Applied Energy 109 (2013) 344351

Contents lists available at SciVerse ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Strategies for enhancing electrochemical activity of carbon-based

electrodes for all-vanadium redox ow batteries
Cristina Flox a,, Marcel Skoumal a, Javier Rubio-Garcia a, Teresa Andreu a, Juan Ramn Morante a,b
a
b

Catalonia Institute for Energy Research (IREC), Jardins de les Dones de Negre 1, 08930 Sant Adri de Bess, Barcelona, Spain
Departament dElectrnica, Facultat de Fsica, Universitat de Barcelona, Mart i Franqus 1-11, 08028 Barcelona, Spain

h i g h l i g h t s
" Improved reactions at the positive electrode in all-vanadium redox ow batteries.
" Graphene-derived and PAN-modied electrodes have been successfully prepared.
" Modication with bimetallic CuPt3 nanocubes yielded the best catalytic behavior.
" N and O-containing groups enhances the vanadium ow battery performance.

a r t i c l e

i n f o

Article history:
Received 1 August 2012
Received in revised form 28 January 2013
Accepted 1 February 2013
Available online 5 March 2013
Keywords:
All-vanadium redox ow battery
Graphene-supported
PAN-functionalized felt
Energy storage
Electrochemical properties

a b s t r a c t
Two strategies for improving the electroactivity towards VO2 =VO
2 redox pair, the limiting process in allvanadium redox ow batteries (VFBs), were presented. CuPt3 nanoparticles supported onto graphene
substrate and nitrogen and oxygen polyacrylonitrile (PAN)-functionalized electrodes materials have been
evaluated. The morphology, composition, electrochemical properties of all electrodes prepared was characterized with eld emission-scanning electrode microscopy, X-ray photoelectron spectroscopy, cyclic
voltammetry, electrochemical impedance spectroscopy and cell chargedischarge test. The presence of
the CuPt3 nanocubes and nitrogen and oxygen functionalities enhance the electrocatalytic activity of
the electrodes materials accelerating the oxygen and electron transfer processes. The battery performance was also evaluated using PAN-functionalized electrodes exhibiting a high of energy efciency of
84% (at current density 20 mA cm2) up to 30th cycle, indicating a promising alternative for improving
the VFB.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Because of the insufcient fossil-fuel-based energy supplies and
the increase of the electricity generated from renewable sources
(e.g. photovoltaic and wind energy), the development of the global
energy storage strategies has become a major issue in order to
compensate the uctuations introduced in the grid by the aforementioned sources [13]. A broad set of different storage technologies has been developed [46]. In this framework, in contrast with
other secondary batteries, redox ow batteries show great promise
for economical storage of electrical energy [710] due to several
attractive features including long cycle life, low maintenance cost
and exible and modularity design which is well-suited for largescale application because of independence between energy capacity and power rating. Redox ow batteries are an electrochemical
energy storage technology where the energy, instead of being
Corresponding author. Tel.: +34 93 3562615; fax: +34 93 3563802.
E-mail address: cox@irec.cat (C. Flox).
0306-2619/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.02.001

stored at electrodes like in conventional batteries, is stored entirely

within the electrolyte. The concentration of the redox species and
the volume of the reservoirs determine the amount of the energy
stored in the system. The system power is determined by the rate
of reaction of redox species at each electrode and their total surface
area. The vanadium redox ow battery (VFB) has unique attributes
among the different types of ow batteries since it employs the
same metal ion on both electrolytes in different oxidation states
minimizing the cross-contamination.
VFB technology is based on electron/proton transfer between
different ionic forms of vanadium, consists of two electrolyte tanks
containing active species of vanadium in different valence states
(in the positive tank: VO2+/VO2+ redox couple; in the negative tank:
V2+/V3+ redox couple). The electrochemical half-cell reactions are
as follows:
Positive electrode reaction:

VO2 2H e

discharge

charge

VO2 H2 O Eo 1:0 V v s: SHE

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C. Flox et al. / Applied Energy 109 (2013) 344351

Negative electrode reaction:

V3 e

charge

discharge

V2

Eo 0:26 V v s: SHE

As a result, the standard open-circuit voltage (OCV) of VFB single cell is 1.26 V. General characteristics of VFB are presented in Table 1 [1015].
A number of technological advantages are often highlighted,
such as, low response time (0.001 s) and long system life since
the electrolytes do not undergo degradation (10,000 cycles with
estimated life of 715 years depending of the application), as well
as a very low self discharge [16]. However, this technology shows
some drawbacks, such as a relatively poor energy-to-weight ratio
approximately 25 Wh kg1[9], which is quite low if compared to
other rechargeable battery types i.e. lithium ion (80200 Wh kg1).
On the other hand, since oxygen and electron processes are necessary for the reaction (1), the positive electrode reaction suffers
from the slow and complex kinetics affecting more signicantly
[1720], in contrast with negative electrode reaction which implies
an electron transfer process. For these reasons the improvement of
the VFB requires a higher energy density electrolyte as well as
higher efciency electrodes. So, aiming to overcome these inconveniences, the development of new electrode materials plays a key
initial role.
Since a sulfuric acid solution is used as the supporting electrolyte in VFB, carbon electrode materials are preferably chosen because of their chemical stability in this medium, high specic
surface area, high strength and wide potential window, but these
materials have been proven to show a poor electrochemical activity to the positive reaction [1722]. In this framework, this study is
focused on the study of characteristics and performance of a novel
electrode for the cathodic reaction of a VFB based on:
(i) Chemical activation of 2-D graphene electrode material
using CuPt3 nanocubes bimetallic nanoparticles, chosen as
preliminary stoichiometric combination, morphology and
size whose effect has been compared with that of Pt nanocubes [23].
(ii) Thermal activation under NH3/O2 (1:1) atmosphere in different temperatures and times conditions applied to 3-D polyacrylonitrile (PAN) graphite felt electrode. Large amounts of
N- and O-containing groups have been introduced onto the
surface electrode [24].
Both activations applied to carbon materials lead to modify the
electron-donor properties of the surface enhancing the oxygen
transfer processes involved in the reaction (1) [19], what causes
a fast faradaic redox reaction. The novel material electrodes have
been investigated by cyclic voltammetry (CV) and electrochemical
impedance spectroscopy (EIS) in order to evaluate their

electrochemical activity towards the positive reaction, estimation

of electrochemical surface area and charge-transfer process. High
resolution transmission microscopy (HR-TEM) and eld emission
scanning electron microscopy (FESEM) has been employed to morphological characterization and X-ray diffraction Spectroscopy
(XPS) to investigate functionalization surface. Finally, in order to
assess the performance of thermal treatment under NH3/O2 (1:1)
atmosphere, different charge/discharge experiments in a VFB single-cell battery have been done.
2. Materials and methods
2.1. Electrode preparation
A graphene oxide (GO)-based electrode has been prepared by
using ink-jet printed techniques onto inert substrate. The GO electrode exhibited a low electrical conductivity and then, required a
reduction with hydrazine solution for 30 min and then the sample
was rinsed with water and dried at 80 C for 24 h (HTGOelectrode). The incorporation of Pt and CuPt3 nanoparticles to the
graphene electrodes was carried out by drop-casting techniques.
Firstly, 0.7 mg of nanoparticles was incorporated on the GO as colloidal solutions in hexane. Upon evaporation of the solvent, the
long alkyl chain stabilizer was removed by ligand exchange using
hydrazine during 30 min followed by a heat treatment at 140 C
for 300 min. The nal electrode is called Pt (or CuPt3)/HTGO. Both,
Pt and CuPt3 nanoparticles with controlled morphology were synthesized by thermal decomposition of platinum acetylacetonate
and copper acetylacetonate in 1-octadecene using a mixture of
oleylamine and 1-dodecanethiol as stabilizers in order to induce
assisted growth [25].
In order to investigate the optimal condition for synthesizing
functionalized PAN-electrodes, (i.e. convenient and inexpensive
condition to fabricate PAN-derived electrodes to increase the interfacial wettability without sacricing its mechanical properties),
samples of PAN-electrodes were treated thermally under NH3/O2
(1:1) atmosphere at 400, 500 and 600 C and different times, i.e.,
6, 12, 24 and 36 h, using a tubular furnace. Hereafter, dPAN (T, t)
is used as the notation for the modied electrodes, with T and t
being the temperature and duration of the treatment, respectively.
2.2. Electrochemical measurements
Electrochemical characterization was performed in a standard
three-electrode glass cell with nitrogen gas used to deaerate all
the solutions. The Hg/Hg2SO4/K2SO4 (sat.) electrode was used as
the reference electrode, being placed into a Luggin capillary, and
a platinum wire was employed as the counter electrode. Each carbon material was used as working electrode with 1 cm2 and
1.5 cm2 geometric area for the graphene and PAN-electrodes,

Table 1
General properties of all-vanadium redox ow battery.

Electrolyte
composition

OCV (V)
100% SOCa

Charge/discharge
current density
(mA cm2)

Cell type

Electrode and membrane materials

used

Overall charge/
discharge
efciency (%)

References

1.62 M VOSO4 in H2SO4

1.6

10130

15 kW bipolar stacks

80% at 40 mA cm2

[11,12]

1.5 M VOSO4, 2 M H2SO4

1.6

40

Flow cell

83%

[13,14]

1.5 M VOSO4 in 3 M H2SO4

1.6

85

10.05 kW14 cells

Graphite felt electrodes. Modied

peruorinated cation exchange
membrane
Sandwich-type sulfonated poly(ether
ether ketone)/tungstophosphoric acid/
polyprolylene composite
875 cm2 of Felt electrode with Naon
(Du Pont) membrane

80% at 85 mA cm2

[15]

OCV is open-circuit voltage; SOC is state of the charge.

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C. Flox et al. / Applied Energy 109 (2013) 344351

respectively. 30 mL of 0.5 mol dm3 VOSO4 (Alfa Aesar) solution in

3 mol dm3 H2SO4 (Sigma Aldrich) [26] were used as the aqueous
electrolyte, being all the electrodes soaked into it for 9 h before
use. Several cyclic voltammetry (CV) experiments were carried
out at several scan rates ranging from 1 to 20 mV s1 and impedance spectroscopy (EIS) at open circuit voltage from 105 to
102 Hz applying an AC voltage of 5 mV amplitude was employed
to conrm the electrocatalytic effect of the dPAN electrodes. All the
electrochemical measurements were carried out with a Biologic
VMP-3 multipotentiostat controlled by EC-lab software. Each
experiment was repeated at least three times to verify the repeatability and ensuring that the nanoparticles were tightly attached to
carbon without experiencing detachment, yielding reproducible
measurements.

2.3. Estimated electrochemical surface area measurements

The estimated electrochemical surface area (ECSA) determines
the area linked to the conductive path available to transfer electrons to and from the electrode surface. And, at the same time, this
area is related to the number of catalytically active sites available
for an electrochemical reaction. ECSA can be estimated from the
RandlesSevcik [2733] Eq. (3), what relates the peak current with
the square root of the scan rate for a Eq. (3) system, or as follows:
1=2

Ip 2:99  105 nan1=2 AD0 C 0 v 1=2

where Ip is the anodic peak current of oxidation peaks of VO2+ (A), n

is the number of exchanged electrons, a is the transfer coefcient
(0.5), A is the ECSA (cm2), C0 is the initial concentration of the electroactive species (mol cm3), D is its diffusion coefcient (cm2 s1)
and v is the scan rate (V s1). The values of the diffusion coefcients
were obtained from bibliography, 1  106 cm2 s1 [34]. Note that
all ECSA are considerated an approximation due to the nature of
the electrodes analyzed which is porous and could introduce deviations due to different diffusion gradients on the surface of the electrode. Also, the RandlesSevcik equation is adequate to be used for

diluted solutions. Nevertheless, a very good linearity was observed

for all studied system [32,33].
2.4. VFB single-cell performance
The VFB performance of the different electrodes (dPAN (500, 24)
and untreated PAN electrodes) was measured using an in-house
designed ow cell system. The system includes one single twocompartment cell, peristaltic pumps (ColeParmer, Masterex),
and two external glass reservoirs.
The single-cell (see Fig. 1) used was designed by sandwiching
the membrane Naon 117 (6 cm  6 cm) between two pieces of
working electrodes. Each electrode in their half-cell was placed
in a groove on outer face of the graphite bipolar plates which were
etched with serpentine ow elds. The area of the electrode in contact with electrolyte solution was 25 cm2. The inner faces of the
bipolar plate were deposited a sputtered layer of copper such as
current collector. Viton gasket is used to avoid the electrolyte leakage. Metallic aluminum end-plates were used to close the cell. The
stack is connected to the external electrolyte reservoirs by 1/800 inner diameter tygon tubing, which by means of a double headed
peristaltic pump allows the ow of electrolyte from the reservoirs
to the stack.
The starting electrolyte was prepared by dissolving VOSO4 3.4
H2O (Alfa Aesar, 98%) in sulfuric acid (Panreac). Positive and nega3
tive electrolyte solutions, 1 mol dm3 VO
V2+,
2 and 1 mol dm
respectively, were prepared by electrochemical oxidation of
1 mol dm3 VOSO4 in 3 mol dm3 sulfuric acid aqueous solution.
Each electrolyte volume was 50 cm3. The electrolyte ow rate to
each side was 10 cm3 min1 and two reservoirs were continuously
purged by nitrogen to minimize oxidation of the active species. The
ow cell was charge to 1.9 V and then discharge to 0.8 V, equivalent to the state of the charged (SOC) of 100% and 0%, respectively,
at 20 mA cm2 to investigate and the longevity of this treatment.
The charge/discharge test was carried out using Parstat 2273
potentiostat/galvanostat (Princeton Applied Research). The coulumbic efciency (CE), voltage efciency (VE), and energy efciency (EE) of the cell are calculated as follows:

Outer face of graphite

bipolar plate with
serpentine flow fields

Nafion membrane

Inner face of
bipolar plate
with sputtered
layer of copper

Viton gasket
Viton gasket
Viton gasket

PAN-felt electrodes

End-plates
Fig. 1. Schematic diagram of in-house VFB single-cell and expanded view of cell components.

C. Flox et al. / Applied Energy 109 (2013) 344351

CE % discharge capacity=charge capacity  100

VE % middle point of discharge voltage=

middle point of charge voltage  100

EE CE  VE

347

3. Result and discussion

3.1. Highly active CuPt3/HTGO electrode for positive reaction in VFB
Fig. 2 depicts the representative HRTEM and FESEM images of the
CuPt3 nanoparticles uniformly dispersed on the surface of HTGO
electrode. It can be seen that the majority of the cubic nanoparticles
exhibit a diameter close to 6.4 0.7 nm with no apparent aggregation, and the uniformity of the particle size and shape are evident.
Several cyclic voltammograms (CV) were obtained at 20 mV s1
for the various graphene-derived in 30 mL of the 0.5 mol dm3
VOSO4 solution in 3 mol dm3 H2SO4 (Fig. 3). The redox peaks
are attributed to the reaction (1).
Notwithstanding the poor electrocatalytic activity exhibited for
GO electrode, well-dened oxidation and reduction peaks for the
reaction (1) can be observed for the HTGO electrode showing a
peak to peak separation (DE) of the 0.3 V suggesting higher reversibility. The reduction with hydrazine was employed as a key step
for the preparation of all the subsequent electrodes in order to increase the electrical conductivity. The positive results yielded by
the HTGO electrodes can then be due to the replacement of the
oxygenated groups by covalent CN bonds on the carbon surface
under the action of hydrazine, ending in a higher electrocatalytic
activity. In order to measure N-content in graphene-derived electrodes, XPS analysis was carried out. The nitrogen atomic content
values found for GO, HTGO, Pt/HTGO and CuPt3/HTGO electrodes
were 0.97%, 2.25%, 2.57% and 2.49%, respectively in the structure,
corroborating the incorporation of nitrogen in the structure.
Another observed effect was the electrical conductivity of the
nitrogen-doped carbonaceous material being increased due to the
ve electrons of the nitrogen atom [35]. For this reason, carbon
atoms adjacent to nitrogen possess a substantially highly positive
charge density which acts as active sites for the oxidation reaction.
This is benecial for the reduction process where for example pyridine-groups have a lone-pair of electrons available. Likewise,
nitrogen addition also changes the wettability of graphene, which
becomes more hydrophilic.
Decorated HTGO electrodes were then prepared following the
methodology described in the experimental section. As revealed
by the CV shown in Fig. 3, both the Pt/HTGO and CuPt3/HTGO
electrodes yielded a pair of well-dened and higher reversible re-

Fig. 3. CV obtained for (1) HTGO, (2) Pt/HTGO and (3) CuPt3/HTGO electrodes in
0.5 mol dm3 VOSO4 solutions in 3 mol dm3 H2SO4 at a scan rate of 20 mV s1.

dox peaks, leading to increment of the higher current values compared to the previous HTGO electrode. This is correlated with the
redox behavior of the electroactive HO-containing functional
groups at the Pt or CuPt3 nanocubes. On the other hand, the current
density increased from 29.4 to 40.2 mA cm2 and the oxidation
peak potential decreased from 0.58 V vs. Hg/HgSO4 to 0.54 V vs.
Hg/HgSO4 when comparing the Pt/HTGO and CuPt3/HTGO electrodes, respectively. The DE is 0.22 V and 0.29 V for CuPt3/HTGO
and Pt/HTGO electrodes, respectively. However, this value was still
larger than the ideal value of 0.059 V for fast electrode kinetics. It is
worth remarking that the CuPt3 nanocubes displayed the highest
electrocatalytic activity among all the electrodes tested, which is
due to the positive synergistic effect from the presence of OH
groups at the surface of CuPt [3638]. These OH groups onto
graphene surface could play an important role because they catalyze the redox reaction by generating active sites for the positive
reaction of VFB
The values of Ipa/Ipc were 1.07 and 1.12 for CuPt3/HTGO and Pt/
HTGO electrodes, respectively. These values are close to the ideal
unity expected for a reversible system, indicating a signicant
enhancement of the electrocatalytic activity.
3.2. N- and O-functionalized PAN electrode for in VFB
Fig. 4 shows the morphology observed by FESEM for the
unmodied PAN and PAN-derived electrodes. Comparing the dPAN
(400, 24) electrode with the untreated one, no obvious change is
observed on the surface morphology. The same effect can be

Fig. 2. HRTEM image of CuPt3 nanoparticles and FESEM images of CuPt3/HTGO.

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C. Flox et al. / Applied Energy 109 (2013) 344351

(a)

(b)

50 nm

(c)

50 nm

(d)

50 nm

30 nm

(e)

30 nm

(f)

30 nm

(g)

30 nm
Fig. 4. FESEM images for (a) untreated PAN, (b) PAN (400, 24), (c) PAN (500, 6), (d) PAN (500, 24), (e) PAN (500, 36), (f) PAN (600, 6) and (g) PAN (600, 12) electrodes.

observed with dPAN (500, 6), but the surfaces of this electrode are
cleaner than those of the untreated one. This phenomenon can be
caused by the weak reaction between NH3 and graphite felt removing the surface contaminants. However, the roughness surface increases treatment time from 6 to 36 h leading to small pores
scattered which became larger and deeper because of the pressure
of the NH3/O2 gas mixture on the ber surface caused by longer
treatments. Finally, when the dPAN material was obtained at
600 C for 6 h, the dPAN bers underwent a clear deformation, as
shown in Fig. 4f and longer treatment leads to a weakening of
the graphite ber mechanical properties (see Fig. 4g). Note that
the dPAN (600, 24) and dPAN (600, 36) bers have not been taken
into account because it would lead to reduce considerably their
electric conductivity and to lower their mechanical properties.
The electrochemical parameters (i.e. anodic peak potential value and current density) obtained from the CV at 1 mV s1 have
been represented in Figs. 5 and 6 as a function of all treatments
in order to understanding of the optimal conditions for the thermal
activation treatment. As can be seen in Figs. 5 and 6, for all temperatures of treatment, the anodic current density increases with time
of treatment until it attains the maximum value and afterwards
displays a downward trend with high time of treatment. The anodic current density approaches a maximum of 27.9, 37.1 and
30.77 mA cm2 for dPAN (400, 24), dPAN (500, 24) and dPAN
(600, 6) electrodes, respectively.
However, the anodic peak potential (Fig. 6) values approaches a
minimum of 0.525 V (vs. Hg/Hg2SO4) for dPAN (400, 24) and dPAN
(500, 24) and 0.528 V (vs. Hg/Hg2SO4) for dPAN (600, 6), respectively. Low anodic peak potential is benecial for improving the
energy storage efciency because it implies a lower charge voltage
for VFB. It should be noticed that duration of treatment higher than
6 h for temperature of 600 C leads to signicant reduction of electric conductivity, and consequently present a poor electrocatalityc
activity towards reaction (1). For this reason, dPAN (600, 24) and
dPAN (600, 36) electrodes have not been taken into account.

Fig. 5. Relationship between anodic peak current density obtained from CV with
0.5 mol dm3 VOSO4 solution in 3 mol dm3 H2SO4 at scan rate 1 mV s1 and
treated time of thermal activation for each temperature applied at untreated
electrode (1), 400 C (2), 500 C (3) and 600 C (4).

Thereby, the electrode that shows better electrocatalytic activity

(i.e. higher current density and lower anodic peak potential) towards reaction (1) is dPAN (500, 24). Fig. 7 shows the enhancement
of these electrochemical parameters in CV of the dPAN (500, 24) in
comparison with untreated electrode. It is noteworthy that the DE
value is decreased from 0.24 to 0.16 V for untreated and dPAN
(500, 24) electrode, respectively.
In order to conrm the performance of the electrodes, electrochemical impedance spectra (EIS) are recorded in the same condition for dPAN (500, 6), dPAN (500, 24) and untreated PAN
electrodes at open-circuit potential. The Nyquist plot is shown in
Fig. 8. A semicircle and a linear part are observed in the frequency
from 105 to 102 Hz, indicating the charge transfer and diffusion

C. Flox et al. / Applied Energy 109 (2013) 344351

Fig. 6. Relation between anodic peak potential obtained from CV with

0.5 mol dm3 VOSO4 solution in 3 mol dm3 H2SO4 at scan rate 1 mV s1 and
treated time of thermal activation for each temperature applied at untreated
electrode (1), 400 C (2), 500 C (3) and 600 C (4).

Fig. 7. CV obtained for untreated PAN and PAN (500, 24) electrodes in
0.5 mol dm3solution in 3 mol dm3 H2SO4 at scan rate 1 mV s1.

349

2
steps involved in the VO
redox reaction. Z real (1.1 X) at Z
2 =VO
imaginary = 0 is the ohmic resistance that combines the solution,
electrode and contact resistance. This ohmic resistance keeps almost constant for all dPAN electrodes. The arc (high frequencies
range) reects the charge transfer reaction at the electrode/electrolyte interface and the radius is the charge transfer resistance. The
smaller arc radius of the semicircle implies a faster reaction, so it
can be seen, the charge transfer reaction resistance follows the order: raw PAN electrodes >> dPAN (500, 6) > dPAN (500, 24). Therefore both EIS and CV result show that both the reduction and
2
oxidation processes of VO
redox couple are enhanced on
2 =VO
dPAN (500, 24) electrode.
Furthermore, ECSA value has been estimated from the Randles
Sevcik equation for electrodes treated at 500 C and the results are
expressed in the following order (the ECSA value obtained in
cm2/mg is given in parenthesis): untreated dPAN (0.78) < dPAN
(500, 6) (1.09) < dPAN (500, 24) (1.35) > dPAN (500, 36) (1.13).
These results demonstrate that the increment of ECSA for the
PAN-derived electrodes treated at 6, 24 and 36 h is 40%, 73% and
45% higher, respectively, compared to that for the untreated PAN
electrode, conrming the remarkable electrocatalytic effect
provides by the N- and O-containing groups. Additionally, the
slope value obtained from the plots of log(Ip) vs. log(v) for all
electrodes studied are approach to 0.50 showing a linear relationship indicating semi-innite diffusion control. Notwithstanding,
these ECSA value are considered estimated or approximate due
to the nature of the porous electrodes analyzed which could
introduce different diffusion gradients on the surface of the
electrode [32,33].
Finally, N- and O-content onto surface created was investigated
by XPS of untreated and dPAN electrodes treated at 500 C for 24 h.
XPS analysis reveal that the content of N-groups are increased from
0.72% to 7.7% for untreated PAN and dPAN (500, 24) electrodes and
the O-groups are increased from 22.3% to 31.7%. The mechanism
proposed for the reaction (1) is represented in Fig. 9 [1720,39].
To corroborate the well-performance of this treatment a comparison of the behavior of the graphite felt electrodes treated in
NH3/O2 atmosphere at 500 C for 24 h vs. that of untreated graphite
felt electrodes has been carried out by galvanostatic cycling of a
monocell battery prototype (Fig. 10). The cycling experiment using
the untreated PAN reveals a 47% energy efciency (85% coulombic
efciency and 55% voltage efciency), whereas the same battery

Fig. 8. Nyquits plots of the untreated PAN, (j); dPAN (500, 6), (d); dPAN (500, 24), and (N) electrodes.

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C. Flox et al. / Applied Energy 109 (2013) 344351

Fig. 9. Mechanism proposed of the O-containing groups towards the VO2 =VO
2
redox couple.

medium has been successfully achieved by means of two strategies: (i) Graphene-decorated with CuPt3 nanoparticles and (ii)
commercial polyacrilonytrile-felt treated at 500 C in NH3/O2
(1:1) atmosphere (dPAN (500, 24) electrode). These highly effective
strategies accelerate the oxygen and electron transfer processes in
the electrode/electrolyte interface by the presence of O-containing
groups at surface of electrode showing good morphological properties and large electrochemical surface area. Furthermore, the performance and longevity of the VFB single-cell prototype using
dPAN (500, 24) electrode have been evaluated showing energy efciency of 84% (85% of VE and 99% of CE) at a current density of
20 mA cm2 up to 30th cycles, leading to step forward in the VFB
scale-up.

Acknowledgements
This research was supported by the European Regional Development Funds (ERDF, FEDER Programa Competitivitat de Catalunya 2007-2013) and by the Ministerio de Economa y
Competitividad-INNPACTO, Project REDOX 2015 (IPT-2011-1690920000), -CONSOLIDER Ingenio 2010, Project MULTICAT
(CSD2009-00050) and NANO-EN ESTO Project MAT2010-21510.
The research was supported by EIT and KIC-InnoEnergy under
the Project KIC-EES (33_2011_IP29_Electric Energy Storage).

References

Fig. 10. Chargedischarge cycling performance of a VFB assembled with (1)

untreated PAN and (2) dPAN (500, 24) electrodes.

Table 2
Cycling performances on the VFB single-cell using dPAN (500, 24) electrodes.
Cycle index

CE (%)

VE (%)

EE (%)

1st
210th
1020th
2030th

98.99
99.14
98.67
98.78

85.02
85.06
85.11
85.60

84.16
84.33
83.98
84.56

hardware using the functionalized treated (500, 24) graphite felt

neared 84% energy efciency (with near 99% coulombic efciency
and 85% voltage efciency) thus conrming this functionalization
treatment as very promising for VFB batteries.
In order to assess the long-term stability of this electrodes, their
cycling performance of the single-cell VFB using dPAN (500, 24) electrodes was carried out for 30 cycles at 20 mA cm2 from 0.8 V to
1.9 V and the corresponding average efciencies are given in Table 2.
As can be seen, the treated electrode possesses higher stability and
efciency. It is noteworthy that the cell efciencies achieved are
comparable, and even superior to efciencies obtained by other
authors [4042]. Consequently, this functionalization treatment
based on thermal treatment in NH3/O2 atmosphere is simple, environmental friendly, facile, cost-effective and very suitable for
large-scale manufacture in comparison with other in the literature.
4. Conclusions
The enhancement of the electrochemical activity of the carbonbased electrodes towards VO2 =VO
2 reaction in all-VFB in sulfuric

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