FULL PAPER
Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors**
By Wei-Yang Li, Li-Na Xu, and Jun Chen*
Co3O4 nanotubes, nanorods, and nanoparticles are used as the anode materials of lithium-ion batteries. The results show that
the Co3O4 nanotubes prepared by a porous-alumina-template method display high discharge capacity and superior cycling
reversibility. Furthermore, Co3O4 nanotubes exhibit excellent sensitivity to hydrogen and alcohol, owing to their hollow, nano-
structured character.
1. Introduction
In the last decade, one-dimensional (1D) inorganic nano-
tubes have constituted an important domain of the family of
nanostructures, owing to their unique structures, intriguing
properties, and potential applications, which differ from those
of the corresponding bulk-state materials.[1,2] Cobalt oxide
(Co3O4) is one of the most intriguing magnetic p-type semicon-
ductors known, and has found use in applications in many
fields, such as heterogeneous catalysts, electrochromic devices,
and solid-state sensors.[3±6]
Previously, Co3O4 nanostructures with various morphologies
have been prepared. He et al.[7] synthesized monodispersed
Co3O4 nanoparticles via the thermal decomposition of the in-
termediate product Co(NO3)2´7C6H13OH in long-carbon-chain
alcohols. Martin's group[8] prepared Co3O4 nanofibers using
the sol±gel method combined with a template-synthesis tech-
nique. Liu et al.[9] reported the fabrication of Co3O4 nanorods
via calcination of precursor powders prepared in an inverse mi-
croemulsion. Selke and co-workers[10] synthesized Co3O4 nano-
tubes from cobalt complexes precoated onto colloidal particles.
By far, most of the studies on 1D Co3O4 nanostructures have
been focused on fabrication. For the formation of 1D nano-
tubes, it has been demonstrated that graphite and inorganic
materials with similar layered structures can be turned into
tubular structures by a rolling process.[11±16] Another simple
route to nanotubes is template synthesis in nanoporous mem-
branes.[17±21] By using the template method, not only layered
structural materials,[22,23] but also various other kinds of materi-
als, such as metals,[24] semiconductors,[25] and polymers,[26] can
be prepared into 1D nanostructures. Since hollow nanostruc-
tures of materials such as metals and semiconductors exhibit
properties quite different from those of their bulk form,[27±33]
Co3O4 nanotubes should be of great interest for potential ap-
plications.
± Co3O4 nanotubes, nanorods, and nanoparticles. It can be ob-
[*] Prof. J. Chen, W. Y. Li, L. N. Xu
Institute of New Energy Material Chemistry
Nankai University, Tianjin 300 071 (P.R. China)
E-mail: chenabc@nankai.edu.cn
[**] This work was supported by the NSFC (20325102 and 90406001) and
TCTPF-Key Project (200248 and 104055).
Adv. Funct. Mater. 2005, 15, No. 5, May DOI: 10.1002/adfm.200400429
It is known that rechargeable lithium-ion batteries are key
components of the portable entertainment, computing, and
telecommunication equipment required by today's informa-
tion-rich and mobile society. The limited gravimetric capacity
(< 370 mA h g±1) of carbon has prompted intensive research for
alternative anode materials that have large capacity at low po-
tentials.[34] Poizot et al.[35] reported that electrodes made of
nanoparticles of transition-metal oxides (MO, where M is Ni,
Fe, or Co) exhibit reversible capacities two- to three-times larg-
er than those that use graphite as the anode electrode. Among
them, CoO demonstrated the best electrochemical properties
in Li-ion batteries. Another major area of application for 1D
nanostructures is likely to be the sensing of certain molecules,
either for medical or environmental-health purposes.[36] The ul-
trahigh surface-to-volume ratios of nanostructured materials
make their electrical properties extremely sensitive to surface-
adsorbed species.[37±40]
Herein, we report on a template synthesis leading to Co3O4
nanotubes; we also fabricated Co3O4 nanorods and nanoparti-
cles by calcining the precursor powder and ball-milling the de-
composition product of Co(NO3)2´6H2O, respectively. The
electrochemical performance of the as-prepared Co3O4 nano-
tubes, nanorods, and nanoparticles as anode materials of Li-ion
batteries was systematically investigated using cyclic voltam-
metry and galvanostatic methods. In addition, the gas-sensing
characteristics of Co3O4 nanotubes exposed to H2 and alcohol
were also studied. The results show that Co3O4 nanotubes are
attractive for application in rechargeable lithium-ion batteries
and gas sensors.
2. Results and Discussion
2.1. Characterization of Nanomaterials
The phase purity and crystallinity of the as-prepared Co3O4
samples were characterized using X-ray diffraction (XRD).
Figure 1 shows the typical XRD patterns of the as-synthesized
served that the position of the characteristic peaks of the three
products is consistent, whereas the peak intensity differs from
one material to the next. Among the XRD patterns, the peak
intensity of the nanoparticles (Fig. 1c) is the strongest, indicat-
ing its highly crystalline structure. The obvious broadening of
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 851
 W. Y. Li et al./Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors
FULL PAPER
Figure 1. XRD patterns of the as-prepared Co3O4 products: a) nanotubes;
b) nanorods; and c) nanoparticles.
peaks for the nanotubes (Fig. 1a) is owing to the very fine grain
size and defects along the tube body produced in the decompo-
sition process. All the diffraction peaks of the three products
can be readily indexed to the pure cubic phase of Co3O4 [space
group: Fd3m (227)]. The lattice constants of the nanotubes
(a = b = c = 0.8090 nm), nanorods (a = b = c = 0.8010 nm), and
nanoparticles (a = b = c = 0.8087 nm) are all in good agreement
with the standard values (Joint Committee for Powder Dif-
fraction Standards-International Centre for Diffraction Data
(JCPDS-ICDD) Card No. 42-1467). No peaks from other
phases have been detected, indicating that the products are of
high purity.
Figure 2 shows scanning electron microscopy (SEM) images
of the as-prepared Co3O4 nanotubes, nanorods, and nanoparti-
cles at different magnifications. Figures 2a,b are typical SEM
images of Co3O4 nanotubes at relatively low magnification. It
can be seen that a large quantity of nanotube bundles and
nanotube filaments were obtained. The length of the nanotube
bundles is approximately 20 ~ 40 lm, which is shorter than the
thickness of the template membrane used in the synthesis pro-
cess, suggesting that long tubes are broken into shorter ones.
This may be due to the limited mechanical strength of oxide
materials. Figure 2c displays an SEM image of one Co3O4
nanotube bundle at a higher magnification, showing that the
Co3O4 nanotubes are arranged roughly parallel to one another
and have smooth surfaces. A typical face-on view exhibiting
the ends of the tubes is shown in Figure 2d. The nanotubes are
hollow inside and the average outer diameter of the open-
ended nanotubes is approximately 200 nm, which is consistent
with the pore diameters of the template used. It can also be ob-
served that the tubes are highly uniform cylinders with wall
thicknesses of around 20 ~ 30 nm. Figure 2e is an SEM image
of the as-prepared Co3O4 nanorods, showing that the nanorods
have good uniformity and are distributed homogeneously.
The diameter of the nanorods is in the range 100 ~ 120 nm.
Furthermore, Figure 2f shows an SEM image of the ball-milled
Co3O4, from which it can be seen that the sample is com-
posed of nanoparticles with typical sizes of about 100 nm.
Brunauer±Emmett±Teller (BET) nitrogen-adsorption mea-
852  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 2. SEM images of the as-prepared Co3O4 samples: a,b) nanotubes
at low magnification; c) walls of nanotube bundles; d) tips of nanotube
bundles; e) nanorods; and f) nanoparticles.
surements show that the specific surface areas of the Co3O4
nanotubes, nanorods, and nanoparticles are 27, 14, and 32 m2 g±1,
respectively.
Further insight into the morphology and microstructure of
the Co3O4 nanotubes was gained using transmission electron
microscopy (TEM) and high-resolution TEM (HRTEM)
(Fig. 3). Figures 3a,b are typical TEM images of the products
synthesized from 0.5 M and 2 M Co2+ nitrate solutions, respec-
tively. Figure 3a shows that when 0.5 M Co2+ nitrate solution
was used, fragile tubular structures with unformed broken
parts were obtained, whereas, when the concentration of the
precursor solution was increased to 2 M, fully developed,
mechanically stable, and mutilayered nanotubes resulted
(Fig. 3b). Many defects can be observed along the nanotubes,
but the geometrical shape is preserved. The formation of the
defects may be attributed to the impact of gas evolution during
the thermal decomposition reaction. Obviously, the nanotubes
are composed of continuous, uniform, multilayered nanoparti-
cles diameters ranging from 10 to 40 nm (Fig. 3c). A HRTEM
image of an individual nanoparticle in a tube wall is shown in
Figure 3d; the highly crystalline structure is clear. A layer sepa-
ration of approximately 0.467 nm can be observed, correspond-
ing to the separation between (111) planes of Co3O4. The
HRTEM analyses of Co3O4 nanorods and nanoparticles are
similar to that of Figure 3d, also displaying highly crystalline
structures.
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W. Y. Li et al./Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors

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sical Li insertion/deinsertion in layered materials,[41] and in-
volves the formation and decomposition of Li2O accompanying
the reduction and oxidation of metal nanoparticles. It appears
that the mechanism of Li reactivity with Co3O4 entails, for the
most part, a displacive redox reaction as follows:

Co3O4 + 8Li+ + 8e± « 4Li2O + 3Co0 (1)

8Li « 8Li+ + 8e± (2)

4Li2O + 3Co0
discharge
Co3O4 + 8Li (3)
charge

Since the oxidation of cobalt in Co3O4 accommodates Co3+

and Co2+, the redox reaction of the phase transformation of
Com+/Co0 is complex (m is between 2 and 3). The electron-cap-
ture and -loss process during the displacive redox reaction is
mutistep, corresponding to the two cathodic current peaks and
one broad anodic current peak shown in Figure 4. From
Table 1, it can be seen that in the first cycle, the current densi-
ties I(ER) and I(EO) for the nanotube electrode were much
larger than that of the nanorod and nanoparticle electrodes, re-
vealing higher capacity and faster kinetics for Com+/Co0 trans-
Figure 3. Representative TEM images of the as-prepared Co3O4 nanotubes: formation in the nanotube electrode. In addition, the current
a) prepared with 0.5 M Co2+ nitrate solution; b,c) prepared with 2 M Co2+
nitrate solution; and d) HRTEM image of the square marked in (c).
densities I(ER) and I(EO) for the nanorod and nanoparticle
electrodes were not obviously different. Note that in the tenth
cycle, a decrease of individual peak intensity and integral areas
for ER1 and ER2 are observed with shifts of the peak potentials
2.2. Application in Lithium-Ion Batteries to the positive direction. Taking the nanotube electrode as an
example, the peak potential of ER1 and ER2 shifted from 1.31
Figure 4 shows the cyclic voltammograms (CVs) of elec- to 1.46 and 0.70 to 0.75 V versus Li+/Li, respectively. The
trodes made from Co3O4 nanotubes, nanorods, and nanoparti- decrease in the peak intensity and integral areas results from
cles at a scan rate of 0.5 mV s±1 and a temperature of 20 C. the irreversible capacity losses due to the incomplete displacive
The first and the tenth CV curves are symbolized by solid and redox reaction. However, the shape of the CV curves in the fol-
dotted lines, respectively. The results describing the features of lowing ten cycles remained similar to those in the tenth one,
the first CV curve are summarized in Table 1. showing reversible reduction and oxidation of the electrode
materials.
Figure 5 shows the initial discharge curves of the electrodes
Table 1. Reduction potentials (ER1, ER2), oxidation potential (EO), and their made from Co3O4 nanotubes, nanorods, and nanoparticles at a
corresponding current densities of the electrodes made by Co3O4 nano-
current density of 50 mA g±1 and a temperature of 20 C. It can
tubes, nanorods, and nanoparticles in the first cyclic voltammogram
curves. be seen that there are two sloping potential ranges for the lithi-
um reaction during the first discharge. Taking the nanotube
Co3O4 Potential values Current densities electrode as an example, the first potential range (1.25±1.0 V),
electrode [V] [mA cm±2] which is related to the reduction process ER1 of Figure 4, is
ER1 ER2 EO I(ER1) I(ER2) I(EO) narrow, while the second range (0.95±0.75 V), which corre-
Nanotubes 1.31 0.70 2.15 5.35 4.30 4.20 sponds to the reduction process ER2 of Figure 4, is much wider
Nanorods 1.26 0.69 2.12 3.60 2.90 3.65 and then slopes down to the cut-off potential of 0.01 V. It is
Nanoparticles 1.31 0.75 2.13 3.65 3.90 3.70
noted that the amplitude of the ~ 1.3 V peaks and ~ 0.7 V
peaks in Figure 4 are close, while the amplitude of the ~ 1.3 V
plateau in Figure 5 is very small; this indicates that the galva-
When the electrodes were scanned cathodically, two peaks nostatic change of the discharge potentials is not in agreement
with the characteristics of reduction potential (ER1, ER2) ver- with the cathodic character of the corresponding CV curves.
sus Li+/Li appeared, corresponding to a multistep electrochem- This may be owing to hysteresis occurring at higher discharge
ical lithium reaction processes. During the following anodic current densities with galvanostatic cycling.
polarization, only one broad peak was observed, which was as- The discharge curve of the nanotube electrode exhibits a
signed to the oxidation potential (EO). Poizot et al.[35] have higher discharging voltage and a longer plateau than that of
proposed that the electrochemical reaction mechanism of Li the nanorod and nanoparticle electrodes, indicating a high
with transition-metal oxides, such as CoO, differs from the clas- power-output behavior. The initial discharge capacities of the

Adv. Funct. Mater. 2005, 15, No. 5, May http://www.afm-journal.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 853
 W. Y. Li et al./Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors
FULL PAPER
Figure 4. Cyclic voltammograms (CVs) of electrodes made by Co3O4:
a) nanotubes; b) nanorods; and c) nanoparticles at a scan rate of
0.5 mV s±1 and 20 C. Solid symbols: the first cycle; dots: the tenth cycle.
three electrodes are ordered as follows: Co3O4 nanotubes
(850 mA h g±1) > Co3O4 nanoparticles (830 mA h g±1) > Co3O4
nanorods (815 mA h g±1).
Figure 6 shows the curves of discharge capacity versus cycle
number for the electrodes made from Co3O4 nanotubes, nano-
854  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 5. The first discharge curves of the electrodes made by the as-pre-
pared Co3O4 nanotubes (solid symbols), nanorods (dots), and nanoparti-
cles (dashes) at the current density of 50 mA g±1 and 20 C.
Figure 6. Cycle life of the electrodes made by the as-prepared Co3O4 nano-
tubes (solids), nanorods (dots), and nanoparticles (dashes) at the current
density of 50 mA g±1 and 20 C.
rods, and nanoparticles. Starting from the first cycle, the dis-
charge capacity decreased with increasing cycles. The rate of
the capacity decay from the first to the twentieth cycle is much
higher than that from the twentieth to the one-hundredth cycle.
After one-hundred cycles, the nanotube and nanorod elec-
trodes maintained 500 and 480 mA h g±1, corresponding to
about 58.8 % and 57.8 % of the initial capacity, respectively,
while the nanoparticle electrode only showed 450 mA h g±1
(about 55.2 % of its initial capacity). This indicates that the rel-
ative rate of capacity decay can be ordered as Co3O4 nanopar-
ticles > Co3O4 nanorods > Co3O4 nanotubes. It is noted that
the present cycling decay is faster than that of Co oxides (CoO
and Co3O4) reported by Poizot et al.,[35] but it is better than
that of Co3O4 nanoparticles with an average particle size of
1 lm,[42] demonstrating that both the morphology and the par-
ticle size have the influence on the electrode cycle life. After
one-hundred cycles, the Co3O4-nanotube electrode in the dis-
charged state was further analyzed using XRD, as shown in
Figure 7. Co peaks can be observed, confirming the Tarascon
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W. Y. Li et al./Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors

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molecules or pollutants. Prompted by the hollow structure and
porous appearance of the as-prepared Co3O4 nanotubes, we
suspected that these semiconducting nanotubes could be useful
in fabricating sensors. Figure 8 shows the sensitivity of the as-
prepared Co3O4 nanotubes to H2 and C2H5OH gases at room
temperature; for comparison, results for of Co3O4 nanoparti-

Figure 7. XRD pattern of the Co3O4 nanotube electrode after 100 cycles in
the discharged state. The peaks marked by arrows can be indexed to Co
(JCPDS ICDD Nos. 05-727 and 15-0806).

reaction, i.e., the formation of very fine metal particles and

Li2O. Note that the peaks of Li2O were not detected, possibly
owing to their relatively weak intensity and the washing away
by diethyl carbonate (DEC) during the treatment.
According to the results presented above, the electrodes of
Co3O4 nanostructured materials (nanotubes, nanorods, and
nanoparticles) displayed superior electrochemical performan-
ces.The most likely interpretation is as follows. First, as is
known, chemical and physical phenomena are strongly affected
when materials become nanometer-sized. With decreasing par-
ticle size, an increasing proportion of the total number of atoms
lies on the surface, making the structural strains more and
more active for lithium electrochemical reaction. Second, the
electrochemical performance of the nanotube electrode is bet-
ter than that of the nanorod and nanoparticle electrodes. This
may be due to the hollow tubular structure which presents a
high surface-to-volume ratio. On one hand, the highly nanopo-
rous structure of the nanotubes contributes to higher specific
surface areas, making the electrochemical reaction with lithium Figure 8. Sensitivity to a) H2 and b) C2H5OH of the sensors made by the
more active. On the other hand, the defects along the tube as-prepared Co3O4 nanotubes (triangles) and nanoparticles (squares) at
body are favorable for the diffusion of lithium ions. The hol- room temperature.
low-inside tube structure makes the lithium ions diffuse from
both outer and inner part of the tube, providing more active
sites. Furthermore, the wall thickness of the nanotubes is only cles (about 100 nm) are also shown. As shown in Figure 8a, it
around 20 ~ 30 nm, which indicates a shorter diffusion length is apparent that the Co3O4 nanotubes exhibit superior gas-
for lithium ions. Third, the cycling performances of the nano- sensing capabilities towards H2 than the Co3O4 nanoparticles.
tube and nanorod electrodes are better than that of the nano- Figure 8b is the plot of the sensitivity of Co3O4 nanotubes and
particle electrode, indicating that orderly arrangements of 1D nanoparticles to alcohol-gas concentration; it can also be seen
nanostructures exhibit better capacity retention. This may that the sensitivity of the Co3O4 nanotubes is about three times
lighten the stress caused by volume change during the numer- greater than that of the Co3O4 nanoparticles. It is found that
ous charge±discharge cycles, and suppress the degradation of the on and off responses for Co3O4 nanotube sensors could be
the electrode. repeated more than fifty times without major changes in the
signal being observed, illustrating its good reversibility for sen-
sor application.
2.3. Application in Gas Sensing The change of resistance in sensors is mainly caused by the
adsorption and desorption of gas molecules on the surface of
It is noted that chemical nanosensors are interesting because the sensing structure. Study of Co3O4 as a gas sensor has been
of their potential for detecting very low concentrations of bio- focused on films made of nanocrystals,[5] and in these setups

Adv. Funct. Mater. 2005, 15, No. 5, May http://www.afm-journal.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 855
 W. Y. Li et al./Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors
FULL PAPER
only a thin layer of the film close to the surface can be activated
during the gas detection due to the dense structure of a com-
pact film. In contrast, the hollow inside tube and the porous
surface of the Co3O4 nanotubes can provide more active sites
in the three-dimensional structure, and enable the detecting
gases to access more surfaces. Thus, the gas sensitivity of Co3O4
was remarkably enhanced when in the form of nanotubes.
3. Conclusions
Co3O4 nanotubes were successfully prepared by a thermal
decomposition of Co(NO3)2´6H2O within an ordered porous
alumina template. Electrochemical measurements of Li-ion
batteries have demonstrated that the electrtode properties of
Co3O4 nanotubes are much better than that of Co3O4 nanorods
or nanoparticles. Moreover, gas-sensing testing of the sensors
made from the Co3O4 nanotubes also indicates excellent sensi-
tivity to hydrogen and alcohol. The improved performance
may arise from the effects of hollow-inside and porous-surface
character of the tubes.
4. Experimental
Sample Preparation and Characterization: Anodic aluminum oxide
membranes (Whatman, Æ 47 mm with 0.2 lm pore and 60 lm thick-
ness) were used as the templates. Co(NO3)2´6H2O and other reagents
were all of analytical grade and used without further purification.
Co3O4 nanotubes were synthesized via chemical thermal decomposi-
tion of Co(NO3)2´6H2O within the alumina membranes by using the
following procedures. 1) 20 mL of 2 M Co(NO3)2´6H2O aqueous solu-
tion was prepared and impregnated through the membrane by re-
duced-vacuum suction, so that the solution could adhere to the pore
walls of the membrane. 2) Excess solution on the membrane surface
was carefully removed by polishing with laboratory tissue. 3) The solu-
tion-impregnated template was dried under vacuum at 60 C for 2 h
and then calcined in a furnace. The temperature was increased linearly
to 500 C and kept at this temperature for 4 h. The off-gases were intro-
duced into a beaker filled with sodium hydroxide solution so that the
exhaust gas would not pollute the air. After the thermal decomposition,
the chamber was cooled to ambient temperature, and it can be ob-
served that the pink membrane (pink indicates the presence of Co2+ ni-
trate) becomes black, the color of cobalt oxide. 4) The solution pene-
tration and the calcination procedure were repeated for two more
cycles to form nanotubes in the template pores as shown in Figure 9.
Figure 9. Schematic diagram showing the preparation of Co3O4 nanotubes.
856  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.afm-journal.de
5) To obtain self-sustained nanotubes, the alumina membrane was dis-
solved in 6 M NaOH for 3 h. The remaining black solid was collected,
then rinsed with deionized water and absolute ethanol several times,
and finally dried at 80 C under vacuum for 2 h. The chemical reactions
involved in the preparation process can be expressed as:
Nanotube preparation:
3Co(NO3)2´6H2O ® Co3O4 + 6NO2­ + O2­ + 6H2O­ (4)
NO2 absorption:
2NO2 + 2NaOH ® NaNO3 + NaNO2 + H2O (5)
Template dissolution:
Al2O3 + 2NaOH ® 2NaAlO2 + H2O (6)
For comparative materials, Co3O4 nanorods were prepared by calci-
nation of precursor powders prepared in a novel inverse microemulsion
as reported previously [9], while Co3O4 nanoparticles were prepared
by ball-milling the decomposition product of Co(NO3)2´6H2O (decom-
position temperature: 500 C) in Ar atmosphere (0.2 MPa) at 500 rpm
(rpm: revolutions per minute) for 1 h.
The as-prepared samples were characterized by powder X-ray dif-
fraction (XRD, Rigaku INT-2000 X-ray generator, Cu Ka radiation),
scanning electron microscopy (SEM, Philips XL-30, 20 kV), transmis-
sion electron microscopy (TEM) and high-resolution TEM (HRTEM)
(Philips Tecnai F20, 200 kV), and Brunauer±Emmett±Teller (BET) ni-
trogen-adsorption±desorption measurements (Shimadzu-Micromeritics
ASAP 2010 Instrument).
Electrochemical Measurements: Electrochemical measurements were
carried out using two-electrode cells with lithium metal as the counter-
and reference electrodes. The working electrode was fabricated by
compressing a mixture of the active materials (Co3O4 nanotubes, nano-
rods, or nanoparticles), conductive material (acetylene black, ATB),
and binder (polytetrafluoroethylene, PTFE) in a weight ratio of
Co3O4/ATB/PTFE = 17:2:1. The electrode was dried at 80 C for 1 h
and cut into a disk (1.0 cm2). The electrolyte solution was 1 M LiPF6
dissolved in a mixture of ethylene carbonate (EC), propylene carbon-
ate (PC), and diethyl carbonate (DEC) with the volume ratio of EC/
PC/DEC = 3:1:1. The cell assembly was performed in a glove-box filled
with pure argon (99.999 %) in the presence of an oxygen scavenger and
a sodium-drying agent. The electrochemical properties were investi-
gated by using a Solartron SI 1260 Potentionstat Analyzer with 1287 In-
terface and an Arbin charge±discharge unit at controlled temperatures.
The cyclic voltammograms (CVs) were measured at the scan rate of
0.5 mV s±1 and a temperature of 20 C. The electrode capacity was mea-
sured by a galvanostatic discharge±charge method at a current density
of 50 mA g±1 and 20 C. Charge±discharge cycles were tested with a cur-
rent density of 50 mA g±1 in the potential range 0.01±3.0 V. The capaci-
ty was based on the amount of the active material, not including the
weight of the additives in the electrode. After cycling, the electrode in
the discharged state was opened in a dry box, and the material was
washed with DEC and dried with cotton. This recovered powder was
mixed with liquid paraffin oil, smeared on a glass substrate, and cov-
ered with an adhesive tape to prevent the sample from reacting with
oxygen and moisture during the XRD measurement process [43].
Fabrication and Analysis of Gas Sensors: Sensors made from as-pre-
pared Co3O4 nanotubes or nanoparticles were fabricated on ceramic
tubes with the connection through gold electrodes that were connected
by four platinum wires [40]. The mixture of the nanotubes (or nanopar-
ticles) and ethanol was cast as a thin film spanning across the two Au
electrodes, as schematically shown in Figure 10. After calcination in air
in 500 C for 1 h, silver paste and platinum wires were used to connect
the leads of the Au electrodes to the instrument for gas-sensing analy-
sis. A Ni±Cr-alloy coil, which crossed through the ceramic tube, was
used as a resistor, and electrical contacts were made with the platinum
wires attached to the electrode. The fabricated sensors were fixed into
the gas-sensing apparatus and kept under a continuous flow of fresh air
Adv. Funct. Mater. 2005, 15, No. 5, May
W. Y. Li et al./Co3O4 Nanomaterials in Lithium-Ion Batteries and Gas Sensors
Figure 10. Schematic diagram of the working principle of the gas-sensing
measurement.
for 30 min before analysis. During the measurement, the heating volt-
age (Vheating) was supplied to the coils for heating the sensors and the
load resistor (RL) was connected in series with the sensors. The signal
voltage (Voutput) across the load, which changed with type and concen-
tration of the gas, was detected. During the measurement, the sensor
was kept in a closed plastic tube equipped with appropriate inlets and
outlets for H2 and C2H5OH flow. A given amount of H2 was injected
into the gas-sensing apparatus by a microinjector, while alcohol liquid
was injected on a heating-device part of the apparatus and gasified
quickly. The sensitivity could be measured when the detecting gas was
mixed homogeneously with the air. The gas sensitivity is defined as the
resistance ratio Rair/Rgas, where Rair and Rgas are the electrical resis-
tance for the sensor in air and in gas, respectively.
Received: September 15, 2004
Final version: November 9, 2004
± [34] J. M. Tarascon, M. Armand, Nature 2001, 414, 359.
[1] G. R. Patzke, F. Krumeich, R. Nesper, Angew. Chem. Int. Ed. 2002,
41, 2446.
[2] R. Tenne, Angew. Chem. Int. Ed. 2003, 42, 5124.
[3] S. Weichel, P. Mùller, J. Surf. Sci. 1998, 399, 219.
[4] F. Svegl, B. Orel, M. G. Hutchins, K. Kalcher, J. Electrochem. Soc.
1996, 143, 1532.
[5] M. Ando, T. Kobayashi, S. Lijima, M. Haruta, J. Mater. Chem. 1997, 7,
1779.
[6] R. J. Wu, C. H. Hu, C. T. Yeh, P. G. Su, Sens. Actuators, B 2003, 96,
596.
[7] T. He, D. R. Chen, X. L. Jiao, Chem. Mater. 2004, 16, 737.
[8] B. B. Lakshmi, C. J. Patrissi, C. R. Martin, Chem. Mater. 1997, 9, 2544.
[9] Y. Liu, G. Wang, C. Xu, W. Wang, Chem. Commun. 2002, 1486.
[10] X. S. Shi, S. Han, R. J. Sanedrin, C. Galvez, D. G. Ho, F. Zhou,
M. Selke, Nano. Lett. 2002, 2, 289.
[11] S. Iijima, Nature 1991, 354, 56.
______________________
Adv. Funct. Mater. 2005, 15, No. 5, May http://www.afm-journal.de
FULL PAPER
[12] R. Tenne, L. Mrgulis, M. Genut, G. Hodes, Nature 1992, 360, 444.
[13] Y. Feldman, E. Wasserman, D. J. Srolovitz, R. Tenne, Science 1995,
267, 222.
[14] N. G. Chopra, R. J. Luyken, K. Cherrey, V. H. Crespi, M. L. Cohen,
S. G. Louie, A. Zettl, Science 1995, 269, 966.
[15] W. K. Hsu, Y. Q. Zhu, N. Yao, S. Firth, R. J. H. Clark, H. W. Kroto,
D. R. M. Walton, Adv. Funct. Mater. 2001, 11, 69.
[16] Y. D. Li, J. W. Wang, Z. X. Deng, Y. Y. Wu, X. M. Sun, D. P. Yu, P. D.
Yang, J. Am. Chem. Soc. 2001, 123, 9904.
[17] C. G. Wu, T. Bein, Science 1994, 266, 1013.
[18] C. R. Martin, Science 1994, 266, 1961.
[19] G. Gu, G. Philipp, X. C. Wu, M. Burghard, A. M. Bittner, A. M. Bitt-
ner, S. Roth, Adv. Funct. Mater. 2001, 11, 295.
[20] B. Gates, B. Mayers, Y. Y. Wu, Y. G. Sun, B. Cattle, P. D. Yang, Y. N.
Xia, Adv. Funct. Mater. 2002, 12, 679.
[21] J. E. Meegan, A. Aggeli, N. Boden, R. Brydson, A. P. Brown, L. Car-
rick, A. R. Brough, A. Hussain, R. J. Ansell, Adv. Funct. Mater. 2004,
14, 31.
[22] G. Che, B. B. Lakshmi, E. R. Fisher, C. R. Martin, Nature 1998, 393,
346.
[23] C. M. Zelenski, P. K. Dorhout, J. Am. Chem. Soc. 1998, 120, 734.
[24] J. K. N. Mbindyo, T. E. Mallouk, J. B. Mattzela, I. Kratochvilova, B.
Razavi, T. N. Jackson, T. S. Mayer, J. Am. Chem. Soc. 2002, 124, 4020.
[25] E. D. Sone, E. R. Zubarev, S. I. Stupp, Angew. Chem. Int. Ed. 2002,
41, 1706.
[26] M. Steinhart, J. H. Wendorff, A. Greiner, R. B. Wehrspohn, K. Nielsch,
J. Schilling, J. Choi, U. Gösele, Science 2002, 296, 1997.
[27] K. L. Wooley, Chem. Eur. J. 1997, 3, 1397.
[28] F. Caruso, Adv. Mater. 2001, 13, 11.
[29] M. A. El-Sayed, Acc. Chem. Res. 2001, 34, 257.
[30] Y. Sun, B. Mayers, Y. Xia, Adv. Mater. 2003, 15, 641.
[31] I. Rubinstein, M. Lahav, T. Sehayek, A. Vaskevich, Angew. Chem. Int.
Ed. 2003, 42, 5575.
[32] M. Steinhart, R. B. Wehrspohn, U. Gösele, J. H. Wendorff, Angew.
Chem. Int. Ed. 2004, 43, 1334.
[33] F. S. Cai, G. Y. Zhang, J. Chen, X. L. Gou, H. K. Liu, S. X. Dou, An-
gew. Chem. Int. Ed. 2004, 43, 4212.
[35] P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, J.-M. Tarascon, Nature
2000, 407, 496.
[36] P. G. Collins, K. Bradley, M. Ishigami, A. Zettl, Science 2000, 287,
1801.
[37] Y. Cui, Q. Wei, H. Park, C. M. Lieber, Science 2001, 293, 1289.
[38] F. Favier, E. C. Walter, M. P. Zach, T. Benter, R. M. Penner, Science
2001, 293, 2227.
[39] M. Law, H. Kind, B. Messer, F. Kim, P. Yang, Angew. Chem. Int. Ed.
2002, 41, 2405.
[40] Y. Wang, X. Jiang, Y. Xia, J. Am. Chem. Soc. 2003, 125, 16 176.
[41] M. Winter, J. O. Besenhard, M. E. Spahr, P. Novµk, Adv. Mater. 1998,
10, 725.
[42] G. X. Wang, Y. Chen, K. Konstantinov, J. Yao, J. Ahn, H. K. Liu,
S. X. Dou, J. Alloys Compd. 2002, 340, L5.
[43] J. Chen, N. Kuriyama, Q. Xu, H. T. Takeshita, T. Sakai, J. Phys. Chem.
B 2001, 105, 11 214.
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 857