J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.

2A

STUDY ON STRUCTURAL, MICROSTRUCTURAL,

OPTICAL AND ELECTRICAL PROPERTIES OF LITHIUM
COBALT OXIDE AND LITHIUM NICKEL OXIDE FOR
THE APPLICATIONS OF SOLID OXIDE FUEL CELLS
Moe Min Min Aye1, Tun Aye2, Htet Naing Lwin3 & Win Kyaw4

Abstract
Solid Oxide Fuel Cell (SOFC) is an electrochemical device that
converts the energy of a chemical reaction directly into electrical
energy. SOFC materials of Lithium Cobalt Oxide (LiCoO2) and
Lithium Nickel Oxide (LiNiO2) were prepared by solid-state reaction
method. Structural, microstructural, optical and electrical properties
were studied by XRD, SEM, UV-VIS-NIR and electrical
conductivity measurement. XRD patterns reveal that the samples
analogous to hexagonal structure. The crystallite sizes of the samples
were also estimated by using the most intense peaks and obtained as
77.14 nm for LiCoO2and 21.40 nm for LiNiO2 respectively. SEM
micrographs indicated that the grain shape of the samples was block
shape with clear grain boundary. The energy band gaps Eg were
estimated by using the (hυ )2 vs. hυ graphs and obtained as 2.69
eV for LiCoO2 and 0.52 eV for LiNiO2. The samples exhibited as the
superionic conductors and their activation energies were obtained as
0.4363 eV for LiCoO2 and 0.4370 eV for LiNiO2.
Keywords: SOFC, LiCoO2, LiNiO2, XRD, SEM, UV-VIS-NIR,
electrical conductivity

Introduction
Solid Oxide Fuel Cell (SOFC) is an electrochemical device that
converts the energy of a chemical reaction directly into electrical energy. In
materials science, fast ion conductors are solids in which ions are highly
mobile [Azurdia, (2006)]. These materials are important in the area of solid-
state ionic, and are also known as solid electrolytes and superionic conductors.
They are mainly useful in batteries and various sensors. Fast ion conductors
1.
Dr, Lecturer, Department of Physics, University of Yangon
2
PhD Candidate, Assistant Lecturer, Department of Physics, Pathein University
3.
PhD Candidate, Assistant Lecturer, Department of Physics, University of Yangon
4.
Dr, Associate Professor, Department of Physics, Pyay University
266 J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A

are used primarily in solid oxide fuel cells. As solid electrolytes they allow the
movement of ions without the need for a liquid or soft membrane separating
the electrodes [Arico, (2005)].
Lithium transition-metal oxides are functional intercalation
compounds for their applications in rechargeable lithium-ion batteries. They
have been widely studied in search of structural stability and improved
electrochemical performance. LiCoO2-based lithium-ion batteries are highly
successful commercial products used for powering consumer devices such as
laptop computers, video cameras, and cellular phones [Julin, (2003)]. This
work deals with the preparation of LiCoO2 and LiNiO2 using solid-state
reaction method and their structural, microstructural, optical and electrical
characteristics were studied by XRD, SEM, UV-VIS-NIR and temperature
dependent electrical resistance measurements.

Experimental Details
Preparation of the Samples
Lithium Cobalt Oxide (LiCoO2) and Lithium Nickel Oxide (LiNiO2)
were prepared by solid state reaction method. The starting materials of
Analytical Reagent (AR) grade Lithium Carbonate (Li2CO3), Cobalt Oxide
(CoO) and Nickel Oxide (NiO) were weighed with molar ratio. The weighed
powders were mixed and ground by an agate mortar for 3 h to be
homogeneous and to obtain fine powder. The fine powder was annealed at
450°C for 8 h and followed by 800°C for 15 h to be crystalline phase. Flow
diagram of the sample preparation procedure of LiCoO2 and LiNiO2 is shown
in Figure 1. Photographs showing the sample preparation processes are shown
in Figures 2(a – i).
J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A 267

(AR grade) (AR grade) (AR grade)

Li2CO3 CoO NiO

Weighed Starting Materials

(Molar ratio) & Mixed
(Grinding by an agate
mortar for 3 h)
Solid Solution

(Heating 450°C for 8 h

followed by 800°C for 15 h)
As-prepared
LiCoO2 & LiNiO2

Figure 1: Flow diagram of the sample preparation procedure of LiCoO2 and

LiNiO2 samples

(a) (b) (c)

Figure 2: Photographs of the weighing of (a) CoO, (b) Li2CO3 and (c) NiO
starting materials
268 J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A

(d)

Figure 2:(d) Photograph of the weighed Li2CO3, CoO and NiO

(e) (f)

Figure 2: Photographs of the JLabTech electric oven (e) at 450°C and

(f) at 800°C
J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A 269

(g) (h) (i)

Figure 2: Photographs of the (g) grinding of LiCoO2, (h) LiNiO2 and (i)
pellets of LiCoO2 and LiNiO2

XRD, SEM and UV-VIS-NIR Measurements

Powder XRD patterns of the samples were observed by Rigaku
MiniFlex 600 X-Ray Diffractometer [Department of Physics, University of
Yangon]. Microstructural properties of the powder samples were investigated
by using JCM-6000Plus Scanning Electron Microscope (SEM) [Department
of Physics, West Yangon University] with the accelerating voltage of 15 kV
and 7000 times of photo magnification. UV-VIS-NIR (Ultraviolet-Visible-
Near Infrared) transmission spectra were collected on PC-controlled
SHIMADZU (UV-1800) UV-VIS-NIR Spectrophotometer in the wavelength
range of 200 nm – 900 nm.

Temperature Dependent Electrical Resistance Measurement

The LiCoO2 and LiNiO2 samples were made into pellets by SPECAC
hydraulic pellet-maker using 5 ton (~70 MPa). Thicknesses and area of the
samples were 2.50 mm and 1.14  10-4 m2. The electrical resistances were
observed by using FLUKE 180 digital multi-meter in the temperature range of
303 K – 673 K. DELTA A SERIES DTA-4896 and K-type thermocouple
were used as the temperature controller and temperature sensor. Photograph of
the experimental setup of temperature dependent electrical resistance
measurement is shown in Figure 3.
270 J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A

Thermocouple

Sample chamber

Temperature controller Digital multimeter

Figure 3: Photograph of the experimental setup of temperature dependent

electrical resistance measurement

Results and Discussion

XRD Study
XRD patterns of the sample are shown in Figures 4(a) and (b). The
observed XRD lines were identified by using standard JCPDS data library
files of
(i) Lithium Cobalt Oxide, LiCoO2, 00-062-0420 for Lithium Cobalt
Oxide (LiCoO2) sample and
(ii) Lithium Nickel Oxide, LiNiO2, 00-062-0468 for Lithium Nickel
Oxide (LiNiO2) sample.
XRD patterns show the formation of single phase hexagonal structure with
dominant peak corresponding to (003) refl ection in LiCoO2 sample and (104)
refl ection in LiNiO2 sample indicating that the crystallites are preferentially
oriented along these planes. The observed lattice parameters of the samples
are tabulated in Table 1. Tao, H. et. al. (2010) has reported that the lattice
parameters of the LiCo0.25Ni0.75O2 sample are a = b = 2.90 Å and c = 14.29 Å
respectively. The obtained lattice parameters in the present study are
acceptable compared with the results of Tao, H. et. al. (2011). The crystallite
sizes of the samples were estimated by using the Scherrer formula,
0.9
D , where D is the crystallite size (nm), λ is the wavelength of
B cos
J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A 271

incident X-ray (Å), θ is the diffraction angle of the peak under consideration
at FWHM (°) and B is the observed FWHM (radians). The obtained crystallite
sizes of samples are 77.14 nm for LiCoO2 and 21.40 nm for LiNiO2
respectively.

(a) (b)

Figure 4: XRD patterns of (a) LiCoO2 and (b) LiNiO2

Microstructural Analysis
Grain size and pore structure have a major effect on the properties in
polycrystalline materials. SEM micrographs of LiCoO2 and LiNiO2 are shown
in Figures 5(a) and (b). The image reveals that the grain shape of the samples
was block shapes with clear grain boundary.
Table 1: The lattice parameters and crystallite sizes of the LiCoO 2 and
LiNiO2 samples

Sample Obs. a=b, c(Å) D (nm)

LiCoO2 a=b = 2.8137 77.14
c = 13.9911
LiNiO2 a=b = 2.9186 21.40
c = 14.4427
272 J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A

(a) (b)
Figure 5: SEM micrograph of (a) LiCoO2 and (b) LiNIO2

The grain sizes of the samples are obtained as in the ranges of 0.80 –
5.80 µm for LiCoO2 and 0.50 – 4.20 µm for LiNiO2. Some pores appeared in
the observed micrographs due to the decomposition of the starting materials.
These pores are important role for the movements of ionic materials and it
follows the increase in ionic conductivity.

UV-VIS-NIR Spectroscopic Analysis

The effects of Co and Ni on the LiCoO2 and LiNiO2 samples on the
optical transmission and energy band gaps were examined by UV-VIS-NIR
(Ultraviolet-Visible-Near Infrared) transmission spectra. Photons, depending
on their energy, interact with matter in a variety of ways. In the present work,
only the effect of UV-VIS-NIR (190 nm –1100 nm) corresponding to the
energy (wavelength) region was studied. UV-VIS-NIR transmission and
absorption spectra of the samples are shown in Figures 6(a) and (b) for
LiCoO2 and Figures 7(a) and (b) for LiNiO2 respectively. The intense
absorption bands were found in the wavelength ranges of about 250 nm –
1100 nm for LiCoO2 and 234 nm –1100 nm for LiNiO2. It was generally
found that the transmission regions of the VIS and NIR light were slightly
decreased with the wavelength.
J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A 273

(nm) (nm)
(a) (b)

Figure 6: UV-VIS-NIR (a) transmission and (b) absorption spectra of

LiCoO2

(nm) (nm)
(a) (b)

Figure 7: UV-VIS-NIR (a) transmission and (b) absorption spectra of LiNiO2

It can be deduced that the transmission of UV-VIS-NIR light of Co and Ni

effects on the optical transparent in UV than the VIS and NIR regions. The
energy band gaps Eg of the samples were determined by using optical
percentage transmission with the corresponding wavelength data. To
determine the energy band gap, the graph of (hυ )2 vs. hυ was plotted. The
intercept of the horizontal line at  = 0 gives the value of energy band gap.
274 J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A

The plots of (hυ )2 vs. hυ of the samples are shown in Figures 8(a) and (b).
The energy band gaps are obtained as 2.69 eV for LiCoO2 and 0.52 eV for
LiNiO2 respectively. Liu., et. al. (2015) has reported the energy band gap
value of LiCoO2 is 2.70 eV. Also, Chan., et. al. (2011) has reported that the
energy band gap value of LiNiO2 is 0.50 eV. It was found that the obtained
energy band gaps are found to be agreed with the results of Liu., et. al. (2015)
and Chan., et. al. (2011).

LiNiO2
LiCoO2
0.60
0.0600
0.50
0.0500
2
( hn ) (nm eV)

0.0400 0.40

2
(hn) (nm eV)
-1

0.0300 -1
2 0.30
2

2.69 eV
0.0200 0.20 0.52 eV

0.0100 0.10

0.0000
0.00
1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60 3.80 4.00

hn (eV) hn (eV)

(a) (b)

Figure 8: Plots of the (hυ )2 vs. hυ graphs of (a) LiCoO2 and (b) LiNiO2

Temperature Dependent Electrical Conductivity Study

Electrical conductivity of the solid oxide materials obeys Arrhenius’s
 Ea
expression,    0 exp( ) where, σ 0 is the pre-exponential factor, Ea is
kT
activation energy (eV), k is Boltzmann’s constant and T is absolute
temperature (K). Arrhenius’s plots of the samples are shown in Figures 9(a)
and (b) respectively. The graph shows that the increase in temperature leads to
increase in conductivity, which is the normal behaviour of superionic
materials and it obeys the well known Arrhenius relation. The higher values of
temperature for the samples help the trapped charges to be librated and
participate in the conduction process which results increase in conductivity.
According to the conduction mechanism in ceramics, the decrease in
resistivity could also be related to the increase in the drift mobility of the
thermally activated electrons. The activation energies were evaluated by using
the slopes of the ln σ vs 1000/T relationship. The obtained activation energies
J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A 275

of the samples were obtained as 0.4363 eV for LiCoO2 and 0.4370 eV for
LiNiO2.
From the experimental results, the samples exhibited as superionic
conductors because their electrical conductivity were 1.04  10-3 S m-1 at
423 K (superionic phase temperature TSI) for LiCoO2 and 1.13  10-3 S m-1 at
403 K for LiNiO2. Since the solid material has the electrical conductivity
σ ~ 1  10-3 S m-1 called the superionic conductor. A few solids conduct
electricity better by ion motion than by electron motion. These unusual
materials are technologically important in making batteries. All batteries have
two electrodes separated by an electrolyte, which is a material that conducts
ions better than electrons.
-1 -1
1000/T (K ) 1000/T (K )

0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50
0.00 0.00

-2.00 -2.00

-4.00 -4.00
ln s (S m )
-1

TSI = 403 K
ln s (S m )

-6.00 TSI = 423 K

-1

-6.00

-8.00 y = -5.058x + 4.7499 y = -5.0664x + 5.1963

-8.00
-10.00
-10.00
-12.00
-12.00
-14.00
-14.00

(a) (b)

Figure 9: Arrhenius plots of the temperature dependent electrical conductivity

of (a) LiCoO2 and (b) LiNiO2

Conclusion
Solid oxide materials of LiCoO2 and LiNiO2 were successfully
prepared by solid state reaction method and their structural, microstructural,
optical and electrical conductivity were studied in this work. XRD patterns
reveal that the investigated samples analogous to hexagonal structure. The
crystallite sizes of the samples were obtained as 77.14 nm for LiCoO2and
21.40 nm for LiNiO2 respectively. From the SEM micrographs, the image
reveals that the grain shape of the samples was block shape with clear grain
276 J. Myanmar Acad. Arts Sci. 2019 Vol. XVII. No.2A

boundary. Some pores appeared in the observed micrographs due to the de-
carbonation of the starting materials. From the observed UV-VIS-NIR
transmission spectra, the samples demonstrated that less than 100%
transmittance of throughout the UV-VIS-NIR region. The energy band gaps
Eg were obtained as 2.69 eV for LiCoO2 and 0.52 eV for LiNiO2. The
obtained energy band gap values indicated that the samples were
semiconducting materials. Temperature dependent electrical resistance
measurements showed that the samples exhibited as the superionic
conductors. The activation energies were obtained as 0.4363 eV for LiCoO2
and 0.4370 eV for LiNiO2. According to experimental results, the samples can
be applied as the solid oxide fuel cell materials because they are
semiconducting materials and/or superionic conductors with the activation
energies lower than 1 eV.

Acknowledgements
The authors would like to acknowledge Professor Dr Khin Khin Win, Head
of Department of Physics, University of Yangon, for her valuable suggestion and
comments for this work.

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