钒电池负极电解液V2(SO4)3溶解性规律

doi:10.3724/SP.J.1077.2012.00469

无机材料学报 ›› 2012, Vol. 27 ›› Issue (5): 469-474.DOI: 10.3724/SP.J.1077.2012.00469 CSTR: 32189.14.SP.J.1077.2012.00469

钒电池负极电解液V₂(SO₄)₃溶解性规律

赵建新^1,2, 武增华¹, 席靖宇¹, 邱新平^1,2

(1. 清华大学深圳研究生院绿色化学电源实验室, 深圳518055; 2. 清华大学化学系, 北京100084)

收稿日期:2011-05-17 修回日期:2011-08-01 出版日期:2012-05-10 网络出版日期:2012-03-31
作者简介:赵建新(1985-), 男, 硕士研究生. E-mail: zjx08@mails.tsinghua.edu.cn
基金资助:
国家自然科学基金(20973099);973项目(2010CB227200);深圳市基础研究计划(JC200903180530A,

Solubility Rules of Negative Electrolyte V₂(SO₄)₃of Vanadium Redox Flow Battery

ZHAO Jian-Xin^1,2, WU Zeng-Hua¹, XI Jing-Yu¹, QIU Xin-Ping^1,2

(1. Lab of Advanced Power Sources, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China; 2. Department of Chemistry, Tsinghua University, Beijing 100084, China)

Received:2011-05-17 Revised:2011-08-01 Published:2012-05-10 Online:2012-03-31
About author:ZHAO Jian-Xin. E-mail: zjx08@mails.tsinghua.edu.cn
Supported by:
National Natural Science Foundation of China (20973099);973 Program (2010CB227200);Basic Research?Program of Shenzhen (JC 200903180530 A, JC 201005310703A)

摘要/Abstract

摘要：

对钒电池负极电解液中活性物质V(III)在不同硫酸浓度、不同温度条件下的溶解性规律进行了深入研究, 同时对V(III)-H₂SO₄体系电化学性能进行了初步探讨. 结果表明: V(III)的溶解是一个放热过程, 在15~40℃范围内, V(III)的溶解度随着温度升高而逐渐降低; 并且溶液中V(III)会以V-O-V形式形成二聚体, 在低硫酸浓度下, V(III)可以高浓度长时间稳定存在, 随硫酸浓度的增大, V(III)溶解度逐渐降低, 其中30℃、1 mol/L H₂SO₄条件下V(III)浓度可高达2.730 mol/L; 进一步通过电化学测试, 发现V(III)-H₂SO₄体系是不可逆体系, H₂SO₄浓度的增大有益于提高V(III)/V(II)氧化还原反应的可逆性.

关键词: 钒电池, 负极电解液, 溶解性

Abstract:

The solubility of V(III) species in negative electrolyte of all vanadium redox flow battery (VRB) was studied and the solubility parameters of V(III) species at various concentrations of H₂SO₄ and different temperatures were preliminarily obtained. The results showed that dissolution of V(III) was an exothermic process. The solubility of V(III) decreased with temperature (15-40℃). Also, the presence of V(III) in the solution was a V-O-V dimmer. The solubility of V(III) decreased with the increasing of H₂SO₄ and low concentration of H₂SO₄ would keep high concentration of V(III) stable for a long time. Especially, concentration of V(III) could reach 2.730 mol/L with 1 mol/L H₂SO₄ at 30℃. Electrochemical properties was further investigated by experiment, the results revealed that V(III)-H₂SO₄ solution was an irreversible system for V(III)/V(II) redox reaction. Increasing of concentration of H₂SO₄ had great benefit to improve the reversibility of V(III)/V(II) redox reaction.

Key words: vanadium battery, negative electrolyte, solubility

中图分类号:

O645

赵建新, 武增华, 席靖宇, 邱新平. 钒电池负极电解液V₂(SO₄)₃溶解性规律[J]. 无机材料学报, 2012, 27(5): 469-474.

ZHAO Jian-Xin, WU Zeng-Hua, XI Jing-Yu, QIU Xin-Ping. Solubility Rules of Negative Electrolyte V₂(SO₄)₃of Vanadium Redox Flow Battery[J]. Journal of Inorganic Materials, 2012, 27(5): 469-474.

图/表 10

图1 相同初始H2SO4浓度, V(III)在不同温度下的浓度随时间的变化曲线

Fig. 1 Concentrations of V(III) with initial concentrations of H2SO4 changing over time at different temperatures

图2 搁置100 d负极电解液中V(III)浓度与H2SO4浓度的关系曲线

Fig. 2 Variation in solubility of V(III) ions with actual concentrations of H2SO4 after static shelving for 100 d

图3 相同温度下V(III)溶液在不同初始H2SO4浓度下的浓度随时间变化曲线

Fig. 3 Concentrations of V(III) with the same temperature changing over time at different initial concentrations of H2SO4

Table 1 Component data of solution after static shelving for 100 d at 30℃

Initial H₂SO₄ / (mol·L^-1)	H⁺ / (mol·L^-1)	HSO₄^- / (mol·L^-1)	SO₄^2- / (mol·L^-1)
1	0.007	2.117	3.040
2	0.041	4.805	1.196
3	1.883	5.959	0.032
4	4.067	5.793	0.015
5	5.668	6.230	0.012

图4 V(III)溶液紫外/可见吸收光谱

Fig. 4 UV-visible absorption spectra of V(III) solution

图5 V(III)溶液在612 nm处的吸光度与浓度关系图

Fig. 5 Relationship between absorbance and concentration of V(III) at 612 nm

图6 30℃不同V(III)浓度的溶液在石墨电极上的循环伏安曲线

Fig. 6 Cyclic voltammograms for V(II)/V(III) reaction on a graphite electrode in V(III) solution with various concentrations of V(III)

Table 2 Cyclic voltammogram data for V(II)/V(III) reaction on a graphite electrode in V(III) solution with various concentrations of V(III)

C_V(III) /(mol·L^-1)	/(mol·L^-1)	ΔV_p /mV	I_pa/I_pc
2.730	1	640	0.747
2.385	2	405	0.831
1.380	3	185	0.845
0.585	4	120	0.895
0.195	5	81	0.905

图7 30℃ 2.730 mol/L V(III)浓度溶液在石墨电极上的循环伏安曲线

Fig. 7 Cyclic voltammograms for V(II)/V(III) reaction on a graphite electrode in V(III) solution with 2.730 mol/L concentration of V(III) at 30℃

图8 V(II)氧化峰电流密度对扫描速度平方根的曲线

Fig. 8 Density of peak current as a function of the square root of scan rate for V(II) oxidation

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钒电池负极电解液V₂(SO₄)₃溶解性规律

Solubility Rules of Negative Electrolyte V₂(SO₄)₃of Vanadium Redox Flow Battery

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