Optimized the vanadium electrolyte with sulfate-phosphoric mixed acids to enhance the stable operation at high-temperature

doi:10.1007/s11705-023-2377-x

2024, Vol. 18

Issue (2) : 14 https://doi.org/10.1007/s11705-023-2377-x

Optimized the vanadium electrolyte with sulfate-phosphoric mixed acids to enhance the stable operation at high-temperature

Ling Ge^1,^2,^3,⁴, Tao Liu^1,^2,^3,⁴(

), Yimin Zhang^1,^2,^3,^4,⁵, Hong Liu^1,^2,^3,⁴

¹. School of Resource 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 University of Science and Technology, Wuhan 430081, China
³. Hubei Collaborative Innovation Center for High Efficient Utilization of Vanadium Resources, Wuhan University of Science and Technology, Wuhan 430081, China
⁴. Hubei Provincial Engineering Technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium Resource, Wuhan University of Science and Technology, Wuhan 430081, China
⁵. School of Resource and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, China

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Abstract

Herein, the influence of the concentration design and comprehensive performance of the sulfate-phosphoric mixed acid system electrolyte is investigated to realize an electrolyte that maintains high energy density and stable operation at high temperatures. Static stability tests have shown that VOPO₄ precipitation occurs only with vanadium(V) electrolyte. The concentration of vanadium ion of 2.0–2.2 mol·L^–1, phosphoric acid of 0.10–0.15 mol·L^–1, and sulfuric acid of 2.5–3.0 mol·L^–1 are suitable for a vanadium redox flow battery in the temperature range from –20 to 50 °C. The equations for predicting the viscosity and conductivity of electrolytes are obtained by the response surface method. The optimized electrolyte overcomes precipitation generation. It has 2.8 times higher energy density than the non-phosphate electrolyte, and a coulomb efficiency of 94.0% at 50 °C. The sulfate-phosphoric mixed acid system electrolyte promotes the electrode reaction process, increases the current density, and reduces the resistance. This work systematically optimizes the concentrations of composition of positive and negative vanadium electrolytes with mixed sulfate-phosphoric acid. It provides a basis for the different valence states and comprehensive properties of sulfate-phosphoric mixed acid system vanadium electrolytes under extreme environments, guiding engineering applications.

Keywords all vanadium redox flow battery mixed-acid vanadium electrolyte concentration optimization response surface methodology high-temperature stability

Corresponding Author(s): Tao Liu

Just Accepted Date: 06 November 2023 Issue Date: 15 January 2024

Cite this article:

Ling Ge,Tao Liu,Yimin Zhang, et al. Optimized the vanadium electrolyte with sulfate-phosphoric mixed acids to enhance the stable operation at high-temperature[J]. Front. Chem. Sci. Eng., 2024, 18(2): 14.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-023-2377-x
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I2/14

Fig.1 Static stability test of the vanadium(V) electrolytes. (a) Stability time and residual vanadium concentration of electrolytes with different phosphoric concentrations (0?0.5 mol·L^–1); (b) residual vanadium concentration of electrolytes with different phosphoric concentrations (0?0.5 mol·L^–1) at 50 °C; residual vanadium concentration of electrolytes with different (c) vanadium concentrations (1.6?2.4 mol·L^–1) and (d) sulfate concentrations (2.5?4.5 mol·L^–1).

Fig.2 XRD patterns of precipitation of electrolytes after static stability test at 50 °C: (a) without H₃PO₄, (b) with 0.1 mol·L^–1 H₃PO₄, (c) with 0.2 mol·L^–1 H₃PO₄, (d) with 0.3 mol·L^–1 H₃PO₄, (e) with 0.4 mol·L^–1 H₃PO₄, and (f) with 0.5 mol·L^–1 H₃PO₄.

Fig.3 Static stability test of the vanadium(II), (III), (IV), and (V) electrolytes with different sulfate concentrations (2.5?3.5 mol·L^–1) and phosphoric concentrations (0?0.2 mol·L^–1) at –25 and 50 °C. The bars indicate the concentration of residual vanadium ions in the different valence states of vanadium electrolyte, purple (II), green (III), blue (IV) and yellow (V).

Fig.4 FTIR and Raman tests of the vanadium(V) and (II) electrolytes with and without H₃PO₄.

Tab.1 Experimental matrix and response values based on BBD

Tab.2 The results of the ANOVA for the fitting model

Fig.5 Plots of predicted values vs. experimental data: (a) viscosity and (b) conductivity.

Fig.6 Three-dimensional response surface graphs. Effect of vanadium ions and H₂SO₄ on (a) viscosity and (d) conductivity; effect of vanadium ions and phosphate acid on (b) viscosity and (e) conductivity; effect of H₂SO₄ and phosphate acid on (c) viscosity and (f) conductivity.

Fig.7 Trend curves of different factors on (a) viscosity and (b) conductivity.

Tab.3 The main data of CV and Tafel curves of different vanadium(IV) electrolytes

Fig.8 The CV and Tafel steady-state polarization curves of vanadium(IV) electrolytes: (a) CV curves, (b) (2, 0, 3), (c) (2, 0.1, 3), (d) (2, 0.15, 3) and (e) (2, 0.2, 3), with R_ct being the charge transfer resistance, i₀ being the exchange current, and k₀ being the standard reaction rate constant.

Fig.9 The VRFB performance of electrolytes with the sulfate-phosphoric mixed acid system and the sulfuric acid system. Electrolytes configurations: I represents (2, 0, 3) at 25 °C, II represents (2, 0, 3) at 50 °C, III represents (2, 0.15, 3) at 25 °C, and IV represents (2, 0.15, 3) at 50 °C. (a) Charge-discharge capacity during 100 cycles; (b) energy density and coulombic efficiency during 100 cycles; (c) discharge capacity vs. voltage; (d) voltage vs. time.

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