Porous ternary complex metal oxide nanoparticles converted ... · PDF filePorous ternary complex metal oxide nanoparticles converted from core/shell nanoparticles Jaewon Lee2, Huazhang

Porous ternary complex metal oxide nanoparticles converted from core/shell nanoparticles

Jaewon Lee2, Huazhang Zhu3, Gautam Ganapati Yadav2,†, James Caruthers2, and Yue Wu1,3 ()

1 School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 200235, China 2 School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN 47907, USA 3 Department of Chemical and Biological Engineering, Iowa State University, Sweeney Hall, Ames, IA 50011, USA † Present address: Energy Institute, City College of New York, New York, NY 10031, USA

Received: 4 November 2015

Revised: 10 December 2015

Accepted: 18 December 2015

© Tsinghua University Press

and Springer-Verlag Berlin

Heidelberg 2016

KEYWORDS

ternary complex metal

oxide,

porous,

nanoparticle,

lithium-ion battery,

core/shell nanoparticles

ABSTRACT

We demonstrate an easy and scalable low-temperature process to convert

porous ternary complex metal oxide nanoparticles from solution-synthesized

core/shell metal oxide nanoparticles by thermal annealing. The final products

demonstrate superior electrochemical properties with a large capacity and high

stability during fast charging/discharging cycles for potential applications as

advanced lithium-ion battery (LIB) electrode materials. In addition, a new

breakdown mechanism was observed on these novel electrode materials.

1 Introduction

Significant progress has been achieved in the growth

of functional nanomaterials since the 1990s; however,

critical issues still remain to be resolved that prevent the

scalable and controllable production of nanomaterials,

especially, complex metal oxide nanomaterials [1]. The

most common preparation method for complex metal

oxide nanostructures is still mixing of precursors of

metal oxides or metal salts, either in the solid state

or in a solution, and then converting the mixture

to complex metal oxides through calcination [2]. This

method is easy and convenient for a large-scale pre-

paration [2]. However, achieving precise control of the

crystal structure, elemental composition, morphology,

and so forth, which often affect the electrical and

thermal properties of the material, is very difficult

because high-temperature syntheses are generally

unpredictable for complex metal oxide systems [3–5].

Here we report a controllable synthetic approach to

Nano Research 2016, 9(4): 996–1004

DOI 10.1007/s12274-016-0987-z

Address correspondence to [email protected]

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

997 Nano Res. 2016, 9(4): 996–1004

grow uniform porous ternary complex metal oxide

nanoparticles. These nanoparticles, which can be very

difficult to grow using conventional methods, can be

produced by an easy and scalable low-temperature

solution synthesis of core/shell binary metal oxide

nanoparticles at atmospheric pressure followed by

thermal annealing [6–8]. The final porous ternary com-

plex metal oxide nanoparticles demonstrate superior

electrochemical properties for potential applications

as advanced lithium-ion battery electrode (LIB)

materials in our preliminary test.

2 Experimental

Our focus on ternary complex metal oxide nano-

structures was motivated by their potential applications

in LIBs, magnetic resonance imaging, and high-

temperature thermoelectrics [9–17]. We chose spinel

Co2MnO4 as an example and grew nanoparticles by

deposition of Mn3O4 nanoparticle shells onto single-

crystal CoO nanoparticle cores in solution-phase

reactions followed by thermal annealing to convert

CoO/Mn3O4 core/shell nanoparticles to porous Co2MnO4

nanoparticles without significant size changes (Fig. 1).

The CoO nanoparticles were synthesized by a simple

thermal decomposition method. Sixty milliliters of

oleyl amine (Aldrich, 70%) were heated to 200 °C

under nitrogen purge. Then, 1.365 mmol of Co(acac)3

(Aldrich) were added quickly to the oleylamine

when it reached a temperature of 200 °C. The mixture

was maintained at 200 °C for 1 h, then heated to 240 °C

and maintained at that temperature for 1 h. After that,

the temperature of the reactants was decreased to

room temperature, and the products were purified

with excess pure ethanol using a centrifuge. CoO

nanoparticles coated by Mn3O4 nanoparticles were

prepared by the thermal decomposition method,

similar to previous experiments. Thirty milliliters of

oleylamine that contained the CoO nanoparticles

(40 mg) were mixed with 0.34 mmol of Mn(acac)3.

The mixture was stirred under nitrogen gas purging.

After the Mn(acac)3 was completely dissolved in the

oleylamine, the mixture was heated slowly (2 °C/min)

to 160 °C and maintained at the temperature for 4 h.

After reaction, the products were purified by the same

process used in previous experiments.

The CoO/Mn3O4 core/shell nanoparticles were then

coated on glass and placed in a tube furnace for

thermal annealing at 600 °C for 6 h in 4% hydrogen

forming gas, after which the temperature of the

chamber was decreased slowly to room temperature.

This process resulted in the production of Co2MnO4

nanoparticles. Similarly, Co3O4 nanoparticles were

prepared by annealing CoO nanoparticles at 600 °C in

4% hydrogen forming gas in a tube furnace for 6 h.

A slurry was then prepared by mixing 80 wt.%

Co2MnO4 nanoparticles as the active material, 10 wt.%

carbon black (Super C65 carbon black, TIMCAL

Graphite and Carbon), and 10 wt.% polyvinylidene

fluoride (PVDF) (Kynar HSV 900 PVDF, Arkema Inc.)

binder. The slurry was initially ground using a mortar

and a pestle. Next, the slurry was mixed with a minimal

amount of N-methylpyrrolidone (NMP, Sigma-Aldrich)

solvent for the working electrode. The resulting slurry

was coated on a Cu foil (MTI Corporation) with a wet

thickness of 200 μm. After overnight drying at 120 °C

under vacuum, 12-mm-diameter disks were punched

out and dried again for 2 h at 120 °C under vacuum.

The half-coin cells were assembled inside an Ar-filled

glove box. The half-coin cells consisted of the prepared

Figure 1 Schematic representation of the synthetic approach for Co2MnO4 nanoparticles as electrode materials for lithium-ion batteries.

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998 Nano Res. 2016, 9(4): 996–1004

slurry-coated Cu foil as the working electrode, lithium

foil as the reference electrode (MTI Corporation), a

separator (polypropylene-polyethylene-polypropylene,

Celgard 2325), and 1-M LiPF6 in a mixed solvent

(ethylene carbonate/diethyl carbonate/dimethyl

carbonate, ratio = 1 :1:1 (MTI Corporation)) as the

electrolyte.

The crystal structures of CoO nanoparticles, CoO/

Mn3O4 nanoparticles, and Co2MnO4 nanoparticles

were characterized via X-ray diffraction (XRD) on a

Bruker D8 Focus X-ray diffractometer with a Cu Kα

source. The morphology of these different types of

nanoparticles was analyzed through transmission

electron microscopy (TEM, FEI Tecnai-20) and high-

resolution TEM (HRTEM, Titan 80-300 kV Environ-

mental Electron Microscope). The surface compositions

of CoO nanoparticles, CoO/Mn3O4 nanoparticles,

and Co2MnO4 nanoparticles were studied by X-ray

photoelectron spectroscopy (XPS), using an AXIS

ULTRA DLD system under ultra-high vacuum (<10−9

torr/mbar). Elemental mapping studies of CoO/Mn3O4

nanoparticle were performed via energy dispersive

spectroscopy (EDX) on a scanning transmission electron

microscope (STEM, FEI Tecnai G2 F30 Super Twin

microscope). Raman spectroscopy of Co2MnO4 nano-

particles and Co3O4 nanoparticles was performed

with a HORIBA Jobin Yvon LabRam HR800 with an

excitation wavelength of 632.18 nm. Finally, the pre-

pared lithium half-cells were galvanostatically cycled

between 3.0 and 0.01 V by using a BAS8-MA analyzer

(MTI Corporation). The charge–discharge curve was

measured with a current density of 0.1 g/A between

0.01 and 3.00 V (vs. Li/Li+). The rate capability was

measured at various current densities between 0.01

and 3.00 V (vs. Li/Li+). After 35 cycles, the current

density switched back to 0.1 g/A. Cyclic voltammetry

(CV) analysis of the Co2MnO4 nanoparticles was also

performed in a lithium half-cell using a Maccor

testing station (model 4304). The scan rate of the CV

test was 0.05 mV/s between 0.01 and 3 V (vs. Li/Li+).

The electrodes after certain electrochemical cycles are

dissembled and immersed in acetonitrile completely

for 10 min to remove the residual electrolyte. The

used electrodes were analyzed by scanning electron

microscopy (SEM, Hitachi S-4800 Field Emission

Microscope) with energy dispersive X-ray spectroscopy.

3 Results and discussion

The XRD studies confirmed the compositions of

the CoO nanoparticles (Fig. 2(a), red curve) and the

CoO/Mn3O4 core/shell nanoparticles (Fig. 2(a), blue

curve), which were consistent with the standard XRD

database. The low-magnification TEM studies (Figs. 2(b)

and 2(c)) of the materials prepared in this way showed

that the CoO nanoparticles (Fig. 2(b)) and the CoO/

Mn3O4 core/shell nanoparticles (Fig. 2(c)) were uniform

in size. The analysis of samples showed that the CoO

nanoparticles had diameters of 47 ± 10 nm. After the

growth of Mn3O4, spherical Mn3O4 nanoparticles with

diameters of about 5–10 nm formed on the surface of

the CoO nanoparticles. The Mn3O4 nanoparticles did

not completely coat the surface, and many empty

spaces between the Mn3O4 nanoparticles were visible

in the core/shell nanoparticle structures.

The HRTEM studies (Figs. 2(d) and 2(e)) clearly

demonstrated the crystallinity of the CoO nanoparticles

(Fig. 2(d)) and the Mn3O4 shell (Fig. 2(e)). The reciprocal

lattice peaks obtained from the two-dimensional fast

Fourier transform (2D FFT) of the lattice-resolved

images (insets, Figs. 2(d) and 2(e)) could be indexed

to the (422) and (220) reflections of the face-centered

cubic CoO structure (inset, Fig. 2(d)) and the (112)

and (211) reflections of Mn3O4 shells with extra (111)

and (220) reflections from the CoO cores (inset, Fig. 2(e)).

In addition, the XPS (Fig. 2(f)) studies showed the

transition from the CoO nanoparticles with only Co

and O peaks (Fig. 2(f), red curve) to the CoO/Mn3O4

core/shell nanoparticles with extra peaks from Mn

(Fig. 2(f), blue curve). Lastly, the EDX elemental

mapping studies on the CoO/Mn3O4 nanoparticles

further confirmed the core/shell structures (Figs. 2(g)

and 2(h), with the cores composed of CoO shown in

Fig. 2(g) and the shells composed of Mn3O4 shown in

Fig. 2(h)).

Figure 3(a) shows the XRD pattern of the converted

Co2MnO4 nanoparticles after annealing. All the peaks

could be indexed to pure spinel phase Co2MnO4.

Further TEM analysis (Figs. 3(b) and 3(c)) showed that

there was no significant change in morphology after

annealing. Visible voids in the Co2MnO4 nanoparticles

could have resulted from the initial empty spaces

between the Mn3O4 nanoparticles coated on the CoO


999 Nano Res. 2016, 9(4): 996–1004

cores as well as the relatively density increases when

Mn3O4 changed to Co2MnO4. The large surface area

and tolerance to volume expansion associated with

the voids could lead to improved electrochemical and

mechanical properties, which will be discussed later.

Because of the similarity in crystal structure between

Co3O4 and Co2MnO4, the Co spectrum of the Co2MnO4

nanoparticles was further measured by high-resolution

XPS and compared with that of the Co3O4 nano-

particles to investigate the binding energy change

(Fig. 3(d)). The two peaks in the Co2MnO4 obviously

shifted compared to the two peaks of Co3O4. This

resulted from the lower electronegativity of Mn (1.55)

compared to that of Co (1.88); thus, electrons were

distorted toward Co, leading to a decrease in the

measured binding energy for the Co core electrons

in Co2MnO4. Lastly, the Raman spectroscopy analysis

(Fig. 3(e)) performed on both Co3O4 nanoparticles

and Co2MnO4 nanoparticles showed that the Co3O4

nanoparticles had two weak peaks at 520 and 608 cm−1,

which disappeared in the Co2MnO4 spectrum. In

addition, the strong peak at 680 cm−1 in Co3O4 nano-

particles shifted to 650 cm−1, further confirming the

successful conversion to Co2MnO4. The yield of the

Co2MnO4 nanoparticles calculated from the starting

precursors was approximately 50%, showing a truly

scalable process.

The rational control to grow porous ternary complex

metal oxide nanoparticles gave us the unique capability

to further investigate their potential applications. In

Figure 2 (a) XRD pattern of CoO nanoparticles and CoO/Mn3O4 core/shell nanoparticles. (b) TEM overview image of CoO nanoparticles.(c) TEM overview image of CoO/Mn3O4 core/shell nanoparticles. (d) HRTEM image of CoO nanoparticle and inset showing the FFTimage. (e) HRTEM image of CoO/Mn3O4 core/shell nanoparticle and upper inset showing the FFT image of CoO core region (orangeregion), and lower inset showing the FFT image of Mn3O4 shell region (red region). (f) XPS evolution pattern of CoO nanoparticles andCoO/Mn3O4 core/shell nanoparticles. The Mn 2p core level spectra were observed at 652 eV (2p1/2) and 640 ev (2p3/2). (g) and (h) EDX images of CoO/Mn3O4 core/shell nanparticles. The green color of (g) indicates the spatial distribution of Co and the orange color of (h) indicatesthe spatial distribution of Mn.


1000 Nano Res. 2016, 9(4): 996–1004

the case of Co2MnO4 nanoparticles, we investigated

their electrochemical properties for possible appli-

cations in LIBs. Figure 4(a) shows the galvanostatic

discharge/charge voltage profiles for a Co2MnO4

nanocomposite electrode. In the first discharge profile,

a broad potential plateau at around 0.8–0.2 V, which

is lower than the potential plateau of Co3O4 (Fig. S7

in the Electronic Supplementary Material (ESM)),

corresponds to the conversion reaction of Co2MnO4.

The Co2MnO4 nanocomposite electrode showed a

discharge capacity of 1,518 mA·h/g (Fig. 4(a)), which is

much higher than the theoretical capacity of Co2MnO4

(905 mA·h/g). The discharge capacity decreased after

the first cycle and reached 942 mA·h/g at the 10th

cycle, which is similar to the theoretical capacity. After

that, the capacity continuously increased until the

200th cycle (1,385 mA·h/g) and stabilized between the

200th and 300th cycles. The capacity of Co2MnO4

nanocomposite was much higher than that of Co3O4

nanoparticles (Fig. S7 in the ESM). We believe that

the additional capacity could arise from the surface

absorption of Li+ and its conversion to Li2O and LiOH,

which has been observed in other metal oxide systems

[18]. The cyclic voltammetry (Fig. 4(b)) measurement

on Co2MnO4 shows two peaks at ~0.8 and ~0.32 V in

the cathodic process. The sharp peak at 0.32 V can be

assigned to the reductions of Co3+ to Co2+ and Co2+

and Mn2+ to metallic Co and Mn. The broad peak at

0.8 V can be attributed to Li2O formation and decom-

position of the organic electrolyte to form a SEI at the

electrode/electrolyte interphase. Two broad oxidation

peaks could be observed at ~1.28 and ~1.98 V in the

anodic scan, corresponding to the oxidation of Mn

to Mn2+ and Co to Co2+. After the second cycle, the

reduction peak gradually moved to 0.4 and 0.9 V, which

was different than the irreversible electrochemical

reaction during the first discharge cycle.

The rate capability was evaluated using multiple-step

charging–discharging at different current densities

ranging from 0.1 to 6.4 A/g (Fig. 4(c)). The discharge

Figure 3 (a) XRD pattern of Co2MnO4 nanoparticles. (b) TEM overview image of Co2MnO4 nanoparticles. (c) HRTEM images of individual Co2MnO4 nanoparticle and inset showing the FFT image. (d) XPS spectra of the Co2MnO4 nanoparticles and the Co3O4

nanoparticles. (e) Raman spectra of the Co2MnO4 nanoparticles and the Co3O4 nanoparticles.


1001 Nano Res. 2016, 9(4): 996–1004

capacity decreased from 800 mA·h/g at 0.1 A/g in the

2nd cycle to 790, 700, 500, 300, 200, and 100 mA·h/g at

current densities of 0.2, 0.4, 0.8, 1.6, 3.2, and 6.4 A/g

in the following cycles, respectively. After charging/

discharging at 6.4 A/g, the capacity of the Co2MnO4

nanocomposite electrode could fully recover and

even start to increase to achieve a capacity higher

than that during the 2nd cycle. However, the capacity

of the Co3O4 nanoparticle electrode did not recover

completely (Fig. S8 in the ESM).

A more interesting observation came from the

long-term lifecycle test. As shown in Fig. 4(d), when

charging/discharging at a rate of 0.1 A/g, a reversible

capacity of 942 mA·h/g was obtained at the 2nd cycle.

After the 2nd cycle, the capacity of Co2MnO4 continued

increasing until it reached 1,400 mA·h/g, which is

more than 3.5 times higher than the theoretical capacity

of graphite (372 mA·h/g) [19]. Even after 300 cycles,

our Co2MnO4 nanocomposite electrode not only showed

very stable behavior but also still possessed a capacity

Figure 4 (a) Charging/discharging curves of the Co2MnO4/Li half-cell cycled at 0.1 A/g. (b) Cyclic voltammetry curves of Co2MnO4/Li half-cell cycled. (c) Retention of discharge capacity of the Co2MnO4/Li half-cell at different charge rates. (d) Discharge capacity of the Co2MnO4/Li half-cell cycled at 0.1 A/g. (e) SEM overview image of the electrode surface after 328 cycles. (f) and (g) areSEM EDX images of (e). The red color of (f) indicates the spatial distribution of Co, and the turquoise color of (g) indicates the spatialdistribution of Mn.


1002 Nano Res. 2016, 9(4): 996–1004

over 1,200 mA·h/g, which is still more than 3 times

higher than the theoretical capacity of graphite. In

addition, the Coulombic efficiency reached 99.11% and

gradually stabilized after 5 cycles. It was maintained

over 300 cycles. Thus, the Co2MnO4 nanocomposite

electrode was superior to graphite as well as Co3O4 in

terms of life cycle (Fig. S9 in the ESM).

Previously, many metal oxide materials such as

Co3O4, Mn3O4, Fe3O4, and NiO have been investigated

as anode materials for LIBs because of their remarkably

high capacity [20–23]. For instance, Co3O4 has twice

the theoretical capacity of graphite [20]. Among

metal oxide materials, complex oxide materials, which

consist of two transition metal oxides such as ZnFe2O4,

NiCo2O4, ZnCo2O4, ZnMn2O4, and MnCo2O4, are

beginning to be studied as anode materials for LIBs

because they are able to create a synergy effect through

complementarity in the Li+ charge–discharge process

[7, 24–31]. For example, manganese has a higher

capacity than cobalt per unit mass because cobalt is

heavier [12]. Moreover, it has been reported that cobalt

has a higher oxidation potential than manganese, thus

leading to a reduced output voltage when it is applied

as an anode for LIBs [7]. However, cobalt-based oxide

materials have excellent conductivity, which is a great

advantage for high current rate or high power density

applications [7, 32–34]. Recently, complex metal oxide

nanomaterials have shown a great advantage in terms

of a high surface area and a short diffusion path length

for Li ions compared to their bulk materials [35–37].

It has been reported that there is a different reaction

step between the surface and bulk [18]. Although

metal oxide materials should be changed to metal,

such as with Li2O and LiH in the bulk reaction, LiOH

can be produced at the surface. Further, LiOH can

react with additional Li in order to form LiO2 and

generate additional capacity [18]. In addition, there are

minor contributions that lead to additional capacity,

such as reversible solid-electrolyte interphase (SEI)

formation and Li adsorption on the surface of active

materials [37, 38]. Therefore, nanomaterials can pro-

vide a large additional capacity because of their high

surface area. Moreover, their short diffusion path

length can lead to an increase in the power density

and a decrease in charging time [36]. However, most

of these nanomaterials show a limited life cycle due

to their habitual aggregation and unstable SEI [12, 19].

The advantages of nanomaterial could quickly

disappear because of aggregation during the cycling

process [39]. In addition, the process of breakdown

and reformation induced by lithiation/delithiation

reactions on the metal oxide surface [14–16] can

negatively affect the Coulombic efficiency because

the SEI could impede charge transport [35, 40–42].

As a result, the Coulombic efficiency might decrease

because accumulated SEI may block charge transport

[35]. In our Co2MnO4 nanoparticles, the void spaces

formed during the conversion from core/shell nano-

particles can provide a buffer zone during volume

expansion/contraction [14, 35, 43]. It can prevent the

deformation of the SEI layer such that the cell has

good Coulombic efficiency. Moreover, the large surface

area in the porous structure also leads to additional

capacity through the interfacial reversible reaction.

Therefore, our Co2MnO4 nanoparticles show a stable

long life cycle with a large energy storage capacity.

To further explore our Co2MnO4 nanoparticle-based

composite LIB electrode, we conducted a series of

experiments to study when and how the breakdown

could occur. After continuously charging/discharging at

1,300 mA·h/g for 328 cycles, we observed a degradation/

breakdown of the nanocomposite electrode (Fig. 4(e)).

Elemental mapping performed on the working

electrode and the electrode after the breakdown

showed a completely new breakdown mechanism;

unlike other material-based electrode systems where

the breakdowns are typically due to the loss of

structural integrity, the breakdown mechanism of

our Co2MnO4 nanoparticle-based composite electrode

was more likely due to phase separation that formed

cobalt- and manganese-rich regions (Fig. 4(f)), while

the working electrodes showed a totally uniform

distribution of cobalt and manganese (Fig. 4(g)). The

reason for this breakdown mechanism is still unclear

and is currently under investigation using in-situ TEM

through collaboration.

4 Conclusions

In conclusion, we demonstrated a novel approach to

synthesize ternary complex metal oxide nanoparticles

as high-performance LIB electrode materials through


1003 Nano Res. 2016, 9(4): 996–1004

the thermal annealing of core/shell nanoparticles. This

method can also be used to grow other ternary complex

metal oxide nanoparticles with well-controlled sizes

and properties and provide future opportunities to

study other interesting electrical, optical, thermal,

mechanical, and magnetic properties of ternary and

quaternary complex metal oxide nanoparticles.

Acknowledgements

The authors acknowledge the support from the

National Science Foundation Electronic and Photonic

Materials (No. 1206425) and the startup fund from

Iowa State University. Y. W. also thanks the support

from the Eastern Scholar Program.

Electronic Supplementary Material: Supplementary

material is available in the online version of this article

at http://dx.doi.org/10.1007/s12274-016-0987-z.

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Nano Res.

Table of contents

Porous ternary complex metal oxide nanoparticles are synthesized by noble thermal annealing of core/shell nanoparticles with well- controlled sizes and properties. It is found that their porous morphology and large surface area can lead to high-performance lithium-ion battery electrode materials.

Nano Res.

Electronic Supplementary Material

Porous ternary complex metal oxide nanoparticles converted from core/shell nanoparticles

Jaewon Lee2, Huazhang Zhu3, Gautam Ganapati Yadav2,†, James Caruthers2, and Yue Wu1,3 ()

1 School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 200235, China 2 School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN 47907, USA 3 Department of Chemical and Biological Engineering, Iowa State University, Sweeney Hall, Ames, IA 50011, USA † Present address: Energy Institute, City College of New York, New York, NY 10031, USA

Supporting information to DOI 10.1007/s12274-016-0987-z

Figure S1 TEM (a) and HADDF STEM (high-angle annular dark field scanning transmission electron microscopy) overview images of CoO/Mn3O4 nanoparticles. Both images are taken by Titan 80-300 kV Environmental Electron Microscope.

Address correspondence to [email protected]


Nano Res.

Figure S2 HRTEM (a) and HADDF STEM images of CoO/Mn3O4 nanoparticles. Both images are taken by Titan 80-300 kV Environmental Electron Microscope.

Figure S3 High-resolution HADDF STEM images of CoO/Mn3O4 nanoparticles with EDX line scanning. This image is taken by Titan 80-300 kV Environmental Electron Microscope.

Figure S4 HRTEM images of Co2MnO4 nanoparticle. This image is taken by Titan 80-300 kV Environmental Electron Microscope.


Nano Res.

Figure S5 FT-IR (Fourier transform infrared) spectra of annealed Co2MnO4 (blue line), oleylamine (red line), and CCl4 (black line). Oleylamine is dissolved in CCl4 solution. FT-IR spectra of Co2MnO4, oleylamine and CCl4 are measured by Nicolet 6700, Thermo Scientific. It is demonstrated that oleylamine attached on surface of CoO/Mn3O4 is removed completely via annealing process with 4% hydrogen forming gas environment.

Figure S6 XRD pattern of Co3O4 nanoparticles. CoO nanoparticles are changed to Co3O4 nanoparticles through annealing with 4% hydrogen forming gas environment.

Figure S7 Charging/discharging curves of the Co3O4/Li half-cell cycled at 0.1 A/g.


Nano Res.

Figure S8 Retention of discharge capacity of the Co3O4/Li half-cell at different charge rates.

Figure S9 Discharge capacity and Coulombic efficiency of the Co3O4/Li half-cell cycled at 0.1 A/g.

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Porous ternary complex metal oxide nanoparticles converted ... · PDF filePorous ternary complex metal oxide nanoparticles converted from core/shell nanoparticles Jaewon Lee2, Huazhang