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New All-Vanadium Redox Flow Cell

M. Skyllas-Kazacos,* M. Rychcik, R. G. Robins, and A. G. Fane
School of Chemical Engineering and Industrial Chemistry, University of New South Wales, Kensington,
New South Wales 2033, Australia

M. A. Green
School of Electrical Engineering and Computer Sciences, University of New South Wales, Kensington,
New South Wales 2033, Australia
Photovoltaic arrays and wind turbine
power generators have already demonstrated
their technical suitability, particularly in
remote area applications.
The more widespread
use of such systems, however, is dependent
upon the development of an inexpensive and
reliable energy storage system.
One such
system is the "redox battery" (i). Of the
number of proposed redox batteries, the NASA
Fe/Cr cell has received the most attention
(2,3).

A laboratory-scale cell was designed

and constructed to test the performance of
the V(II)/V(III) and V(IV)/V(V) half-cells in
an all-vanadium redox battery.
Graphite
plates were used as electrodes and the membrane was a sulphonated polyethylene anionselective material.
The negative and positive
half-cell electrolytes consisted of 0.i M V
(III) and 0.i M V(IV) in 2 M H2SO~ respectively. A typical charge-discharge curve is
shown in Figure i.

Although significant advancements have

been achieved in the development of the Fe/Cr
redox flow cell by NASA and other groups (4,5),
two major problems can still be identified,
namely the poor reversibility of the chromium
half-cell and the difficulty in developing an
efficient ion selective membrane.
Both electrocatalysts and higher operating temperatures
have led to improvements in the reversibility
of the chromium half-cell.
The shift to
higher temperatures, however, has dramatically
reduced the selectivity of the membrane, this
leading to studies with a mixed reactant redox
cell (6).

The cell was charged at a current

density of 3 mA/cm2and the voltage varied from
2 . 1 V to 2.4 V for full charge.
Minor
oxygen and hydrogen evolution could be observed on the electrodes when the cell was almost
fully charged.
The average charging efficiency was over 90%. The stability of the open
circuit cell voltage after full charging, was
tested over 72 hours and the potential remained constant at 1.3 V 0.05 V.
At a discharge current density of 3 mA/
cm~ the current efficiency was over 90%, up to
a state-of-discharge of 70%. It should be
emphasized, however, that the cell design is
far from optimum, and high efficiences at over
70% state-of-discharge should be possible with
improved design and electrolyte pumping.

The use of a single-metal system for

both halves of the cell has been proposed (7)
to overcome the problem of cross-contamination
as well as any limitations resulting from the
use of pre-mixed solutions (6). In two recent
publications (8,9) we discussed the concept of
an all-vanadium redox flow cell. Results from
an electrochemical study of the various
vanadium redox couples in acidic solutions,
indicated that the V(II)/V(III) and V(IV)/
V(V) couples possessed many of the requirements for redox flow cell applications.
Sulphuric acid solutions of VCI3 , VOSO4 and
V205 are stable, although V(II) is readily
oxidized in the presence of air. This would
not be a problem, however, if the cell is
deaerated and air-tight.

Stability tests on the reduced and

oxidized electrolytes over the temperature
range -5~ to 60~
showed no accelerated
decomposition at high temperatures, nor
crystallization at the lower temperatures.
A
slow deterioration of the positive electrode
and the membrane was, however, observed after
prolonged usage.
Thus, although the graphite
plates showed acceptable reaction rates for
the vanadium species, they were not resistant
in the oxidizing solution during the charging
cycle. After several charge-discharge cycles,
the surface of the graphite appeared "etched"
and a fine dispersion of carbon particles was
observed in the positive 89
electrolyte.
The negative electrode remained unchanged
after several experiments.

*Electrochemical Society Active Member

Key words: redox cell, vanadium.

1057
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1058

J. Electrochem. Soc.: A C C E L E R A T E D B R I E F COMMUNICATION

The sulphonated polyethylene membrane

material used in the test cell alsodeteriorated
with time. Although it performed well, maintaining a constant open-circuit cell voltage
for over 70 hours, after seVeral experiments
it changed its colour and consistency.
It
became more rigid and harder, and its electrical resistivity increased.
The above results from charge-discharge
experiments on the laboratory scale test cell,
indicate that the concept of an all-vanadium
redox cell shows great promise for the
development of a new, highly efficient and
reliable energy storage system. Further
testing of commercially available membrane and
electrode materials is currently underway, so
that the optimum materials can be selected and
further evaluated in a larger-scale redox flow
cell.

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ACKNOWLEDGEMENT S
Support for this project was provided
under the National Energy Research Development
and Demonstration Program which is administered
by the Australian Commonwealth Department of
Resources and Energy.

May 1986

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a - Change of voltage during chargFig. i.

ing: b - Stability of open circuit voltage
of charged cell.

REFERENCES
i. L.H. Thaller, NASA TMX-71540, National
Aeronautics and Space Administration, U.S.
Dept. of Energy, 1974, U.S. Patent 3996064.
2. Redox Flow Cell Development and Demonstration Project NASA, TM-79067, National Aeronautics and Space Administration, U.S. Dept. of
Energy, 1979.
3. N.H. Hagedorn and L.H. Thaller, NASA TM81464, National Aeronautics and Space Administration, U.S. Dept. of Energy, 1980.
4. K. Nozaki and T. Ozawa, Prog. Batteries Sol.
Cells, 5, 327 (1984).
5. K. Nozaki, H. Kaneko, A. Negishi and T.
Ozawa, Proc. Electrochem. Soc. 84, 143 (1984).
6. N.H. Hagedorn, Ext. Abstr. No. 19, Fall
Meeting, Electrochem. Soc., 1983, p 30.
7. Y-W. D. Chen, K.S.V. Santhanam and A.G.
Bard, J. Electrochem. Soc., 128, 1460 (1981).
8. E. Sum and M. Skyllas-Kazacos, J. Power
Sources, 15, 179 (1985).
9. E. Sum, M. Rychcik and M. Skyllas-Kazacos,
J. Power Sources, 16, 85 (1985).
Manuscript

received

Jan.

29,

1986.

The U n i v e r s i t y
of N e w S o u t h W a l e s
a s s i s t e d in m e e t i n g the p u b l i c a t i o n
c o s t s of t h i s a r t i c l e .

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