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2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim (1 of 6) 1300912 wileyonlinelibrary.com Adv. Energy Mater. 2014, 4, 1300912
Three-Dimensionally “Curved” NiO Nanomembranes as
Ultrahigh Rate Capability Anodes for Li-Ion Batteries with
Long Cycle Lifetimes
Xiaolei Sun, Chenglin Yan,* Yao Chen, Wenping Si, Junwen Deng, Steffen Oswald,
Lifeng Liu, and Oliver G. Schmidt
X. Sun, Dr. C. Yan, Dr. Y. Chen, W. Si, J. Deng,
Prof. O. G. Schmidt
Institute for Integrative Nanosciences
IFW Dresden, Helmholtzstrasse 20
Dresden, 01069, Germany
E-mail: c.yan@ifw-dresden.de
X. Sun, W. Si, J. Deng, Prof. O. G. Schmidt
Material Systems for Nanoelectronics
Chemnitz University of Technology
Reichenhainer Strasse 70, Chemnitz, 09107, Germany
S. Oswald
Institute for Complex Materials
IFW Dresden, Helmholtzstrasse 20
Dresden, 01069, Germany
L. Liu
International Iberian Nanotechnology Laboratory (INL)
4715–330, Braga, Portugal
O. G. Schmidt
Cluster of Excellence MERGE
Reichenhainer Strasse 70, Chemnitz, 09126, Germany
DOI: 10.1002/aenm.201300912
The depletion of traditional energy resources has stimulated
significant research interest in developing renewable energy
sources, including solar radiation, wind, and waves.
[1]
Because
of the intermittent availability of these resources, the exploita-
tion of their full potential requires the development of energy
storage systems. Lithium-ion batteries (LIBs), as a class of
energy storage devices, are now attracting great attention for
applications in portable electronic devices and electrical vehi-
cles.
[1–8]
To meet the ever-increasing demand for efficient
energy storage systems in hybrid electric vehicles and plug-
in hybrid electric vehicles, LIBs must be developed further to
improve their ability to deliver high power and their energy
density with ensured safety in operation and reduced cost.
[1,9]
As a transition metal oxide, nickel oxide (NiO) is low cost,
environmentally friendly, and abundant in nature. It is consid-
ered as one of the most appealing anode materials due to its
high lithium storage capacity. However, the performance of the
NiO anode has been limited by its poor electrochemical reac-
tivity and large volume variation during the lithium uptake/
release process.
[10]
To address these issues, various nanostruc-
tured NiO anode materials have been fabricated to achieve
improved electrochemical performance.
[11–16]
Despite signifi-
cant progress, the NiO electrodes are still far from commer-
cialization. Therefore, new strategies for building advanced
NiO electrodes with ultrafast power rates and long lifespans are
urgently needed.
Recently, curved nanomembranes, an important family
of functional materials, have attracted considerable interest
because of their properties and potential applications in energy
storage, fluidic sensor, biocatalysis, etc.
[17–20]
In terms of LIBs,
the large interstitial space in the curved nanostructure can effi-
ciently increase the surface area accessible to the electrolyte,
which allows lithium ions to intercalate at the interior and exte-
rior of the curved nanomembranes and to accommodate large
and frequent mechanical strain from the electrochemical reac-
tions of the active materials with lithium ions.
[17,21]
Here, we report three-dimensionally “curved” NiO nanomem-
branes made using a simple fabrication technique followed by
a thermal oxidation process, based on above considerations.
[22]
The curved NiO nanomembranes exhibit both superior power
rate and ultralong cycle life when utilized as the anode material
for LIBs. The electrodes deliver a high capacity of 721 mAh g
-1
at 1.5 C (1 C = 718 mA g
-1
) after 1400 cycles. Notably, even after
cycling at an extremely high C-rate of 50 C (i.e., current density
of 35 400 mA g
-1
), the capacity is able to recover to the initial
value when the current rate is set back to 0.2 C after 110 cycles.
To the best of our knowledge, such impressive superior power
rate and ultralong lifespan for nickel-oxide-based electrodes
have not been reported previously.
The chemical composition of the product was determined
by X-ray powder diffraction (XRD), as shown in Figure 1 a. All
three characteristic diffraction peaks can be assigned to NiO in
the face-centered cubic phase (JCPDS card No. 47–1049). The
corresponding Raman spectrum (see Supporting Information,
Figure S1) reveals five broad peaks centered at 402, 520, 695,
879, and 1069 cm
-1
, which are of vibrational origin and cor-
respond to the one-phonon first-order transverse optical mode
(TO, at 402 cm
-1
), one-phonon longitudinal optical mode (LO,
at 520 cm
-1
), two-phonon modes (2TO, at 695 cm
-1
), TO + LO
(at 879 cm
-1
), and 2LO (at 1069 cm
-1
) modes, respectively.
[23]
Further, the composition and valence states of the material
were investigated by X-ray photoelectron spectroscopy (XPS;
Supporting Information, Figure S2), where the O 1s and Ni
2p core levels were examined. The O 1s spectrum consists
of a main peak at 530.7 eV with a shoulder at 532.4 eV. The
two regions in the Ni 2p spectrum could be assigned to the Ni
2p
1/2
(870–885 eV) and Ni 2p
3/2
(850–865 eV) spin-orbit levels,
respectively. From these spectra it follows that Ni is at the sur-
face, mainly in the Ni
2+
state with some Ni
3+
contribution, and
no metallic Ni is observed.
[24]
The low-magnification scanning electron microscopy (SEM)
image in Figure 1b provides an overview of the morphology