The ultraviolet-visible spectra of catholytes for vanadium flow batteries (VFBs) were measured and analyzed for a range of V IV :V V ratios and vanadium concentrations. Using a model of V 2 O 3 3+ in equilibrium with VO 2+ and VO 2 + , the spectra were characterized in terms of an excess absorbance parameter p and the molar extinction coefficients ε 4 and ε 5 of VO 2+ and VO 2 + , respectively. The results showed that p varies weakly with the vanadium concentration C and this variation was quantified relative to a reference concentration C r by means of a concentration coefficient φ r . Experimental data showed that plots of φ r versus Cφ r and plots of 1/φ r versus C are linear and, based on this linearity, φ r was expressed as a simple function of C in terms of its reference concentration C r and a single parameter M that is independent of the choice of C r . Standard spectra of p at a concentration C 0 = 1 mol dm −3 and of ε 4 and ε 5 were generated from which the spectrum of any catholyte may be simulated using the measured value of M in a governing equation. This enables determination of the state of charge for any VFB catholyte using absorbance measurements at a small number of wavelengths. The use of non-dispatchable power sources such as solar, wind and ocean energy is increasing.1 Due to the intermittency of these sources, their use is restricted unless there is a means of storing the energy they produce in periods of high availability for utilization in periods of limited availability. 2,3 There is considerable interest in flow batteries for storing energy from such sources and for other large and medium scale energy storage applications. 4,5 Vanadium flow batteries (VFB), 5-13 also known as vanadium redox flow batteries (VRFB or VRB), are particularly attractive because, in addition to having long cycle life, they are essentially immune to cross-contamination problems due to mass transfer across the membrane that can limit the service life of the electrolyte in other systems. 3,4,7,[14][15][16][17][18][19] This is because both the positive and negative sides of a VFB are based on vanadium species, eliminating the need for costly re-purification processes. 1,12 Typical cells have carbon felt electrodes; both cell design and the electrochemical behavior of electrodes are active areas of research.
20-31The cells can operate at coulombic efficiencies of over 90% 32,33 and their carbon electrodes have very good stability as long as the positive half-cell is not overcharged. 34,35 Accurate monitoring of state of charge (SoC) is intrinsically important for the reliability of energy storage systems, particularly large systems in critical applications. Furthermore, independent monitoring of the SoC of both electrolytes is important for effective operation of flow battery technology. For example in a VFB, transfer of vanadium ions across the membrane [36][37][38] and side reactions such as hydrogen formation 12,39-44 at the negative electrode can cause the battery to become unbalanced (e.g. more V V on the posi...