battery by activating vanadium pentoxide with highly concentrated sulfuric acid

Chao HU¹^,²^,³(), Yuming DONG¹^,²(), Wei ZHANG³, Hongling ZHANG¹^,²^,⁴, Peng ZHOU¹^,², Hongbin XU¹^,²^,⁴

^1.CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.National Engineering Research Center of Green Recycling for Strategic Metal Resources, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.Hebei Key Laboratory of Applied Chemistry, School of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, Hebei，China
^4.University of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-11-30 Revised:2023-01-19 Online:2023-06-05 Published:2023-09-27
Contact: Yuming DONG

摘要/Abstract

摘要：

全钒液流电池是大规模储能领域首选的化学储能技术之一。因电解液成本占比较高，通常采用成本相对较低的五氧化二钒作为原料来制备全钒液流电池电解液。针对五氧化二钒在硫酸中溶解度较小、直接使用硫酸溶解五氧化二钒难以制备出高浓度电解液的问题，本研究通过将硫酸与五氧化二钒进行升温活化处理，水溶后即可实现高浓度五价钒电解液的制备。采用XRD、Raman、FT-IR等手段对活化后固体的组成、结构和溶解过程进行分析。结果表明，在活化温度为180℃、活化时间为3 h、硫酸与五氧化二钒摩尔比为4时，五氧化二钒溶解质量分数高达98.5%，溶解的钒离子浓度高达3 mol·L^-1。硫酸与五氧化二钒升温活化后生成V₂O₃(SO₄)₂，改变原有的五氧化二钒的结构，导致活化后的物质水溶时溶解性增加，并且溶解后的钒离子价态以V(Ⅴ)形式存在。溶液中高浓度的V(Ⅴ)离子会与 $S O 4 2 -$ 络合反应生成 $V O 2 S O 4 -$ ，同时溶液中 $V O 2 +$ 也会发生聚合形成 $V 2 O 3 4 +$ 、 $V 2 O 4 2 +$ 等多聚体。

关键词: 五氧化二钒, 正极电解液, 全钒液流电池, 溶解度, 升温活化

Abstract:

Vanadium redox flow battery (VRFB) is one of the most promising chemical electric source technologies for large scale stationary energy storage. Currently, since a large share of the VRFB costs is attributed to the cost of the electrolyte, vanadium pentoxide was usually chosen as the raw materials of vanadium. However, due to the low solubility of vanadium pentoxide in sulfuric acid, the direct dissolution of vanadium pentoxide in sulfuric acid is unable to prepare an electrolyte with high vanadium concentration. In this study, pentavalent vanadium electrolyte is directly prepared from vanadium pentoxide solid by activating vanadium pentoxide with sulfuric acid at elevated temperatures. The composition, structure, and dissolution processes of the activated solid mixture are analyzed by XRD, Raman, and FT-IR. The results indicate that when the activating temperature is 180°C and the molar ratio of sulfuric acid to vanadium pentoxide of 4, the dissolution performance of vanadium pentoxide after activation is greatly enhanced, and its dissolution mass percentage is up to 98.5%. And the vanadium ion concentration can be dissolved successfully up to 3 mol·L^-1. After activation, sulfuric acid and vanadium pentoxide form V₂O₃(SO₄)₂. The original structure of vanadium pentoxide is changed and the solubility of the substance is increased. At the same time, it is found that V(Ⅴ) ions with high concentration will react with $S O 4 2 -$ to produce $V O 2 S O 4 -$ , while $V O 2 +$ in solution would also polymerize to form polymers such as $V 2 O 3 4 +$ and $V 2 O 4 2 +$ .

Key words: vanadium pentoxide, positive electrolyte, vanadium redox flow battery, solubility, activation at elevated temperature

中图分类号:

TQ 152

胡超, 董玉明, 张伟, 张红玲, 周鹏, 徐红彬. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(S1): 338-345.

Chao HU, Yuming DONG, Wei ZHANG, Hongling ZHANG, Peng ZHOU, Hongbin XU. Preparation of high-concentration positive electrolyte of vanadium redox flow battery by activating vanadium pentoxide with highly concentrated sulfuric acid[J]. CIESC Journal, 2023, 74(S1): 338-345.

图/表 8

图1 在不同温度、H2SO4用量和活化时间下V2O5溶解质量分数

Fig.1 Dissolved mass fraction of V2O5 at different temperatures, amounts of H2SO4 and calcination time

图2 180℃在不同H2SO4比例下的滤液紫外光谱

Fig.2 UV-Vis spectra of filtrates at 180℃ and different H2SO4 ratios

图3 180℃下H2SO4与V2O5摩尔比为4时固体溶解稀释后钒离子和硫酸根浓度

Fig.3 Concentration of vanadium ion and sulfate after dissolution and dilution of calcined solid at 180°C and molar ratio of H2SO4 to V2O5 of 4

图4 不同钒浓度下溶液的电导率和黏度

Fig.4 Conductivity and viscosity of solutions at different vanadium concentrations

图5 180℃活化后固体与溶解过滤后固体的XRD谱图

Fig.5 XRD patterns of solid after calcination and dissolve the filtered solids at a temperature of 180℃

图6 含有不同浓度H2SO4与V2O5活化后固体红外光谱

Fig.6 FT-IR spectra of solids containing different concentrations of H2SO4 and V2O5 after calcination

图7 含有不同浓度H2SO4与V2O5活化后固体

Fig.7 Images of solids containing different concentrations of H2SO4 and V2O5 after calcination

图8 不同浓度下溶液Raman光谱

Fig.8 Raman spectra of solutions containing different V(Ⅴ) and SO42- concentrations

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浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液

Preparation of high-concentration positive electrolyte of vanadium redox flow battery by activating vanadium pentoxide with highly concentrated sulfuric acid

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