The aggravation of side reactions caused by insufficient localized liquid supply in an all-vanadium redox flow battery stack

doi:10.19799/j.cnki.2095-4239.2021.0578

Abstract

Abstract:

In an operating all-vanadium redox flow battery stack, uneven electrolyte flow through each individual electrode is common, if not inevitable. Moreover, localized insufficiencies of liquid supply may become severe in a long-term operation, which not only directly affects overall stack performance, but also exacerbates harmful side reactions (including oxygen evolution, hydrogen evolution, and carbon corrosion). These reactions may in turn lead to blockages and increased resistance. This paper reports a model-based quantitative study of an all-vanadium redox flow battery stack under conditions of local liquid supply shortage. A two-dimensional steady-state simulation was carried out for charge/discharge under galvanostatic operation, focusing on the impact of local fluid supply deficiency on electrode potential and side reactions. The results show that decreased flow rate in one or several electrodes has little effect on the overall voltage of the stack, but that it does cause local sharp changes in current and ion concentrations inside the electrodes. It may also lead to an ultra-high potential gradient, causing seriously deviation of the potential from its normal value. This in turn reduces the uniformity of distribution of the main reaction and intensifies the progress of side reactions on the electrode surface, potentially compromising the energy efficiency and safety of the stacks. Since the rate of side reactions also depends on the material properties of the electrode, this paper provides qualitative conclusions based on representative working conditions. These conclusions allow general guidance to be suggested for the design and testing of flow battery stacks.

Key words: all-vanadium redox flow battery stack, insufficient local liquid supply, side reactions, potential

CLC Number:

TM 911

Xuan WANG, Qiang YE. The aggravation of side reactions caused by insufficient localized liquid supply in an all-vanadium redox flow battery stack[J]. Energy Storage Science and Technology, 2022, 11(5): 1455-1467.

Figures/Tables 17

Fig. 1

Table 1

Table 2

Parameters of the components"

参数	参数值
电极电导率σ_e	500 S/m
双极板电导率σ_bp	1000 S/m
电端板电导率σ_ep	1×10⁵ S/m
膜电导率σ_m	10 S/m
电极孔隙率ε	0.93
电极比表面积 $a$	3.5×10⁴ m^-1
二价钒离子扩散系数 $D V 2 +$	4×10^-11 m²/s
三价钒离子扩散系数 $D V 3 +$	4×10^-11 m²/s
四价钒离子扩散系数 $D V O 2 +$	6.5×10^-11 m²/s
五价钒离子扩散系数 $D V O 2 +$	6.5×10^-11 m²/s
氢离子扩散系数 $D H +$	1.55×10^-9 m²/s
硫酸氢根离子扩散系数 $D H S O 4 -$	2.2×10^-10 m²/s
硫酸根离子扩散系数 $D S O 4 2 -$	1.8×10^-10 m²/s

Table 2

Table 3

Kinetic parameters"

参数	数值
V²⁺/V³⁺反应速率常数 $k V 2 + / V 3 +$	7.0 × 10^-8 m/s ^[7]
VO²⁺/VO₂⁺反应速率常数 $k V O 2 + / V O 2 +$	2.5 × 10^-8 m/s ^[7]
析氧反应交换电流密度j_{0_OER}	1 × 10^-9 A/m²^[8]
V³⁺/VO²⁺反应速率常数 $k V 3 + / V O 2 +$	2.5 × 10^-15 m/s
负极反应电荷转移系数α_-	0.45^[7]
正极反应电荷转移系数α₊	0.55 ^[7]

Table 3

Fig. 2

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Fig. 8

Fig. 9

Fig. 10

Fig. 11

Fig. 12

Fig. 13

Fig. 14

References 11

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参数	值
电极长度H_e	20 cm
电极厚度L_e	4 mm
电极深度W_e	2.85 cm
膜厚度L_m	0.203 mm
双极板长度H_bp	20 cm
双极板厚度L_bp	2 mm
端板长度H_ep	21 cm
端板厚度L_ep	10 mm

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