Applied Surface Science 507 (2020) 145137

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Applied Surface Science

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Full Length Article

Enhanced rate and cycling performances of hollow V2O5 nanospheres for T

aqueous zinc ion battery cathode
⁎
Linlin Chena,b, Zhanhong Yanga, , Fan Cuia,b, Jinlei Menga,b, Hongzhe Chena,b, Xiao Zenga,b
a
Hunan Province Key Laboratory of Chemical Power Source, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
b
Innovation Base of Energy and Chemical Materials for Graduate Students Training, Central South University, Changsha 410083, China

A R T I C LE I N FO A B S T R A C T

Keywords: Vanadium pentoxides (V2O5) show potential in aqueous zinc ion batteries (AZIBs) originating from their layered
Hollow V2O5 nanospheres structure and high theoretical capacity. However, most of the reported V2O5 cathodes suffer from rapid capacity
Aqueous zinc ion battery decay and sluggish Zn2+ diffusion kinetics. Herein, hollow V2O5 nanospheres with a diameter of about 450 nm
Cycle performance and shell thickness of 50 nm were constructed via a template-free solvothermal method combined with sub-
Pseudocapacitive behavior
sequent calcination treatment. The nano-sized hollow structure can not only alleviate the structural stress upon
cycling, but also provide shortened ion and electron transport paths, and enhance the surface capacitive be-
havior. When applied as cathode for AZIBs, it delivers ultrahigh reversible capacity (327 mAh g−1 at 0.1 A g−1),
superior rate performance (146 mAh g−1 at 20 A g−1), and excellent cyclic performance (147 mAh g−1 after
6000 cycles at 10 A g−1; 122 mAh g−1 after 10,000 cycles at 15 A g−1), showing clear superiority over com-
mercial V2O5 with irregular appearance. Such attractive capabilities demonstrate that hollow V2O5 nanospheres
are a prospective cathode material for AZIBs.

1. Introduction
With the accelerated expansion of new energy industry, secondary
batteries, as the carrier of energy conversion and storage, have been
widely used in the fields of consumer electronics, electric vehicles and
other energy consumption systems. Among various types of metal sec-
ondary batteries, aqueous zinc ion batteries (AZIBs) have captured
significant scientific and technical interest because of their advantage of
environmental friendless, low cost and safety [1]. What makes it even
more appealing is that compared with conventional organic lithium ion
batteries (LIBs), it possesses a high charge density that allowing for
excellent storage capacity, and it uses an environment-friendly and safe
waterborne electrolyte that enabling high ionic conductivity [2–4].
However, the large hydration radius and high charge density of divalent
zinc ions lead to unexpected difficulties of insertion/extraction in the
host materials, such as the collapse of the electrode structure and the
sluggish diffusion kinetics, which in turn affects the rate and cycle
performance [2]. Therefore, it is of great significance to explore suitable
cathode materials for AZIBs.
In recent two years, numerous vanadium-based compounds have
been extensively studied as cathodes for AZIBs owing to their open-
framework structure and various valence states, such as V2O5, VO2,
MxVnOm (M = Zn, Ca, Li, Ag, NH4+, etc.) [5]. Among these materials,
the V2O5 electrode achieves a superior specific capacity arising from the
multiple valence variation of V5+→V3+. Liang et al. [6] established an
economic secondary aqueous Zn/V2O5 system by using 3 M ZnSO4
electrolyte, which delivers a remarkable discharge capacity of 224 mAh
g−1 at 100 mA g−1. In order to further improve the electrochemical
performance, their team proposed to use V4+-V2O5 with mixed vana-
dium valences as cathode material for AZIBs [7]. It was found that the
V4+-V2O5 cathode delivers higher electrochemical activity, lower po-
larization, faster ions diffusion rate, and higher electronic conductivity
than pure-phase V2O5 without V4+, leading to an improved perfor-
mance with a high capacity of 140 mAh g−1 after 1000 cycles at 10 A
g−1. Despite all this, the long term cycle performance at high rates still
requires further improvement. To the best of our knowledge, the
structure of V2O5 constructed by VO5 layers forming square pyramids
that share edges and corners is unstable [8,9]. In addition, the divalent
zinc ions with strong electrostatic repulsion are more likely to be
trapped in the V2O5 lattice, and further cause slow migration rate and
severe structural distortion, thus leading to poor cyclic stability. It has
been reported that the hollow nanostructure with large internal space
can effectively alleviate the structural stress caused by the guest ion
intercalation/extraction or surface Faraday reaction during repeated
charge/discharge process [10]. Furthermore, electrodes with hollow
nanostructure can significantly improve the electrochemical reaction

⁎
Corresponding author.
E-mail address: zhyangcsu611@163.com (Z. Yang).

https://doi.org/10.1016/j.apsusc.2019.145137
Received 19 August 2019; Received in revised form 13 December 2019; Accepted 19 December 2019
Available online 23 December 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
L. Chen, et al. Applied Surface Science 507 (2020) 145137

Fig. 1. (a and b) SEM, (c) elemental mapping, (d and e) TEM, and (f) HRTEM photographs of hollow V2O5 nanospheres.

kinetics and increase the surface capacitance contribution benefiting
from high specific surface area, abundant exposed reactive sites, and
short diffusion pathways for ions and electrons. This unique structure is
theoretically conducive to the improvement of electrochemical perfor-
mance. Hollow Co3V2O8 micro-pencils [11], for instance, were applied
as a promising anode candidate for LIBs, which can deliver much higher
initial specific capacity of 1200 mAh g−1 as compared to that of the
solid ones (~680 mAh g−1).
In this paper, hollow V2O5 nanospheres with a diameter of about
450 nm and shell thickness of 50 nm were constructed by the template-
free solvothermal approach and a subsequent calcination process. When
used as a cathode material for AZIBs, the hollow V2O5 nanospheres
display ultrahigh discharge capacity of 327 mAh g−1 at 0.1 A g−1,
outstanding rate performance (146 mAh g−1 at 20 A g−1), and long-
term cycle life (147 mAh g−1 with 69.7% capacity retention after 6000
cycles at 10 A g−1; 122 mAh g−1 with 71.3% capacity retention after
10,000 cycles at 15 A g−1) in 3 M ZnSO4 electrolyte. As we know, the
rate and cycling properties of the hollow V2O5 nanospheres is superb
among commercial V2O5 and other recently reported vanadium-based
cathodes. This impressive electrochemical performance together with
the simple fabrication method suggest that it is a prospective cathode
material for AZIBs.
2. Experimental
2.1. Materials synthesis
Hollow V2O5 nanospheres were prepared following previously re-
ported procedures [12]. Briefly, 3.56 g of oxalic acid and 2.0 g of
commercial V2O5 powder were mixed in 100 mL of deionized water,
and stirred at 60 °C to form the blue vanadyl oxalate solution, which
was then dried at 75 °C for 2 days and ground for further use. After that,
60 mg of the vanadyl oxalate precursor obtained above was dissolved
into 60 mL methanol/water (4:1, v/v) mixed solution. The suspension
was then transferred to a Teflon-sealed autoclave with capacity of
100 mL and hydrothermally reacted at 200 °C for 24 h. Lastly, the
solvothermal products were calcined in air at 350 °C for 2 h to gain the
target powder of hollow V2O5 nanospheres.
2.2. Materials characterization
The XRD patterns of the as-fabricated products were recorded on
PANalytical Empyrean XRD analyzer with Cu Ka radiation. The mi-
croscopic appearance of the sample was characterized by using the FEI
Helios NanoLab G3 UC scanning electron microscopy (SEM) and JEM-
2100F transmission electron microscopy (TEM). The XPS data was
collected through a Phi Quantum 2000 spectrophotometer with Al Kα
radiation. The nitrogen adsorption–desorption experiment was con-
ducted by a Mike ASAP 2460 apparatus at − 196 °C with prior de-
gassing under vacuum at 150 °C for 12 h.
2.3. Electrochemical tests
The electrochemical performance tests were conducted by assem-
bling CR2025 coin batteries with hollow V2O5 nanospheres or com-
mercial V2O5 as cathode, metal Zn foil as anode, and 3 M ZnSO4 aqu-
eous solution as electrolyte. The cathode was prepared by mixing as-
synthesized active materials, conductivity agent (Super-P) and poly-
tetrafluoroethylene (PTFE) with a weight ratio of 7:2:1. The resulting
fully ground slurry was evenly loaded on the titanium mesh and then
dried under vacuum at 65 °C for 12 h. The mass loading of active
materials on the electrode was approximately 1.3–1.6 mg cm−2.
Galvanostatic charge-discharge (GCD) experiments were finished on
Neware CT-4008 instrument (Shenzhen, China) in the voltage range of
0.2–1.5 V (vs. Zn2+/Zn). Cyclic voltammetry (CV) and Electrochemical
impedance spectroscopy (EIS) tests were all performed on an electro-
chemical workstation (CHI 660E, Chenhua). EIS spectra was collected
in a frequency region from 100 kHz to 0.01 Hz with an amplitude of
5 mV.
3. Results and discussion
SEM images of the as-prepared hollow V2O5 nanospheres are dis-
played in Fig. 1a and b. It is visible that the sample exhibits a uniform
spherical shape, and its surface is rough and uneven, which is composed
of numerous rice-like particles (Fig. S1). Meanwhile, from the broken
spheres marked with a red square, typical hollow features can be ob-
viously discerned. The elemental mapping image showed in Fig. 1c
reveals the homogeneous distribution of V and O elements. Fig. 1d and
e present the TEM images of the sample, from which we can clearly see
the apparent contrast between the interior core and outside shell, which
further validates the hollow structure. The average diameter of these
spheres is about 450 nm, and the thickness of shell is about 50 nm. The
favorable structure of hollow V2O5 nanospheres with small nano-size

2
L. Chen, et al.
Fig. 2. (a) XRD patterns, (b) XPS survey spectrum, (c) the V 2p core-level spectrum, (d) N2 adsorption–desorption isotherms and the pore size distribution profiles
(inset) of the hollow V2O5 nanospheres.
and thin outer shell can not only facilitate the penetration of electro-
lyte, reduce the ion diffusion paths, and promote the electrochemical
reaction kinetics; but also provide sufficient active sites based on its
larger inner and outer surface areas, thus increase the pseudocapaci-
tance contribution produced at or near the surface of active materials.
HRTEM image (Fig. 1f) shows the well-resolved lattice fringes with an
interplanar distance of around 0.218 nm, which correspond to the
(0 0 2) plane of V2O5. For comparison, the commercial V2O5 sample
was also characterized. As can be observed from Fig. S2, the commer-
cial V2O5 exhibits an irregular bulk structure stacked by many rod-like
or sheet-like substances.
The crystal structure of the synthesized hollow V2O5 nanospheres
and commercial V2O5 were identified by XRD patterns (Fig. 2a). For
both two samples, all the diffraction peaks could be well assigned to the
orthorhombic V2O5 with a space group of Pmmn (59) (PDF#41-1426,
a = 11.516 Å, b = 3.565 Å, c = 4.372 Å), and no impurity phase was
detected. In addition, the sharp and narrow features of these peaks
reveal high crystallinity of the sample. As displayed in the interior of
Fig. 2a, the sample of V2O5 presents a typical layered structure com-
posed of VO5 tetragonal pyramids through sharing edges and corners. It
is common knowledge that the large interlayer spacing can serve as a
good pathway for the diffusion and transport of zinc ions [9]. Fig. 2b
shows the XPS full spectrum of hollow V2O5 nanospheres, from which
only V, O, C elements are noticed. It is necessary to point out that the C
element, which is located at the binding energy of 284.8 eV, is derived
from the contaminated carbon introduced by the need of XPS correc-
tion. The V 2p core-level spectrum in Fig. 2c illustrates two typical
peaks related to V 2p1/2 (524.7 eV) and V 2p3/2 (517.4 eV), and the
binding energy separation is about 7.3 eV, which is in good agreement
with the oxidation state of V5+ in V2O5 [13,14]. In order to assess the
textural properties of as-prepared hollow V2O5 nanospheres, N2 ad-
sorption–desorption test was implemented, as shown in Fig. 2d. Ac-
cording to the IUPAC classification, it displays a typical type IV iso-
therm with a H3-type hysteresis loop, implying the existence of slit-
shaped mesopores [15]. According to the Brunauer–Emmett–Teller
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Applied Surface Science 507 (2020) 145137
(BET) and Barrett-Joyner-Halenda (BJH) models, the calculated specific
surface area, pore volume and average pore size of hollow V2O5 na-
nospheres are 15.543 m2 g−1, 0.080 cm3 g−1 and 23.654 nm, respec-
tively. This large specific surface area is higher than the commercial
V2O5 (Fig. S3, Table S1) and some V2O5-based cathode materials for
AZIBs reported in the literature [16,17]. To the best of our knowledge,
high specific surface area can significantly enlarge the contact area at
the electrode–electrolyte interface, offer sufficient active sites for
electrochemical reactions, and thereby improve the guest ions diffusion
kinetics [18].
The electrochemical zinc-storage properties of hollow V2O5 nano-
spheres were evaluated in CR2025 coin-type batteries. Fig. S4a shows
the first six CV profiles within the voltage region of 0.2–1.5 V (versus
Zn2+/Zn) at 0.5 mV s−1. As we have noticed, the first CV scan exhibits
multiple redox peaks, suggesting a multi-step zinc ion intercalation/
deintercalation reaction mechanism. As the scan progressed, the strong
oxidation peak at 1.33 V gradually weakened and shifted negatively,
and it completely disappeared after 6th cycles. This change in peak
intensity is very ubiquitous in vanadium oxide cathodes, which may be
related to the structure evolution caused by the incomplete extraction
of the inserted Zn2+ ions in V2O5 lattice [6,14,17]. However, it is no-
teworthy that two couples of redox peaks situated at 0.81/0.56 and
1.08/0.85 V, accompanying with the valence evolution of vanadium
from V5+ to V4+ to V3+ [19], are well overlapped with subtle changes
between 7th to 15th cycles (Fig. 3a), demonstrating good reversibility
of the electrode. GCD curves of the hollow V2O5 nanospheres during the
initial six cycles are presented in Fig. S4b. The charging platform at
around 1.3 V (marked with a yellow rectangle) gradually becomes
unclear until disappeared, which is in good agreement with the CV
analysis. More importantly, the GCD profiles are almost completely
coincident after 7th cycles, and two distinct charging and discharging
platforms are displayed (Fig. 3b), showing high reversibility and ex-
cellent electrochemical stability. Meanwhile, the specific discharge
capacity gradually increases over the first 10 cycles at 0.1 A g−1, and
finally stabilizes at a high value of 327 mAh g−1 (Fig. S4c). Generally,
L. Chen, et al.
Fig. 3. (a) CV curves of hollow V2O5 nanospheres at 0.5 mV s−1, (b) GCD profiles of hollow V2O5 nanospheres at 0.1 A g−1, (c) cycle stability at 3.0 A g−1 and (d)
rate performance of hollow V2O5 nanospheres and commercial V2O5, (e) GCD profiles of hollow V2O5 nanospheres at varied current densities.
the rise in capacity is interpreted as an activation process, as evidenced
by the EIS observations (Fig. S4d). With the increase of cycle number,
the semicircular diameter representing the charge transfer resistance in
the high frequency region gradually decreases, and the straight line
representing the Warbug impedance in the low frequency area become
steeper, suggesting that improved electron transfer and ion diffusion
kinetics can be obtained after initial cycling. However, the comparative
sample of commercial V2O5 possess a long pre-activation time. Until 30
cycles of CV scans, the peak position and intensity become gradually
stable (Fig. S5a). When cycling at 0.1 A g−1, the specific capacity
gradually increases with the increase of cycle number, and gradually
stabilizes at 225 mAh g−1 when it reaches 30 times (Fig. S5b). Mean-
while, the highest specific capacity of commercial V2O5 with irregular
appearance at 0.1 A g−1 is significantly lower than that of V2O5 hollow
nanospheres.
Fig. 3c displays the cyclic performance of hollow V2O5 nanospheres
and commercial V2O5 at 3.0 A g−1. It can be seen that hollow V2O5
nanospheres exhibit a remarkable initial reversible capacity of 253 mAh
g−1, and still retains 184 mAh g−1 with ca. 72.7% capacitance reten-
tion after 1200 cycles. For the compared experiment, the batteries with
commercial V2O5 only deliver an initial capacity of 37 mAh g−1, and
slowly increase to 161 mAh g−1 after 200 cycles, indicating a very slow
increase in active ingredient utilization. After that, the capacity can be
maintained at 125 mAh g−1 after 1200 cycles. The improvement of
electrochemical performance of hollow V2O5 nanospheres is mainly due
to the hollow nanostructure and large specific surface area, which are
conducive to the full infiltration of electrolyte and enhanced material
utilization of the electrode. More importantly, the nanosphere appear-
ance can be basically preserved after cycling (Fig. S6), indicating a good
structural stability of the electrode material. In addition, the rate per-
formance is of great significance for practical utilizations, especially in
the face of increasing demand for fast charging. Fig. 3d illustrates the
rate capability of hollow V2O5 nanospheres and commercial V2O5.
When cycled at varied current rates of 0.1, 0.5, 1, 3, 5, 7, 10, 15, and 20
A g−1, the reversible capacities of hollow V2O5 nanospheres are 314,
273, 267, 231, 211, 196, 178, 159, and 146 mAh g−1, respectively.
Surprisingly, 325 mAh g−1 (slightly higher than initial state because of
4
Applied Surface Science 507 (2020) 145137
activation) could be regained with the current rate constantly descend
to 0.1 A g−1, implying a strong tolerance for rapid Zn2+ (de)inter-
calation. In contrast, the rate performance of commercial V2O5 is sig-
nificantly lower than that of hollow V2O5 nanospheres. It is necessary to
point out that a pre-activation process for 30 cycles at 0.1 A g−1 (Fig.
S5b) was performed before the rate test, if not, its accurate rate cap-
ability cannot be discerned (Fig. S5c). The corresponding GCD curves of
hollow V2O5 nanospheres under a series of current rates are shown in
Fig. 3e, from which the settled platforms even at a high current density
of 20 A g−1 could be still noticed.
In order to obtain a deeper insight into the excellent rate capability
of hollow V2O5 nanospheres, the electrode reaction kinetics were ana-
lyzed by CV and Galvanostatic intermittence titration techniques
(GITT). Fig. 4a exhibits the CV profiles at various sweep rates ranging
from 0.2 to 5.0 mV s−1. Obviously, with the increasing of the scan
speed, all CV curves inherit their original shape, and meantime the
gradually increased current intensity and broadened redox peak po-
tential difference is noticed. On the basis of the power-law formula of
peak current (i) versus scan rate (v) [20], the kinetic process was
evaluated to distinguish whether it is dominated by diffusion or capa-
citance.
i= av b (1)
Generally, the value of b varies in the range of 0.5–1.0. The b value
of 0.5 suggests a diffusion-induced insertion mechanism, whereas that
of 1.0 indicates surface capacitive behavior. As depicted in Fig. 4b, the
calculated b values of the redox peaks (R1, R2, O1, O2) are 0.64, 0.74,
0.50, and 0.83, respectively, implying the coexistence of the capacitive-
controlled and diffusion-dominated mechanism upon cycling. The
specific capacitance contribution to the total capacity at a fixed voltage
was quantitatively clarified according to the following equation [21]:
i(V) = k1 v + K2 v1/2 (2)
where k1v means the contribution derived from capacitive behavior,
while k2v1/2 stands for the portion of diffusion-limited insertion pro-
cesses. Through calculating, 64.7% of the total charge is provided by
capacitive behavior at 1.0 mV s−1 (Fig. 4c). Histogram of Fig. 4d clearly
L. Chen, et al.
Fig. 4. Investigation of reaction kinetics of hollow V2O5 nanospheres. (a) CV profiles at different sweep rates, (b) linear plot of log (peak current) versus log (scan
rate), (c) capacitance contribution at 1.0 mV s−1, (d) proportion of diffusion and capacitance-dominated contributions at various scan rates, (e) GITT profiles and
calculated DZn values during the 6th and 7th cycles.
displays the contribution percentages at various scan rates. It is
worthwhile mentioning that the portion of capacitive contributions
becomes higher with increased sweep rate, and it can reach a maximum
value of 85.5% at 5.0 mV s−1. Such a high capacitance contribution can
be ascribed to its advantageous hollow architecture with large inner
and outer surface areas and short ion diffusion pathways, which is
beneficial for high rate capability of electrodes. To determine the zinc
ion diffusion coefficient (DZn), GITT measurement was implemented.
The details for the test procedure and calculation method were de-
scribed in Supplementary information (Fig. S7). Fig. 4e presents the
typical GITT profiles and corresponding calculated DZn values. We can
see that the zinc ion diffusion rate for the hollow V2O5 nanospheres is in
the order of 10−9 − 10−11 cm2 s−1, which is comparable to that of
some previously reported vanadium oxide cathodes for AZIBs (Table
S2).
Excellent rate performance is the advantage of hollow V2O5 nano-
spheres, so long-term enduring cyclic stability at high current densities
were evaluated. It can retain an excellent reversible capacity of 147
mAh g−1 with about 69.7% capacity retention after 6000 cycles at 10 A
g−1 (Fig. 5a). More impressively, when cycling at a superhigh current
of 15 A g−1 (Fig. 5b), the electrode with hollow V2O5 nanospheres
demonstrates outstanding Zn2+ storage ability on the basis of high
initial reversible capacity of 171 mAh g−1 and superior cyclic stability
(122 mAh g−1 with a high retention rate of 71.3% undergo 10,000
cycles). Table S3 compares the electrochemical performance of as-
prepared hollow V2O5 nanospheres with some previously recorded
vanadium-based cathodes for AZIBs. It turns out that the hollow nano-
sized V2O5 sphere is much more competitive as compared with earlier
results, not only in high specific reversible capacity, but also excellent
cycle stability, showing good application prospects for energy storage.
In addition, the electrode with our proposed hollow V2O5 nanospheres
exhibits higher energy density (240.2 Wh kg−1) and power energy
density (14106.3 W kg−1) than that of the reported SVO [22],
Na2V6O16·1.63H2O [23], Zn2V2O7 [24], Na3V2(PO4)3 [25], K2V8O21
[26], V2O5 [27], LiV3O8 [28], H2V3O8 [29], K2V6O16·2.7H2O [30], etc
(Fig. S8). Meanwhile, a colorful LED bead with a working voltage of
5
Applied Surface Science 507 (2020) 145137
2.0 V can be lightened by three coin batteries assembled with electrode
of hollow V2O5 nanospheres and held for several minutes (Fig. 5c).
4. Conclusions
In this paper, hollow V2O5 nanospheres were evaluated as a cathode
material for AZIBs. Series of electrochemical tests demonstrate that they
display excellent zinc storage capability on the basis of extraordinarily
high reversible capacity (327 mAh g−1 at 0.1 A g−1), remarkable rate
performance (273, 267, 231, 211, 196, 178, 159, and 146 mAh g−1 at
0.5, 1, 3, 5, 7, 10, 15, and 20 A g−1), and outstanding long-term cyclic
stability (147 mAh g−1 after 6000 cycles at 10 A g−1; 122 mAh g−1
after 10,000 cycles at 15 A g−1). Moreover, electrochemical kinetic
analysis shows that the electrode presents a high solid-state diffusion
rate of Zn2+, and the pseudocapacitance contribution dominates re-
markably high rate capability. Such attractive properties of hollow
V2O5 nanospheres exceed most of recently reported vanadium-based
cathodes for AZIBs, showing a broad application prospect in energy
storage.
CRediT authorship contribution statement
Linlin Chen: Data curation, Writing - original draft, Writing - re-
view & editing. Zhanhong Yang: Conceptualization, Methodology,
Funding acquisition, Supervision. Fan Cui: Investigation. Jinlei Meng:
Validation. Hongzhe Chen: Visualization. Xiao Zeng: Formal analysis.
Declaration of Competing Interest
The authors declared that there is no conflict of interest.
Acknowledgements
This work was supported by the Natural Science Foundation of
China (No. 21371180) and Hunan Provincial Science and Technology
Plan Project (No. 2017TP1001).
L. Chen, et al.
Fig. 5. Long-term cycling performance of hollow V2O5 nanospheres at (a) 10 A g−1 and (b) 15 A g−1. (c) Digital photos of three coin batteries powering a colorful
LED bead.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2019.145137.
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