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Vanadium Redox-Flow-Battery Electrolyte


Preparation with Reducing Agents
CONFERENCE PAPER in ECS TRANSACTIONS MAY 2013
DOI: 10.1149/05307.0093ecst

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Vanadium Redox-Flow-Battery Electrolyte Preparation with Reducing Agents


W. N. Li, R. Zaffou, C. Shovlin, M. Perry, and Y. She
United Technologies Research Center (UTRC), East Hartford, CT, 06108, USA
A waste-free method was developed to prepare electrolytes using
reducing agents for vanadium redox flow battery. Via this
approach, both the electrolyte cost and waste can be reduced by
33% which are favored financially and environmentally.
Thermodynamic-model calculations show 100% conversion on
reaction between fully-charged vanadium positive solution (VO2+)
and oxalic acid. The kinetics on the redox reaction is discussed as
well.
Introduction
To meet increasing energy demands, research effort has been devoted to the
development of new and renewable energy resources. A Redox-Flow-Battery (RFB) is
attractive due to its applications in large-scale energy storage [1]. RFB is a type of
rechargeable battery consisting of two tanks of soluble redox reactants, which determine
the system energy storage capacity, and the battery stack, which determines the system
power capacity. Since the Iron/Chromium (Fe/Cr) RFB was initiated by NASA in 1970s,
various redox chemistries have been developed and evaluated, such as
polysulphide/bromine RFB, all-vanadium RFB, and others [2]. Among these RFB
systems, Vanadium Redox Flow Batteries (VRFB) are considered especially attractive,
since the electrochemically active reactants are vanadium species in four different
oxidation states in both electrolyte solutions. As such, the undesired cross-contamination
of negative and positive electrolytes through the cell separator is eliminated, although
reactant crossover still results in coulombic-efficiency losses.
VRFB employs the redox couples of V2+/V3+ as negative electrolyte and VO2+/VO2+
(i.e., V4+/V5+) as positive electrolyte, both dissolved in aqueous-acid solutions, which are
stored in two external tanks. During charge and discharge, the two electrolyte solutions
are pumped from the storage tanks to cells in one or more cell stacks, where the
conversion between chemical energy and electrical energy takes place. The reversible
potentials of the V2+/V3+ couple and V4+/V5+ couple are -0.26 V (RHE) and 1.0 V (RHE),
respectively.
The electrolyte solutions are one of the key components of a VRFB system. Therefore,
research has been devoted to the development of VRFB electrolyte production, including
on a large scale [3]. However, many of the reported preparations have various
disadvantages, which limit scalability and/or have negative cost implications. For
example, in order to lower the electrolyte cost, the use of commodity vanadium
compound of V2O5 as the starting vanadium material to prepare VRFB electrolytes has
attracted much research attention [4]. However, the very low solubility of V2O5 prevents
the direct production of solutions with high vanadium concentrations. Other vanadium
compounds, such as V2O3 and VCl3, have been investigated as initial compounds.

However, their applications are restricted due to cost, low solubility and/or low stability,
especially for large scale systems. Therefore, currently, a common route to make VRFB
electrolytes, especially on a lab-scale, is to dissolve vanadyl sulfate (V4+) in sulfuric-acid
solution because it readily dissovles in aqueous solutions and is an electrolyte solution
with excellent stability. Subsequently, the vanadyl sulfate (V4+) acid solution is charged
to V2+ and V5+ in negative and positive electrolytes, respectively. However, in order to
accommodate a change of two oxidation states in the negative solution (i.e., convert V4+
to V2+), the initial volume of positive electrolyte is twice that required, and the excess
positive electrolyte (33%) must be disposed of as waste. This is obviously not
environmentally or financially desirable.
This paper will discuss approaches to produce VRFB electrolyte solutions with high
energy densities without generating waste, which is accomplished by utilizing reducing
agents at relatively benign conditions.
Experimental
1. Electrolyte preparation
This approach enables starting a VFRB with equal volumes of vanadyl sulfate (V4+) in
aqueous acid for the negative and positive solutions. After an initial charge of the VRFB
to V3+ in the negative electrolyte and V5+ in the positive electrolyte, a reducing agent is
introduced into the positive side to reduce the produced V5+ solution back to V4+, which
provides discharged VRFB electrolytes of V3+ on negative and V4+ in the positive
solutions, respectively. The overall process is depicted in Figure 1. The reducing agent
discussed in this work is-oxalic acid.
2. Thermodynamic model
The thermodynamic model is built up to evaluate the reaction conversion and
equilibrium constant for the redox process of V5+ and oxalic acid using HSC
Chemistry5.0 software (Outotec Research Oyj, Finland).
3. Analysis:
3.1 Chemical analysis
Vanadium concentrations before and after the reduction are determined by titration,
which is also used to calculate the reaction conversion and monitor the kinetics.
3.2 Electrochemical test
Electrochemistry test was carried out on UTRC subscale cell, which are composed of
Nafion 117 membranes between identical carbon electrodes on both sides. The cell active
area was 23 cm2. The electrolyte reservoirs contain 70 mL of electrolyte on each side
under nitrogen purge. Constant current at 87mA.cm-2 was used to charge and discharge
the cell and polarization curves were collected during the tests.

Figure 1. Simple VRFB electrolyte preparation method with no waste stream.

Results and Discussions


The selection of reducing agents for VRFB is dictated by several key requirements
including no introduction of foreign cations, mild redox reaction conditions, high reaction
conversion, and high rate. To meet the requirement of no foreign cations in the system,
only several reducing agents which have lower standard electrode potentials than
VO2+/VO2+ (i.e., V4+/V5+) can be chosen for this system, such as oxalic acid, formic acid,
and sulfur dioxide as shown in Equations 1-4 [5]. However, the other two requirements
further restrict the selection. According to the equation of Gibbs free energy and total
potential as indicated in Equation 5, reducing agents with lower standard electrode
potentials will have a higher tendency for the redox reaction to occur spontaneously.
Therefore, oxalic acid is the most favorable reducing agent in this system.
The standard electrode potentials of VO2+/VO2+ (i.e., V4+/V5+) and oxalic acid are
shown in Equations 1-2. Equation 3 indicates the chemical reaction between them, which
results in the total potential to 1.49V (Equation 6). The Gibbs free energy of the reaction
is around -144kJ at standard conditions (Equation 5) which indicates that oxalic acid can
theoretically convert V5+ solution to V4+. Equations (1), (2), and (6) can be represented
by a full chemical reaction without electric charges in Equation (7). HSC Chemistry5.0
thermodynamic software was used to calculate the equilibrium constant and equilibrium
compositions of the reaction presented by Equation (7). Equilibrium conversion of
(VO2)2SO4 was also calculated. Figure 2 shows the equilibrium constant and the
equilibrium conversion as a function of temperature. The equilibrium constant values
were between 1*1050 and 1*1055 at temperatures between 20 C and 100 C, indicating
that the reaction can be completed thermodynamically. As a result, the equilibrium
conversions were 100% in the temperature range calculated. However, in practice,

100% conversion cannot be obtained at lower temperatures such as room temperature in a


short period of time. For instance, around 6-8 hours is necessary to reach 90-95%
conversion at room temperature, compared to 90-95% in 2 hours at 60 oC. Therefore, a
reasonable amount of heat is preferentially provided to the reaction to trigger the light-off
of the reaction. Once the reaction initiated, no additional heat was needed because the
reaction was exothermic. The use of reducing agents has been discussed by others to
convert vanadium pentaoxide to V4+ (e.g., [4]). However, the reaction kinetics observed
here are significantly better than what one might expect with the two-phase reaction than
what was reported before [4].
VO2+ + 2H+ + eVO2+ + H2O
E0 = +1.00V
+
1/2 CO2 + 2H + 2eH2C2O4
E0 = -0.49V
CO2 + 2H+ + 2eHCOOH (aq)
E0= -0.199V
2+
1/2 SO4 + 2H + e1/2 H2SO3 + 1/2 H2O
E0= 0.172V
Go = -nEoF
2VO2+ + H2C2O4
2VO2+ + 2CO2 + 2H2O E0 = +1.49V
(VO2)2SO4 + H2SO4 + H2C2O4 = 2VOSO4 +2H2O + 2CO2

[1]
[2]
[3]
[4]
[5]
[6]
[7]

100%

Initial amounts for equilirbium


conversion calculation:
(VO2)2SO4: 1 kmole
H2SO4
: 1 kmole
H2C2O4 : 1 kmole

Equilibrium constant

1.0E+54

1.0E+53

90%
80%
70%
60%
50%

1.0E+52

40%
30%

Pressure = 1 atm

1.0E+51

20%

Equlibrium constant
Equilibrium conversion

10%

1.0E+50

Equilibrium conversion

1.0E+55

0%
0

20

40

60

80

Temperature (C)

100

120

Figure 2. Equilibrium constant and conversion calculation on equation 7. (HSC


Chemistry5.0 software (Outotec Research Oyj, Finland))
Also electrochemical performance of a moderate power density VFRB cell, both with
and without oxalic acid, was investigated in the lab to determine if this new preparation

process had any impact on cell performance. The baseline electrochemical performance
of the cell was done in the conventional procedure below:
1) Double volume of V4+ sulfuric acid solution was used for positive electrolyte as
compared to that of negative electrolyte.
2) The electrolytes were fully charged to obtain V2+ and V5+ on negative and positive
solutions, respectively.
3) Half volume of the positive charged V5+electrolyte was decanted as waste.
4) The remaining half of positive electrolyte and the negative electrolytes are now
equal volumes, which were then used for the cell polarization measurements.
Another cell experiment was accomplished by utilizing the addition of reducing agent
of oxalic acid to eliminate the waste, as follows:
1) Equal volumes of V4+ solutions were employed as the initial electrolytes;
2) V4+ solutions were charged until fully-charged yellow V5+ was obtained in the
positive side.
3) Oxalic acid was added into the V5+ electrolyte at either 60 oC for 2 hours or at room
temperature for overnight.
4) When 85-95% of conversion of V5+ to V4+ was achieved, the positive electrolyte was
poured back to the electrolyte reservoir.
5) Polarization curve was performed.
During the reaction time between V5+ and oxalic acid, V2+ solution in negative side
was stored for the subsequent use by protection of N2 blanket above solution. The color
change of the solution can be used as an indicator to determine if the reaction is
completed. Usually, the solution will be in dark blue color after the reaction at 60 oC for 2
hours or room temperature for overnight, which indicates 90-95% V5+ was reduced to V4+.
A much longer time, such as a week at room temperature, is required to obtain bright blue
V4+ solution.
Figure 3 shows that the electrochemical performance of cell is not affected by the
electrolyte-production method described herein (open-black line), relative to the results
obtained with the more conventional, waste-generating method (filled-grey line).

Figure 3. Polarization curves of VRFB using electrolytes without H2C2O4


(baseline) and with H2C2O4 addition.

Conclusions
A method to prepare waste-free VRFB electrolytes was developed via an
introduction of a reducing agent in the fully-charged positive electrolyte. Thermodynamic
modeling predicts the reaction conversion can be 100% from room temperature to 100 oC,
which has been confirmed with experimental data given sufficient reaction periods. The
electrochemical tests showed the cell performance was not affected by the oxalic acid
preparation method, which therefore offers a more benign approach for VRFB
researchers and developers to make electrolyte solutions for both lab-scale experiment
and larger scale systems.

Acknowledgements
The authors would like to thank their flow-battery project colleagues at UTRC. The
work presented herein was funded, in part, by the Advanced Research Projects Agency Energy (ARPA-E), U.S. Department of Energy (DOE) under Award Number DEAR0000149.
The information, data, or work presented herein was funded in part by an agency of
the United States Government. Neither the United States Government nor any agency
thereof, nor any of their employees, makes any warranty, express or implied, or assumes
any legal liability or responsibility for the accuracy, completeness, or usefulness of any
information, apparatus, product, or process disclosed, or represents that its use would not
infringe privately owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or otherwise does not
necessarily constitute or imply its endorsement, recommendation, or favoring by the
United States Government or any agency thereof. The views and opinions of authors
expressed herein do not necessarily state or reflect those of the United States Government
or any agency thereof.

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