Novel carbon fiber microelectrode (CFME) and flow cell experiments were used to investigate electrode treatments for vanadium batteries (VFBs). Linear sweep voltammetry (LSV) electrochemical impedance spectroscopy (EIS) on CFMEs showed that at positive potentials enhance the kinetics of V2+/V3+ inhibit VO2+/VO2+, while negative VO2+/VO2+. XPS analysis changes in oxygen-containing species surfaces after treatment, supporting suggestion such are responsible observed effects. The VO2+/VO2+...

The UV-visible spectra of VIII-VII electrolytes in 3 mol dm−3 H2SO4 showed a linear relationship absorbance to mole fraction but those VIV-VV did not. At all wavelengths, mixtures excess over that expected for combination the components. Plots Aex against f VIV were found be symmetrical parabolas reach peak at = 0.5. Excess is attributed strongly absorbing 1:1 mixed-valence complex, V2O33+, equilibrium with VO2+ and VO2+. Based on this, an expression derived relates from this it shown when...

The ultraviolet-visible spectra of catholytes for vanadium flow batteries (VFBs) were measured and analyzed a range VIV:VV ratios concentrations. Using model V2O33+ in equilibrium with VO2+ VO2+, the characterized terms an excess absorbance parameter p molar extinction coefficients ɛ4 ɛ5 respectively. results showed that varies weakly concentration C this variation was quantified relative to reference Cr by means coefficient ϕr. Experimental data plots ϕr versus Cϕr 1/ϕr are linear and,...

Two aspects of vanadium flow batteries are reviewed: electrochemical kinetics on carbon electrodes and positive electrolyte stability. There is poor agreement between reported values kinetic parameters; however, most authors report that rates faster for V IV /V than II III . Cycling the electrode potential increases both reactions initially due to roughening but when no further observed, affected oppositely by pretreatment potential. Anodic activates reaction, deactivates it Three states...

We showed that it is easy, in principle, to measure the state of charge (SoC) VRFB negative electrolytes by ultraviolet-visible (UV-Vis) absorption spectroscopy because spectra are a linear combination components, V II and III . In contrast we showed, for range mole percentages at several different concentrations total vanadium, UV-Vis positive electrolyte do not exhibit similar linearity absorbance measurements two wavelengths required SoC. All an excess A ex which have proposed be...

It was shown by cyclic voltammetry, current measurements at constant potential and electrochemical impedance spectroscopy that polarization pretreatment of glassy carbon electrodes affects the kinetics VO 2+ /VO 2 + V /V 3+ redox reactions. After potentials more positive than ~0.7 (sat. Hg/Hg SO 4 ), were less active both for oxidation reduction . The activity electrode remained depressed indefinitely but recovered negative potentials. However, converse observed reactions: after Both...

The stability of typical vanadium flow battery (VFB) catholytes was investigated at temperatures in the range 30–60°C for VV concentrations 1.4–2.2 mol dm−3 and sulfate 3.6–5.4 dm−3. In all cases, V2O5 precipitates after an induction time, which decreases with increasing temperature. Plots logarithm time versus inverse temperature (equivalent to Arrhenius plots) show excellent linearity have similar slopes. also increases linearly concentration concentration. slopes these plots give values...

We propose a three-step model of electrochemical nanopore formation in n-InP KOH that explains how crystallographically oriented etching can occur even though the rate-determining process (hole generation) occurs only at pore tips. The shows competition kinetics between hole diffusion and reaction determines average distance holes along semiconductor surface this, turn, whether is crystallographic. If are slow relative to diffusion, preferred crystallographic sites within zone vicinity tip,...

The stability of typical vanadium flow battery (VFB) catholytes with respect to precipitation V2O5 was investigated at temperatures in the range 30–60°C. In all cases a precipitate formed after an induction time, which decreased increasing temperature and concentration VV increased sulfate. Arrhenius-type plots are shown for two solutions. These have excellent linearity similar slopes yield apparent activation energy 1.79 eV (172 kJ mol−1). variation time various concentrations simulated,...

Pore propagation during anodization of (100) n-InP electrodes in aqueous KOH was studied detail by scanning and transmission electron microscopy (SEM TEM). Pores emanating from surface pits propagate along the 〈111〉A crystallographic directions to form, early stages anodization, porous domains with shape a tetrahedron truncated symmetrically through its center plane parallel electrode. This confirmed comparing predictions detailed model pore SEM TEM observations. The showed how leads plane....

The conductivity of vanadium flow battery (VFB) catholytes was measured over a range concentrations [V], sulfur [S], states charge (SoC) and temperatures. In general, variations are highly linear. particular, the linear variation with SoC suggests that VFB catholyte can be empirically modelled to high degree accuracy as simple sum constituent VIV VV solution conductivities. A model function [V] [S] developed for both solutions. temperature then by simply adding individual conductivities...

Pores are formed electrochemically in n-InP KCl electrolytes with concentrations of 2 mol dm-3 or greater. The pore morphology is similar to what seen other halide-based electrolytes. At low potentials, crystallographically oriented (CO) pores formed. higher current-line (CLO) Crystallographically walls observed for both morphologies. When at a constant current, potential oscillations which have been correlated the width. CLO wall smoothness and overall uniformity increase as concentration...

Rates of water transfer across a Nafion membrane between vanadium electrolytes (VV, VIV, VIII and VII) H2SO4 solutions various concentrations were measured the concentration corresponding to zero-transfer rate was thus estimated. The difference in sulfate an electrolyte equivalent solution varies considerably with oxidation state vanadium. value is close zero for VIV but has large positive VV negative values VII. Both affinity, defined terms chemical potential water, thermodynamic activity...

Based on careful experimental measurements, a model for the stability of vanadium flow battery (VFB) catholytes was developed which quantifies their precipitation behavior as function temperature and composition. The enables simulation induction time at T any catholyte with concentrations sulfate VV within range applicability. results such simulations are in good agreement experiment. can predict using three alternative metrics: τ, relative parameter ρ TW. is measure overall stability;...

Flow batteries offer a lot of promise for large scale energy storage applications. 1 In particular, Vanadium Redox Batteries (VRFB) have received attention and significant commercialisation the system has already begun. 2,3 VRFB cells can operate at coulombic efficiencies over 90% 4,5 their carbon electrodes very good stability as long positive half-cell is not overcharged. 6,7 Since active species anolyte catholyte are just different forms vanadium in H 2 SO 4 , cross-contamination problems...

Both visual observation and light-scattering measurements were used to investigate the stability of typical vanadium flow battery (VFB) catholytes. V2O5 precipitates after an induction time that decreases with increasing temperature concentration VV increases sulphate. This was observed at 30-60°C for sulphate concentrations 1.4–2.11 3.7–5.3 mol dm-3, respectively. Arrhenius plots show excellent linearity logarithm varies linearly both concentration. An plot times normalized standard...

Anodization of highly doped (10 18 cm -3 ) n-InP in 2 – 5 mol dm KOH under potentiostatic or potentiodynamic conditions results the formation a nanoporous sub-surface region. Pores originate from surface pits and an individual, isolated porous domain is formed beneath each pit early stages anodization. Each such separated by thin non-porous layer (typically ~40 nm) connected to electrolyte its pit. emanate these points along <111>A crystallographic directions form domains with shape...

Pores formed anodically in InP at different temperatures, electrolyte (KOH) concentrations, carrier concentrations and current densities exhibit significant pore width variations. The decreases as the temperature, concentration or density are increased. also when KOH is increased up to 9 mol dm-3, but increases slightly further. These variations explained by a three-step model for formation based on competition kinetics between steps etching mechanism. variation of with explicitly terms...

Anodization of n-InP electrodes was carried out over a range temperatures and KOH concentrations. Scanning electron microscopy showed <111>A aligned pore growth with width decreasing as the temperature increased. This variation is explained in terms relative rates electrochemical reaction hole diffusion supports three-step model proposed earlier. As increased, both areal density surface pits decrease resulting large increase current through pits. explains an observed porous layer thickness:...

We report a new additive, monobasic potassium arsenate (KH2AsO4), for improving the thermal stability of VFB catholytes. Using our standard accelerated testing methodology at 30–70°C, we showed that effect increases continuously with increasing concentration over range investigated (0 – 0.10 mol dm−3). In comparison to similar experiments phosphate (H3PO4), magnitude was greater arsenate. A combination and also effective. Based on these results, speculate other Group-V elements in +5...

Vanadium redox flow batteries (VRFBs) are a promising technology to meet energy storage requirements for large scale and remote area applications. 1 Flow offer long cycle-life 2 the capacity can be scaled separately from power capacity. This design flexibility makes them suitable wide range of VRFBs have additional advantage having same element on both sides membrane which eliminates cross-contamination issues that arise in mixed-element batteries. As result electrolyte maintenance reduced;...