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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.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
100%
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
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).
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.
References
1. Z. Yang, J. Zhang, M.C.W. Kintner-Meyer, X. Lu, D. Choi, J.P. Lemmon, and J. Liu,
Electrochemical Energy Storage for Green Grid, Chem. Reviews, 111, 3577-3613
(2011).
2. A. Z. Weber, M. M. Mench, J. P. Meyers, P. N. Ross, J. T. Gostick, and Q. Liu,
Redox flow batteries: a review J. Appl Electrochem., 41, 1137-1164 (2011).
3. G. Kear, A. A. Shah, and F. C. Walsh, Development of the all vanadium redox flow
battery for energy storage: A review of technological, financial and policy aspects, Int.
J. Energy Res., 36, 11051120 (2012).
4. M. Skyllas-Kazacos and M. Kazacos. Vanadium compound dissolution process WO
89 / 05363 (1989) (No issued patent found).
5. D. R. Lide, CRC Handbook of Chemistry and Physics, 71 Ed. P 8-16, CRC Press, Inc.
(1990)