Abstract
A number of redox systems have been investigated in this work with the aim of identifying electrolytes suitable for testing redox flow battery cell
designs. The criteria for the selection of suitable systems were fast electrochemical kinetics and minimal cross-contamination of active electrolytes.
Possible electrolyte systems were initially selected based on cyclic voltammetry data. Selected systems were then compared by charge/discharge
experiments using a simple H-type cell. The all-vanadium electrolyte system has been developed as a commercial system and was used as the starting
point in this study. The performance of the all-vanadium system was significantly better than an all-chromium system which has recently been
reported. Some metalorganic and organic redox systems have been reported as possible systems for redox flow batteries, with cyclic voltammetry
data suggesting that they could offer near reversible kinetics. However, Ru(acac)3 in acetonitrile could only be charged efficiently to 9.5% of
theoretical charge, after which irreversible side reactions occurred and [Fe(bpy)3 ](ClO4 )2 in acetonitrile was found to exhibit poor charge/discharge
performance.
2006 Elsevier Ltd. All rights reserved.
Keywords: Redox flow battery; Vanadium; Chromium; Ru(acac)3 ; [Fe(bpy)3 ](ClO4 )2
1. Introduction
Redox flow batteries are electrochemical energy storage
devices that utilise the oxidation and reduction of two soluble
redox couples for charging and discharging. They differ from
conventional batteries in that the energy-bearing chemicals are
not stored within at the electrode surface, but in separate liquid
reservoirs and pumped to the power converting device for either
charging or discharging [1,2]. Due to the use of two soluble redox
couples, solid-state reactions with their accompanying morphological changes at the electrodes are absent [3]. Thus, there are
no fundamental cycle life limitations associated with these processes such as shedding or shape changes, which usually occur
in conventional storage batteries.
Despite these advantages, the redox flow battery has not been
widely exploited to date. One disadvantage of the systems developed to date is the use of two separate redox species in the halfcells, leading to the potential for cross-contamination of active
Corresponding author. Tel.: +44 161 306 8849; fax: +44 161 306 4399.
E-mail address: edward.roberts@manchester.ac.uk (E.P.L. Roberts).
0013-4686/$ see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.08.052
2190
In this study, the following series of redox systems in acetonitrile electrolyte were selected which apparently offered fast
electrode kinetics (based on literature data, e.g. [19] and [20])
and the potential to operate with a single electrolyte using a
species with three oxidation states.
(i) Ruthenium organic complexes
A number of ruthenium organic complexes which can
be both oxidized and reduced electrochemically have been
reported in the literature, and some of these have been
suggested as suitable candidates for a redox flow battery
[21]. Tris(2,2 -bipyridine) ruthenium (II) tetrafluoroborate
[Ru(bpy)3 (BF4 )2 ] has exhibited fast kinetics [19]. In addition, this system offers the possibility of cell voltages of up
to 2.6 V, much higher than is possible in aqueous battery
systems [19]. Ruthenium acetylacetonate [Ru(acac)3 ] has
also been reported as offering fast oxidation and reduction
kinetics [22] and a possible cell voltage of around 1.75 V.
(ii) Tris(2,2 -bipyridine) iron(II) perchlorate
This species can be oxidized and reduced [19] and offers
a possible cell potential of 2.4 V. This compound is available commercially and is significantly cheaper than the
ruthenium complexes.
(iii) Rubrene
Rubrene, a neutral organic species, can be oxidized and
reduced electrochemically [23]. The redox potentials of
these reactions offer a possible cell potential of around
2.3 V. Again this compound is available commercially,
although it is significantly more expensive than the other
redox species.
These systems are compared to the all vanadium redox flow
battery system, which has previously been investigated in detail
([3,711]) and has been commercialized in recent years [17].
In this system, vanadium in four different oxidation states is
used: V(II)/V(III) at the negative electrode and V(IV)/V(V) at
the positive electrode.
Each system was first tested by cyclic voltammetry in order
to evaluate the electrode kinetics. While cyclic voltammetry can
2.1. Electrolytes
Vanadium electrolytes were prepared from vanadium (IV)
sulphate (>99.99% purity, Aldrich), with the V(II)/V(III) couple
generated by electro-reduction. Sulphuric acid was used as the
background electrolyte.
Reagent grade tris(2,2 -bipyridine) ruthenium (II) chloride
is available from Aldrich. Since oxidation of the chloride salt
was known to be irreversible [24], the tetrafluouroborate salt
[Ru(bpy)3 (BF4 )2 ] was prepared by addition of NaBF4 in acetonitrile and precipitation of NaCl. Ruthenium acetylacetonate
[Ru(acac)3 , 97% purity, Aldrich], tris(2,2 -bipyridine) iron(II)
perchlorate (reagent grade, GFS) and rubrene (reagent grade,
Aldrich) were used for the preparation of the respective electrolytes (Caution: perchlorate salts are potentially explosive and
should be handled with appropriate care). Tetraethyl-ammonium
tetrafluoroborate and tetraethyl-ammonium perchlorate were
used as the background electrolyte.
To remove dissolved oxygen, electrolytes were sparged for at
least 10 min with oxygen-free dry argon (aqueous electrolytes)
or nitrogen (organic electrolytes). Water was removed from the
organic electrolytes using zeolite 4A (Merck) to a moisture level
of below 0.005 wt%.
2.2. Cyclic voltammetry
A graphite rod (Goodfellow) of surface area 0.06 cm2 was
used as the working electrode for cyclic voltammogram experiments with the vanadium battery electrolytes. A glassy-carbon
electrode (I.J. Cambria Scientific) of surface area 0.07 cm2 was
used for cyclic voltammetry in organic media. The electrode
was polished with alumina washed with de-ionised water and
acetone following the procedure described in literature [21].
The reference electrode used in aqueous solutions was the
saturated calomel electrode along with a salt bridge. Organic
media required the use of a silver wire quasi-reference electrode (AgQRE). A platinum counter electrode was used in each
case.
Cyclic voltammetry was conducted using a standard threeelectrode cell, with a Autolab/PGSTAT30 potentiostat for potential control. All solutions were de-aerated prior to experiments.
The solution headspace was purged with inert gas for the duration of experiments.
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Table 1
The characteristics of the redox species studied in acetonitrile
Chemical
Solubility in solvent
Ru(acac)3
Ru(bpy)3 (BF4 )2
[Fe(bpy)3 ](ClO4 )2
Rubrene
1.77
2.62
2.41
2.33
High
Poor
Moderate
Poor
Reversible
Quasi-reversible
Reversible
Reversible
12 [i]
21 [i]
2 [ii]
37 [i]
Costs were obtained from SigmaAldrich [i] and GFS Chemicals [ii].
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Positive electrode:
[Ru(acac)3 ] [Ru(acac)3 ]+ + e
Negative electrode:
[Ru(acac)3 ] + e [Ru(acac)3 ]
Fig. 5 shows the charging profile to 8.3% state of charge
(SOC). A rapid rise in potential occurred beyond 7.6% SOC
possibly due to a side reaction at the positive electrode or an
increasing concentration overpotential. Note that the electrode
potentials shown in Fig. 5 (and the subsequent charge/discharge
data in Figs. 610) were measured relative to a silver quasi reference electrode and hence the absolute values of the potentials are
not meaningful. However, the electrode potential data show that
the rapid rise in the cell potential was associated with an increase
in potential at the positive electrode. Fig. 6 shows the discharge
of the charged Ru(acac)3 at a constant current of 0.5 mA. The
variations in the potential were due to the addition of solvent
during the long discharging process (to make-up for solvent
evaporation). With the low currents used, a relatively high energy
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Table 2
A comparison of the key results obtained from the charge/discharge experiments conducted on Ru(acac)3 and [Fe(bpy)3 ](ClO4 )2 in a stirred H-type glass cell
Electrolyte
0.85
1.30
1.50
74
57
6
11.0
12.0
0.6
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