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Determining Vanadium Concentrations Using the UV-Vis Response

Method
To cite this article: R. Paul Brooker et al 2015 J. Electrochem. Soc. 162 A608

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A608 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015)

Determining Vanadium Concentrations Using the UV-Vis

Response Method
R. Paul Brooker,a,∗,z Curtis J. Bell,b Leonard J. Bonville,c H. Russell Kunz,c,∗
and James M. Fentona,∗∗
a Florida Solar Energy Center, University of Central Florida, Cocoa, Florida 32922, USA
b Univerisity of Bath, Claverton Down, Bath, Somerset BA2 7AY, United Kingdom
c Center for Clean Energy Engineering, University of Connecticut, Storrs, Connecticut 06269, USA

The ability to determine the state of charge of vanadium solutions is critical to understanding reaction mechanisms and charge
transport dynamics. This paper describes in detail the methods used to generate quantitative concentrations of three of the four
species in an all-vanadium flow battery. The UV-Vis method was shown to provide concentration values that were more reliable than
using either an electrode voltage or the integrated current with respect to time. Furthermore, a method was proposed to bring flow
battery system into charge balance by independently reducing the negative electrolyte.
© The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/),
which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any
way and is properly cited. For permission for commercial reuse, please email: [email protected]. [DOI: 10.1149/2.0371504jes]
All rights reserved.

Manuscript submitted October 17, 2014; revised manuscript received December 22, 2014. Published January 22, 2015.

Future energy needs will likely be met through a combination Crossover V O2+ + V 3+ → 2V O 2+ [7]
of various renewable energy sources, such as solar and wind, how-
ever, due to the variable nature of these sources, there is a need
to be able to capture the energy that is produced during periods of Side reaction 2H + + 2e− → H2 [8]
low demand. Potential energy storage options include compressed
air storage, pumped-hydro, flywheels, and electrochemical systems.
Each energy storage option has advantages and disadvantages, there-
fore, just as energy production will not be met with a single solution, Side reaction 2H2 O → 4H + + O2 + 4e− [9]
so too energy storage will likely be met through application of many
systems, depending on geography and need. One storage option that
is currently showing significant potential is the all-vanadium flow 1
Oxidation by air V 2+ + O2 + 2H + → V 3+ + H2 O [10]
battery (VFB). 2
The vanadium flow battery is composed of a proton exchange
membrane (PEM), carbon-based electrodes, and two solutions con- Reaction 4 will occur whenever V O 2+ is present at the negative elec-
taining vanadium ions in acid. The energy is stored in the oxidation trode during charging of the flow battery. Crossover reactions 5–7
states of the vanadium ions, i.e. V 2+ , V 3+ V O 2+ , and V O2+ . In the are a result of the ability of vanadium to migrate through the mem-
charged state, the negative electrolyte solution consists of 100% V 2+ brane, either through concentration differences or through the electric
ions, while the positive electrolyte solution consists of 100% V O2+ field. Vanadium species may migrate from the positive electrolyte
ions. Discharge, and subsequent release of energy, is realized through to the negative electrolyte, or vice versa. Side reaction 8 will occur
the following reactions: at very low negative electrode potentials, while side reaction 9 may
generate oxygen at high positive electrode potentials. Oxidation of
Negative electrode : V 2+ → V 3+ + e− [1] the V 2+ species occurs easily in the presence of air, requiring the
negative electrolyte solution to be continuously purged with an inert
gas.
Positive electrode : V O2+ + 2H + + e− → V O 2+ + H2 O [2] The simplest and most direct source of vanadium in the initial setup
of the cell is V O 2+ in the form of VOSO4 . Since the goal is to generate
100% V 2+ in the negative electrolyte, using a starting solution of
Overall reaction : V 2+ +V O2+ +2H + → V 3+ +V O 2+ +H2 O [3] V O 2+ requires two electrons transferred per mole of vanadium. Thus,
During ideal operation, the following schematic illustrates the oxida- when starting with V O 2+ in both reservoirs, the volume in the positive
tion states of the two reservoirs at 100% charge (Figure 1a) and 0% electrolyte must be at least twice that of the negative electrolyte,
charge (Figure 1b). assuming 100% charge efficiency. Hydrogen evolution (reaction 8) at
Due to the wide variety of oxidation states available, and the facility the negative electrode will require a positive electrolyte volume that
with which they can be achieved, additional reactions are also possible is greater than double that of the negative electrolyte volume.
within the typical operating voltage of the cell, as indicated below: Due to the several different mechanisms for oxidation and reduc-
tion of the various vanadium species, measuring the state of charge
Charging intermediate V O 2+ + 2H + + e− → V 3+ + H2 O [4]

Crossover V O2+ + V 2+ + 2H + → V O 2+ + V 3+ + H2 O [5]

Crossover V O 2+ + V 2+ + 2H + → 2V 3+ + H2 O [6]

∗
Electrochemical Society Active Member.
∗∗
Electrochemical Society Fellow.
z
E-mail: [email protected] Figure 1. Flow battery at (a) 100% SoC and (b) 0% SoC.
 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015) A609

(SoC) of all-vanadium flow batteries (VFBs) is challenging. The con-

ductivity of the positive and negative electrolytes has been used, but
this approach is highly dependent on the concentration of vanadium.
Since conductivity measurements are non-selective with respect to
the charge-carrying ion, an increase in vanadium or an increase in
proton concentrations will lead to increased conductivity. Thus, this
method cannot identify precisely the concentration of vanadium with-
out also knowing the concentration of protons.1,2 The half-cell poten-
tials have also been employed to monitor the SoC of the individual
electrolyte reservoirs, and has been shown to demonstrate imbalance
during cycling.1 However, this approach requires the use of a stable
reference electrode, which is also influenced by proton concentrations. Figure 2. (a) Schematic of “regen” cell. (b) Schematic of in-situ Pt-H2 refer-
A concept that has received significant attention is the UV-Vis re- ence electrode.
sponse method.3–5 This method makes use of the strong absorbance
changes of the various vanadium oxidation states. Since the absorp-
tion is so strong, it is necessary to either dilute the solution prior to was held at –0.6 V vs. SHE, causing the V O 2+ to be reduced to V 2+ .
obtaining the spectrum, or to employ a short-pathlength cell as in The reduction of the solution was monitored by UV-Vis, and complete
Ref. 3. In either case, online SoC-monitoring using UV-Vis is chal- reduction of V O 2+ was defined as the point when subsequent UV-Vis
lenging. However, UV-Vis is still a valuable tool that could be used spectra showed no change over a 30 minute interval. Once the solution
for ex-situ studies such as vanadium crossover and charge imbalance was completely reduced to V 2+ , samples were obtained and diluted
experiments. to various concentrations using 4M H2 SO4 .
Most of the focus in the literature has been on the response of the To obtain solutions with V O2+ , a flow cell was used with carbon
V O 2+ species. This paper demonstrates the response of V 2+ and V 3+ paper as both positive and negative electrodes, separated by an NR112
solutions, and identifies unique peaks for each ion. Additionally, an membrane (Ion-power). A solution of 0.1M VOSO4 was pumped
in-operando electrochemical method of monitoring state of charge is through the positive electrode, while a solution with a mixture of
compared to the UV-Vis response. V O2+ and V O 2+ was pumped through the negative electrode. The
potential of the positive electrode was held at 1 V vs. that of the
negative electrode until current density dropped below 4 mA/cm2 ,
Experimental
at which point the positive electrolyte solution was fully oxidized
UV-Vis measurements were obtained with a Shimadzu UV- to V O2+ . Several concentrations of the fully-oxidized solution were
2401PC spectrometer, using 1 cm plastic cuvettes. Flow rates of the prepared by diluting with 4M H2 SO4 and were analyzed with UV-Vis.
electrolytes and voltage control of the cells were accomplished using A flow battery experiment was also conducted, using an NR112
an 857 redox flow-cell test system (Scribner Assoc., Inc, Southern membrane (Ion-power) with SGL 10AA carbon paper (Ion-power) at
Pines NC), and electrolyte flow rates were constant at 100 mL/min. both positive and negative electrodes. The starting solution was 0.69M
Cells were assembled using 25 cm2 fuel cell hardware (Fuel Cell Tech- VOSO4 in 4M H2 SO4 , and was the same for both positive and negative
nologies, Albuquerque NM) that was modified for liquid-phase flow. electrolytes. The initial positive electrolyte volume was 50 mL, while
Teflon gaskets provided sealing and compression of approximately the negative electrolyte volume was 55 mL. Initial charging required
23% was applied on the carbon paper (SGL 10 AA, Ion-Power) for a two-step process. First, the positive electrolyte was fully oxidized
all electrodes. Electrolyte reservoir headspaces were purged continu- by pumping both solutions through the cell and holding the positive
ously with nitrogen to limit V 2+ oxidation by air, and all experiments electrode at 1.55 V vs. the negative electrode, until current dropped
were conducted at room temperature. below 4 mA/cm2 . At this point, the negative electrolyte contained a
A solution of 0.1M VOSO4 (VWR) in 4M H2 SO4 (FisherSci) was mixture of V 3+ and V O 2+ . The second step in initial charging was
used as the starting solution for all UV-Vis experiments, and all dilu- to achieve 100% V 2+ in the negative electrolyte. To accomplish this,
tions were prepared with 4M H2 SO4 . To reduce V 2+ oxidation by air the “regen” cell was employed by pumping the negative electrolyte
during UV-Vis measurements, the cuvettes were purged with N2 prior through the negative electrode of the “regen” cell, and holding the
to adding the sample, and were then sealed with parafilm to exclude voltage at –0.6 V vs. the Pt/C-H2 positive electrode.
air. Measurements were also taken as quickly as possible. The V O 2+ After completely charging the negative electrolyte, the flow cell
spectrum was obtained from the initial 0.1M VOSO4 starting solu- was re-attached to the test stand, and discharged at 1 A, collecting
tion and several concentrations were prepared through dilution with UV-Vis samples every 9 minutes. Electrode potentials of the flow
4M H2 SO4 . To obtain solutions with vanadium in different oxidation cell were obtained through the use of an in-situ hydrogen/platinum
states, different approaches were required. reference electrode (see Figure 2b). A platinum/carbon electrode with
To obtain V 2+ , a “regen” cell was used, an approach that was Nafion binder was prepared on a Teflon sheet, then decal-transferred
similar to one employed by NASA during development of the Fe/Cr to a region of the NR112 membrane that was outside the active area.
redox cell.6 In NASA’s Fe/Cr redox system, a separate “rebalance” Channels were drilled into the negative flow field graphite plate to
cell was employed to reduce the state of charge at the positive allow hydrogen to flow past the Pt/C electrode, and a wire was used
Fe3+ electrolyte, thereby bringing this electrolyte into balance with to sense the voltage between this electrode and the negative current
the negative Cr2+ electrolyte. In the current study, the “regen” cell collector. Teflon gaskets provided electrical insulation and a gastight
was assembled with a 7-mil thick Nafion membrane (N117, Ion- seal between the graphite flow field and the Pt/C electrode. It was
Power), carbon paper electrode as the negative electrode, and an in- assumed that the potential at the Pt/C electrode was 0 V vs. the
house platinum-carbon (Pt/C) electrode as the positive electrode (see standard hydrogen electrode.
Figure 2a). The Pt/C electrode was fabricated by first homogeniz- The UV-Vis technique to determine concentrations was compared
ing a mixture of 46% platinum on carbon (TKK), methanol (Sigma to two other methods: the Coulombic method, and the Nernst Method.
Aldrich), 5% 1100 EW Nafion dispersion (Ion-Power) and water. This In the Coulombic method, the concentrations are expected to change
catalyst ink was then sprayed onto a Teflon film, dried, and decal trans- linearly with the amount of charge transferred between electrolytes.
ferred to the N117 membrane. The 0.1M VOSO4 solution was pumped The change in concentrations can be determined by integrating the
past the negative electrode, while the Pt/C electrode was exposed to current-time curve to determine the total charge transferred, and then
pure hydrogen. With hydrogen at the Pt/C electrode, the positive using Faraday’s law to determine the number of moles reacted. Starting
electrode served as a pseudo-reference electrode, with an assumed with an initial concentration of 0.69M V 2+ and 0.69M V O2+ , the
potential of 0 V vs. SHE. The negative electrode of the “regen” cell concentrations within the electrolytes can be estimated.
A610 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015)

Figure 3. (a) Spectra for 0.1M, 0.06M and 0.02M V O 2+ in 4M H2 SO4 . (b) Peak absorbance (@ 760 nm) vs. concentration for V O 2+ in 4M H2 SO4 .

The Nernst method makes use of the in-situ Pt-H2 electrode to mined, the concentrations of V O 2+ in the various solutions could be
determine the potentials of each electrode in the flow cell. The neg- determined.
ative electrode potential was measured against the Pt-H2 reference at
open circuit voltage just prior to obtaining the UV-Vis sample. Once V 2+ /V 3+ spectra.— Determining the V 3+ UV-Vis spectrum was
the negative electrode potential was known, the positive electrode challenging due to the facility with which V 3+ can be reduced to V 2+
potential (E pos ) was calculated by the following: and oxidized to V O 2+ . However, generating V 2+ through the use
of the “regen” cell was straightforward. This approach differed from
E pos = E cell − E neg − E Don [11]
others in that large volumes of V 2+ can be easily generated using the
  same electrodes as were employed in a full cell. Furthermore, since
RT [H + ] pos this approach employs the oxidation of H2 (instead of V O 2+ ), this
E Don = ln [12] approach could be used in an operating flow battery (vide infra) to
F [H + ]neg
bring the negative electrode into balance with a fully-charged positive
where E cell is the cell voltage, E neg is the negative electrode potential, electrode.
and E Don is the Donnan potential between the positive and negative The approach taken herein was to produce a V 2+ solution with
electrodes. The Donnan potential exists due to the difference in proton known concentration and then to add a known amount of VOSO4 to
concentrations between the positive and negative electrolytes, and the V 2+ solution. The addition of VOSO4 will cause oxidation of V 2+
was determined to be 10 mV for this system. Concentrations of the to V 3+ , creating a solution where both V 2+ and V 3+ concentrations
vanadium species are related to the electrode potentials through the are known. The UV-Vis spectra for the pure V 2+ solution and the
Nernst equations, and can be determined as follows: V 2+ /V 3+ mixture will then allow deconvolution of the peaks. In this
 3+  case, a mixture with 0.015M V 2+ and 0.02M V 3+ was created. The
RT [V ]
E neg = E neg
o
+ ln [13] pure V 2+ spectrum was then subtracted from the mixture spectrum,
nF [V 2+ ] giving the unique V 3+ spectrum (see Figure 4). This spectrum agrees
  qualitatively with reported spectra.7
RT [V O2+ ][H + ]2 The molar absorptivity was also determined for the V 2+ ions in
E pos = E pos +
o
ln [14]
nF [V O 2+ ] 4M H2 SO4 . This was accomplished by using the pure 0.1M V 2+ so-
lution generated through the “regen” cell, and diluting it to several
[V 3+ ] = [V 2+ ]o − [V 2+ ] [15] different concentrations. Figure 5 shows the UV-Vis spectra for V 2+
in 4M H2 SO4 , as well as the absorbance vs. concentration for several
dilutions. The intensity at 800 nm was selected to determine the ab-
[V O2+ ] = [V O2+ ]o − [V O 2+ ] [16] sorptivity coefficient of V 2+ because the peaks at 283, 373 and 567 nm
overlap with peaks for V 3+ . As can be seen from Figure 5b, the inten-
3+ o
where [V ] and [V O2+ ]o
represent the initial concentrations at 100% sity at 800 nm shows good linearity, and the absorptivity coefficient
SoC, which were assumed to be 0.69M. By substituting equations 15 was determined to be 2.42 L mol−1 cm−1 .
and 16 into 13 and 14, the following relationships can be achieved:
[V 2+ ]
o V O2+ spectrum.— The UV-Vis response for the V O2+ species is
[V 2+ ] =   [17] predominantly in the UV-region, with very little absorbance in the
E −E o n F
ex p ( neg RTneg ) +1

[V O2+ ]
o
[V O 2+ ] =   [18]
( E pos −E opos )n F
ex p RT
+1
[H + ]2

Results
VOSO4 spectrum.— The spectrum for 0.1M VOSO4 in 4M H2 SO4
is shown in Figure 3a, with peaks around 760 nm and 275 nm
clearly evident. The peak at 275 nm was too intense for Beer’s
law dependency, therefore the peak at 760 nm was used to deter-
mine the molar absorptivity coefficient. Figure 3b shows the relation-
ship between peak intensity and concentration, resulting in a slope of
17.17 L mol−1 cm−1 , which was used as the molar absorptivity co-
efficient for V O 2+ . Once the molar absorption coefficient was deter- Figure 4. Spectra for 0.015M V 2+ and 0.02M V 3+ .
 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015) A611

Figure 5. (a) Spectra for 0.1M, 0.06M and 0.02M V 2+ in 4M H2 SO4 . (b) Absorbance (@ 800 nm) vs. concentration for V 2+ in 4M H2 SO4 .

visible spectrum (see Figure 6). All vanadium ions studied in this
system exhibited absorbance below 300 nm, however V O2+ had a
much higher absorbance than the other vanadium ions. Due to the very
high absorbance of V O2+ , concentrations below 1 mM are required
for reliable results. At this point in time, V O2+ concentrations were
not determined through UV-Vis. Future efforts will be devoted to
developing the molar absorptivity coefficient for V O2+ .
Some reports have indicated that formation of dimers between
V O 2+ and V O2+ at or near 50% SOC will influence the applicability
of UV-Vis for reliable concentration determination.3,8 The dimer effect
was not observed in the current study, probably due to the lower con-
centrations employed during UV-Vis measurements. The formation
of dimers was observed in solutions with vanadium concentrations
greater than 0.24 mol/L vanadium, while the concentrations for UV-
Vis experiments in this study were 0.1M. The higher dilution during
UV-Vis may have prevented the formation of dimers within the UV- Figure 7. UV-Vis spectra after first step in charging.
Vis sample.

Flow cell testing.— The flow battery was assembled and reservoirs mol/L V 3+ . This is in close agreement to the predicted 0.06 mol/L
were filled with 0.69M VOSO4 , as described in the experimental of remaining V O 2+ that should have resulted from the imbalanced
section. For the purpose of demonstrating UV-Vis to detect out-of volumes.
balance cells, 55 mL of solution was added to the negative electrolyte After the first step in charging, the positive electrolyte was at a
reservoir, while 50 mL of solution was added to the positive electrolyte 100% SoC, while the negative electrolyte was near 0%. To com-
reservoir. In this way, the positive electrolyte will be fully charged, pletely charge the cell, the negative electrolyte solution was pumped
while the negative electrolyte will have residual starting solution. through the “regen” cell’s negative electrode, which was maintained at
After 20 minutes of charging the cell at 1.55 V, the current density –0.6 V vs. hydrogen. The “regen” cell continued operating for nearly
dropped below 6 mA/cm2 , indicating a high state of charge. The UV- 90 minutes, with periodic pauses for UV-Vis sampling (0, 3, 25, 47, 65
Vis spectra of the positive electrolyte indicated complete oxidation of and 86 minutes), as shown in Figure 8. The concentration of V 2+ at the
V O 2+ to V O2+ , as the peak at 760 nm was undetectable (see Figure 7). end of “regen” cell operation was determined to be 0.71 mol/L, with
The negative electrolyte UV-Vis response shows presence of V 3+ , but an additional 0.04 mol/L V 3+ . This result indicates that the “regen”
residual absorbance at 800 nm indicates the presence of V O 2+ , due to cell could have been operated for a longer period of time to achieve a
the initial volume imbalance. The UV-Vis spectrum was modeled as a higher negative electrolyte state of charge.
mixture of V 3+ /V O 2+ , to determine the final V O 2+ concentration in After completely charging the negative electrolyte through the
the negative electrolyte. In this case, the modeled V 3+ /V O 2+ mixture “regen” cell, the flow cell was re-attached to the stand, and the UV-
gave a very good fit, and resulted in about 0.04 mol/L V O 2+ and 0.65 Vis spectra of the fully-charged electrolytes were obtained. The open

Figure 6. Spectra for several dilutions of V O2+ in 4M H2 SO4 . Figure 8. UV-Vis spectra of negative electrolyte after regen cell application.
A612 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015)

Figure 9. Concentration of (a) V 2+ and (b) V 3+ in the negative electrolyte during discharge, as determined using different methods.

circuit voltage before and after applying the “regen” cell to the negative
electrolyte was 1.06 V and 1.64 V, respectively. The increase in the
cell voltage demonstrates the utility of the “regen” cell to bring the
entire system to a higher state of charge by selectively reducing the
negative electrolyte. The cell was then discharged in four steps of
about 530 coulombs each. After each discharge step, the UV-Vis
spectra were obtained and the concentrations of V 2+ , V 3+ , and V O 2+
were determined.
Figure 9 illustrates the concentrations of V 2+ , and V 3+ in the
negative electrolyte determined using the UV-Vis, Coulombic and
Nernst methods, as described in the experimental section. As can be
seen, there exist significant differences between each method. The
Coulombic method relies on the assumption that no side reactions oc-
cur due to crossover. Thus, this method likely over-estimates the actual
V 2+ concentration and under-estimates the V 3+ concentration in the
negative electrolyte. Additionally, the negative electrolyte volume de- Figure 11. UV-Vis spectra of discharged positive and negative electrolytes.
creased slightly during “regen” cell operation, due to residual solution
(<2 mL) being retained within the “regen” cell. In these tests, accu-
rate measurement of the electrolyte volume was not possible. How- positive electrode. Since this result is obtained using the potential at
ever, real-time volume measurements may improve the accuracy of the negative electrode, any error from the negative electrode would be
the Coulombic method. propagated to the positive electrode. Thus, in the case of the positive
The Nernst method provided values of concentration that showed electrode, the Nernst method likely contains error and the concen-
deviation from UV-Vis that was even greater than the Coulombic trations obtained in this manner are likely overestimated. Utilizing
method. This approach provides a value of the concentration at the a reference electrode on the positive electrode would eliminate the
electrode surface, which may not be indicative of the bulk. Due to influence of the negative electrode potential.
the porous nature of the carbon paper electrodes, some charged elec- The UV-Vis concentrations provided the highest values of any of
trolyte could have been retained within the electrode, which could the methods employed here. The final concentrations provided by
lead to a higher than expected voltage. Notwithstanding the errors in UV-Vis appear in line with the fact that the negative electrolyte was
determining the concentration, monitoring the potential of the elec- limiting during the discharge. This is evidenced by the significant
trodes during flow battery operation is very beneficial in understanding amount of V O2+ remaining after discharge, as indicated by the strong
reaction mechanisms. absorbance below 400 nm (see Figure 11). In contrast, the UV-Vis
The concentration of V O 2+ in the positive electrolyte is shown spectrum of the negative electrolyte after discharge shows very little
in Figure 10. Once again, the Coulombic method resulted in under- absorbance at 800 nm, indicative of almost no V 2+ remaining. The
estimating the V O 2+ concentration, although the effect is not as sig- fact that the negative electrolyte became capacity-limiting is likely
nificant as was observed for the negative electrolyte. Additionally, the due to the loss of volume during “regen”-cell operation. The periodic
Nernst method appears to agree closely with the UV-Vis method at the removal of samples for UV-Vis analysis as well as volume retained
within the “regen”-cell combined to reduce the total volume of the
anode by about 3–4 mL, representing nearly 10% of the total reactant
volume. Another factor that could cause the negative electrode to
be limiting is the oxidation of V 2+ by oxygen. Since the reservoirs
were purged with nitrogen throughout the experiments, it is expected
that very little oxygen would be introduced to the reservoir. Oxygen
may be produced at the positive electrode during charging, but this
would not have impacted the negative electrolyte during discharge.
Thus it is not expected that oxygen would have a large impact on the
charge imbalance between the positive and negative electrolytes, and
the limiting capacity is due to negative electrolyte volumetric losses.

Conclusions
Molar absorptivity coefficients are presented for V O 2+ and V 2+
in 4M H2 SO4 . Using a “regen”-cell, a solution of V 2+ with known
Figure 10. Concentration of V O 2+ in the positive electrolyte during dis- concentration was generated, allowing the identification of peaks for
charge, as determined using different methods. V 2+ in the UV-Vis spectrum and subsequent determination of a molar
 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015) A613

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