Electrochimica Acta 116 (2014) 129–136

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

High-performance and renewable supercapacitors based on TiO2

nanotube array electrodes treated by an electrochemical doping
approach
Hui Wu a,b , Dongdong Li b , Xufei Zhu a , Chunyan Yang a , Dongfang Liu b , Xiaoyuan Chen b ,
Ye Song a,∗ , Linfeng Lu b,∗
a
Key Laboratory of Soft Chemistry and Functional Materials of Education Ministry, Nanjing University of Science and Technology, Nanjing 210094, China
b
Shanghai Advanced Research Institute, Chinese Academy of Sciences, 99 Haike Road, Zhangjiang Hi-Tech Park, Pudong, Shanghai 201210, China

a r t i c l e i n f o a b s t r a c t

Article history: Although one-dimensional anodic TiO2 nanotube arrays have shown promise as supercapacitor electrode
Received 22 July 2013 materials, their poor electronic conductivity embarrasses the practical applications. Here, we develop
Received in revised form a simple electrochemical doping method to significantly improve the electronic conductivity and the
20 September 2013
electrochemical performances of TiO2 nanotube electrodes. These TiO2 nanotube electrodes treated by the
Accepted 11 October 2013
electrochemical hydrogenation doping (TiO2 -H) exhibit a very high average specific capacitance of 20.08
Available online 18 November 2013
mF cm−2 at a current density of 0.05 mA cm−2 , ∼20 times more than the pristine TiO2 nanotube electrodes.
The improved electrochemical performances can be attributed to ultrahigh conductivity of TiO2 -H due
Keywords:
Electrochemical doping
to the introduction of interstitial hydrogen ions and oxygen vacancies by the doping. The supercapacitor
Hydrogenation device assembled by the doped electrodes delivers a specific capacitance of 5.42 mF cm−2 and power
TiO2 nanotubes density of 27.66 mW cm−2 , on average, at the current density of 0.05 mA cm−2 . The device also shows an
Supercapacitor outstanding rate capability with 60% specific capacitance retained when the current density increases
from 0.05 to 4.00 mA cm−2 . More interestingly, the electrochemical performances of the supercapacitor
after cycling can be recovered by the same doping process. This strategy boosts the performances of the
supercapacitor, especially cycling stability.
© 2013 Elsevier Ltd. All rights reserved.

1. Introduction conductivity. Therefore, substantial improvement in conductivity

Anodic TiO2 nanotube arrays have attracted considerable atten-
tion due to their remarkable functionalities in light harvesting
[1–3], electrochromic switching [4], environmental sensing [5],
energy storage devices [6,7], etc. Particularly, one-dimensional
TiO2 nanotube arrays fabricated by anodization of titanium (Ti)
have been extensively investigated as a promising electrode mate-
rial for supercapacitors because of their high surface area, excellent
chemical stability and wide potential window. Furthermore, this
vertically oriented TiO2 nanotube arrays provide a direct pathway
for electron transport along the long axis of nanotubes to the Ti
foil substrate and can be employed directly as a supercapacitor
electrode. However, the pristine (without intentional doping or
modification) TiO2 nanotube arrays generally suffer from poor
capacitive behavior, since TiO2 is a wide bandgap semiconduc-
tor (3.2 eV for anatase and 3.0 eV for rutile) [8] with a limited
∗ Corresponding author. Tel.: +86 25 84315949; fax: +86 25 84276082.
E-mail addresses: soong ye@sohu.com (Y. Song), lulf@sari.ac.cn (L. Lu).
of TiO2 is needed for supercapacitor electrode materials. It is known
that an increase in electrical conductivity of TiO2 can be achieved
through introducing metal [9] or nonmetal impurities [10] into
the oxide, which can generate donor or acceptor states in the
bandgap and thereby increase the concentration of charge carriers.
Consequently, numerous research efforts concerning the doping
or modification of TiO2 material have been made. For instance,
Nakamura et al. [11] prepared plasma-treated TiO2 powders by
radio-frequency discharge under 2 Torr H2 at 673 K. The photocat-
alytic activity for NO removal appeared in the visible light region
up to 600 nm after treating the TiO2 powders in the hydrogen
plasma. They attributed the improved photocatalytic activity of the
plasma-treated TiO2 powders to the newly formed oxygen vacancy
states between the valence and the conduction bands in the TiO2
band structure. Schmuki et al. [12] indicated that TiO2 nanotube
arrays could be converted to a highly conductive phase by a high-
temperature treatment in acetylene. The as-prepared C-doped TiO2
nanotube arrays showed semimetallic conductivity, which could
be used as a highly efficient support for electrocatalytic reactions.
Recently, Lu et al. [13] have shown that hydrogenation can improve
significantly the electrochemical performance of TiO2 as electrode

0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.10.092
130 H. Wu et al. / Electrochimica Acta 116 (2014) 129–136
materials for supercapacitors. The hydrogenated TiO2 electrodes
were obtained by calcination of anodic TiO2 nanotube arrays in
hydrogen atmosphere at high temperatures. They found that TiO2
nanotube arrays hydrogenated at 400 ◦ C achieved the highest spe-
cific capacitances (i.e., capacitance per unit planar area) of 3.24 mF
cm−2 at a scan rate of 100 mV s−1 with excellent rate capability and
long-term stability. They suggested that the enhanced capacitive
performance could be ascribed to the combined contribution from
the improved donor (oxygen vacancy) density and the increased
density of surface hydroxyl groups of TiO2 nanotube arrays.
However, it is worth noting that the above-mentioned doping
or treatment methods were realized by using either expensive
facilities [11], or high processing temperatures [12,13], or a long
duration process [13]. For practical applications, a simple and fast
approach to modification of TiO2 for improved electrochemical
properties is highly desirable. In fact, TiO2 can also be modi-
fied at ambient temperature by electrochemical doping processes
[2,3,14,15]. For example, Schmuki and coworkers [15] have devel-
oped a reductive doping process to form a more conductive layer at
the bottom of TiO2 nanotubes (i.e., the barrier layer). In the doping
process, the Ti4+ ions at the nanotube barrier layer can be reduced
to Ti3+ ions (Ti4+ O2 + e− + H+ → Ti3+ (O)(OH)). The presence of Ti3+
dopant as a donor center results in a high-conductivity barrier layer.
Based on a similar reductive doping technique, a high-quality tube-
in-tube structure (copper and nickel nanotubes embedded in TiO2
nanotubes) has been fabricated in our recent work, demonstrat-
ing enhanced solar cell performance [2]. More recently, we tried to
detach the TiO2 nanotube film from the Ti foil substrates by uti-
lizing the impact of H2 evolution, which was generated when the
TiO2 nanotube film was biased to enough negative potentials for the
hydrogen evolution reaction. Although the experimental attempt
has failed, the color of the TiO2 nanotube film was found to become
darker during H2 evolution. This color change was reminiscent of
black hydrogenated TiO2 nanocrystals [16], which motivated us to
explore the electrochemical properties of the TiO2 nanotube films
treated via H2 evolution processing. On the basis of the experimen-
tal results, we developed a facile, fast and low-cost electrochemical
hydrogenation doping method to enhance electrochemical per-
formances of TiO2 nanotube films. The capacitive properties of TiO2
nanotube films show a substantial enhancement after the electro-
chemical hydrogenation, which are well beyond those previously
reported [13,17,18]. More interestingly, the degradation of perfor-
mance for the TiO2 nanotube electrodes after cycling can be readily
recovered by the same doping process, which makes it possible to
fabricate a renewable supercapacitor whose performances can be
reversibly restored.
2. Experimental details
2.1. Reagents
Ti foils (99.9% purity, 0.2 mm thickness) were purchased from
Shanghai Shangmu Technology Co. Ltd, China. Acetone, ethanol,
sodium sulfate (Na2 SO4 ), lithium sulfate (Li2 SO4 ) were obtained
from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China).
Ammonium fluoride (NH4 F) was purchased from Sigma-Aldrich
Chemie GmbH. All chemical reagents were analytical grade. The
deionized water was used throughout the whole experiment.
2.2. Preparation of TiO2 nanotube arrays
Highly ordered TiO2 nanotube array films were fabricated by
two-step anodization of Ti foils (1 cm × 2 cm) in a two-electrode
configuration with a carbon rod as cathode. The details were
described elsewhere [2,3]. Briefly, Ti foils were cleaned by
ultrasonication for 10 min in acetone, ethanol and deionized water
sequentially after thermal annealing (450 ◦ C for 2 h). Then, the
cleaned Ti foils were firstly anodized at 60 V for 2 h in ethylene
glycol electrolyte containing 0.5 wt. % NH4 F and 2 vol. % H2 O. The
as-prepared nanotube films were removed by ultrasonication in
deionized water for 30 min. Subsequently, the second anodization
was performed under the same conditions as the first anodization
process. Finally, the fabricated TiO2 nanotube arrays were annealed
in air at 150 ◦ C for 2 h, then up to 450 ◦ C for 3 h to form TiO2 anatase
phase.
2.3. Electrochemical doping of TiO2 nanotube films and assembly
of supercapacitor devices
Electrochemical hydrogenation doping of TiO2 nanotube films
were also performed in the above two-electrode cell except that
the TiO2 nanotube films (1 cm × 1 cm) were used as cathode and the
carbon rod as anode. The optimum doping process was as follows:
a voltage of 5 V was applied across the two electrodes for 30 s in
a 0.5 M Na2 SO4 solution and the distance between the electrodes
was 2.5 cm. This was actually a process of electrolysis of water,
during which hydrogen and oxygen evolution could be observed
obviously at the surface of the TiO2 nanotube films and the car-
bon rod, respectively. The doped samples (denoted as TiO2 -H) were
washed by deionized water and dried in air at ambient tempera-
tures. Symmetric supercapacitors were assembled by two identical
pieces of TiO2 -H electrodes (each with area of 0.7 cm2 ), which were
sandwiched by a glass fibre separator (Whatman) soaked with a
2 M Li2 SO4 aqueous solution. To assess renewability of the super-
capacitors, the TiO2 -H electrodes were taken out from the devices
after 2500 charge-discharge cycles and re-doped using the same
doping process as described above. Then the supercapacitors were
reassembled by employing the re-doped TiO2 -H electrodes and the
same cycle-life tests were carried out again.
2.4. Materials and devices characterization
The morphology and crystal structure of the TiO2 samples were
examined by field emission scanning electron microscopy (FESEM,
NOVA Nano SEM 230, with an accelerating voltage 5 kV) and X-
ray diffractometer (XRD, Bruker-AXS D8 ADVANCE at 40 kV voltage
and 40 mA current with Cu-K␣ radiation). Their composition and
chemical state analysis were characterized by the X-ray Photo-
electron Spectroscopy (XPS, Shimadzu-kratos AXIS Ultra DLD) and
Raman spectroscopy (Thermo Scientific DXR Raman microscope
with 532 nm excitation laser). Electrochemical performances of
the samples were evaluated using AUTOLAB PGSTAT302 N/FRA2.
Unless otherwise stated, electrochemical experiments for TiO2
electrodes were carried out in 2 M Li2 SO4 aqueous solution in a
three-electrode configuration, where a Ag/AgCl (3 M KCl) electrode
was used as reference electrode and a Pt sheet as counter elec-
trode. Cyclic voltammetry (CV) and galvanostatic charge-discharge
tests for the TiO2 electrodes with active area of 0.7 cm2 were
performed over a potential range from -0.3 to 0.6 V. Electrochemi-
cal impedance spectroscopy (EIS) measurements were carried out
over a frequency range of 100 kHz to 0.1 Hz with AC signal ampli-
tude of 10 mV at 0 V bias potential. The symmetric supercapacitors
were subjected to a galvanostatic charge-discharge test between
0 and 0.9 V under different current densities in the range of 0.05
to 4.00 mA cm−2 . The cycling stability for the supercapacitors was
tested by using a continuous charge-discharge cycling at a current
density of 0.10 mA cm−2 . The impedance spectra were analyzed
using the software of ZSimpWin (V3.10). The cycle life of the
supercapacitors was investigated by a battery test system (LAND,
CT2001A).
 H. Wu et al. / Electrochimica Acta 116 (2014) 129–136
3. Results and discussion
Generally, the electrochemical hydrogenation doping of TiO2
nanotube films is accompanied by a remarkable color change.
Specifically, the nanotube powders reveal a color evolution from
white (pristine TiO2 ) to gray-blue (TiO2 -H) when they were scraped
off Ti foil substrates with a razor blade, as shown in the inset of
Fig. 1b and c. The evolution of optical properties could be attributed
to the increased defect density [16,19]. The FESEM images of TiO2
nanotube films before and after the electrochemical doping are
shown in Fig. 1. The pristine TiO2 nanotubes have an inner diameter
of ∼60 nm, a wall thickness of ∼35 nm and a tube length of about
15 ␮m. These parameters of the nanotubes do not show any sig-
nificant change after the electrochemical doping. Highly ordered
nanotube arrays can still be observed for TiO2 -H, indicating that
the H2 evolution during the doping process does not damage the
nanotube structure of the films.
XRD patterns of the nanotube films without and with the doping
are shown in Fig. 2a. All peaks for both pristine and doped TiO2 can
be readily indexed to anatase TiO2 (JCPDF No. 21-1272) except for
the peaks at 40.05o , 52.87o and 70.05o originated from Ti metal sub-
strates. The average crystallite sizes (D) of pristine TiO2 and TiO2 -H
are about 32.0 and 31.0 nm, estimated from (101) and (200) peaks
by using Scherrer’s equation [20]. It is concluded that there is no
change in the crystal structure and particle sizes of TiO2 nanotube
arrays after the electrochemical doping.
Their structural properties are further characterized by Raman
spectroscopy analysis. Fig. 2b exhibits the Raman spectra of pris-
tine TiO2 and TiO2 -H treated by the electrochemical doping for 10
s, 30 s and 60 s, respectively. In general, the Raman peaks of pristine
TiO2 are recorded at 145.6 cm−1 (Eg ), 198.6 cm−1 (Eg ), 397.3 cm−1
(B1g ), 517.8 cm−1 (A1g /B1g ) and 639.3 cm−1 (Eg ), which correspond
to anatase TiO2 . The Eg peak is more sensitive to oxygen deficiencies
than the Ti–O stretching mode [17]. A slightly blue-shift and broad-
ening of the Eg peaks at 145.6 and 198.6 cm−1 can be identified in
all TiO2 -H samples. Several factors such as phonon confinement
[21], non-homogeneity of the particle size [22], nonstoichiometry
lattice defect [23], can contribute to the changes in the peak posi-
tion and shape of the Eg Raman mode in anatase TiO2 . The phonon
confinement is the dominant factor by finite grains size (<10 nm)
or short correlation length [19]. However, the relatively big crystal
size (D > 20 nm) obtained from XRD data rules out the possibility
of size confinement effects. Hence, the blue-shift and peak broad-
ening are attributed to oxygen vacancies that originate from Ti4+
reduction. The O 1s XPS spectroscopies of pristine TiO2 and TiO2 -H
are shown in Fig. 2c. Both the peaks of TiO2 and TiO2 -H centered at
529.8 and 531.1 eV are attributed to Ti-O and Ti-OH [24]. There is no
noticeable change in the peak at 531.1 eV between TiO2 and TiO2 -
H, implying that the incorporated hydrogen does not contribute to
form new O–H bonds in TiO2 nanocrystals.
Fig. 3a displays the CV curves of pristine TiO2 nanotube films
as a function of scan rates. A reduction peak at around -0.06 V is
observed, which is believed to be associated with intraband gap
localized states [25,26]. It can be seen that the electroactivity of
pristine TiO2 is very low at the anodic end of the cycles, suggesting
poor capacitive behavior. The low electroactivity of pristine TiO2
at positive potentials can be ascribed to its high resistance at high
potentials [25]. Fig. 3b compares the CV responses for pristine
TiO2 and TiO2 -H electrode at a scan rate of 100 mV s−1 . Clearly,
the CV curve of TiO2 -H electrode exhibits a larger integrated area
and higher current response than those of pristine TiO2 electrode,
implying a markedly enhanced capacitive behavior after the
electrochemical doping. Furthermore, the CV curve for TiO2 -H
electrode is close to an ideal rectangular shape with no identifiable
redox peaks, which is typical characteristic of double-layer capac-
itance. Fig. 3c shows the CV curves for TiO2 -H electrode collected
131
at different scan rates over the wide range from 0.1 to 1.5 V s−1 .
These curves can still retain quasi-rectangular shape even at the
scan rate up to 1.5 V s−1 , indicating excellent capacitive behavior
and high rate capability. In addition, the average discharge current
density continues to increase linearly with the scan rate as high
as 0.50 V s−1 (Fig. 3d). The deviation of the linear dependence at
higher scan rates is believed to result from the diffusion limit of
electrolyte ions to the electrode materials [27].
The rate capability of the electrodes is also evaluated by galvano-
static charge-discharge tests at different current densities. Again,
TiO2 nanotube films exhibit dramatic differences in capacitive per-
formances between the samples without and with the doping. For
the pristine TiO2 electrode, the largest discharge current density
appears to be limited to 0.05 mA cm−2 owing to a big voltage drop
at the beginning of discharge (Fig. 4a). A relatively low areal spe-
cific capacitance of 0.97 mF cm−2 at 0.05 mA cm−2 is obtained from
the discharge curve in Fig. 4a. In contrast, TiO2 -H electrode deliv-
ers a much improved capacitance with excellent rate capability.
The doped electrode can be steadily operated over a wide range of
applied current densities from 0.05 to 4.00 mA cm−2 (Fig. 4b and
c). It is worth mentioning that the largest current density applied
in this work is significantly higher than those reported previously
[13,17,18,28]. The nearly symmetric and linear charge-discharge
curves indicate great Coulombic efficiency of the TiO2 -H electrode
at all operated current densities. In addition, the average specific
capacitances and voltage drops for the TiO2 -H electrode at different
current densities are shown in Fig. 4d. As expected, the areal specific
capacitance decreases with increasing current density due to the
limited ion diffusion. At the lowest current density (0.05 mA cm−2 ),
the TiO2 -H electrode delivers an average areal capacitance of 20.08
mF cm−2 , with areal power density of 19.29 mW cm−2 and energy
density of 2.26 mWh cm−2 . The areal specific capacitance is ∼20
times larger than that of the pristine TiO2 electrode at the same
current density, which is also higher than those reported in previ-
ous literature [13,18,29]. On the other hand, at the highest current
density (4.00 mA cm−2 ), the average areal capacitance, power den-
sity and energy density are 9.07 mF cm−2 , 31.75 mW cm−2 and
1.02 mWh cm−2 , respectively. A rather low voltage drop (0.057 V)
at the highest current density of 4.00 mA cm−2 demonstrates the
high conductivity of TiO2 -H electrode (Fig. 4d). In conclusion, the
TiO2 -H electrode exhibits only ∼55% of capacitance loss with an
80 times increase in the discharge current density (from 0.05 to
4.00 mA cm−2 ), also suggesting excellent rate capability.
In the above electrochemical process, hydrogen generated dur-
ing electrolysis will diffuse and react with TiO2 . Thus, hydrogen
ionizes to H+ with the electron being delocalized in the oxide
conduction band to result in ultrahigh electronic conductivity for
TiO2 -H [30,31]. The highly conducting TiO2 -H achieved by the
doping process is responsible for the high power characteristics
with great double-layer capacitance. Unexpectedly, a prolonged
doping time results in a deterioration of capacitance, as depicted in
Fig. 5. Under the conditions of the electrochemical hydrogenation
doping, the average areal capacitance reaches its maximum after a
doping duration of 30 s. A longer doping duration leads to a decrease
in capacitance, which could be ascribed to increased surface defect
density and the corresponding recombination rate [32,33].
Electrochemical impedance spectroscopy (EIS) is subsequently
used to evaluate the electrical conductivity and capacitive charac-
teristics of electrode materials. Fig. 6 shows the Nyquist plots of
the pristine TiO2 and TiO2 -H electrodes. At first glance, one can
note that the impedance plot for the TiO2 -H electrode exhibits a
nearly vertical line, which stands for ideal capacitor characteristics.
By contrast, the Nyquist plot for the pristine TiO2 electrode bends
down to the real axis, suggesting a poor capacitive behavior. For
quantitative analysis, experimental data of impedance spectra have
been fitted to the model depicted by the equivalent circuit shown
132 H. Wu et al. / Electrochimica Acta 116 (2014) 129–136

Fig. 1. FESEM images for (a) top view (b) side view of pristine TiO2 and (c) side view of TiO2 -H. The insets show (a) the length, (b) the color of pristine TiO2 powders and (c)
the color of TiO2 -H powders, respectively.

Fig. 2. (a) XRD patterns of pristine TiO2 and TiO2 -H. (b) Raman spectra of pristine TiO2 and TiO2 -H treated by the doping for 10 s, 30 s and 60 s. (c) O 1s core level XPS spectra
of pristine TiO2 and TiO2 -H.

Fig. 3. (a) CV curves of pristine TiO2 nanotube film at different scan rates. (b) CV curves of pristine TiO2 and TiO2 -H electrodes at a scan rate of 100 mV s−1 . (c) CV curves
of TiO2 -H recorded at different scan rates from 0.1 to 1.5 V s−1 . (d) Dependence of the discharge current density (J) on the scan rate for TiO2 -H electrode (linear relation is
obtained up to 0.50 V s−1 ).

Table 1
Best fit parameters of the equivalent circuit for the Nyquist plots shown in Fig.6.

Samples R1 ( cm2 ) C (mF cm−2 ) R2 ( cm2 ) Y (S sn cm−2 ) n R3 ( cm2 ) 2

−5
pristine TiO2 4.18 0.33 4927 4.56 × 10 0.82 2478 1.96 × 10−3
TiO2 -H 4.44 18.93 0.16 1.42 × 10−2 0.93 899 1.47 × 10−4
 H. Wu et al. / Electrochimica Acta 116 (2014) 129–136 133

Fig. 4. Galvanostatic charge-discharge curves of (a) pristine TiO2 achieved from 0.01 to 0.10 mA cm−2 and TiO2 -H achieved (b) from 0.05 to 0.50 mA cm−2 and (c) from 1.00
to 4.00 mA cm−2 . (d) The average specific capacitances and voltage drops for TiO2 -H at different discharge current densities.

in the inset of Fig. 6a [28,34,35]. The fitting curves are presented

as a solid line and the experimental data are denoted as an indi-
vidual symbol. In this model, R1 is the resistance of the electrolyte
(2 M Li2 SO4 solution). R2 and C are the resistance and Helmholtz
double-layer capacitance of TiO2 nanotube arrays, respectively. The
parallel combination of the interfacial charge transfer resistance
(R3 ) and the constant phase element (CPE) is also included in this
circuit. The CPE instead of a capacitor is taken to account for fre-
quency dispersion [28]. It is well known that the impedance of CPE
is given by ZCPE = Y−1 (jω)-n , where Y is a frequency-independent fit
parameter, n the CPE exponent, ω (=2f) the angular frequency. The
exponent n has the meaning of a phase shift, which lies between -1
and 1. Table 1 lists the fitted parameter values for pristine TiO2 and
TiO2 -H electrodes. As expected, the R1 (solution resistance) value
is similar for both TiO2 electrodes because of the utilization of the
same test solution (2 M Li2 SO4 solution). The resistance R2 of TiO2
Fig. 5. Average areal capacitances at 0.05 mA cm−2 for TiO2 -H doped with different
times.
nanotube arrays is significantly reduced from 4927  cm2 (pristine
TiO2 ) to 0.16  cm2 (TiO2 -H), whereas the electrochemical double-
layer capacitance is increased from 0.33 mF cm−2 (pristine TiO2 )
to 18.93 mF cm−2 (TiO2 -H). The TiO2 -H electrode also presents a
noticeable decrease in charge transfer resistance R3 compared with

Fig. 6. Nyquist plots for (a) pristine TiO2 and (b) TiO2 -H electrodes. The solid line is the fitting curve. The insets show (a) the equivalent circuit used in the simulation and (b)
the magnified high-frequency region.
134 H. Wu et al. / Electrochimica Acta 116 (2014) 129–136

Fig. 7. Galvanostatic charge-discharge curves of supercapacitors as a function of current density: (a) 0.05 to 0.50 mA cm−2 and (b) 1.00 to 4.00 mA cm−2 . (c) The average areal
capacitances and voltage drops of supercapacitor at different discharge current densities.

the pristine TiO2 electrode. Moreover, the capacitance of 18.93 mF
cm−2 for the TiO2 -H electrode is close to the value 20.08 mF cm−2
obtained in the above galvanostatic charge-discharge tests. The EIS
experiments also demonstrate that the conductivity and capacitive
performance of TiO2 nanotube films can be markedly enhanced by
the electrochemical doping.
To more accurately evaluate the capacitive performances of the
TiO2 -H electrodes, a symmetric supercapacitor device was assem-
bled by two identical pieces of TiO2 -H electrodes in this study.
The galvanostatic charge-discharge tests for the supercapacitors
are also conducted at different current densities as shown in Fig. 7a
and b. The smooth and symmetrical curves confirm great capac-
itive behavior of the device. Fig. 7c exhibits the average specific
capacitances and voltage drops for the device at different current
densities. The supercapacitors deliver a high average specific capac-
itance of 5.42 mF cm−2 with a power density of 27.66 mW cm−2
at 0.05 mA cm−2 . While applying elevated charge-discharge cur-
rent density up to 4.00 mA cm−2 , a significantly enhanced power
density of 97.45 mW cm−2 is achieved with an average specific
capacitance of 3.28 mF cm−2 . In other words, the devices exhibit
only ∼40% loss in capacitance and ∼252% increase in power density
when the discharge current density increases 80 times (from 0.05
to 4.00 mA cm−2 ), indicating an outstanding rate capability. The EIS
spectrum of the supercapacitor device is shown in Fig. 8c (curve 1).
Generally, the Nyquist plot of the electrochemical supercapacitor
is composed of a high frequency semicircle and a low frequency
nearly vertical line. The semicircle intersection with the abscissa
depends on the internal resistance (including the solution resis-
tance, the charge transfer resistance, the electrode resistance, etc.),
and the vertical line implies good capacitive behaviors of super-
capacitors [27]. The very small semicircle diameter in the high
frequency region of curve 1 (Fig. 8c, inset) suggests low internal
resistance of the supercapacitor device, which coincides with slight
voltage drops in charge-discharge curves (Fig. 7c).
The cycling stability is one of the most important properties
of supercapacitors. Fig. 8a shows the specific capacitance of an
as-fabricated supercapacitor as a function of cycle numbers. The
specific capacitance of the supercapacitor decreases considerably
during the first 1000 cycles, with about 30% loss in capacitance.
Thereafter, it decreases slowly and still retains more than 60% of
initial capacitance at the end of 5000 cycles. The gradual loss of
capacitance during cycling can be attributed to the metastable fea-
ture of the incorporated hydrogen in TiO2 [30]. It has been proposed
that hydrogen as a shallow donor can ionize to H+ with the electron
being delocalized in the oxide conduction band. Then the H+ ions
form some weak bonds with more than one surrounding O site and
exist as a metastable interstitial rather than a strong O-H bond in
TiO2 [30,31]. This is consistent with the above XPS results. Since
the interstitial hydrogen ions are only metastable, they could grad-
ually diffuse out from TiO2 -H nanotube electrodes during cycling. It
is believed that the gradual loss of incorporated hydrogen in TiO2 is
responsible for the degradation of capacitance of the supercapacitor
during cycling.
On the other hand, the performances of the supercapacitor
assembled by the TiO2 -H electrodes are also expected to be
recovered by re-introducing hydrogen into TiO2 via the same
electrochemical hydrogenation doping. Therefore, in order to
demonstrate this idea, another as-fabricated supercapacitor was
subjected to a continuous cycling for 2500 cycles under the
same condition as the above cycling test. The specific capaci-
tance of the supercapacitor is 5.78 mF cm−2 at the beginning
of cycling, then gradually decreases to 3.78 mF cm−2 at the end

Fig. 8. (a) Capacitance retention vs. cycle number for a supercapacitor up to 5000 cycles. (b) Capacitance retention vs. cycle number for a supercapacitor whose electrodes were
re-doped after 2500 cycles. The inset shows galvanostatic charge-discharge curves of 1st and 2500th cycles at different cycling stages. (c) Nyquist plots of (1) as-fabricated
supercapacitor, (2) after the first cycling test, (3) renewed supercapacitor and (4) after the second cycling test. The inset shows the high frequency regions of Nyquist plots.
 H. Wu et al. / Electrochimica Acta 116 (2014) 129–136
of 2500 cycles as shown in Fig. 8b (curve 1). Further, the semi-
circle diameter in the high frequency region in Nyquist plot of
the supercapacitor becomes larger as shown in Fig. 8c (inset,
curve 2), implying an increased internal resistance of the super-
capacitor after 2500 cycles. Subsequently, the supercapacitor was
disassembled and the electrodes were taken out, followed by
the same doping process on the electrodes. The re-doped TiO2 -
H electrodes were then reassembled into supercapacitor device
once again. As expected, the renewed supercapacitor displays an
excellent capacitance recovery, which has an initial specific capac-
itance of 6.11 mF cm−2 even higher than the one before the first
cycling test (Fig. 8b, curve 2). In addition, the semicircle diam-
eter in the high frequency region in Nyquist plot returns to a
low value, as shown in Fig. 8c (inset, curve 3), indicating that the
doping method is really capable of increasing the conductivity of
TiO2 -H electrodes and decreasing the internal resistance of the
supercapacitor.
The renewed supercapacitor was also subjected to cycling for
another 2500 cycles as shown in Fig. 8b (curve 2). The cycle-
life plot shows a similar decreasing tendency as the first cycling
test, demonstrating that the performance of the supercapacitor
can indeed be recovered by simply applying the electrochem-
ical doping. To further confirm the feasibility of this renewal
method, we performed the third cycling test for the superca-
pacitor renewed once more by the same method as above. As
shown in Fig. 8b (curve 3), the variation in capacitance is still
similar to what was observed in the first cycling test. In addi-
tion, the inset of Fig. 8b illustrates galvanostatic charge-discharge
curves of 1st and 2500th cycles in three cycling tests. It is evident
that the charge-discharge curves of the first and the last cycles
in three cycling tests are close to each other, also indicating a
good capacitance recovery. These experiment results unambigu-
ously prove that the attenuated performance of the supercapacitor
after cycling can be recovered by the simple doping process.
This technology makes the supercapacitor have a prolonged cycle
life.
4. Conclusions
In summary, we have reported a facile and cost-effective
electrochemical hydrogenation doping method to enhance elec-
trochemical properties of TiO2 nanotube array films, which make
them good candidates to be used in renewable supercapacitors
whose performances can be repeatedly refreshed. The nanotube
array electrode through the electrochemical doping delivers the
average specific capacitances of 20.08 mF cm−2 at 0.05 mA cm−2
and 9.07 mF cm−2 at 4.00 mA cm−2 , respectively. And the super-
capacitor device assembled by two identical pieces of the TiO2 -H
electrodes shows an excellent rate capability with the average spe-
cific capacitances of 5.42 mF cm−2 at 0.05 mA cm−2 and 3.28 mF
cm−2 at 4.00 mA cm−2 , respectively. The improved electrochemical
performances can be attributed to the ultrahigh conductivity due
to introduced oxygen vacancies and the interstitial ionized hydro-
gen. More interestingly, the electrochemical performances of the
supercapacitor after the charge-discharge cycling can be recovered
easily by the simple electrochemical doping. Further, this renew-
able technology may be more effective and convenient for the
unsymmetric supercapacitor (e.g., TiO2 -H as cathode and carbon
material as anode) because it is a cathodic reduction process in
nature.
Acknowledgments
This work was financially supported by the National Natu-
ral Science Foundation of China (51102271, 51077072, 61171043,
135
11174308), Science & Technology Commission of Shanghai Munic-
ipality (10DZ1210300), Natural Science Foundation of Shanghai
(11ZR1436300), Shanghai Rising-Star Program (11QA1406400),
and Shanghai Municipal Human Resources and Social Security
Bureau (2011033).
References
[1] O.K. Varghese, M. Paulose, C.A. Grimes, Long vertically aligned titania nano-
tubes on transparent conducting oxide for highly efficient solar cells, Nature
Nanotechnology 4 (2009) 592.
[2] D.D. Li, P.C. Chang, C.J. Chien, J.G. Lu, Applications of tunable TiO2 nanotubes
as nanotemplate and photovoltaic device, Chemistry of Materials 22 (2010)
5707.
[3] D.D. Li, C.J. Chien, S. Deora, P.C. Chang, E. Moulin, J.G. Lu, Prototype of a
scalable core-shell Cu2 O/TiO2 solar cell, Chemical Physics Letters 501 (2011)
446.
[4] A. Ghicov, S.P. Alba, J.M. Macak, P. Schmuki, High-contrast electrochromic
switching using transparent lift-off layers of self-organized TiO2 nanotubes,
Small 4 (2008) 1063.
[5] H.G. Moon, Y.S. Shim, D. Su, H.H. Park, S.J. Yoon, H.W. Jang, Embossed
TiO2 thin films with tailored links between hollow hemispheres: synthe-
sis and gas-sensing properties, Journal of Physical Chemistry C 115 (2011)
9993.
[6] W.K. Zhang, L. Wang, H. Huang, Y.P. Gan, C.T. Wang, X.Y. Tao, Light energy stor-
age and photoelectrochemical behavior of the titanate nanotube array/Ni(OH)2
electrode, Electrochimica Acta 54 (2009) 4760.
[7] J.H. Kim, K. Zhu, J.Y. Kim, A.J. Frank, Tailoring oriented TiO2 nanotube morphol-
ogy for improved Li storage kinetics, Electrochimica Acta 88 (2013) 123.
[8] A. Bendavid, P.J. Martin, A. Jamting, H. Takikawa, Structural and optical proper-
ties of titanium oxide thin films deposited by filtered arc deposition, Thin Solid
Films 355 (1999) 6.
[9] Z.K. Zheng, B.B. Huang, X.Y. Qin, X.Y. Zhang, Y. Dai, M.H. Whangbo, Facile in situ
synthesis of visible-light plasmonic photocatalysts M@TiO2 (M = Au, Pt, Ag) and
evaluation of their photocatalytic oxidation of benzene to phenol, Journal of
Materials Chemistry 21 (2011) 9079.
[10] X. Chen, S.S. Mao, Titanium dioxide nanomaterials: synthesis, properties, mod-
ifications, and applications, Chemical Reviews 107 (2007) 2891.
[11] I. Nakamura, N. Negishi, S. Kutsuna, T. Ihara, S. Sugihara, E. Takeuchi, Role of
oxygen vacancy in the plasma-treated TiO2 photocatalyst with visible light
activity for NO removal, Journal of Molecular Catalysis A-Chemical 161 (2000)
205.
[12] R. Hahn, F. Schmidt-Stein, J. Salonen, S. Thiemann, Y.Y. Song, J. Kunze, V.P. Lehto,
P. Schmuki, Semimetallic TiO2 nanotubes, Angewandte Chemie-International
Edition 48 (2009) 7236.
[13] X.H. Lu, G.M. Wang, T. Zhai, M.H. Yu, J.Y. Gan, Y.X. Tong, Y. Li, Hydro-
genated TiO2 nanotube arrays for supercapacitors, Nano Letters 12 (2012)
1690.
[14] F. Fabregat-Santiago, E.M. Barea, J. Bisquert, G.K. Mor, K. Shankar, C.A. Grimes,
High carrier density and capacitance in TiO2 nanotube arrays induced by elec-
trochemical doping, Journal of the American Chemical Society 130 (2008)
11312.
[15] J.M. Macak, B.G. Gong, M. Hueppe, P. Schmuki, Filling of TiO2 nanotubes by
self-doping and electrodeposition, Advanced Materials 19 (2007) 3027.
[16] X.B. Chen, L. Liu, P.Y. Yu, S.S. Mao, Increasing solar absorption for photocatalysis
with black hydrogenated titanium dioxide nanocrystals, Science 331 (2011)
746.
[17] M. Salari, K. Konstantinov, H.K. Liu, Enhancement of the capacitance in TiO2
nanotubes through controlled introduction of oxygen vacancies, Journal of
Materials Chemistry 21 (2011) 5128.
[18] H. Zhou, Y. Zhang, Enhancing the capacitance of TiO2 nanotube arrays by a facile
cathodic reduction process, Journal of Power Sources 239 (2013) 128.
[19] A. Naldoni, M. Allieta, S. Santangelo, M. Marelli, F. Fabbri, S. Cappelli, C.L. Bianchi,
R. Psaro, V. Dal Santo, Effect of nature and location of defects on bandgap nar-
rowing in black TiO2 nanoparticles, Journal of the American Chemical Society
134 (2012) 7600.
[20] S. Sathyamoorthy, G.D. Moggridge, M.J. Hounslow, Controlling particle size
during anatase precipitation, AICHE Journal 47 (2001) 2012.
[21] K.R. Zhu, M.S. Zhang, Q. Chen, Z. Yin, Size and phonon-confinement effects on
low-frequency Raman mode of anatase TiO2 nanocrystal, Physics Letters A 340
(2005) 220.
[22] M.J. Šćepanović, M. Grujić-Brojčin, Z.D. Dohčević-Mitrović, Z.V. Popović,
Temperature dependence of the lowest frequency Eg Raman mode in laser-
synthesized anatase TiO2 nanopowder, Applied Physics A-Materials Science &
Processing 86 (2007) 365.
[23] J.C. Parker, R.W. Siegel, Calibration of the Raman-spectrum to the oxygen stoi-
chiometry of nanophase TiO2 , Applied Physics Letters 57 (1990) 943.
[24] K.R. Reyes-Gil, E.A. Reyes-García, D. Raftery, Nitrogen-doped In2 O3 thin film
electrodes for photocatalytic water splitting, Journal of Physical Chemistry C
111 (2007) 14579.
[25] F. Fabregat-Santiago, I. Mora-Seró, G. Garcia-Belmonte, J. Bisquert, Cyclic
voltammetry studies of nanoporous semiconductors. Capacitive and reactive
136 H. Wu et al. / Electrochimica Acta 116 (2014) 129–136
properties of nanocrystalline TiO2 electrodes in aqueous electrolyte, Journal of
Physical Chemistry B 107 (2003) 758.
[26] G. Boschloo, D. Fitzmaurice, Spectroelectrochemical investigation of surface
states in nanostructured TiO2 electrodes, Journal of Physical Chemistry B 103
(1999) 2228.
[27] W. Chen, R.B. Rakhi, L.B. Hu, X. Xie, Y. Cui, H.N. Alshareef, High-performance
nanostructured supercapacitors on a sponge, Nano Letters 11 (2011)
5165.
[28] M. Salari, S.H. Aboutalebi, A.T. Chidembo, I.P. Nevirkovets, K. Konstantinov,
H.K. Liu, Enhancement of the electrochemical capacitance of TiO2 nanotube
arrays through controlled phase transformation of anatase to rutile, Physical
Chemistry Chemical Physics 14 (2012) 4770.
[29] M.S. Kim, T.W. Lee, J.H. Parka, Controlled TiO2 nanotube arrays as an active
material for high power energy-storage devices, Journal of the Electrochemical
Society 156 (2009) A584.
[30] W.P. Chen, Y. Wang, H.L.W. Chan, Hydrogen A metastable donor in TiO2 single
crystals, Applied Physics Letters 92 (2008) 112907.
[31] W.P. Chen, Y. Wang, J.Y. Dai, S.G. Lu, X.X. Wang, P.F. Lee, H.L.W. Chan, C.L. Choy,
Spontaneous recovery of hydrogen-degraded TiO2 ceramic capacitors, Applied
Physics Letters 84 (2004) 103.
[32] N.L. Wu, Nanocrystalline oxide supercapacitors, Materials Chemistry and
Physics 75 (2002) 6.
[33] A.G. Muñoz, Semiconducting properties of self-organized TiO2 nanotubes, Elec-
trochimica Acta 52 (2007) 4167.
[34] P. Xiao, B.B. Garcia, Q. Guo, D. Liu, G. Cao, TiO2 nanotube arrays fabricated by
anodization in different electrolytes for biosensing, Electrochemistry Commu-
nications 9 (2007) 2441.
[35] V.C. Anitha, D. Menon, S.V. Nair, R. Prasanth, Electrochemical tuning of titania
nanotube morphology in inhibitor electrolytes, Electrochimica Acta 55 (2010)
3703.