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

doi:10.3724/SP.J.1077.2012.00469

Abstract

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

CLC Number:

O645

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.

Figures/Tables 10

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

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

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

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

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

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

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℃

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

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

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