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: oa@electrochem.org. [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
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
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,
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
battery (VFB).
The vanadium flow battery is composed of a proton exchange
membrane (PEM), carbon-based electrodes, and two solutions con-
taining vanadium ions in acid. The energy is stored in the oxidation
states of the vanadium ions, i.e. V 2+ , V 3+ V O 2+ , and V O2+ . In the
charged state, the negative electrolyte solution consists of 100% V 2+
ions, while the positive electrolyte solution consists of 100% V O2+
ions. Discharge, and subsequent release of energy, is realized through
the following reactions:
Negative electrode : V 2+ → V 3+ + e−
Positive electrode : V O2+ + 2H + + e− → V O 2+ + H2 O
Overall reaction : V 2+ +V O2+ +2H + → V 3+ +V O 2+ +H2 O
During ideal operation, the following schematic illustrates the oxida-
tion states of the two reservoirs at 100% charge (Figure 1a) and 0%
charge (Figure 1b).
Due to the wide variety of oxidation states available, and the facility
with which they can be achieved, additional reactions are also possible
within the typical operating voltage of the cell, as indicated below:
Charging intermediate V O 2+ + 2H + + e− → V 3+ + H2 O
Crossover V O2+ + V 3+ → 2V O 2+ [7]
Side reaction 2H + + 2e− → H2 [8]
Side reaction 2H2 O → 4H + + O2 + 4e− [9]
1
Oxidation by air V 2+ + O2 + 2H + → V 3+ + H2 O [10]
2
Reaction 4 will occur whenever V O 2+ is present at the negative elec-
trode during charging of the flow battery. Crossover reactions 5–7
are a result of the ability of vanadium to migrate through the mem-
brane, either through concentration differences or through the electric
field. Vanadium species may migrate from the positive electrolyte
to the negative electrolyte, or vice versa. Side reaction 8 will occur
at very low negative electrode potentials, while side reaction 9 may
generate oxygen at high positive electrode potentials. Oxidation of
[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.
[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
[3] V O 2+ requires two electrons transferred per mole of vanadium. Thus,
when starting with V O 2+ in both reservoirs, the volume in the positive
electrolyte must be at least twice that of the negative electrolyte,
assuming 100% charge efficiency. Hydrogen evolution (reaction 8) at
the negative electrode will require a positive electrolyte volume that
is greater than double that of the negative electrolyte volume.
Due to the several different mechanisms for oxidation and reduc-
tion of the various vanadium species, measuring the state of charge
[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: pbrooker@fsec.ucf.edu Figure 1. Flow battery at (a) 100% SoC and (b) 0% SoC.

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 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015)
(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.
A concept that has received significant attention is the UV-Vis re-
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
obtaining the spectrum, or to employ a short-pathlength cell as in
Ref. 3. In either case, online SoC-monitoring using UV-Vis is chal-
lenging. However, UV-Vis is still a valuable tool that could be used
for ex-situ studies such as vanadium crossover and charge imbalance
experiments.
Most of the focus in the literature has been on the response of the
V O 2+ species. This paper demonstrates the response of V 2+ and V 3+
solutions, and identifies unique peaks for each ion. Additionally, an
in-operando electrochemical method of monitoring state of charge is
compared to the UV-Vis response.
Experimental
UV-Vis measurements were obtained with a Shimadzu UV-
2401PC spectrometer, using 1 cm plastic cuvettes. Flow rates of the
electrolytes and voltage control of the cells were accomplished using
an 857 redox flow-cell test system (Scribner Assoc., Inc, Southern
Pines NC), and electrolyte flow rates were constant at 100 mL/min.
Cells were assembled using 25 cm2 fuel cell hardware (Fuel Cell Tech-
nologies, Albuquerque NM) that was modified for liquid-phase flow.
Teflon gaskets provided sealing and compression of approximately
23% was applied on the carbon paper (SGL 10 AA, Ion-Power) for
all electrodes. Electrolyte reservoir headspaces were purged continu-
ously with nitrogen to limit V 2+ oxidation by air, and all experiments
were conducted at room temperature.
A solution of 0.1M VOSO4 (VWR) in 4M H2 SO4 (FisherSci) was
used as the starting solution for all UV-Vis experiments, and all dilu-
tions were prepared with 4M H2 SO4 . To reduce V 2+ oxidation by air
during UV-Vis measurements, the cuvettes were purged with N2 prior
to adding the sample, and were then sealed with parafilm to exclude
air. Measurements were also taken as quickly as possible. The V O 2+
spectrum was obtained from the initial 0.1M VOSO4 starting solu-
tion and several concentrations were prepared through dilution with
4M H2 SO4 . To obtain solutions with vanadium in different oxidation
states, different approaches were required.
To obtain V 2+ , a “regen” cell was used, an approach that was
similar to one employed by NASA during development of the Fe/Cr
redox cell.6 In NASA’s Fe/Cr redox system, a separate “rebalance”
cell was employed to reduce the state of charge at the positive
Fe3+ electrolyte, thereby bringing this electrolyte into balance with
the negative Cr2+ electrolyte. In the current study, the “regen” cell
was assembled with a 7-mil thick Nafion membrane (N117, Ion-
Power), carbon paper electrode as the negative electrode, and an in-
house platinum-carbon (Pt/C) electrode as the positive electrode (see
Figure 2a). The Pt/C electrode was fabricated by first homogeniz-
ing a mixture of 46% platinum on carbon (TKK), methanol (Sigma
Aldrich), 5% 1100 EW Nafion dispersion (Ion-Power) and water. This
catalyst ink was then sprayed onto a Teflon film, dried, and decal trans-
ferred to the N117 membrane. The 0.1M VOSO4 solution was pumped
past the negative electrode, while the Pt/C electrode was exposed to
pure hydrogen. With hydrogen at the Pt/C electrode, the positive
electrode served as a pseudo-reference electrode, with an assumed
potential of 0 V vs. SHE. The negative electrode of the “regen” cell
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A609
Figure 2. (a) Schematic of “regen” cell. (b) Schematic of in-situ Pt-H2 refer-
ence electrode.
was held at –0.6 V vs. SHE, causing the V O 2+ to be reduced to V 2+ .
The reduction of the solution was monitored by UV-Vis, and complete
reduction of V O 2+ was defined as the point when subsequent UV-Vis
spectra showed no change over a 30 minute interval. Once the solution
was completely reduced to V 2+ , samples were obtained and diluted
to various concentrations using 4M H2 SO4 .
To obtain solutions with V O2+ , a flow cell was used with carbon
paper as both positive and negative electrodes, separated by an NR112
membrane (Ion-power). A solution of 0.1M VOSO4 was pumped
through the positive electrode, while a solution with a mixture of
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 ,
at which point the positive electrolyte solution was fully oxidized
to V O2+ . Several concentrations of the fully-oxidized solution were
prepared by diluting with 4M H2 SO4 and were analyzed with UV-Vis.
A flow battery experiment was also conducted, using an NR112
membrane (Ion-power) with SGL 10AA carbon paper (Ion-power) at
both positive and negative electrodes. The starting solution was 0.69M
VOSO4 in 4M H2 SO4 , and was the same for both positive and negative
electrolytes. The initial positive electrolyte volume was 50 mL, while
the negative electrolyte volume was 55 mL. Initial charging required
a two-step process. First, the positive electrolyte was fully oxidized
by pumping both solutions through the cell and holding the positive
electrode at 1.55 V vs. the negative electrode, until current dropped
below 4 mA/cm2 . At this point, the negative electrolyte contained a
mixture of V 3+ and V O 2+ . The second step in initial charging was
to achieve 100% V 2+ in the negative electrolyte. To accomplish this,
the “regen” cell was employed by pumping the negative electrolyte
through the negative electrode of the “regen” cell, and holding the
voltage at –0.6 V vs. the Pt/C-H2 positive electrode.
After completely charging the negative electrolyte, the flow cell
was re-attached to the test stand, and discharged at 1 A, collecting
UV-Vis samples every 9 minutes. Electrode potentials of the flow
cell were obtained through the use of an in-situ hydrogen/platinum
reference electrode (see Figure 2b). A platinum/carbon electrode with
Nafion binder was prepared on a Teflon sheet, then decal-transferred
to a region of the NR112 membrane that was outside the active area.
Channels were drilled into the negative flow field graphite plate to
allow hydrogen to flow past the Pt/C electrode, and a wire was used
to sense the voltage between this electrode and the negative current
collector. Teflon gaskets provided electrical insulation and a gastight
seal between the graphite flow field and the Pt/C electrode. It was
assumed that the potential at the Pt/C electrode was 0 V vs. the
standard hydrogen electrode.
The UV-Vis technique to determine concentrations was compared
to two other methods: the Coulombic method, and the Nernst Method.
In the Coulombic method, the concentrations are expected to change
linearly with the amount of charge transferred between electrolytes.
The change in concentrations can be determined by integrating the
current-time curve to determine the total charge transferred, and then
using Faraday’s law to determine the number of moles reacted. Starting
with an initial concentration of 0.69M V 2+ and 0.69M V O2+ , the
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+ .

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

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 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-
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-
ever, real-time volume measurements may improve the accuracy of
the Coulombic method.
The Nernst method provided values of concentration that showed
deviation from UV-Vis that was even greater than the Coulombic
method. This approach provides a value of the concentration at the
electrode surface, which may not be indicative of the bulk. Due to
the porous nature of the carbon paper electrodes, some charged elec-
trolyte could have been retained within the electrode, which could
lead to a higher than expected voltage. Notwithstanding the errors in
determining the concentration, monitoring the potential of the elec-
trodes during flow battery operation is very beneficial in understanding
reaction mechanisms.
The concentration of V O 2+ in the positive electrolyte is shown
in Figure 10. Once again, the Coulombic method resulted in under-
estimating the V O 2+ concentration, although the effect is not as sig-
nificant as was observed for the negative electrolyte. Additionally, the
Nernst method appears to agree closely with the UV-Vis method at the
Figure 10. Concentration of V O 2+ in the positive electrolyte during dis-
charge, as determined using different methods.
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Figure 11. UV-Vis spectra of discharged positive and negative electrolytes.
positive electrode. Since this result is obtained using the potential at
the negative electrode, any error from the negative electrode would be
propagated to the positive electrode. Thus, in the case of the positive
electrode, the Nernst method likely contains error and the concen-
trations obtained in this manner are likely overestimated. Utilizing
a reference electrode on the positive electrode would eliminate the
influence of the negative electrode potential.
The UV-Vis concentrations provided the highest values of any of
the methods employed here. The final concentrations provided by
UV-Vis appear in line with the fact that the negative electrolyte was
limiting during the discharge. This is evidenced by the significant
amount of V O2+ remaining after discharge, as indicated by the strong
absorbance below 400 nm (see Figure 11). In contrast, the UV-Vis
spectrum of the negative electrolyte after discharge shows very little
absorbance at 800 nm, indicative of almost no V 2+ remaining. The
fact that the negative electrolyte became capacity-limiting is likely
due to the loss of volume during “regen”-cell operation. The periodic
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
concentration was generated, allowing the identification of peaks for
V 2+ in the UV-Vis spectrum and subsequent determination of a molar
 Journal of The Electrochemical Society, 162 (4) A608-A613 (2015) A613

absorptivity coefficient. Furthermore, a “regen”-cell was employed References

to bring the negative electrolyte into charge balance with the posi-
tive electrolyte. This demonstrates a novel technique for ensuring full
charge of both electrolytes in an operating flow battery. The use of
UV-Vis to determine electrolyte concentrations was compared with
Nernst equation and Coulombic methods. The use of an in-situ ref-
erence electrode demonstrated this approach, but it needs to be opti-
mized before adopting this as a technique for online monitoring the
electrolyte state of charge. However, the UV-Vis method provides a
reliable off-line approach to determining vanadium concentrations,
both for the positive and negative electrolytes.
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