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530 S. Xiao et al. / Electrochimica Acta 187 (2016) 525–534 Fig. 5. (a)-(g) CV curves of V(IV)/V(V) redox couple record at 50 C – -10 C with different scan rates; (h) Values of –Ipc/Ipa with different scan rates at different temperatures; (i) Plots of peak current density versus the square root of scan rates at different temperatures. temperature can facilitate the redox reactions of V(IV)/V(V) couple. Fig. 5(i) illustrates the relationship between the redox peak current density and the square root of the scan rate. A linear relationship can be seen from the two parameters, and the slope of the line is decreasing with the reducing of temperature. From the above discussion, the V(IV)/V(V) redox couple here is a quasi-reversible reaction. In theory, the value of the diffusion coefficient (D) for a quasi-reversible reaction is between that for a reversible one (D1) and an irreversible one (D2) [47]. For a one-step and one electron reversible and irreversible reaction, the peak current density ip is given in the following equations [48]: ip = 0.4958(F3/RT)1/2a1/2ACD21/2n1/2 (irreversible reaction) (2) where F is the Faraday constant, T is the Kelvin temperature, R is the universal gas constant, C is the bulk concentration of primary reactant,A is the geometric area of the working electrode, D1 and D2 represent the diffusion coefficient for a reversible reaction and an irreversible reaction respectively, n is the scan rate, a stands for the transfer coefficient for an irreversible reaction. Though the Eqs. (1) and (2) were used to calculated diffusion coefficients in dilute solutions, they can be used here to allow indicative estimates and trends of the diffusion coefficients under different temperatures. On accounting of Eqs. (1) and (2), when T = 50C = 323.15K, based on the known experimental factors, D1 and D2 can be finally deduced to the following equations: ip = 0.4463(F3/RT)1/2ACD11/2n1/2 (reversible reaction) Table 1 (1) Diffusion coefficient D1 (cm2 s1) and D2 (cm2 s1) of positive and negative electrolytes at different temperatures. Temperature (C) -10 0 10 20 30 40 50 Positive electrolyte Negative electrolyte Oxidation Reduction Oxidation D1 D2 D1 D2 D1 Reduction D2 D1 D2 5.3210-8 7.3710-8 1.0510-7 1.3110-7 1.4210-7 1.5910-7 1.9210-7 1.7810-8 5.4110-8 1.0410-7 1.5410-7 4.0210-7 6.6810-7 9.8710-7 2.8910-8 8.7910-8 1.6910-7 2.4910-7 6.5110-7 1.0810-6 1.6010-6 4.7910-11 4.8110-9 1.0310-8 5.0110-8 2.2310-7 4.0410-7 5.6010-7 7.7710-11 7.7910-9 1.6710-8 8.1310-8 3.6110-7 6.5510-7 9.0710-7 1.3510-8 2.0310-8 2.9710-8 4.6510-8 6.5910-8 9.6110-8 1.2810-7 2.1910-8 3.2910-8 4.8210-8 7.5310-8 1.0710-7 1.5610-7 2.0710-7 3.2810-8 4.5510-8 6.4810-8 8.0910-8 8.7810-8 9.8310-8 1.1810-7PDF Image | Broad temperature adaptability vanadium redox flow battery
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