Journal of Power Sources 299 (2015) 301e308

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Journal of Power Sources

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

Porous carbon derived from disposable shaddock peel as an excellent

catalyst toward VO2þ/VO2 þ couple for vanadium redox battery
J. Liu a, c, d, Z.A. Wang b, X.W. Wu a, **, X.H. Yuan a, c, J.P. Hu a, c, Q.M. Zhou d, ***,
Z.H. Liu a, ****, Y.P. Wu a, c, d, *
a
College of Science, National Research Center of Engineering Technology for Utilization of Functional Ingredients from Botanica, College of Agronomy,
Hunan Agricultural University, Changsha 410128, China
b
School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
c
College of Energy, Nanjing Tech University, Nanjing 211816, Jiangsu Province, China
d
Department of Chemistry, Fudan University, Shanghai 200433, China

h i g h l i g h t s

 A porous carbon (PC) is for the first time prepared from bio-friendly shaddock peel.
 It can act as good catalyst for vanadium redox flow battery (VRB).
 The prepared VRB presents good electrochemical performance.

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

Article history: Functional porous carbon (PC) derived from bio-friendly shaddock peel has been firstly explored as
Received 2 June 2015 catalyst for vanadium redox flow battery (VRB). The prepared PC is micro-mesoporous with high BET
Received in revised form surface area of 882.7 m2 g1, has some surface oxygen-containing functional groups, and is doped with N
14 August 2015
and P heteroatoms. These three factors greatly favor the electrochemical reactions of VO2þ/VO2 þ on the
Accepted 1 September 2015
PC modified glass carbon (PC-GC). Compared with the naked GC and graphite modified GC, the PC-GC
Available online xxx
presents a lower peak separation (66 mV), higher anodic current density (17.1 mA cm2) and cathodic
current density (15.0 mA cm2). The VRB using PC modified graphite felt (GF) as positive electrode
Keywords:
Redox flow battery
demonstrates an enhanced voltage efficiency of 82.7% at the current density of 60 mA cm2, and a better
Vanadium rate performance than that from the virginal GF.
Porous carbon © 2015 Elsevier B.V. All rights reserved.
Catalyst
Biomass

1. Introduction issues [1]. Renewable energy possesses the characteristics of inex-

haustible and environmentally friendliness. However, their inherent
With the deveopment of current economy, there is an increasing properties like variable and intermittent limit their broad utilization.
demand for electricity to meet people's daily life. Electricity pro- According to an analysis, if the renewable energy is >15% capacitance
duced from fossil fuels leads to the depletion of fossil resource and a of grid without energy storage, the electric grid could be destabilized.
serial of environmental pollution such as air pollution and water Therefore, there is an unprecedentedly demand for high-efficiency
contamination. Energies derived from renewable resources such as electric energy storage systems (EESs) as an intermediate to con-
wind, solar and tide provide a solution to deal with these challenging nect renewable energy and electric grids [2e4].
Lithium ion batteries with higher energy density have been
developed as portable power sources. Their inherent safety prob-
* Corresponding author. College of Energy, Nanjing Tech University, Nanjing lem introduced by the used organic electrolyte blocks their wide
211816, Jiangsu Province, China. application in large-scale EES. Aqueous rechargeable batteries are
** Corresponding author.
of great potential to overcome these shortcomings since non-
*** Corresponding author.
**** Corresponding author.
flammable aqueous electrolytes are used instead of flammable
E-mail address: [email protected] (Y.P. Wu). organic electrolytes [5e7]. Among them, vanadium redox flow

http://dx.doi.org/10.1016/j.jpowsour.2015.09.004
0378-7753/© 2015 Elsevier B.V. All rights reserved.
302 J. Liu et al. / Journal of Power Sources 299 (2015) 301e308

batteries (VRBs) are one of the most promising technologies In detail, a disposable shaddock peel was cut into small cubes and
because of their superior characteristics such as safety, longevity, dried in oven at 80  C for 24 h prior to use. During the hydrothermal
low-cost and flexible design. Furthermore, the issue of cross- process, 1.5 g dried shaddock peel powder after grinding was put
contamination caused by the diffusion of ions from membrane is into a Teflon-lined stainless autoclave contains 35 ml 55% H3PO4.
eliminated due to the use of identical vanadium element in both Then, the autoclave was sealed and placed in a muffle at a tem-
positive and negative electrolytes [8,9]. perature of 180  C for 12 h. After cooled down to room temperature,
In spite of the above advantages, the energy efficiency of VRB is the sample was taken out, filtered by vacuum filtration, and dried at
unsatisfied due to the high cell polarization at high charge/ 105  C. Next, the black products were calcified at 800  C under the
discharge current density, and should be improved prior to its protection of Ar flow for 3 h to ensure the adequate carbonization of
targeted commercialization. Both positive and negative electrodes the black products to PC. At last, the PC was washed with distilled
act as the redox reaction area, and the charge transfer resistance water to remove the residual H3PO4, and dried at 80  C under
between electrode/electrolyte surfaces contributes most of the cell vacuum for 12 h.
polarization [10]. Therefore, improvements on electrode materials The prepared PC (20 mg) was ultrasonic dispersed into 5 ml 0.1%
are of great value to enhance the energy efficiency of VRBs. Carbon Nafion solution to get a dispersion. Then graphite felt (GF, thickness
felts with the features of excellent chemical stability, porous 5 mm, and length 2 cm, width 2 cm) was immersed into the above
structure and high specific surface area are commonly used for the dispersion, and completely dried under an infrared lamp. The above
electrodes in VRBs. However, it presents low electro-catalytic ac- steps were repeated until all the dispersion was sucked up. The PC
tivity and inferior reversibility toward the redox reaction process, modified GF was named as PC-GF.
especially for VO2 þ /VO2þ redox reaction at the positive electrode
[11e15]. Therefore, lots of strategies have been exploited to 2.2. Materials characterization and electrochemical test
enhance their electrochemical performance.
It was reported that carbon felt integrated with moderate The morphology of the prepared PC was characterized by using
surface-active oxygen functional groups exhibits much better a field emission scanning electron microscope (FESEM) and a
electrochemical catalytic property due to the introduction of oxy- transmission electron microscope (TEM). X-ray powder diffraction
gen functional groups such as hydroxyl, carbonyl and carboxyl (XRD) pattern was obtained by using a Bruker Analytical X-ray
groups that not only increase the hydrophility of carbon electrode, System with a CuKa radiation. Nitrogen adsorptionedesorption
but also act as active sites for the vanadium redox reactions isotherm was conducted at Micromeritics analyzer (Quantachrome,
[11e13]. Metals or metallic oxides such as Pt, Au, and Pd deposited USA). The XPS measurement was carried out on the physical Elec-
on the carbon electrode surface have been studied to improve the tronics Quantum 2000 Scanning ESCA Microprobe. The Raman
reaction activity of the redox couples during operation [4,14e18]. spectrum test was performed on a LabRam-1B Raman system with
However, some of them also facilitate the evolution of hydrogen 532 nm excitation laser.
and oxygen, and are not practical for use because of the high cost. The cyclic voltammetry (CV) and electrochemical impedance
Significant achievements have been obtained by depositing bis- spectroscopy (EIS, frequency range: 0.1e10 kHz, amplitude: 5 mV,
muth nanoparticle and Nb2O5 on carbon felt [14,15]. Recently, many onset potential: 0.75 V vs. SCE) tests were carried out on a
researches have been focused on modified carbon materials such as computer-controlled electrochemical workstation (CHI604C,
reduced graphene oxide (r-GO) [19e21], functionalized carbon Chenhua Co.Ltd., Shanghai, China), and were performed in a three-
nanotubes [22e24], and mesoporous carbons [25]. They present electrode electrochemical cell by using a saturated calomel elec-
considerable electro-catalytic activities toward vanadium redox trode (SCE) as the reference electrode, Pt net as the counter elec-
reaction because of the abundant residual oxygen-containing trode and PC modified glassy carbon (PC-GC) as working electrode.
functional groups served as reaction active sites for redox re- The electrolyte used for measurement was 0.1 M VOSO4 with
actions. In addition, heteroatom doping has been explored to 3 M H2SO4. The PC-GC was achieved by dropping 10 ml suspension
further enhance their electrochemical performance due to the (10 mg PC were ultrasonically dispersed in 5 ml dimethylforma-
formation of more defect sites for ion diffusion and electron mide) onto the pre-polished GC electrode (diameter: 3 mm). After
transfer reaction. Nevertheless, their preparation processes are the ink was dried, 10 ml 0.05% Nafion was dropped on the surface of
tedious, toxic, and not environmental friendly. GC, and completely dried under infrared lamp. The naked GC
Recently, functional carbon materials prepared from low cost, electrode and graphite modified GC (G-GC) electrode were used as
abundant and environment friendly biomaterials have been controls.
spotlighted. The electrochemical properties of these materials have The chargeedischarge test was carried out by using a small VRB
been intensively studied in lithium ion batteries and electro- on a battery system CT2001A. The PC-GF or GF was used as positive
chemical capacitors [26,27]. However, to our best knowledge, their electrode and the virginal GF was used as negative electrode,
application in VRBs has not yet been reported. respectively. A Nafion 212 membrane (DuPont, USA) was used as
Herein, we present a two-step strategy to convert disposable separator that was sealed with rubber washer. The initial positive
shaddock peels into functional porous carbon (PC) that involved and negative electrolytes were 15 ml 1.5 M V (V(III)/V(IV) ¼ 1:1) in
hydrothermal treatment with phosphoric acid (H3PO4) followed by 3 M H2SO4. The upper and lower cut-off charge and discharge
pyrolysis. Shaddock peels present large surface area and high voltages are 1.6 V and 0.8 V, respectively.
content of oxygen. After pyrolysis, some oxygen functional groups
are well retained, and could act as effective electro-catalyst toward 3. Results and discussion
the redox reaction of VO2þ/VO2 þ .
During the fabrication process of PC, the added H3PO4 was used
2. Experimental as an activating agent to create porous structure in the carbon
materials [27]. It is well-known that H3PO4 are typically dehy-
2.1. The preparation of functional porous carbon (PC) and PC drating agents capable of removing oxygen and hydrogen from raw
modified graphite felt materials in the form of water to increase porosity. In order to
ensure the activating agent to be sufficiently incorporated into the
The functional PC was prepared from disposable shaddock peel. shaddock peel bulk, hydrothermal treatment was exploited instead
 J. Liu et al. / Journal of Power Sources 299 (2015) 301e308 303

of simple mixing with shaddock peel followed by drying [28]. The graphitic layers can be identified from the magnified TEM micro-
morphology of the PC is shown in Fig. 1a. The prepared PC consists graph (Fig. 1c), indicating that the prepared PC consists of amor-
of small individual nanoparticles in the range of several nanome- phous and graphitized carbons.
ters. TEM observation (Fig. 1b) reveals the formation of mesopores According to the nitrogen adsorptionedesorption isotherm of
in the prepared PC by means of hydrothermal treatment and py- the prepared PC (Fig. 2), it reveals a combined porosity character-
rolysis with H3PO4 as activating agent. The distinct disordered istic of types I and IV according to IUPAC classification, corre-
sponding to micro-mesoporous materials. The steep increase of N2
adsorption at low relative pressure suggests the existence of mi-
cropores. The type IV isotherm with small hysteresis loops and final
increasing tail at high relative pressure is a characteristic of mes-
oporous material [29]. The micro-mesoporous feature of the pre-
pared PC is further confirmed by the pore size distribution
calculated from the corresponding DFT (density functional theory),
which is shown in Fig. 2b. It is conspicuous to found that the pores
size of the prepared PC has a wide range of size distribution, mainly
in the region of 0.5e1, 1e2, 2e4 nm and >4 nm. The determined
BET data reveal that the prepared PC possesses high specific area of
882.7 m2 g1, and average pore size of 9.02 nm. The total pore
volume is calculated to be 1.99 cm3 g1 according to the data ob-
tained at a relative pressure of 0.99. It is well known that carbon
materials with high specific area and appropriate pore size are
more accessible to the adsorption and diffusion of vanadium ions,
thus better electrochemical performance for the redox reaction of
vanadium ions will be achieved.
Fig. 3a shows the X-ray diffraction of the prepared PC, which
exhibits two broad diffraction peaks located at about 24 and 43 .

Fig. 2. (a) Nitrogen adsorptionedesorption isotherms and (b) the corresponding DFT
Fig. 1. (a) FESEM, (b) and (c) TEM micrographs of the prepared PC. pore size distribution curve of the prepared PC.
304 J. Liu et al. / Journal of Power Sources 299 (2015) 301e308

mainly arises from the oxygen-containing groups in the shaddock

peel, and was partially retained after the pyrolysis. In addition, the
activating agent H3PO4 supposes to be a source of incorporating O
into the prepared PC [27]. The O/C ratio was calculated to be 0.22,
confirming that lots of defects are formed in the prepared PC, which
is well consistent with the Raman spectra analysis. Furthermore,
small amounts of N (0.31%) and P (0.49%) elements are also
detected. The detected N element may be a component of shaddock
peel and be partially retained after carbonization. In the case of P
element, it is mainly introduced by using H3PO4 as activating agent
during the preparation processes since H3PO4 can react with the
polymer structure in the shaddock peel, which is similar to the
addition of H3PO4 into melamine resin [32].
The curve-fitted XPS spectra of C1s and P2p for the prepared PC
are demonstrated in Fig. 4, and their respective percentages are
summarized in Table 1. As shown in Fig. 4a, the XPS spectra of C1s
can be deconvoluted into five peaks, corresponding to C]C
(284.4 eV), CeC (285.1 eV), CeOH (286.2 eV), C]O (287.5 eV), and
HOeC]O (290.6 eV) [22,33]. It is obvious to found the prepared PC
has abundant oxygen-containing functional groups, and the main
functional group is identified to be C]O with a relative content of
22.5%. The P2p spectra curve in Fig. 4b show two well-defined peaks
located at 133.0 and 134.1 eV, respectively, which are assigned to

Fig. 3. (a) XRD pattern and (b) Raman spectra of the prepared PC.

The broad diffraction pattern at about 24 can be indexed to the

diffraction of the (002) planes of the graphitic lattice. The weak
diffraction centered at around 43 corresponds to a superposition
of the (100) and (101) reflection of a graphitic structure of the
prepared PC [29], indicating that the graphitization degree of the
prepared PC is low or weak due to the low pyrolysis temperature of
800  C, in line with the result obtained from TEM (Fig. 1c).
As shown in Fig. 3b (Raman spectra), two well-defined peaks
centered at about 1340 cm1 and 1580 cm1 are observed, which
correspond to D and G bands of carbon, respectively. The D band is
associated to the defect mediated zone-edge (near K-point) pho-
nons, which can be used to evaluate the defects, edges and disor-
dered carbon. The G band is related to the in-plane vibration of sp2
carbon atoms in graphite lattices, which is doubly degenerated E2g
mode at Brillouin zone center. The ratio of intensities for the D band
and G band (ID/IG) reflects the presence of defects and disorder
within carbon materials [30,31]. The ID/IG value of the prepared PC
is calculated to be 1.13, suggesting that there are plentiful disorder
structures and edged defects in the prepared PC.
The detail information on elemental composition and functional
groups of the prepared PC was studied through XPS analysis. The
prepared PC presents a predominant C1s signal with a stronger O1s Fig. 4. (a) XPS analysis and its fitting from high resolution: (a) C1s peak and (b) P2p
peak at 533 eV. The detected O element with the content of 18.01% peak.
 J. Liu et al. / Journal of Power Sources 299 (2015) 301e308 305

Table 1 CePeO and CeOeP, respectively [34]. It is noteworthy that the

Assignment of XPS peaks of C1s and P2p for the prepared PC. prepared PC was completely washed to pH ¼ 7. Therefore, the
Assignment Binding energy/eV Fraction of species/% observed result confirms that the P was successfully incorporated
C]C 284.4 11.6
into the carbon lattice.
CeC 285.1 45.4
CeOH 286.2 16.0 3.1. Electrochemical performance
C]O 287.5 22.5
COOH 290.6 4.4
CePeO 133.0 42.1 The CV curves of GC, G-GC and PC-GC in a solution of 0.1 M
CeOeP 134.1 57.9 VOSO4 and 3 M H2SO4 at the scan rate of 50 mV s1 are shown in
Fig. 5a. Only oxidation peak is detected on the GC during the
sweeping voltage ranges from 0.4 to 1.4 V (vs. SCE), suggesting the
redox reaction on GC electrode is quite irreversible, and that is in

Fig. 5. (a) CV curves of the GC, G-GC and PC-GC at the scan rate of 50 mV s1 in 0.1 M VOSO4 and 3 M H2SO4, (b) the Nyquist plots of the PC-GC and G-GC (inserted) obtained in
0.1 M VOSO4 and 3 M H2SO4 solution at the onset potential of 0.75 V vs. SCE, and the CV curves of (c) the G-GC and (d) PC-GC at different scan rate in 0.1 M VOSO4 with 3 M H2SO4,
(e) plot of peak current densities versus square of the scan rate and (f) catalytic mechanism of the prepared PC for the VO2þ/VO2 þ redox reaction.
306 J. Liu et al. / Journal of Power Sources 299 (2015) 301e308

line with the reported result [22]. After modifying with graphite or electron transfer, which is similar to the favorable actions of lithium
the prepared PC, two well-defined redox peaks are observed. The intercalation into N- and/or P-doped amorphous carbons [32].
anodic peak is related to the oxidation process of VO2þ to VO2 þ , and According to the above results, the PC exhibits exceptional good
the cathodic peak is associated with the reduction process. This catalytic activity for the reaction of VO2þ/VO2 þ , and it can be
indicates that the electrochemical activity of GC electrode is anticipated that the electrochemical over-potential of a cell during
significantly improved. While, the onset reduction potentials on the cycling will be remarkably reduced by attaching PC catalyst on the
G-GC and PC-GC electrodes are about 1.08 and 1.0 V, and those for surface of GF. This is much beneficial for improving the energy ef-
oxidation process are about 0.85 and 0.7 V (vs. SCE), respectively. ficiency of VRB.
This means that the redox reaction performs more easily on the PC- The micrograph of PC modified GF (PC-GF) is shown in Fig. 6a. It
GC electrode compared with that of G-GC. The gap between the is clear to be seen the PC is uniformly attached on the surface of GF
oxidation and reduction peaks (DE) and the intensity of the redox by using Nafion as a binder. The PC not only increases the surface
peak current (calculated from Fig. 5) are utilized to estimate the area of the virginal GF, but also provides amounts of active sites for
electrochemical catalytic activity of the prepared PC. The PC-GC the VO2þ/VO2 þ redox reaction. Even after cycling for 35 times, the
exhibits a slight smaller DE of 66 mV, along with much higher PC is still well retained (Fig. 6b), indicating a stable catalytic per-
anodic (Ipa) and cathodic (Ipc) current densities of 17.1 mA cm2 and formance for the redox reaction.
15.0 mA cm2, respectively. However, for G-GC it delivers much The voltage profiles of the PC-GF and the virginal GF at the
lower peak current densities (8.9 mA cm2 for Ipa, and 4.1 mA cm2 current density of 100 mA cm2 are shown in Fig. 7a. The PC-GF
for Ipc), and larger DE (214 mV). Furthermore, the value of Ipa/Ipc of presents a lower charge and higher discharge plateaus, indicating
PC-GC and G-GC are calculated to be 1.14 and 2.17, respectively. The that the electrochemical polarization of the cell is notably sup-
value of Ipa/Ipc closed to 1 suggests better redox reversibility on the pressed by the PC covered on the positive electrode. As a result, the
PC-GC. The Nyquist plots of the G-GC and PC-GC (Fig. 5b) consist of PC-GF delivers a much higher discharge capacity of 11 Ah l1 than
a semicircle at high frequency region and a slope line at the low the untreated GF (5 Ah l1).
frequency region, indicating that the redox reaction of VO2þ/VO2 þ
couple is a mix-controlled process by charge and diffusion [19,35].
The value of Z0 at Z00 ¼ 0 is the total Ohmic resistance from the
solution, electrode and the contact resistance, and the arc in the
Nyquist plots is associated with the charge transfer resistance at the
electrolyte/electrode interface. The values of Z0 on G-GC and PC-GC
are almost the same due to the enhanced hydrophility of the PC-GC
that compensate for the relative low conductivity compared with
graphite. Smaller radius of the arc indicates the faster charge
transfer at the electrolyte/electrode interface. It is evident that the
PC-GC presents a much lower charge transference resistance,
which is well consistent with the CV results. The above results
imply that the PC-GC possesses of a better electrochemical
reversibility and exceptional electrochemical catalytic activity for
the VO2þ/VO2 þ couple.
Fig. 5c and d shows the CV curves of the PC-GC and G-GC at
various scan rates. The peak separation for the redox reaction of
VO2þ/VO2 þ on G-GC is significantly enlarged along with the in-
crease of the scan rate. However, in the case of the PC-GC (Fig. 5d),
the shift of peak potentials for the redox reaction are almost
negligible with the increase of the scan rate, indicating that the PC-
GC has a much better rate performance. The plots of peak current
densities as a function of the square root of the scan rate for both
PC-GC and G-GC (Fig. 5e) show that the current densities of both
anodic and cathodic peaks increase for both PC-GC and G-GC
electrodes with the increment of v1/2. Nevertheless, the slopes of
PC-GC are much steeper than those of G-GC for both anodic and
cathodic process, implying a faster mass transfer process on the
surface of PC-GC.
As demonstrated in Fig. 5f, the superior electrochemical per-
formance of the prepared PC may result from its high surface area,
abundant oxygen-containing functional groups as well as the N and
P-doped defect sites, that could act as reaction activity sites for the
redox reaction of VO2þ/VO2 þ couple. In addition, the enhanced
wettability and hydrophility of the PC resulted from the formation
of abundant oxygen-containing functional groups on the surface,
and the porous feature of the PC that facilitates the diffusion of
reactant ions on the electrode surface. Furthermore, similar to N-
dope materials, the relative high negative charge density of the
incorporated P also facilitates the adsorption of oxygen and posi-
tively charged reactant ions on the active site [19,36]. In addition,
both of them have one lone pair electrons, which can complex or Fig. 6. SEM micrographs of the prepared PC-GF: (a) before cycling and (b) after 35
coordinate with the empty orbits from VO2þ or VO2 þ, and favor the cycles.
 J. Liu et al. / Journal of Power Sources 299 (2015) 301e308 307

Fig. 7. (a) Charge-discharge curves of the PC-GF and the virginal GF at the current density of 100 mA cm2, (b) Coulombic efficiency and voltage efficiency of the PC-GF and the
virginal GF at various current densities, (c) energy efficiency and (d) discharge capacity of the PC-GF and the virginal GF at different rate.

Fig. 7b shows the Coulombic efficiency (CE) and voltage effi- enhanced electrochemical performance of the PC-GF can be
ciency (VE) of the PC-GF and the virginal GF at various current attributed to the presence of increased surface area from porous
densities. The CE of the battery is the ratio between the charge and structure, oxygen-containing functional groups and P-doped defect
discharge capacities and the VE is determined by the voltage dif- sites in the prepared PC that favor the redox reactions of vanadium
ference between the average charge and discharge voltages. The ion for fast electron and mass transfer.
average CE for the PC-GF is about 96.8% at the current density of
60 mA cm2, and increases to about 98.1% with the current density 4. Conclusion
up to 100 mA cm2 due to the reduced time of ion cross-over
through membrane. Conspicuously, the PC has insignificant influ- In summary, functional porous carbon material has been suc-
ence on the CE of the cell, but results in an enhanced VE as ex- cessfully synthesized from low-cost and environmental benign
pected. The PC-GF presents an average VE of about 82.7% at the biomaterial, viz. shaddock peel, through a hydrothermal and
current density of 60 mA cm2, increased by about 3.8% compared carbonization strategy. Microstructure analysis demonstrates that
with the virginal GF. Although the increased current density inev- the prepared PC has a high surface area with abundant oxygen-
itably results in a fast decline of VE for both PC-GF and the virginal containing functional groups and doped with N and P. The high
GF because of the fast chargeedischarge rate leading to large surface area provides more active reaction sites for vanadium ions,
electrochemical over-potential in the cell, the rate performance of and functional groups and doped heteroatoms improve electro-
the PC-GF is much better than that of the virginal GF. Even at the chemical catalytic activity for VO2þ/VO2 þ redox couple. As a result,
current density of 100 mA cm2, the PC-GF still presents an average the energy efficiency, discharge capacity and rate performance of
VE of 70%, about 9.2% higher than that of the virginal GF. VRB have been significantly enhanced.
As shown in Fig. 7c, a similar phenomenon is observed for en-
ergy efficiency (EE) since EE is a derivative of the CE and VE
Acknowledgment
(EE ¼ VE  CE). After altering the chargeedischarge rate from 100
to 60 mA cm2, the initial EE is remarkably recovered for the PC-GF,
Financial support from China National Funds for Distinguished
indicating the PC is well retained on the surface of GF even after 35
Youth Scientists (NSFC No. 51425301), Hunan Provincial Natural
cycles, and could provide a stable catalytic activity for the positive
Science Foundation of China (2015JJ3074), Science and Technology
side. The plots of discharge capacities for the PC-GF and the virginal
project of Changsha (KL403147-11) is greatly appreciated.
GF(Fig. 7d) show that the average discharge capacity of PC-GF at a
rate of 60 mA cm2 is about 25.4 Ah l1, much higher than that of
the virginal GF (22.4 Ah l1). In addition, the PC-GF presents much References
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