Journal of Science: Advanced Materials and Devices 2 (2017) 233e244

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Journal of Science: Advanced Materials and Devices

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Original Article

Structural, impedance, dielectric and modulus analysis

of LiNi1-x-y-0.02Mg0.02CoxZnyO2 cathode materials for
lithium-ion batteries
N. Murali a, b, *, S.J. Margarette b, V. Kondala Rao b, V. Veeraiah b
a
Advanced Analytical Laboratory, DST-PURSE Programme, Andhra University, India
b
Department of Physics, Andhra University, Visakhapatnam, Andhra Pradesh, 530003, India

a r t i c l e i n f o a b s t r a c t

Article history: Mg, Co and Zn co-substituted layer-structured cathode materials LiNiCoxZnyMg0.02O2 (x ¼ y ¼ 0.0, 0.02
Received 4 October 2016 and 0.04) were prepared by a solid-state reaction method. The materials were systematically charac-
Received in revised form terized by X-ray diffraction (XRD), field effect scanning electron microscopy (FESEM), Fourier transform
24 April 2017
infrared spectroscopy (FT-IR), and electrical impedance spectroscopy (EIS) techniques. XRD analyses
Accepted 26 April 2017
Available online 5 May 2017
revealed the formation of a rhombohedral structure in the prepared materials with a typical a-NaFeO2
layered structure within R3m space group. The grain size was determined by FESEM in the range from
3.19 to 3.85 mm for all materials synthesized. The site of the local cation (LieO) and of the transition metal
Keywords:
X-ray diffraction
cations (MeO) in the materials were identified by FT-IR. The complex impedance and modulus studies
FESEM suggested the presence of a non-Debye type of multiple relaxations in these materials. The dielectric
Dielectric constant was found to increase with increasing Co and Zn concentrations. The ac conductivity studies
Impedance revealed a typical negative temperature coefficient of resistance (NTCR) behavior, and the conductivity
Electric modulus values varied from 1.58  105 to 8.46  106 S cm1. The activation energy determined from the
Arrhenius plots at 50 Hz was in the range of 0.23e0.78 eV.
© 2017 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

1. Introduction easy to synthesize, but it is very expensive when compared to

The lithium-ion battery cathode materials are known to be
structured of layered compounds such as lithium transition metal
oxides LiMO2 (M ¼ Co, Ni and Mn), spinel compounds like LiMn2O4
and olivine compounds like LiMPO4 (M ¼ Fe, Ni, Co and Mn) [1e4].
The layered compound of LiCoO2 was commonly used as the
cathode material in lithium-ion batteries because of its high volu-
metric energy density, excellent cyclability and the ease with which
it can be synthesized from raw materials. LiCoO2 has, however,
three major disadvantages, including the high material cost,
toxicity and low (only 50%) use of the theoretical capacity. Layered
LiCoO2 and LiNiO2 exhibit complementary behaviors; LiCoO2 was
* Corresponding author. Advanced Analytical Laboratory, DST-PURSE Programme,
Andhra University, India.
E-mail address: muraliphdau@gmail.com (N. Murali).
Peer review under responsibility of Vietnam National University, Hanoi.
LiNiO2. Moreover, LiNiO2 shows the better electrochemical perfor-
mance and is a low cost material. The nickel containing compound
LiNiO2 and their doped derivatives have been extensively studied.
LiNiO2 had the advantage of presenting a higher specific capacity
for lithium cycling, but it was difficult to prepare in the layered
structure due to the tendency of lithium and nickel, leading to the
deterioration of their electrochemical performance. Many re-
searchers have undertaken the search for new cathode materials to
overcome these shortcomings. To reduce the cost and to improve
the cell voltage and specific energy, other transition and non-
transition metals, such as Cr, Mn, Fe, Al, Ca, Mg, Zn, Mn, Co, Ga,
Sn, Sr, Ti, Zr, Cu, Rh and rare earth elements Ce and Y were used in
LiNiO2 [5,6]. These materials have been synthesized by various
methods, such as solegel, combustion, co-precipitation and solid-
state reaction etc. Among them, the latter method was desirable
due to its simple and low cost route of fabrication [7]. In this case, in
order to obtain high performance well-ordered Li[Ni1/3Co1/3Mn1/3]
O2 and LiNixMnyCo1xyO2 cathode materials, the optimizing and

http://dx.doi.org/10.1016/j.jsamd.2017.04.004
2468-2179/© 2017 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
234 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244

control of material parameters and synthesis procedure are rather rhombohedral crystal structure in the R3m space group in accor-
important [8,9]. LiNi1xCoxO2, Al doped LiNiO2 and Mg doped dance with JCPDS Card No. 740919. The lattice constants a, c and the
LiNiO2, have also been extensively investigated for their safety unit cell volume of the synthesized materials were calculated by
characteristics. Thus, electro-inactive non-transition metal ions, the Unit-Cell Software (1995) [13] using the XRD data of Fig. 1(aec)
partially Mg2þ and Al2þ, have been of great interest as depots for and the results are listed in Table 1. The lattice constants a and c are
cathode materials. However, to our best knowledge, another po- identified to be slightly increasing from 2.870 to 2.873 Å and 14.280
tential non-transition metal ion Zn2þ, has not received as much to 14.321 Å respectively and the c/a ratio also increased from 4.980
attention as a dopant for layered cathode materials [10]. to 4.985 as Mg, Co and Zn content was increased. The synthesized
In the present work, we report a systematic study of the materials showed a clear splitting of the (006) (102) and (108) (110)
morphology, structure, dielectric and impedance performance of Bragg peaks broadening of all other diffraction peaks. For the as-
LiNi1xy0.02CoxZnyMg0.02O2 (x ¼ y ¼ 0.0, 0.02 and 0.04) cathode synthesized materials, the highest c/a, I(0 0 3)/I(1 0 4) ratios and the
materials. Here Zn and Mg acted as the electrochemically active lowest R factor have also been found, indicating the least cation
elements. mixing and the best hexagonal ordering structure [14].
The average crystallite size was calculated from the full width at
2. Experimental half maxima (FWHM) of the diffraction peaks using the Debye
Scherrer's equation given by
The cathode compositions were synthesized by a solid-state
reaction method using appropriate stoichiometric amounts of D ¼ kl=bcosq
Li2CO3 (Merck 99.9%), MgO (Merck 99.9%), NiO (Merck 99.9%), CoO
(Merck 99.9%) and ZnO (Merck 99.9%). where D is the average crystalline size, k is shape factor, l is the
A slight excess amount of lithium (5%) was used to compensate wavelength of X-ray radiation, b is FWHM and q is the Bragg's angle.
for any loss of the metal which might have occurred during the The most intense peak (103) in the XRD pattern was used to
calcination at high temperatures. The mixture of the starting ma- calculate the average crystalline size and the results are listed in
terials was sufficiently mixed and after grinding the powder, it was Table 1. The average crystalline size increased with the increase in
then heat treated in air at 500  C for 5 h and it was again ground Co and Zn concentrations. The layered structure of the synthesized
and mixed, and calcined at 750  C for 20 h. Then, this powder was materials was Li (3a: 0, 0, 0), Ni/Mg/Co/Zn (3b: 0, 0, 0.5) and O (6c:
cooled at the rate of 5  C/min. Finally, the powder was ground and 0, 0, ~0.24), due to the absence of cation-mixing, i.e. Ni and Li in the
mixed, and calcined again at 850  C for 20 h in air using a muffle 3a- and 3b-sites, respectively [15].
box furnace [11]. The calcined powder was further annealed at
750  C for 20 h. After being added with polyvinyl alcohol (PVA) as a 3.2. Field effect scanning electron microscopy study
binder, the powder was reground and then finally pressed at 5 tons/
cm2 pressure into a circular disk shaped pellet. The pellets were FESEM images of LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02
heated up at a heating rate of 5  C/min and then sintered at 850  C and 0.04) samples are shown in Fig. 2(aec). The particles have
for 20 h in air. Finally they were cooled down at the rate of 5  C/min regular shapes with well defined faces and the microstructure
to room temperature. The sintered pellets were carefully polished obtained indicates the good crystallinity. The electrochemical per-
on one side to obtain a smooth surface and then washed with formance of the Lithium-ion battery depends directly on the
acetone. After some proper drying, the pellets were coated with
silver paste on the opposite surface which then acted as an
electrode.
The powder XRD data of the sample were collected on a Rigaku
Cu-Ka diffractometer with diffraction angles ranging from 20 and
80 in an increment of 0.02 . Unit cell lattice parameters were
obtained by the least square fitting method from the d-spacing and
(hkl) values. Further, the crystal size of the sample was obtained by
applying the Scherrer's equation from XRD pattern. The particle
morphology of the powders was observed using a field effect
scanning electron microscopy image taken from CarlZeiss, EVOMA
15, Oxford Instruments, Inca Penta FETx3.JPG. Fourier transform
infrared (FT-IR) spectra was obtained on a Shimadzu FT-IR-8900
spectrometer using a KBr pellet technique in the wave number
range between 400 and 1200 cm1. The impedance study was
performed by a Hioki 3532-50 LCR Hitester in the frequency range
50 Hz to 1 MHz at temperatures between room temperature and
120  C.

3. Results and discussion

3.1. X-ray diffraction analysis

XRD patterns of the as-synthesized LiNi1xy0.02Mg0.02

CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) calcined at 850  C for 20 h are
shown in Fig. 1. XRD patterns matched to LiNiO2 of the a-NaFeO2
structure of the rhombohedral system indicating R3m space group
[12]. The formation of single phase compounds is revealed by the Fig. 1. XRD patterns of LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04)
fact that all the observed peaks could be indexed within the materials.
 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244 235

Table 1
Lattice parameters, unit cell volume, I(003)/I(104) ratios and R-factor of LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) compounds.

Compound a (Å) c (Å) c/a Cell volume (Å)3 I(003)/I(104) R-factor Crystallite size (nm)

LiNi0.98Mg0.02O2 2.870 14.28 4.98 101.78 1.17 0.461 62.31

LiNi0.94Mg0.02Zn0.02Co0.02O2 2.872 14.312 4.983 102.339 1.16 0.508 67.289
LiNi0.9Mg0.02Zn0.04Co0.04O2 2.873 14.321 4.985 102.356 1.10 0.504 73.15
LiNi0.98Mg0.02O2 [23] 2.8724 14.187 e e e e e
Mg doped LiNiO2 [24] 2.8775 14.2144 4.9398 101.81 1.22 e e

Fig. 2. (a), (b) and (c): FESEM images for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04).

particle size, particle size distribution and the morphology of the
cathode materials as well. The grain growth at the higher calcina-
tion temperature was considered as rapid, leading to the larger
grain size. The calculated particle sizes for x ¼ y ¼ 0.0, 0.02 and 0.04
were 3.19, 3.53 and 3.85 mm respectively. The size or the texture of
the particles was highly even, which indicates high crystallinity and
the absence of defects in the pristine crystallites [16]. The FESEM
images revealed the well crystallized particles with a similar
accumulative morphology [17]. The primary particles of the syn-
thesized samples became well shaped and their size increased with
the increase of Co and Zn content. The synthesized materials with a
smaller particle size with high capacity and uniform particle size
distribution enhance the overall battery performance by the uni-
form depth of charge of each particle [18].
100
80
60
40
Transmittance (%)
3.3. Fourier transform infrared spectra analysis
Fig. 3(aec) show the FT-IR spectra of synthesized
LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) calcined
at 850  C for 20 h. The band found around 536 cm1, is assigned to
LieO stretching vibration, which indicates the formation of LiO6
octahedra [19]. The characteristic vibrations of CoeO, NieO, ZneO
and MgeO were 560e590, 579, 611e735 and 630 cm1, respec-
tively and are listed in Table 2. In this work, the broadband located
at around 638.69 cm1 was attributed to the asymmetric stretching
modes of MO6 (M ¼ Ni, Mg, Co and Zn) group [20].
3.4. Complex impedance spectroscopy analysis
Complex impedance spectroscopy (CIS) technique was used
to analyze the electrical properties of a polycrystalline sample and
its interface with electronically conducting electrodes in a wide
(c) frequency range (50 Hze1 MHz) at different temperatures
(30 e120  C).
Finally, Z0 and Z00 are displayed in a Nyquist plot in order to

20
0 visualize the influence of the parameters. The real impedance
100 (b) spectrum Z0 as a function of the frequency and temperature is
80
60
plotted in Fig. 4(aec) for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0,
40 0.02 and 0.04) materials. The decreased values Z0 have been
20 observed for the rise in temperature at low frequency. It also shows
0 a decrease of Z0 with an increase of frequency, forming a plateau
100
80 (a) like behavior which indicates the increase in conductivity of the
60
material. The dispersion at low frequency is attributed to the
40 release of space charge polarization with the increased tempera-
20 ture and frequency. This shows that the conduction mechanism has
0 improved with increasing temperature and frequency [21]. This
400 600 800 1000 behavior suggests that the material possesses a negative temper-
-1 ature coefficient of resistance (NTCR) [22]. It was found that the Z0
Wavenumber (cm )
values decreased with the increase of temperature, indicating
Fig. 3. FT-IR spectra for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) the reduction of the grain size, the grain boundaries and the elec-
materials. trode interface resistance. The Z0 values decreased slowly for the
236 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244

Table 2
FT-IR wavenumbers for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.

Compound Wavenumbers (cm1)

LiNi0.98Mg0.02O2 406.413 419.318 568.1691 613.271 846.128 876.578

LiNi0.94Mg0.02Zn0.02Co0.02O2 407.96208 430.144 568.1691 613.27189 856.1488 881.5067
LiNi0.9Mg0.02Zn0.04Co0.04O2 407.96208 430.144 568.1691 614.35248 863.56968 882.471

6
1.56x10
6
1.56x10
0
120 C

a
6 0
1.30x10
0
120 C
110 C 6 0
1.30x10 110 C

b
0
100 C 100 C
0

Z' (Ohm)
6
1.04x10 0
Z' (Ohm)

90 C 6
0
90 C
0
1.04x10
80 C 0
80 C
5
7.80x10 0 0
70 C 5 70 C
0 7.80x10 0
60 C 60 C
5 0 0
5.20x10 50 C 5
50 C
0 5.20x10 0
40 C 40 C
0 0
5
2.60x10 30 C 30 C
5
2.60x10

0.00
0.00

1 2 3 4 5 6 1 2 3 4 5 6

log f (Hz) log f (Hz)

0
6.60x10
5
120 C
0

c
110 C
0
5.50x10
5 100 C
0
90 C
0
5
80 C
4.40x10 0
70 C
Z' (Ohm)

0
60 C
5
3.30x10 0
50 C
0
40 C
5 0
2.20x10 30 C

5
1.10x10

0.00

2 3 4 5 6 7

log f (Hz)
Fig. 4. (a), (b) and (c): Real part of impedance as a function of frequency at different temperatures for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.
 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244 237

frequency depending on the temperature, and continuously with
an increase in frequency.
Fig. 5(aec) show the imaginary part Z00 of impedance as
a function of the frequency and temperature for
LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.
The relaxation species are possibly attributed to the presence of
electrons at low temperatures and of defects/vacancies at higher
temperatures. It is clearly seen that the curves display broad and
low intensity peaks. The peak frequency shifts to the high fre-
quency side with the increasing temperature, and the relaxation
occurs over several decades of frequency. The plots show that Z00
values initially increased, attained a peak (Z00 max) and then
decreased with frequency at all measured temperatures. Such a
Debye-like relaxation peak in the frequency dependence of Z00
usually indicates the presence of space charges since the electrical
behavior of space charges is dependent on the frequency. It is also
observed that the peak value of Z00 decreased with the increased
temperature, and the peak position was shifted to the high fre-
quency side. Peak broadening with the increase in temperature
suggests the presence of a temperature dependent dielectric
relaxation phenomenon [23].
The impedance diagram (Nyquist plot) is shown in Fig. 6(aec)
for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) ma-
terials for different temperatures. All the semicircles exhibited

0
120 C 5
6.60x10
0
5
6.60x10 110 C 0
0
120 C
100 C 0
0
5
5.50x10 110 C

b
5
5.50x10 90 C 0
100 C

Z'' (Ohm)
0
80 C 0
5
4.40x10 90 C

a
0
70 C
Z'' (Ohm)

5
4.40x10 0
0 80 C
60 C 0
0 5
3.30x10 70 C
5
3.30x10
50 C 0
0 60 C
40 C 0
0
30 C 5
2.20x10
50 C
5
2.20x10 0
40 C
0
5 30 C
5
1.10x10 1.10x10

0.00 0.00

1 2 3 4 5 6 1 2 3 4 5 6

log f (Hz) log f (Hz)

5
3.0x10
0
120 C
0
5
2.5x10 110 C

c
0
100 C
0
90 C
Z'' (Ohm)

5
2.0x10
0
80 C
0
5
70 C
1.5x10 0
60 C
0
50 C
5
1.0x10 0
40 C
0
30 C
4
5.0x10

0.0

2 3 4 5 6 7

log f (Hz)
Fig. 5. (a), (b) and (c): Imaginary part of impedance as a function of frequency at different temperatures for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.
238 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244

Fig. 6. (a), (b) and (c): Nyquist plots at different temperatures for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04).

some depression degree instead of the one, centered on the x-axis.
This can be referred to as the Non-Debye type of relaxation in which
there is a distribution of relaxation time [24]. This non-ideal
behavior can be correlated to several factors, such as grain orien-
tation, grain boundary, stressestrain phenomena and atomic defect
distribution. The presence of two semicircles at higher temperature
exhibits the presence of both grain interior (bulk property) and
grain boundary effect. The contribution peak positioned at low
frequency corresponds to the grain boundary response and that in
the high frequency range, corresponds to the bulk property of the
material [25]. The depression of the semicircle is considered as an
additional evidence of the polarization phenomena with a distri-
bution of relaxation times. The assignment of the two semicircular
arcs to the electrical response is due to the grain interior and grain
boundary, and considered to be consistent with the “brick-layer
model” for polycrystalline samples [26].
The ion transport process in ionic conductors was studied in
terms of the electrical modulus spectrum. In the present study, the
impedance data were converted into electrical modulus by using
the relation given by,
 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244 239

while at lower ones, it approached to zero for all temperatures,

M 0 ¼ uC0 Z 0 ðreal partÞ and
00 00
M ¼ uC0 Z ðimaginary partÞ;
where M0 and M00 are respectively real and imaginary parts of the
modulus, and C0 ¼ ε0A/L, with A as the area of the sample, L as the
thickness of the sample, and ε0 as the permittivity of the free space
(8:854  1014 F/cm).
The real part of the modulus spectrum variation at
different temperatures is shown in Fig. 7(aec) for
LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) samples.
It is observed that M0 showed a constant value at higher frequencies
albeit showing a dispersion in the range of intermediate fre-
quencies which increased as the temperature was increased. It
is seen that at lower frequencies, M0 approached zero, indicating
that the electrode polarization had a negligible contribution to
M0 only, and the dispersion is mainly due to the conductivity
relaxation. The gradual variation of M0 indicates that the relaxation
processes are spread over a range of angular frequencies [27].
The frequency dependence of the imaginary part of the electric
modulus M00 at different temperatures is shown in Fig. 8(aec) for
LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.
Well defined peaks are seen in the modulus spectra. These peaks
represent the re-orientation relaxation process of mobile Liþ ions.
The low-frequency side of the peaks as seen in the region where Liþ

Fig. 7. (a), (b) and (c): Real part of modulus as a function of frequency at different temperatures for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.
240 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244

Fig. 8. (a), (b) and (c): Imaginary part of modulus as a function of frequency at different temperatures for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04).

ions are capable of performing successful hopping from one site to
the next one, whereas the high frequency side of the peak is where
Liþ ions perform local motion (reorientation) only [28]. The posi-
tion of the peaks in the modulus spectra shifted towards high fre-
quency as the temperature increased, which indicates a thermally
activated relaxation process. The most probable conductivity
relaxation time is determined by the frequency of the peak ac-
cording to the relaxation. It is clearly seen that the values of M00
increased with frequency at each temperature and were constant
for both high frequencies and low temperatures. Between these
plateaus, the polarization effect is evidenced. From the M00 (u), we
can observe a relaxation process with increased temperature that
exhibits a maximum value, with M00 max at the center in the
dispersion region of M0 (u).
Fig. 9(aec) show the frequency dependence of the dielectric
constant (ε) at room temperature for LiNi1xy0.02Mg0.02CoxZnyO2
(x ¼ y ¼ 0.0, 0.02 and 0.04) samples. The high value of the dielectric
constant at low frequency and the low value of the dielectric con-
stant at high frequency indicate a large dielectric dispersion due to
the MaxwelleWagner type interfacial polarization. The dielectric
constant decreased with increasing frequency and temperature.
There is a sharp rise in the dielectric constant at low frequency and
the shape of the rise changes with the temperature, due to the
conducting ion motion. The high value of the dielectric constant
reflects the effect of the space charge polarization and the con-
ducting ionic motion. When an external electric field is applied, the
electrons reach the grain boundary through hopping. If the resis-
tance due to the grain boundary is high, the electrons pile up at the
 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244 241

Fig. 9. (a), (b) and (c) the frequency dependence of dielectric constant (ε) at room temperature for LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.

grain boundaries and induce the polarization. This is called space where ε0 ¼ 8.854  1014 F/cm is the permittivity of free space, C is
charge polarization [29]. the measured capacitance in Farads, L and A are the sample thick-
The relative dielectric constant εr of all the samples was ness and the electrode area, respectively.
measured by the capacitance method based on the equation Fig. 10(aec) shows the a.c. conductivity of
LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials
CL as a function of frequency at different temperatures. The a.c. con-
εr ¼
ε0 A ductivity of the synthesized compounds was calculated from the
242 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244

Fig. 10. (a), (b) and (c): Variation of a.c. conductivity of LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials as a function of frequency at different temperatures.

values of the dielectric constant. From Fig. 11(aec) it is observed

that the plot shows two regions: one at low frequency dispersion,
which can be ascribed to space charge polarization of blocking
electrodes, and the second region which is independent of fre-
quency. The conductivity in this region is almost constant.

t
s¼
RA

where t is the thickness, A is the area of cross-section, and R is the

bulk resistance of the sample. The R value decreased with increase
in temperature.
It can be observed that sac increased with increasing frequency.
This can be explained in terms of conducting grains separated by
highly resistive grain boundaries. According to this model, the a.c
conductivity at low frequencies exhibited the grain boundary
behavior, while the dispersion at high frequency is attributed to the
conductivity of grains [30]. The calculated a.c. conductivity values
at different temperatures are shown in Table 3. These ionic
conductivity values are varied between 1.58  105 and Fig. 11. Arrhenius plots of a.c. conductivity of LiNi1xy0.02Mg0.02CoxZnyO2
8.67  1007 S/cm for x ¼ y ¼ 0.0, 0.02 and 0.04. It was observed (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.
 N. Murali et al. / Journal of Science: Advanced Materials and Devices 2 (2017) 233e244 243

Table 3
a.c. conductivity values of LiNi1xy0.02Mg0.02CoxZnyO2 (x ¼ y ¼ 0.0, 0.02 and 0.04) materials.

Temperature ( C) a.c. conductivity (S/cm)

LiNi0.98Mg0.02O2 LiNi0.94Mg0.02Zn0.02Co0.02O2 LiNi0.9Mg0.02Zn0.04Co0.04O2

07 07
30 9.05  10 8.67  10 2.59  1006
40 2.15  1006 1.52  1006 3.91  1006
50 2.62  1006 2.13  1006 5.59  1006
60 3.26  1006 3.45  1006 7.71  1006
70 4.07  1006 4.87  1006 1.05  1006
80 4.96  1006 6.88  1006 1.38  1006
90 5.96  1006 9.46  1006 1.81  1006
100 6.95  1006 1.27  1005 2.35  1006
110 7.59  1006 1.58  1005 2.62  1006
120 8.14  1006 1.3  1005 8.46  1006

that the sample with x ¼ y ¼ 0.02 possessed good ionic conductivity
compared to those with x ¼ y ¼ 0.0 and 0.04. Finally, these results
also reveal a high ionic conductivity in samples with low additive
concentrations (x ¼ y ¼ 0.02).
The temperature dependence of the a.c. conductivity of the
materials can be expressed by the Arrhenius equation,
 
A E
s ¼ exp 
T kT
where s is conductivity, T is the absolute temperature, k is the
Boltzmann constant, A is the pre-exponential factor and E is the
activation energy. When log (s) is plotted against 1/T, a straight line
is expected with slope (E/k) and an intercept on the log (s) axis of
log A. The slope of the line leads us to determine the activation
energy. The plots between log s and 1000/T K in Fig. 11(aec) are
found to be almost linear. For the activation energy of the synthe-
sized samples, the lowest values of 0.78, 0.23 and 0.25 eV have been
derived for the 50 kHz frequency.
4. Conclusion
We have successfully synthesized LiNi1xy0.02Mg0.02CoxZnyO2
(x ¼ y ¼ 0.0, 0.02 and 0.04) materials using the solid-state reaction
method. The XRD studies have revealed single phase formation of
the orthorhombic structure in these materials. The FESEM images
show the grain size in the range of 2 to 1 mm and the presence of
agglomeration. FESEM micrographs have revealed that the grain
size in the synthesized samples increases with increasing Co and Zn
content. The complex impedance spectroscopy study of the
dielectric, impedance and modulus properties of the samples has
suggested the multiple relaxation behavior. In addition, at high
frequencies, the dielectric constant becomes nearly frequency in-
dependent. Nyquist plots have shown both grain and grain
boundary contributions to the impedance. The shape of the imag-
inary part of the modulus suggests that the relaxation processes in
these materials are of non-Debye in nature. The good ionic con-
ductivity of 1.58  105 S/cm1 has been obtained for
LiNi0.9Mg0.02Co0.02Zn0.02O2 at 383 K. The lowest value of the acti-
vation energy of 0.23 eV has been found at 50 kHz.
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