Homologous V2O3/C box-in-box and V2O5 box for lithium-ion full cells

Article abstract of DOI:10.1039/c6ta03335k

Rational construction of metal oxides-based electrode materials for Li-ion batteries (LIBs) is essential to simultaneously overcome their low conductivity and vulnerable nanostructure. Here, we demonstrate the design and synthesis of homologous V₂O₃/C box-in-box and V₂O₅ boxes as anodes and cathodes for all-nanobox based LIB full cells, which are subsequently obtained by thermal treatment in different atmospheres. While the V₂O₅ box cathodes can provide abundant active sites, short ionic diffusion distances and partial volume flexibility, the key design concept of the V₂O₃/C box-in-box is the carbon box-in-box, which further enhances the structural durability during lithiation/delithiation, hence giving rise to an extended lifespan. As proof-of-concept, the V₂O₃/C box-in-box anodes deliver a high reversible capacity of 641 mA h g^-1 even after 1200 cycles at 1000 mA g^-1, while the V₂O₅ box cathodes possess a specific capacity of 119 mA h g^-1 at 10C with superior cycling stability. Importantly, a V₂O₃/C//V₂O₅ LIB full cell is assembled, which shows an impressive specific capacity of 97 mA h g^-1 at 500 mA g^-1 with a capacity retention of 81 mA h g^-1 even after 100 cycles based on the cathode material weight.

Full text of DOI:10.1039/c6ta03335k

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Homologous V O /C box-in-box and V O box for lithium-ion full
2
3
2
5
cells
Received 00th January 20xx,
Accepted 00th January 20xx
Xue Liu, Yanjie Hu, Guiqi Jia, Haoxuan Zhang, Hao Jiang*, Chunzhong Li*
DOI: 10.1039/x0xx00000x
Rational construction of metal oxides based electrode materials for Li-ion batteries (LIBs) is crucially essential to
simultaneously get over their low conductivity and vulnerable nanostructure. Here, we demonstrate the design and
www.rsc.org/
synthesis of homologous V
which are subsequently obtained by thermal treatment in different atmospheres. Except that the V
provide abundant active sites, short ions diffusion distance and part volume flexibility, the key design concept of the
/C box-in-box is the carbon box-in-box can further enhance the structural durability during lithiation/delithiation, and
hence giving rise to an extended lifespan. As proof-of-concept, the V /C box-in-box anodes deliver a high reversible
capacity of 641 mAh g even after 1200 cycles at 1000 mA g , while the V box cathodes possess a specific capacity of
2
O
3
/C box-in-box and V
2
O
5
box as anodes and cathodes for all-nanobox based LIBs full cell,
2
O
5
box cathodes can
2 3
V O
2
O
3
-1
-1
2
O
5
-
1
1
19 mAh g at 10 C with superior cycling stability. Importantly, the V
2
O
3
/C//V
2
O
5
LIBs full cell is assembled, which shows
-
1
-1
-1
an impressive specific capacity of 97 mAh g at 500 mA g with capacity retention of 81 mAh g even after 100 cycles
based on the cathode material weight.
3 4
designed Fe O /C yolk-shelled nanoboxes, which exhibited a
-
1
Introduction
high reversible capacity of around 470 mAh g after 8000
cycles even at 10 C. It can be observed that the box structures
possess abundant active sites, short ions diffusion distance and
part volume flexibility, and hence remarkably enhancing their
Hollow nanostructures, with the advantages of large surface
area, low effective density as well as good permeation, have
been widely used in optoelectronics, catalysis, drug delivery,
1
-5
electrochemical performances. Nevertheless,
a
main
energy storage, and so forth. Especially in recent years,
hollow-structured transition metal oxides (TMOs) based
contradiction between high capacity and long cycle life still
exists for both hollow TMOs and their corresponding hybrids
+
because the incorporation of abundant Li will cause in the
electrode materials have shown
a huge potential for
promoting lithium-ion batteries (LIBs), owing to low cost,
6
abundant source and high theoretical capacity. To date,
various hollow-structured TMOs have been synthesized to
-7
structure collapse, resulting in a limited cycle lifespan.
Therefore, the exploitation of the controllable metal oxides
based nanobox is very meaningful for achieving high
energy/power densities and extended lifespan for LIBs.
enhance LIBs performance, including Fe O
3
hollow
4
8
nanospheres, scroll-shape VO , multi-shelled Co O hollow
9
x
3 4
11
1
microspheres, as well as V O -SnO nanocapsules, and so
0
Among various metal oxides, vanadium oxides have
attracted much attention in energy storage and conversion
2
5
2
on. Meanwhile, hollow TMOs/C and even more complex
nanohybrids have also been extensively developed, e.g.
1
MnO/C hollow microspheres, carbon-coated CNT@Fe O
fields in view of their rich valence states, e.g. V
etc. Detailed speaking, the high valence V
substitute for the conventional LiMn , LiCoO
cathodes owing to its higher specific capacity of binding
2
O
5
, V
is a promising
and LiFePO
2 3 2
O , VO ,
2
2 5
O
2
3
1
3
2
O
4
2
4
hollow
nanohorns,
and
Fe O @Fe C-C
3
yolk-shell
3
4
1
4
nanospindles, etc. Among them, box structure inherits all
merits of these hollow structures, being a key morphology of
hollow family with excellent electrochemical performance. For
-1
multiple lithium ions, e.g. 294 mAh g for intercalating two
1
7-19
lithium ions.
potential as LIBs anode materials considering that the
electrical resistance of bulk V (~ 10 Ω at 150-350 K) is much
lower than other TMOs (Co
theoretical capacity (1070 mAh g ).
2 3
While for low valence V O , it shows a huge
1
5
example, Lou et al.
synthesized TiO2 submicroboxes,
-1
2 3
O
delivering an improved specific capacity of 210 mAh g at 1 C
1
compared to TiO2 microparticles. Accordingly, Paik et al.
6
3
O
4
, MnO
2
, etc.), as well as its high
-1
20-22
Furthermore, the
anode/cathode materials from the same source are reckoned
to achieve strong synergistic effects between them, and hence
further optimizing specific capacity of the full cell. Although
these unique advantages of vanadium oxides, an all-nanobox
based LIBs full cell using a V
2 3 2 5
O based anode and a V O based
cathode has yet not to be reported so far.
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ARTICLE
Journal Name
2 3
Scheme 1. Schematic illustration for the synthesis of the V O /C box-in-box.
Herein, we demonstrate a new type of all-nanobox based
LIBs full cell with V /C box-in-box anode and V box
2
O
3
2 5
O
cathode, homologously obtained from the same precursors
with different thermal treatment atmospheres. The key design
concept for the V
further enhance
lithiation/delithiation. As a consequence, the V
2 3
O /C box-in-box is the carbon box-in-box can
the
structural
integrity
during
2
O
3
/C box-in-
-1
box anodes deliver a high reversible capacity of 641 mAh g
-1
even after 1200 cycles at 1000 mA g . Meanwhile, the V
2
O
5
-1
box cathodes also show a specific capacity of 119 mAh g at 10
C with superior cycling stability. To top it off, the assembled
X
Figure 1. (a) SEM image of carbon hollow cubes, (b) SEM image of VO /C precursor, (c)
V
2
O
3
/C//V
2 5
O LIBs full cell shows an impressive specific
2 3
low- and (d) high-magnification SEM images of V O /C box-in-box.
-1
-1
capacity of 97 mAh g at 500 mA g with capacity retention of
-1
81 mAh g even after 100 cycles based on the cathode
spectrometer.
material weight. The present work might shed more light on
the importance of structural design and provide a new insight
on constructing high-performance LIBs full cells.
Electrochemical Measurements. The working electrode was
prepared by mixing active materials, carbon black, and poly(vinyl
difluoride) (PVDF) binder into N-methyl-2-pyrrolidone (NMP) with a
mass ratio of 7:2:1. Coin cell (type CR2016) was assembled with Li
Experimental section
foil as counter electrode and 1 M LiPF
EC)/dimethyl carbonate (DMC) (1:1 by weight) as electrolyte. For
full cell assembly, the V /C box-in-box and pre-lithiated V box
6
in ethylene carbonate
(
Synthesis of the V
Fe nanocubes serving as templates were obtained firstly via
2 3
previous report. Subsequently, as-synthesized Fe O and
2 3 2 5
O box-in-box and the V O box. Typically,
2
O
3
2 5
O
2 3
O
1
5
were serving as anodes and cathodes with optional capacity match.
Cyclic voladtammetry (CV) experiments were performed with an
dopamine were dispersed into 2-amino-2-hydroxymethyl-
propane-1,3-diol (Tris) solution (10 mM) with a mass ratio of
-1
Autolab PGSTAT302N at a scan rate of 0.2 mV s . Galvanostatic
charge/discharge measurements were conducted by LANDCT2001A
test system. The impedance spectra were recorded on constant
voltage mode over the frequency range between 100 kHz to 0.01 Hz.
1:1 under continuous stirring for 5 h at ambient temperature.
The black products were acquired by centrifugation and
washed with deionized water and ethanol, followed with
drying at 60 °C. The carbon hollow cube (C-box) was obtained
by annealing the precipitates in argon and subsequent
removing the iron oxide core by HCl etching (4 M). And then,
Results and discussion
The synthesis process for hierarchical V O /C box-in-box is
2
3
1
0 mg of C-box and 50 mg of dopamine were dispersed into
Tris solution (100 mL, 10 mM) again with magnetic stirring for
h. The precipitates were collected and then dissolved into 30
schematically depicted in Scheme 1. The C-box was firstly
synthesized by using Fe O as a template (Figure 1a), and then
2
3
2
coated a layer of polydopamine (PDA) on its surface. With the
assistance of rich functional groups of PDA, vanadium
oxytriisopropoxide (VOT) is very easy to nucleate and grow
into vanadium oxide precursor nanoflakes on C-box surface by
a simple hydrothermal method (Figure 1b). After annealing in
mL of isopropanol (IPA). After sonicating for 5 min, 0.2 mL of
vanadium oxytriisopropoxide (VOT) was added into above
mixture with stirring for 30 min. The suspension was
transferred into an autoclave and maintained at 200 °C for 12
2 3 2 5
h. Finally, V O /C box-in-box and V O box were obtained by
2 3
argon, the precursor nanoflakes are converted into the V O
treating hydrothermal products at 500 °C for 2 h in argon and
at 350 °C for 2 h in air, respectively.
multi-scaled hierarchically nanostructures composed of
nanoparticles (NPs) and nanoflakes, which firmly attached on
carbon box-in-box. Figure 1c shows the panoramic morphology
of as-obtained products with uniform nanoboxes. The mean
size is about 500 nm. An enlarged SEM image (Figure 1d)
Characterization. The crystal phases of as-prepared V O /C box-in-
2
3
box and V O box were studied by X-ray diffractometer (XRD) with
2
5
Cu Kα radiation. Scanning electron microscopy (SEM, S-4800) and
transmission electron microscopy (TEM, JEOL-2100) were
performed at 200 kV to investigated microscopic morphologies. The
surface area was tested on a Micromeritics ASAP 2010 analyzer at
2 3
reveals that the outer shell of V O /C box-in-box is composed
of many nanoparticles lied on ultrathin nanoflakes, forming a
hierarchical nanostructure. Additionally, the formation of
carbon box-in-box can be attributed to their different densities
7
7K. Thermogravimetric analysis (NETZSCH STA409PC) was carried
-1
out with a temperature ramp of 10 °C min under air flowing.
Raman spectrum was obtained using NEXUS 670 FT-IR Raman
2 3 2 3
of V O and carbon. The shell V O with a larger density can
2
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ARTICLE
Figure 3. (a) The capacity retention of the V
2
O
3
/C box-in-box, V
2
O
3
HNSs and V
/C box-in-
HNSs at 1000 mA g , respectively. (c) Electrochemical impedance spectra
/C box-in-box before and after cycling and the V HNSs, (d) SEM image of
2 3
V O /C box-in-box after cycling.
2 3
O NPs
-
1
at 100-5000 mA g , (b) cycling behaviour and Columbic efficiency of the V
2 3
O
Figure 2. (a) Low-, (b-c) high-magnification and (d) high-resolution TEM images of the
-1
box and V
of the V
2 3
O
2 3
V O /C box-in-box (insert of (d) showing the corresponding FFT pattern).
2
O
3
2 3
O
provide a strong driving force to promote the shrinkage
outward from the core C-box during the carbonization, and densities for LIBs.
therefore generating the unique V O /C box-in-box
3
The electrochemical performances have been evaluated
through assembling our V O /C box-in-box powder in coin-type
2
architectures.
2
3
Detailed interior structure of the V O /C box-in-box is 2016 half-cells. The initial three cyclic voltammograms (CVs) of
2
3
further elucidated by TEM (Figure 2). Clearly, a double-shell the V O /C box-in-box are tested in the potential window of
3
2
-1
hollow nanocube can be observed in Figure 2a. The V O
2
0.01-3.0 V at 0.2 mV s (Figure S5a). In the first cathodic scan,
3
nanoflakes as well as nanoparticles are strongly contacted with a well-defined peak around ~ 0.61 V appears but disappears in
carbon box-in-box, being in good agreement with the the following cycles, which is closely related to the formation
2
0,25
corresponding SEM observations. Partial precursor nanoflakes of solid electrolyte interface (SEI) film.
are preserved during annealing process. No other separated /C box-in-box are nearly overlapped in the subsequent
nanoparticles can be observed even through ultrasonic two cycles, suggesting highly electrochemical reversibility. The
Notably, the CVs of
2 3
V O
-1
treatment, implying a strong adhesion force between V
2 3
O and charge-discharge curves for an initial three cycles at 100 mA g
outer carbon. A representative morphology is also provided in within 0.01-3.0 V are also provided in Figure S5b. The first
-1
Figure 2b, obviously observing the coexistence of V
nanoparticles and nanoflakes in the shell, as well as the carbon efficiency (CE) of 74.8%. The rate performance of V
box-in-box carbon structure with an obvious gap. When we in-box is further evaluated at various current densities from
2
O
3
discharge capacity can reach 993 mAh g with a Coulombic
2 3
O
/C box-
-
1
removed the V
box nanostructure can be observed in Figure S1. In addition,
we also find a V /C box-in-box (Figure 2c), where the V
2
O
3
by HCl etching, the distinct carbon box-in- 100 to 5000 mA g , as shown in Figure 3a. The as-obtained
2 3
V O
/C box-in-box delivers a mean reversible discharge
-1
2
O
3
2
O
3
capacity of 794, 693, 614, 544, 481 and 406 mAh g at a
-
nanoflakes have been fully well-maintained. From high- current rate of 100, 300, 500, 1000, 3000 and 5000 mA g ,
resolution TEM image (Figure 2d), clear lattice fringes are respectively. After through five deep charge/discharge cycles,
1
-1
visible. The interconnected distance is measured to be about a reversible capacity as high as 778 mAh g can still be
-1
0
.37 nm, matching well with the distance of the (012) plane of obtained when scanned again at 100 mA g
，
which further
. A fast Fourier transformation (FFT) pattern is also proves the superior Li storage. Accordingly, the pure carbon
provide in insert of Figure 2d, showing pure V with high box electrodes were also tested under the identical current
crystallinity. The corresponding XRD pattern is shown in Figure densities (Figure S6). For comparison, we also synthesized the
S2. All peaks can be assigned to standard pattern of the pristine V NPs with sizes of ~ 100 nm and the V hollow
No nanospheres (HNSs), as shown in Figure S7. It can be found
+
2 3
pure V O
2 3
O
2
O
3
2 3
O
2
3,24
rhombohedra V
2 3
O phase (JCDPS card No.: 34-0187).
-
other detectable impurity exists, further demonstrating the that they deliver a lower discharge capacity of 479, 694 mAh g
1
successful preparation of the target products. The content of
-1
at 100 mA g , respectively. Particularly at a high rate of 5000
-1
-1
carbon is estimated to ~ 29.3% (Figure S3) with relatively high mA g , only 197, 279 mAh g can be retained for each of
graphitization degree (Figure S4a), which will be favorable to them. The remarkably enhanced electrochemical performance
2
accelerate electrons rapid transfer. Combining with the large can be mainly attributed to the V
5
2
O
3
multi-scaled hierarchical
2
specific surface area of 45.2 m g (Figure S4b), the unique nanostructures with rich active sites and short ions diffusion
-1
V
2
O
3
/C box-in-box is reckoned to deliver high energy/power
path as well as their hybridization with high-conductive carbon
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ARTICLE
boxes. We further evaluate the cycling performance of the
Journal Name
-1
V
2
O
3
/C box-in-box for another 1200 cycles at 1000 mA g , as
shown in Figure 3b. The discharge capacity gradually increases
-1
and reaches the maximum value of 641 mAh g after nearly
00 cycles, and then keeps stable for the subsequent 500
cycles. For the V HNSs, they also show an increasing trend
in the first 400 cycles and then gradually decrease to 422 mAh
7
2 3
O
-1
g after 700 cycles. The increasing capacity for both samples in
the beginning has been widely attributed to the activation
process with the appearance of high valence vanadium,
confirmed by X-ray photoelectron spectroscopy (XPS)
2
0,26,27
measurements (Figure S8).
3
It can be observed that a
relative V content reduces from 59% to 27% for the V O /C
+
2
3
3
+
5+ 28-30
box-in-box, suggesting its partial oxidation of V into V .
The long cycle life is mostly related to its unique and robust
structure. In particular, the carbon box-in-box plays a crucial
role in maintaining the structural integrity during repeated
charge/discharge process, which at least possesses dual
functions. The void space between carbon boxes will
accommodate the distinct volume expansion when lithiation.
And meanwhile, the inner carbon box can be expected to
support the outer V O /C shell/core hybrids, and therefore
Figure 5. (a) Schematic illustration of the all-nanobox based V
2 3 2 5
O /C//V O LIBs full cell.
-
1
(
b) Rate performance of V /C//V full cell at 100-5000 mA g within 1-3.5 V, (c)
2
O
3
2 5
O
-1
cycling behaviour and Columbic efficiency of the full cell at 500 mA g (insert of (c)
showing the lighted LEDs).
the electrode surface before and after cycles, as shown in
Figure S9. These results are good at supporting our forecast
that the carbon box-in-box is favorable to improve the
structural stability of electrode materials. Therefore, the
present V O /C box-in-box demonstrates an excellent and
2
3
strongly enhancing the structural durability, giving rise to an
extended lifespan.
Electrochemical
impedance
spectra
(EIS)
were
2
3
characterized to provide further insights on the electron/ion
transfer characteristics within the electrodes and the
corresponding structural robustness, as shown in Figure 3c.
The V O /C box-in-box exhibits a much lower charge transfer
comprehensive electrochemical performance in terms of high
energy/power densities and extended lifespan.
On the other hand, the V O box can also be obtained if
2
5
2
3
annealing the same precursor in air at 350 °C for 2 h. The pure
and orthorhombic phase V O has been confirmed by the
resistance (~ 99 Ω) than the V O HNSs (~ 176 Ω). After cycles,
2
3
2
5
a little bit drop can be seen for the V O /C box-in-box due to
2
3
corresponding XRD pattern (Figure S10). The SEM (Figure 4a)
the full infiltration by the electrolyte, which also implies the
structural stability. To further clarify it, the SEM image of
V O /C box-in-box after cycling is provided in Figure 3d. The
and TEM (Figure 4b) images show the typical and uniform V O5
2
box morphology composed of V O nanoflakes with the almost
5
2
2
3
similar diameter with V O /C box-in-box. When served as
2
3
cubic shape has been well-maintained without obvious
pulverization. In addition, there is no obvious change about
cathode materials for LIBs, the V O box delivers a high specific
2
5
-1
capacity of 142 mAh g at 2/3 C, closed to the theoretical
-1
capacity of 147 mAh g when tested within 2.5-4 V, as shown
in Figure 4c. Even at a very high current density of 50 C, the
-
1
specific capacity can still be maintained as high as 83 mAh g .
Importantly, The V O box also demonstrates a good cycling
2
5
stability with nearly 100% Coulombic efficiency at 10 C, as
shown in Figure 4d. The specific capacity can retain 111 mAh g-
1
at the 400th cycle with only 7.5% capacity fading. Considering
their much lower specific capacity of cathode materials
compared to anode materials, the volume change is also
inconspicuous. Therefore, the unique V O box structure is
2
5
enough for ensuring a superior electrochemical performance
in terms of its abundant active sites, short ions diffusion
distance and part volume flexibility. Such an excellent
performance with a high output voltage makes V O box be a
2
5
desired cathode to couple with V O /C box-in-box anode for
2
3
assembling all-nanobox based LIBs full cell.
Before assembling a full cell, the V O /C anode was pre-
2
3
lithiated by electrochemically activated for 6 cycles within
.01-3 V, subsequently discharged to 0.01 V. And then, a
/C box-in-box//V box LIBs full cell was obtained (Figure
Figure 4. (a) SEM and (b) TEM images of the V
box at various rates in the voltage range of 2.5-4 V, (d) cycling behaviour and Columbic
efficiency of the V box at 10 C.
2 5 2 5
O box, (c) rate performance of the V O
0
V
2
O
3
2 5
O
2 5
O
4
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a), which has been evaluated by galvanostatically
ARTICLE
5
Notes and references
charge/discharge measurement at 1.0-3.5 V. The initial 3
charge-discharge curves were shown in Figure S11 at 100 mA
1
F. Xu, Z. Tang, S. Huang, L. Chen, Y. Liang, W. Mai, H. Zhong,
R. Fu, D. Wu, Nat. Commun. 2015, , 7221.
6
-1
-1
g . A high reversible capacity of 130 mAh g is achieved based
on the cathode materials weight, which can still be maintained
2
X. Lai, J. E. Halpert, D. Wang, Energy Environ. Sci. 2012,
5604.
Y. Zhao, L. Jiang, Adv. Mater. 2009, 21, 3621.
5,
-
1
-1
3 mAh g even at a very high rate of 5000 mA g (Figure 5b).
3
4
4
H. Zhang, Q. Zhu, Y. Zhang, Y. Wang, L. Zhao, B. Yu, Adv.
Funct. Mater. 2007, 17, 2766.
F. skandar, A. B. D. Nandiyanto, K. M. Yun, Jr. C. J. Hogan, K.
Okuyama, P. Biswas, Adv. Mater. 2007, 19, 1408.
H. Liu, Z. Li, Y. Liang, R. Fu, D. Wu, Carbon 2015, 84, 419.
J. S. Cho, Y. C. Kang, Small 2015, 11, 4673.
The full cell also possesses a high cycling stability. It can still
-1
deliver a high specific capacity of 81 mAh g (~ 80% capacity
retention) after 100 cycles with nearly 100% Coulombic
5
-1
efficiency at 500 mA g , as shown in Figure 5b. It is worth
noting that the comprehensive electrochemical performance
of the all-nanobox based full cell is superior, at least
comparable to the most reported full cells in the literatures
6
7
8
F. X. Ma, H. B. Wu, Z. Xu, L. Zhen, Adv. Mater. 2015, 27
097.
,
4
9
Q. Wei, S. Tan, X. Liu, M. Yan, F. Wang, Adv. Funct. Mater.
2015, 25, 1773.
(Table S1), possibility due to the strong synergistic effects from
the homologous anode and cathode materials. Furthermore, 10 J. Wang, N. Yang, H. Tang, Z. Dong, Q. Jin, M. Yang, D.
Kisailus, H. Zhao, Z. Tang, D. Wang, Angew. Chem. 2013, 52
417.
1 J. Liu, F. Liu, K. Gao, J. Wu, D. Xue, J. Mater. Chem. 2009, 19
073.
,
2 3 2 5
our V O /C//V O full cell is able to lighten the ECUST logo
6
composed of 220 light-emitting diodes (LEDs) with rated
voltage of 3.7 V (insert of Figure 5c). Such an excellent
1
,
6
electrochemical performance will promote the design and 12 Y. Xia, Z. Xiao, X. Dou, H. Huang, X. Lu, R. Yan, Y. Gan, ACS
synthesis of other homologous electrode materials for high
energy/power LIBs.
Nano 2013,
3 Z. Wang, D. Luan, S. Madhavi, Y. Hu, X. W. Lou, Energy
Environ. Sci. 2012, , 5252.
4 J. Zhang, K. Wang, Q. Xu, Y. Zhou, F. Cheng, S. Guo, ACS Nano
015, , 3369.
7, 7083.
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
5
2
9
Conclusions
5 X. Y. Yu, H. B. Wu, L. Yu, F. X. Ma, X. W. Lou, Angew. Chem.
Int. Ed. 2015, 54, 4001.
In conclusions, we developed an effective strategy for the
6 Z. M. Liu, X. Y. Yu, U. Paik, Adv. Energy Mater. 2016, 15
318.
7 X. F. Zhang, K. X. Wang, X. Wei, J. S. Chen, Chem. Mater.
,
synthesis of homologous V
box cathodes by thermal treatment of the same precursor in
different atmospheres. As for the V /C box-in-box, the
2 3 2 5
O /C box-in-box anodes and V O
2
2
O
3
2011, 23, 5290.
8 J. Yan, A. Sumboja, E. Khoo, P. S. Lee, Adv. Mater. 2011, 23
,
unique carbon box-in-box can greatly enhance the structural
stability during lithiation/delithiation, leading to an extended
7
46.
9 H. C. Pang, P. Cheng, H. B. Yang, J. L. Lu, C. X. Guo, G. L. Ning,
C. M. Li, Chem. Commun. 2013, 49, 1536.
0 H. Jiang, G. Jia, Q. Cheng, Y. Fu, C. Li, Ind. Eng. Chem. Res.
2015, 54, 2960.
1 C. Müller, A. A. Nateprov, G. Obermeier, M. Klemm, R.
Tidecks, A. Wixforth, S. Horn, J. Appl. Phys. 2005, 98, 084111.
2 C. M. Zheng, X. M. Zhang, S. He, Q. Fu, D. M. Lei, J. Solid State
Chem. 2003, 170, 221.
3 Z. F. Li, H. Y. Zhang, Q. Liu, Y. D. Liu, L. Stanciu, J. Xie, ACS
Appl. Mater. Interfaces 2014, 6, 18894.
4 Y. Zhang, F. Zhang, L. Yu, M. Fan, Y. Zhong, X. Liu, Y. Mao, C.
Huang, Colloids Surf. A 2012, 396, 144.
5 Q. An, F. Lv, Q. Liu, C. Han, K. Zhao, J. Sheng, Q. Wei, M. Yan,
L. Mai, Nano Lett. 2014, 14, 6250.
6 C. Niu, M. Huang, P. Wang, J. Meng, X. Liu, X. Wang, K. Zhao,
Y. Yu, Y. Wu, Nano Res. 2016, 1, 128.
7 Y. Dong, R. Ma, M. Hu, H. Cheng, J. M. Lee, Y. Y. Li, J. A.
Zapien, J. Power Sources 2014, 261, 184.
lifespan. The V
2 3
O /C box-in-box anodes deliver a high
-1
reversible capacity of 641 mAh g even after 1200 cycles at
-
1
1
000 mA g . Accordingly, the V
2 5
O box cathodes with
abundant active sites and part volume flexibility also show a
-
1
desirable specific capacity of 119 mAh g at 10 C with superior
cycling stability. Importantly, an all-nanobox based
V
2
O
3
/C//V
2 5
O LIBs full cell is also assembled, which exhibits an
-1
-1
impressive specific capacity of 97 mAh g at 500 mA g with
-1
capacity retention of 81 mAh g even after 100 cycles based
on the cathode material weight. The present work not only
clarifies the importance of the structural design, but also paves
the way to fabricate other homologous electrode materials for
enhanced LIBs.
8 M. Yu, Y. Zheng, Y. Han, X. Cheng, W. Zhao, C. Liang, Y. Tong,
H. Tang, X. Lu, Adv. Funct. Mater. 2015, 25, 3534.
This work was supported by the National Natural Science 29 M. Li, G. Sun, P. Yin, C. Ruan, K. Ai, ACS Appl. Mater.
Acknowledgements
Interfaces 2013,
0 X. Pan, G. Ren, M. N. F. Hoque, S. Bayne, K. Zhu, Z. Fan, Adv.
Mater. Interface 2014, , 398.
5, 11462.
Foundation of China (21236003, 21522602, 91534202), the
Research Project of Chinese Ministry of Education (113026A),
the Program for New Century Excellent Talents in University
3
1
(NCET-13-0796), the International Science and Technology
Cooperation Program of China (2015DFA51220), the 111
Project (B14018) and Fundamental Research Funds for the
Central Universities.
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