CARBON

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Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/carbon

Thermochemical treatments based on NH3/O2 for improved

graphite-based fiber electrodes in vanadium redox flow
batteries
Cristina Flox
Morante a,b
a
b

a,*
,

Javier Rubio-Garca a, Marcel Skoumal a, Teresa Andreu a, Juan Ramon

Catalonia Institute for Energy Research, IREC, Jardins de les Dones de Negre 1, 08930 Sant Adria` de Beso`s, Barcelona, Spain
Departament dElectro`nica, Facultat de Fsica Universitat de Barcelona, Mart i Franque`s 1, 08028 Barcelona, Spain

A R T I C L E I N F O

A B S T R A C T

Article history:

Electrochemical behavior of the polyacrylonitrile (PAN)-based graphite as a low cost elec-

Received 4 December 2012

trode material for vanadium based redox batteries (VFB) in sulfuric acid medium has been

Accepted 9 April 2013

improved by means of the successful introduction of nitrogen and oxygen-containing

Available online 18 April 2013

groups at the graphite surface by thermal activation under NH3/O2 (1:1) atmosphere. Influence of the temperature and treatment duration times have been studied towards the posi-

Keywords:

tive reaction of VFB. The structure, composition, and electrochemical properties of the

Polyacrylonitrile fiber

treated samples have been characterized with field emission scanning electron microscopy,

Electrochemical properties

X-ray photoelectron spectroscopy, cyclic voltammetry and electrochemical impedance

Electrochemical surface area

spectroscopy. The estimation of electrochemical surface area has also been evaluated.

Energy storage

The treatment of PAN graphite material at 773 K for 24-h leads to electrode materials with

Vanadium redox flow battery

2+
redox couple. This method prothe best electrochemical activity towards the VO
2 /VO

duces an increase of the nitrogen and oxygen content at the surface up to 8% and 32%,
respectively, and is proved to be a straightforward and cost-effective methodology. This
improvement of the electrochemical properties is attributed to the incorporation of the
nitrogen and oxygen-containing groups that facilitate the electron transfer through the
electrode/electrolyte interface for both oxidation and reduction processes.
 2013 Elsevier Ltd. All rights reserved.

1.

Introduction

The redox flow energy storage systems have recently received

considerable attention as they possess promising characteristics such as long life, flexible design and high reliability, as
well as a low operation and maintenance cost [1,2]. The allvanadium redox flow battery (VFB) employs solutions of
2+
as the catholyte and V3+/V2+ as the anolyte, both
VO
2 /VO
of them in sulfuric acid medium. Their main advantage over
other available redox flow batteries lies in the fact that ions of

the same chemical element are used in both half cells, thus
preventing cross-contamination by metal cation crossover
through the ion exchange membrane.
Although unlike other energy storage systems, in VFB, the
energy and power capabilities are independently scalable, the
major drawback of this technology is its low energy-to-weight
ratio (i.e., about 2535 Whkg1 of electrolyte) [3]. The general
improvement of these batteries requires a higher energy density electrolyte as well as higher efficiency electrodes offering
a better chemical reaction performance. Aiming to overcome

* Corresponding author: Fax: +34 93 3563802.

E-mail address: cflox@irec.cat (C. Flox).
0008-6223/$ - see front matter  2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.04.038

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these inconveniences, the development of new electrode materials plays a key initial role without whom it becomes even
more difficult to take advantage of the improved electrolyte.
In this framework, polyacrylonitrile (PAN)-based graphite
fiber felt is one of the more suitable electrode materials for
the VFB because of its wide operation potential range, stability as either anode or cathode and availability of high surface
area at an affordable cost [4] taking into account the strong
acidity of the supporting electrolyte.
However, graphite-felt electrodes usually lead to a slow
charge transfer, a low reversibility and a low current density
which must be optimized [5]. Consequently, much attention
has been paid to the modification of this material [6], trying
to enhance its electrochemical properties in order to improve
its charge transfer capability as it is a low cost material with a
tridimensional structure which allows for a higher specific
area. The main objective of such modifications is the introduction of functional groups onto the surface in order to increase
its hydrophilicity, wetting properties and to improve the
charge-exchange ability of electron [7,8]. Particularly, oxygen
and nitrogen functionalization of carbonaceous materials have
been proven to yield materials exhibiting a higher electrocatalytic activity [9,10], as demonstrated in many electrochemical
devices such as fuel cells and biosensors [11,12].
In recent years, several processes have been developed for
synthesizing functionalized carbon electrodes [13]. These
methods usually involve inconveniences such as dangerous
and complicated operation, CN and CO functionalities (e.g.,
amine) that are unstable under strong catalysis conditions
(e.g., acid electrolyte) and leads to low concentration of oxygenand nitrogen-containing groups and short-term stability electrodes. Thus, there is still a high demand for exploring new convenient and inexpensive methods to fabricate functionalized
PAN-based electrodes to increase the interfacial wettability
and the concentration of N- and O-functional groups without
sacrificing the mechanical properties of graphite fibers.
It has been shown that the redox reactions involving the
V3+/V2+ couple are highly reversible and exhibit very fast reac2+
reaction kinetics are
tion kinetics. In contrast, the VO
2 /VO
much slower and more complex, since they involve at least
three elementary steps (i.e., one electron and oxygen transfer
and two proton exchanges) and several complex intermediates depending on the electrolyte pH and electrode potentials
[13]. Therefore, the electrochemical kinetics limitation of the
VFB arises from the positive side and thus, the development
of novel electrodes with a higher catalytic activity toward
2+
system is mandatory.
the VO
2 /VO
This paper focuses on the synthesis of PAN-derived (dPAN) electrodes using a simple and viable thermal-chemical
post-synthesized method to functionalize with active nitrogen and oxygen-like groups identified from NH3/O2 (1:1)
atmosphere treatments, aimed at yielding a higher cathode
performance compared to that for the unmodified PAN electrode. Unlike other previous studies, special emphasis has
been addressed to the influence of the time and temperature
of the treatment. These parameters have been evaluated in
order to find the optimal experimental conditions to ensure
the best electrochemical, morphological and stability electrode properties. Different electrochemical techniques have
been employed to study the behavior of the synthesized

281

2+
electrodes regarding the VO
couple, in order to assess
2 /VO
the estimation of electrochemical surface area and their electrochemical activity.

2.

Experimental

2.1.

Electrode preparation

Samples of PAN-based graphite felt (Beijing Great Wall) with

1.5 104 m2 geometric area were treated thermally under
NH3/O2 atmosphere (1:1) at 673 K, 773 K and 883 K and for different treatment times, i.e., 6-h, 12-h, 24-h and 36-h, using a
tubular furnace. Hereafter, d-PAN (T, t) is used as the notation
for the modified electrodes, with T and t being the temperature and duration of the treatment, respectively. After the
treatment, the samples were cooled down under vacuum before carrying out the measurements.

2.2.

PAN-derived electrodes characterization

The morphology of the PAN electrodes was examined using a

Hitachi H-4100FE field emission scanning electron microscope (FESEM). The chemical composition changes of the surface of the d-PAN electrodes were analyzed by X-ray
photoelectron spectroscopy (XPS) using a PHI instrument
model 5773 Multitechnique with A1 Ka radiation (1486.6 eV).

2.3.

Electrochemical measurements

In order to determine the electrochemical properties of the

modified electrodes, a standard three-electrode glass cell
was employed and nitrogen gas was 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 of the thin layer PAN-based electrodes was used as the
working electrode, being attached to a platinum plate that
acted as the current collector. A 500 mol m3 VOSO4 (Alfa Aesar) solution in 3000 mol m3 H2SO4 (SigmaAldrich) [14] was
used as the aqueous electrolyte, being all the electrodes
soaked into it for 9 h before use. In order to evaluate the electrochemical activity and estimate the electrochemical surface
area (ECSA) [1519], several cyclic voltammetry (CV) experiments were carried out between 0.4 V and 1.2 V at several
scan rates ranging from 0.001 to 0.02 V s1.
Likewise, electrochemical impedance spectroscopy (EIS) at
open circuit voltage from 105 to 102 Hz, was employed to
confirm the electrocatalytic effect of the d-PAN electrodes.
The solutions were prepared with ultra-pure water and potential are reported with respect to Hg/Hg2SO4/K2SO4 (sat.).
All the electrochemical measurements were carried out
with a Biologic VMP-3 multipotentiostat controlled by EC-lab
software.

3.

Results and discussion

3.1.

Morphology of PAN electrodes

Fig. 1 shows the surface morphology observed by FESEM for

the unmodified PAN (Fig. 1a), as well as that of the d-PAN

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(a)

(b)

(c)

(d)

e)

(f)

(g)

(h)

Fig. 1 Surface morphology of several PAN-based electrodes: (a) raw PAN felt as received, (b) d-PAN (673, 24), (c) d-PAN (773, 6),
(d) d-PAN (773, 12) , (e) d-PAN (773, 24), (f) d-PAN (773, 36), (g) d-PAN (873, 6), (h) d-PAN (873, 12).
(Fig. 1bh) electrodes obtained upon different treatments. By
comparing Fig. 1a and b, it can be seen that the d-PAN (673,

24) maintains the initial fiber morphology and, apparently,

the surface roughness remains unaltered. However, a higher

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283

temperature leads to a decrease of the roughness, as can be

observed in the image of the d-PAN (773, 6) in Fig. 1c because
of binder removing. Fig. 1d and e shows that this roughness
increases with longer treatment times (i.e., from 12-h to 24h). These features corroborate the surface degradation as a
consequence of high density of defects in the fibers which
is enhanced by the treatment conditions. It was found that
when the raw PAN was treated at such high temperature over
a prolonged time period, i.e., 773 K for 36-h, the initial small
pores scattered on the surface identified at 773 K 6-h
(Fig. 1c) became larger, as shown in Fig. 1f. The presence of
these large pores is caused by the over effect of the pressure
of the NH3/O2 gas mixture on the fiber surface taking place
during longer treatments. Finally, when the d-PAN material
was obtained at 873 K for 6-h, the PAN fibers underwent a
clear deformation, as shown in Fig. 1g. The bending observed
due to the lower stiffness at high temperature was even more
pronounced as the duration of the treatment increased,
which also led to a larger consumption of the graphitic carbon, as can be seen in the worn-out fibers of Fig. 1h.
As a general observation, the prolonged treatment at a given temperature led to both the increase of the surface roughness and the appearance of a larger number of pores. The best
treatment conditions are those generating the highest num2+
process. In order
ber of active sites favouring the VO
2 /VO
to identify the best material treatment, the PAN-derived electrodes will be electrochemically characterized.

3.2.

Electrochemical behavior of the d-PAN electrodes

The influence of temperature and time of treatment of PAN

electrodes were evaluated by cyclic voltammetry using solutions of supporting electrolyte, yielding the voltammograms
of Fig. 2a and b, respectively. Well-defined anodic and catho2+
redox couple. The
dic peaks were recorded for the VO
2 /VO
redox peaks are attributed to the following reversible
reaction:


VO2 H2 O VO
2 2H e

The electrochemical activity (basically, peak current density, Ia and peak potential values, Ep-ox) and the reversibility
(DEp) of reaction (1) (summarized in Table 1) are the key criteria for evaluating the performance of a given electrode when
2+
redox couple in a VFB.
considering the VO
2 /VO
Regarding the temperature dependence, as it can be deduced from these values, the electrochemical kinetics of the
oxidation process in reaction (1) on the electrodes decrease
in the order: d-PAN (773, 12) > d-PAN (673,12) > d-PAN
(873,12)  untreated PAN. On the other hand, regarding the
influence of treatment duration for all d-PAN electrodes treated at 773 K (values are given in the Table 1 and shown in
Fig. 2b), the electrochemical ability follows the order as dPAN (773, 24) > d-PAN (773, 12)  d-PAN (773, 6) > d-PAN (773,
36)  untreated PAN electrode.
In comparison with the untreated PAN electrode, we find
that the anodic current density is increased from 254 to
371 A m2, and the anodic peak potential values is decreased
from 0.58 to 0.52 V at the electrode d-PAN (773, 24). It should
be noticed that treatments times over 6-h at a temperature
of 873 K leads to reduce considerably the electric conductivity,

Fig. 2 Effect of temperature treatment (a) cyclic

voltammograms of untreated PAN electrodes (1); d-PAN (673,
12) (2); d-PAN (773, 12) (3) and d-PAN (873, 12) (4). Effect of
time of treatment (b) cyclic voltammograms of untreated
PAN electrodes (1), d-PAN (773, 6) (2), d-PAN (773, 12) (3),
d-PAN (773, 24) (4) and d-PAN (773, 36) (5). (c) Influence of
thermal and chemical effect upon electrocatalytic activity (a)
cyclic voltammograms of untreated PAN electrodes (1);
d-PAN (773, 24) in inert atmosphere (2); d-PAN (773, 24) in
NH3/O2 atmosphere (3). Measurements were performed
using 30 cm3 of a 500 mol m3 VOSO4 in 3000 mol m3
H2SO4 solution. Scan rate: 0.001 V s1.

and consequently these electrodes presented a poor electrochemical activity towards reaction (1). For this reason,

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Table 1 Electrochemical parameters for all PAN-derived electrodes studied obtained from CVs at 0.001 V s1 in the Fig. 2.
Anodic peak potential values (Ep-ox), anodic peak current density (Ia), and the reversibility (DEp).
Electrode
Untreated
d-PAN (673,
d-PAN (673,
d-PAN (673,
d-PAN (673,
d-PAN (773,
d-PAN (773,
d-PAN (773,
d-PAN (773,
d-PAN (873,
d-PAN (873,

6)
12)
24)
36)
6)
12)
24)
36)
6)
12)

Ep-ox (V)

Ia (A m2)

DEp (V)

0.576
0.539
0.539
0.525
0.525
0.532
0.525
0.527
0.543
0.528
0.565

254.1
271.6
270.9
279.7
273.5
288.3
306.1
370.3
229.0
307.7
228.9

0.24
0.18
0.17
0.17
0.16
0.18
0.17
0.16
0.19
0.16
0.19

d-PAN (873, 24) and d-PAN (873, 36) electrodes have not been
taken into account.
Note that the difference between anodic and cathodic
peak potential values decreases strongly from 0.24 to 0.16 V
for untreated PAN electrode and d-PAN (773, 24) electrode,
respectively. This value remains larger than the ideal value
of 0.057 V for fast electrode kinetics. The values of Ipa/Ipc were
close to unity for both redox couples for the electrode d-PAN
(773, 24). Therefore, the d-PAN (773, 24) electrode not only
exhibits high stability and morphology after the treatment,
but also a higher electrochemical activity towards the reaction (1). It is noteworthy that the important role of the chemical treatment upon the electrocatalytic activity towards the
positive reaction. As it is showed in the Fig. 2c, the thermal
treatment in inert atmosphere leads to decrease the current
density collected in comparison with chemical and thermal
treatment.
These results suggest that the best treatment conditions to
improve the PAN electrode electrochemical activity consist of
thermal treatment of the d-PAN at 773 K for 24-h in NH3/O2
atmosphere. Such conditions lead to a higher reversibility, a
lower anodic potential peak value and a higher current density for the reaction (1).

3.3.

Surface characterization of PAN electrodes

Based on the above analysis, we can conclude that

PAN-derived electrodes treated at 773 K show the best electrochemical activity. For the sake of a better understanding of
the enhancement of the electrochemical properties, the nature of the chemical functionalities onto surface created was
investigated by XPS for d-PAN electrodes treated at 773 K for

6-h, 12-h, 24-h. Note that the d-PAN (773, 36) electrode was excluded due to the loss of the electrochemical properties toward the reaction (1).
Table 2 shows a XPS comparison of the atomic content and
weighted concentration of N- and O-containing groups for
each electrode treated at 773 K. The weighted concentration
is calculated by multiplying relative concentrations in atomic% by the total atomic content of either nitrogen or oxygen.
Based on the signal intensity of oxygen in these spectra, the
oxygen content in the samples treated at 773 K is higher than
that in the raw PAN, and then it slightly increases in the order:
PAN < d-PAN (773, 6) < d-PAN (773, 12)  d-PAN (773, 24), as
summarized in Table 2. Fig. 3 shows the high-resolution
XPS O1s and N1s spectra of the d-PAN electrodes prepared
at 773 K during 24-h of treatment. The deconvolution of
the O1s spectra yielded the following peaks: peak O1
(531.5 0.2 eV), carbonyl oxygen atoms in esters, anhydrides
and oxygen atoms in hydroxyl groups; peak O2 (533.8
0.2 eV), non-carbonyl (ether type) oxygen atoms in esters
and anhydrides; peak O3 (535.5 0.2 eV), adsorbed molecular
water and oxygen [20]. On the other hand, the nitrogen content in the samples treated at 773 K increases in a similar
trend. The high resolution XPS N1s spectrum given in
Fig. 3b reveals the presence of N-functional groups in the
PAN structure associated with peaks: peak N1 (398.7
0.2 eV), pyridine-N; peak N2 (400.3 0.2 eV) pyrrole-N; peak
N3 (401.4 0.2 eV) Quaternary-N, that is, graphite-like nitrogen incorporated into the structure of extended aromatic system of the PAN-graphite fibers and peak N4 (404.1 0.2 eV)
[21], that has been proposed to be pyridine-N-O groups [22].
It is noteworthy that the d-PAN (773, 24) electrode presents
the highest functionalization compared to other treatment

Table 2 Relative contents of functional groups in O1s and N1s from XPS spectra for untreated and d-PAN (773, t) electrodes.
PAN electrode

Untreated
6-h
12-h
24-h
a C + N + O = 100%.

Atomic concentrationa

O1s-w%

N1s-w%

O1

O2

O3

N1

N2

N3

N4

77.0
68.8
64.6
60.8

22.3
29.9
31.7
31.5

0.7
1.3
3.7
7.7

9.52
18.45
10.68
4.95

11.82
10.02
18.13
22.52

0.96
1.44
2.88
4.03

0.14
0.28
0.96
1.71

0.56
0.89
2.56
3.97

n.d.
0.13
0.18
1.65

n.d.
n.d.
n.d.
0.37

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Fig. 3 High-resolution of O1s (a) and N1s (b) spectrum for dPAN (773, 24) electrode.

conditions, which is correlated and explains its higher electrochemical activity.

3.4.
Estimation of electrochemical surface area of PANderived electrodes
The estimation of electrochemical surface area (ECSA) that is
available for the electron transfer to/from the species contained in solution can be estimated from the RandlesSevcik
2+
redox system [23]. The values of
equation (2) for VO
2 /VO
the diffusion coefficients were obtained from bibliography
(1.0 1010 m2 s1) [23].

1=2
/ nFvD
Ip 0:4961 nFAC0
2
RT
where Ip is the anodic peak current of oxidation peaks of VO
2
(A), n is the number of exchanged electrons, F the Faraday
constant, A is the ECSA (cm2), C0 is the initial bulk concentration of the electroactive species (mol cm3), a is the transfer
coefficient (0.5), v is the scan rate (V s1) and D is its diffusion
coefficient of the molecule in solution (cm2 s1), R the universal gas constant and T the absolute temperature.

285

Fig. 4 (a) Plot of the anodic peak current from cyclic

voltammograms of PAN-derived electrodes treated at 773 K
during 6, 24 and 36 h vs. the square root of the scan rate. (b)
log (Ip: anodic peak current) vs. log (v: scan rate).

The slopes of the Ip vs. v1/2 plots shown in Fig. 4a allowed

the estimation of the ECSA for each PAN electrode presented
in Table 3. The dependence of the anodic peak current on
scan rate can be described using the following relationship:
Ip Kvx

logIp logK xlogv

where Ip is the peak oxidation current, v is the scan rate and x is

the exponent of scan rate and K is the proportionality constant.
The log of peak oxidation current was plotted against the log of
scan rate for the data shown in Fig. 4b. A linear relationship was
obtained with slope values of 0.58, 0.56, 0.58 and 0.57 for untreated PAN, d-PAN (773, 6), d-PAN (773, 24) and d-PAN (773,
36) electrode, respectively. Ideally, the slope should approach
0.50 under semi-infinite diffusion conditions where the diffusion of vanadium ions from bulk solution to the electrode surface is rate limiting. This small deviation from the theoretical
0.5 value can be explained by 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 [24,25].

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Table 3 Estimated ECSA values and atomic concentration ratios obtained from XPS analysis for untreated electrode and PAN
derived electrodes prepared at 773 K.
PAN electrode

ECSA (m2 kg1)

DECSA (%)

N/C

O/C

Untreated
6-h
24-h
36-h

78
98
135
91

25
73
16

0.0090
0.0188
0.0572

0.2896
0.4345
0.4907

Actually, the increase estimated ECSA from 25% to 73% can

only be interpreted in terms of the higher catalytic activity
associated with a higher density of O- and N-containing
groups onto the surface of electrode d-PAN (773,6) and dPAN (773, 24) which can form good electron pathways between electrode and electrolyte. The better performances of
the N- and O-contained PAN electrodes may be ascribed to
the higher wettability and the change of the density of electronic states (DOEs) around the Fermi level of PAN electrode
2+
redox reaction is still
[26]. The mechanism of the VO
2 /VO
controversial. Some theories of catalysis have hypothesized
that the aforementioned O- and N-functional groups at the
PAN electrodes play an important role in this reaction because
they favor the interaction of a larger amount of vanadium
ions and oxygen onto the electrode surface. As a result, the
electron and oxygen transfer processes involved in reaction
(1) become accelerated at these derived electrodes.

3.5.

Electrochemical impedance spectra

In order to ensure the faster capability of electron and oxygen

transfer processes of the d-PAN (773, 24) electrode in comparison with untreated electrode, electrochemical impedance spectra (EIS) are recorded in the same experimental conditions at
open-circuit potential. The Nyquist plot is shown in Fig. 5. A
semicircle and a linear part are observed in the frequency from
2+
redox reaction is
105 to 102 Hz, indicating that the VO
2 /VO
controlled by both charge transfer and diffusion process. The
semicircle part at high frequencies reflects the charge-transfer
process and the linear part at low frequencies reflects the diffusion processes in graphite felt. The smaller arc radius implies a
faster reaction, so it can be seen, the resistance related to the
charge transfer reaction increases in the following order: raw

Fig. 5 Nyquist plot obtained for PAN-derived electrode

treated at 773 K and 24-h and untreated electrode.

PAN electrodes <<< d-PAN (773, 24). Therefore, both EIS and
CV results show that both the reduction and oxidation pro2+
redox couple are best enhanced at the
cesses of the VO
2 /VO
surface of the d-PAN (773, 24) electrode.

3.6.

Role of O- and N-containing groups

Fig. 6a shows the variation of anodic current density obtained

from CVs of the Fig. 2 as a function of the total amount of
nitrogen and oxygen for each electrode shown in Table 3.
These results suggest that the increment of the electrochemical activity is proportional to the total amount of N- and Ocontaining groups introduced onto surface of the PAN-derived
electrodes at the first stages of treatment. The decrease in
current density after 12-h of treatment is evident.
A detailed analysis (Fig. 6b) of the individual influence of
the amount of the nitrogen and oxygen content onto the variation of anodic current density points out the increment of
the anodic current density caused by the incorporation, first,
of a high amount of O-containing groups onto the surface
electrode. After 6-h of treatment, the role of the N-containing
groups becomes much more significant. They are incorporated onto the electrode surface and they become the principal responsible of variation of current density. In this stage,
the concentration of oxygen onto surface is constant, probably because of saturation of its chemisorption process. It is
noteworthy that the incorporation of N-containing groups is
a key step due to substantial improvement of the electrochemical activity (i.e., higher current density, low oxidation
potential and higher reversibility). This enhancement of the
electrocatalytic activity is attributed to the N atoms that
would decorate the PAN electrode and introduce changes on
the electro conductivity properties.
In order to study the effect of nitrogen on the electrochemical activity of the electrodes towards the positive reaction of
the VFB, the weighted nitrogen concentration of the species detected from XPS analysis are plotted against the variation of
anodic current density and shown in Fig. 6c. It is observed that
all types of N-containing groups have a positive effect on the
anodic current density due to the enhancement of the electron
transfer process. The most influential species on the enhancement of electron conductivity can be five-member pyrrole rings
which clearly act as electron-donors (N2), or more stable sixmember rings where nitrogen contributes to the p-system with
one p-electron, if present in pyridine (N1). However, surprisingly, the d-PAN (773, 24) electrode contains the highest
amount of quaternary groups (i.e., nitrogen in aromatic electron-donor groups, (N3) and it is possible that these groups
may play also an important role for the enhancement of the
electrochemical activity [22]. Therefore, N-containing groups
might play an important role in regulating the electronic

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properties and enhancing the electrochemical activity of the

PAN-derived electrodes in electrochemical systems.
Therefore, due to these O- and N-containing groups onto
surfaces of the d-PAN (773, 24) electrode, more reactive ions
can be interact on the electrode surface [27] and the electron
and oxygen transfer process can also be catalyzed thus making the d-PAN (773, 24) electrode the most effective one. The
abundant surface area as well as surface sites introduced by
the thermal treatment onto d-PAN (773, 24) surface electrode
can promote the electrochemical reactions.

3.7.
Long-term
electrode

assessment

of

the

d-PAN(773,

24)

In order to assess the long-term stability of the d-PAN (773, 24)

electrode, up to 50th repetitive cyclic voltammetric were performed and showed in the Fig. 7a. Fig. 7b shows the FE-SEM
image of this electrode after this measurement. No significant
change in electrocatalytic activity (i.e., peak current density
and reversibility), neither the morphology. Consequently, this
functionalization treatment supposes a step forward for VFB
system due to their outstanding properties. A detail study of
atmosphere composition applied in the thermal treatment
with lower quantities of oxygen is required and will be published in elsewhere.

Fig. 6 (a) Relationship between the total amount of the

weighted nitrogen and oxygen concentrations of species
detected from XPS analysis and variation of anodic
current density obtained from de CVs in the Fig. 2 for
the untreated PAN, d-PAN (773, 6), d-PAN (773, 12) and
d-PAN (773, 24) electrode. (b) Relationship between the
individual amount of the nitrogen and oxygen atomic
concentration of species detected from XPS analysis and
variation of anodic current density obtained from de CVs
in the Fig. 2 for the untreated PAN, d-PAN (773, 6), dPAN (773, 12) and d-PAN (773, 24) electrodes. (c)
Relationship between the weighted N-containing groups
concentrations of species detected from XPS analysis and
variation of anodic current density obtained from de CVs
in the Fig. 2.

Fig. 7 (a) Stability test of the d-PAN (773, 24) electrode in

30 cm3 of a 500 mol m3 VOSO4 in 3000 mol m3 H2SO4
solution. Scan rate: 0.001 V s1. (b) FESEM image of the
d-PAN (773, 24) electrode after 50th cycle.

288

4.

CARBON

6 0 ( 2 0 1 3 ) 2 8 0 2 8 8

Conclusions

In order to improve the cathode at the VFB in sulfuric acid

medium, the surface of a PAN electrode was functionalized
with N- and O-containing groups as a result of a thermal
treatment under NH3/O2 (1:1) atmosphere within different
temperatures and residence times. The highest electrochem2+
redox couple was found for
ical activity towards the VO
2 /VO
PAN electrode treated at 773 K for 24 h. Experimental results
reveal that the d-PAN (773, 24) electrodes possess advantages
such as a high N and O content up to 8% and 32%, respectively, and morphological stability. These results suggest that
the amount of graphite-like CN bonds is increased with the
time of treatment being mainly responsible of the enhancing
of electrochemical activity. When comparing the PAN-derived
electrodes, the d-PAN (773, 24) electrode appears to be the
most promising with 73% increase in its electroactive surface
compared to the untreated electrode given rise to an effective
increase of the electrode current of almost 50%. Due to the
enhancement of the electrochemical activity of the long-term
d-PAN (773, 24) electrode is expected to be a potential application of electrode materials in VFB.

[9]

[10]

[11]

[12]

[13]

[14]

[15]

Acknowledgements
[16]

The research was supported by European Regional Development Funds (ERDF, FEDER Programa Competitivitat de Catalunya 20072013), MINECO-INNPACTO, project REDOX 2015
(IPT-2011-1690-920000), by MINECO, project NANO-EN-ESTO
(ref. MAT2010-21510), and by Ministerio de Economa y Competitividad-CONSOLIDER Ingenio 2010, project MULTICAT
(CSD2009-00050). The research was supported by EIT and
KIC-InnoEnergy under the project KIC-EES (33_2011_IP29_
Electric Energy Storage).
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