Solid State Ionics 267 (2014) 1–8

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Solid State Ionics

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Structure and electrical properties of lithium nickel manganese oxide

(LiNi0.5Mn0.5O2) prepared by P123 assisted hydrothermal route
P. Senthil Kumar a, A. Sakunthala a,⁎, M. Prabu b, M.V. Reddy c, R. Joshi d
a
Department of Physics, Karunya University, Coimbatore 641114, Tamilnadu, India
b
Dept of Energy Systems Engineering, Daegu Gyeongbuk Institute of Science & Technology, South Korea
c
Department of Physics, National University of Singapore, 117542, Singapore
d
School of Physical Sciences, Central University of Karnataka, 585311, India

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

Article history: Lithium nickel manganese oxide (LiNi0.5Mn0.5O2) cathode material was prepared using the triblock polymer
Received 4 May 2014 Pluronic (P123) as a capping agent by hydrothermal method. The XRD analysis shows the importance of prepa-
Received in revised form 20 July 2014 ration conditions to prepare phase pure LiNi0.5Mn0.5O2 compound. FTIR and Raman analysis confirmed the
Accepted 1 September 2014
layered hexagonal structure. SEM and particle size analysis show the presence of submicron sized particles and
Available online xxxx
few percentages of nanosized particles as secondary distribution. The electrical conductivity of the compound
Keywords:
LiNi0.5Mn0.5O2 was measured by AC impedance and four-probe DC measurements and compared. The total
Lithium nickel manganese oxide electrical conductivity of the compound was found to be 2.4 × 10−6 S/cm. A mixed ionic and electronic conduction
Cathode material was observed from the transference number measurement.
Polymer P123 © 2014 Elsevier B.V. All rights reserved.
Hydrothermal
Conductivity

1. Introduction
Layered lithium nickel manganese oxide (LiNi0.5Mn0.5O2) (LNMO)
is extensively studied as a promising positive electrode material for
lithium ion batteries, because of its many advantages like high revers-
ible capacity, good cyclic performance, high thermal stability, low
cost and non-toxicity [1–4]. In this compound the nickel ion (Ni2+) is
electrochemically active and manganese ion (Mn4+) is found to be
electrochemically inactive. The Mn4+ ion mainly contributes to the
structural stability [5]. The major drawback in this material is that it is
difficult to prepare it as a phase pure compound, and also it has an
intrinsic insulating nature leading to poor rate performance of the
battery [2,6]. But the structural properties and electrochemical perfor-
mance of the LiNi0.5Mn0.5O2 electrode material strongly depends on
the preparation procedure [2,7–9]. So far various preparation methods
like solid state reaction, ball milling, co-precipitation, ion exchange
method and mixed hydroxide method were adopted to prepare
the above compound [8–13]. But the preparation of phase pure
LiNi0.5Mn0.5O2 was always a great challenge due to the formation of
impurity likes NiO and also results in Li2MnO3 super lattice. Apart
from impurities, the cation mixing/disorder during compound forma-
tion was found to be a major hindrance for the diffusion of lithium
⁎ Corresponding author.
E-mail addresses: meetsaku@gmail.com, sakunthala@karunya.edu (A. Sakunthala).
ions. The cation mixing occurs due to the considerable amount of Li+
and Ni2+ being exchanged between the Li (3a) and Ni/Mn (3b) sites
due to the similar size of the Li+ and Ni2+ cations (Li+ = 0.69 Ǻ;
Ni2+ = 0.76 Ǻ) [14]. Many reports were seen to overcome the cation
mixing and impurities by means of doping with different metal ions
like aluminum, titanium and cobalt [15–17]. The suppression of cation
mixing of the compound mainly depends on the ionic radii of the
dopant element and its level of doping [16]. Very few reports were seen
on the preparation of phase pure pristine compound (without doping)
with low level or without any cation mixing [14,18–21]. Among the
above discussed preparation routes, the co-precipitation and ion
exchange methods were found to be successful in overcoming cation
disorder [10,11]. Kang et al [4] has reported on the rate performance of
LiNi0.5Mn0.5O2 prepared by ion exchange method. In the above report,
though the compound prepared by ion exchange method had bigger par-
ticle size than the one prepared by conventional solid state method, it was
found to give better rate capability owing to its less cation disorder and
better lattice parameter prepared by ion exchange method. The author
has stressed on the requirement of adopting proper preparation methods
to get LiNi0.5Mn0.5O2 with less cation disorder, low strain and proper
doping for better results. But, either the co-precipitation or the ion
exchange method involves complex steps in preparation, and therefore
research focus on any simple preparation process for LiNi0.5Mn0.5O2 is a
must. In this context we have adopted hydrothermal route to prepare
LiNi0.5Mn0.5O2. Hydrothermal preparation is a quick, easy, inexpensive
and feasible method to synthesize phase pure cathode materials with

http://dx.doi.org/10.1016/j.ssi.2014.09.002
0167-2738/© 2014 Elsevier B.V. All rights reserved.
2 P. Senthil Kumar et al. / Solid State Ionics 267 (2014) 1–8

homogeneous smaller particle size. Various cathode materials like The pellet was gold coated, dried and sandwiched between stainless
LiFePO4, LiNiVO4, LiMn2O4, LiV3O8 and LiFe1 − xMnxPO4 were successfully steel blocking electrodes and subjected to electrical studies. The AC im-
prepared by hydrothermal method [22–26]. Cho et al [27] reported on the pedance study was made using computer-controlled CH-Instrument
preparation of Li(Ni0.41Li0.08Mn0.51)O2 using multistep hydrothermal (CHI-6008E) in the frequency range of 40 Hz–1 MHz at room tempera-
method with a mixed solution of LiOH.H2O and Ni0.14Mn0.86O2, which in ture. The amplitude was fixed as 50 mV during the measurement. Four-
turn was prepared from K0.32MnO2 Birnessite, which again required a probe DC conductivity measurement was made using the 4-probe in-
separate preparation procedure. To the best of our knowledge no other struments make by SES instruments Pvt. Ltd. The transference number
reports were seen on the preparation of LiNi0.5Mn0.5O2 by hydrothermal measurement was carried out by Keitheley 4001 source meter.
method. Here we report a very simple polymer P123 (Pluronic-P123
((Poly (ethylene glycol)-block-poly (propylene glycol)-block-poly
3. Result and discussion
(ethylene glycol)) assisted hydrothermal route for the preparation of
LiNi0.5Mn0.5O2 compound at a calcination temperature of 950 °C and a
3.1. TG-DTA analysis
shorter calcination time of 10 h. Also, to the best of our knowledge, the de-
tailed electrical property of the above material is yet to be explored, and is
TG-DTA curves of the nitrate precursor (precursor of H950) obtained
crucial for the improvement of rate capability in view of the battery as a
using P123 assisted hydrothermal method is shown in Fig. 1. The initial
whole. The rate capability of any battery could be improved only when
weight loss of 4 wt.% observed between 40 and 180 °C could be due to
the electrical conductivity is very high for its electrode materials. Capacity
the removal of loosely bound water molecules and absorbed gasses
fading due to the intrinsic insulating nature (poor electronic conductivity
during the formation of the precursor. There was a further weight loss
~2.5 × 10−6 S/cm) of the C/LiNi0.5Mn0.5O2 cell at virgin state and charged
of 3 wt.% between 180 and 350 °C which could be due to the decompo-
state (SOC) was reported by Kang et al [28,13]. The importance of ionic
sition of residual nitrates after hydrothermal treatment [18]. The major
conductivity rather than the electronic conductivity value on the rate per-
weight loss of 12 wt.% from 350 to 850 °C is attributed to the combustible
formance of LiFePO4 was explored by Wang and Hong [29]. In this con-
organic materials and decomposition of P123 as supported by exothermic
text, in the present paper, the electrical properties of the prepared
peak around 480 °C in DTA. Above this temperature range there was no
LNMO material was explored using AC impedance analysis, Four-probe
weight loss observed, suggesting that the compound forms above
measurement and transference number studies.
850 °C. So, based on thermal studies, the precursor was slightly calci-
nated at a high calcination temperature of 950 °C for 10 h, as discussed
2. Experimental
in experimental part.

LiNi0.5Mn0.5O2 was prepared using nitrate precursors in the presence

of the polymer Pluronic P123 as a capping agent. The LNMO was 3.2. X-ray diffraction analysis
prepared in two ways, with and without hydrothermal treatment
using P123. This was made in order to understand the role of hydrother- The powder X-ray diffraction patterns of LiNi0.5Mn0.5O2 (taken at a
mal treatment in forming the hexagonal layered structure. All the step size of 0.02°) are shown in Fig. 2(a) and Fig. 2(b). The Rietveld
chemicals used were received from Sigma-Aldrich. (i) LNMO prepared refined XRD pattern of the compound prepared by P123 assisted hydro-
with hydrothermal treatment: The preparation methodology of the thermal method at a calcination temperature of 950 °C (H950)
Sample H950 was as follows: 0.3 M of P123 was added to 100 ml of (Fig. 2(a)) shows the formation of phase pure LiNi0.5Mn0.5O2. The com-
distilled water and stirred well. To this a stoichiometric ratio of high pound was found to have α-NaFeO2 structure with space group R3m
purity lithium nitrate (0.1 M), nickel nitrate (0.05 M) and manganese and indexed as hexagonal lattice. Generally the oxygen sub-lattice in
nitrate (0.05 M) were mixed to get a homogeneous solution. The pH the α-NaFeO2 hexagonal structure forms a close packed face centered
of the medium was found to be neutral. The solution was then taken (fcc) lattice with a distortion in the c-direction [30], which confirms
in a Teflon beaker of 120 ml and treated hydrothermally using a hydro- the compound to be hexagonal. Otherwise the structure is totally con-
thermal set up for 6 h at 200 °C inside a muffle furnace. The solution was sidered as a cubic. The presence of distortion in the c-direction of the
then cooled and heated on a hot plate until it becomes a dry powder. LNMO compound was confirmed by the peak splitting at 2θ ~ 37 and
The black dry powder was then calcinated at 950 °C for 10 h in a muffle 64°. This corresponds to (006/012) and (018/110) plane doublets,
furnace at a heating rate of 3 °C/min. The sample code was fixed H950. respectively, as observed in the XRD pattern. The intense peaks corre-
(ii) LNMO prepared without hydrothermal treatment: The preparation sponding to the planes (003), (101) and (104) suggest the well layered
method of the Sample WH950 was as follows: The above procedure
was repeated except for hydrothermal treatment and the precursor
was calcinated at 950 °C for 10 h at a heating rate of 3 °C/min. The
black powders obtained after calcinations were ground and taken for
further studies. The sample code was fixed WH950.
Thermo gravimetric and differential thermal analysis (TG-DTA)
studies were performed with the NETSZCH Thermogravimetric analyzer
at a scan rate of 10 °C/min in the temperature range of room temperature
to 1000 °C. X-ray diffraction patterns (XRD) of the samples were obtained
using SHIMADZU-XRD-6000 diffractometer with Cu-Kα radiation
(wavelength = 0.1541 nm) as the source at 40 kV with a scanning
range 2θ between 10° and 80°. Morphology and EDX analysis were
studied using JEOL-JSM 6000 scanning electron microscope. The
HRTEM images were taken with instrument JEOL JEM 2100. Fourier
transform infrared spectroscopy (FTIR) studies were carried out using
a BRUKER-FTIR spectrometer in the range 400 to 4000 cm−1. Particle
size measurement was carried out using a MALVERN Zetasizer ZS-90.
Raman spectra (RS) were recorded using 514.5 nm line of an Argon
laser at the power level of 16 mW. The sample was made into a pellet Fig. 1. TG-DTA analysis of LiNi0.5Mn0.5O2 precursor prior to calcination prepared by
at a pressure of 7 t and sintered at a temperature of 500 °C for 10 h. hydrothermal method.
 P. Senthil Kumar et al. / Solid State Ionics 267 (2014) 1–8
Fig. 2. (a) Rietveld refined XRD pattern of LiNi0.5Mn0.5O2 prepared by P123 assisted hydro-
thermal method at a calcination temperature of 950 °C for 10 h (H950). (b) XRD pattern of
LiNi0.5Mn0.5O2 prepared using P123 without hydrothermal method at a calcination tem-
perature of 950 °C for 10 h (WH950) [Inset: expanded regions of XRD pattern between
2θ values of 37° to 39° and 2θ values of 63° to 66°].
structure. The intensity ratio of 003/104 planes (I003/I104) is an indicator
of the degree of displacement of ions between lithium layers (at 3a site)
and transition metal layers (at 3b site), called as cation mixing/disorder.
The low intensity value of I003/I104 is an indicator of high cation disorder
which leads to poor electrochemical performance of the battery [2]. In
the present work, the observed intensity ratio of I003/I104 for the above
compound (H950) was found to be 1.71. The degree of cation disorder
obtained was found very less compared to literature reports [2,12,16,
18,31].
During the Rietveld refinement the occupancy of the 3b site by
Mn4 + was maintained at 0.5 and the distribution of Li+ and Ni2 +
between 3a and 3b sites was allowed to vary [32]. The lattice parameter
values were found to be a = 2.894 Ǻ and c = 14.296 Ǻ and it was sim-
ilar to the reported values (a = 2.894 Ǻ and c = 14.277 Ǻ, a = 2.888 Ǻ
and c = 14.269 Ǻ, a = 2.887 Ǻ and c = 14.262 Ǻ) in literatures [33–35].
The lattice parameter values slightly changes depending on the prepa-
ration conditions. The cell volume and the ratio of lattice parameter
(c/a & c/3a) were found to be 103.67 Ǻ, 4.94 and 1.644 respectively.
The obtained refinement residuals of RBragg = 0.334 and Rp = 1.62%
show that the proposed model agrees well with the experimental re-
sults. The XRD pattern of the sample WH950 shows the formation of
3
cubic phase (Fig. 2(b)) with no peak splitting at 2θ ~ 37 and 64° (inset
of Fig. 2(b)). This suggests the need for hydrothermal treatment during
preparation in order to get phase pure well layered hexagonal phase.
Based on the XRD results further discussions of morphological, vibra-
tional and electrical studies were made for the sample H950.
3.3. Morphology and elemental analysis
The SEM and HRTEM images of the LiNi0.5Mn0.5O2 compound
(H950) are shown in Fig. 3(a) i & ii, respectively. The SEM image
shows the particles to be agglomerated with spherical morphology.
The sub-micron average size of the particle was confirmed by HRTEM
image, reflecting few particles with size less than 100 nm. Further, the
particle size distribution spectrum of the above compound obtained
from particle size analyzer measurement (Fig. 3(b)) confirms the
average size of the particle to be in sub-micron range and shows the
six percentages of the particles to be in the range less than 100 nm.
The compositions of the sample were estimated by energy disper-
sive spectroscopy (EDX) and shown in Fig. 3(c). The atomic percentage
of Ni and Mn was found to be 17.46 and 19.86 respectively. The obtained
results were slightly different from the stoichiometric formula. The
deviation was attributed to the equipment limitation and the accuracy
of EDX depends on many factors like the orientation and density of
the material [36].
3.4. Vibrational analysis
3.4.1. FT-IR analysis
FTIR studies help to investigate the local environment of cations in a
close packed cubic array of oxygen constituted by LiO6 and MO6 octahe-
dra in LiNi0.5Mn0.5O2 lattice. Fig. 4(a) shows the deconvoluted FTIR
spectrum for LiNi0.5Mn0.5O2 (H950) in the 400–700 cm− 1 region.
These recorded regions were associated with the vibrations of LiO6
and MO6 octahedral units (M = Mn, Ni) (Fig. 4(b) shows schematic
vibrations). The vibrational bands at 597 and 532 cm−1 were due to
the bending modes of MO6 (O–Mn–O, (or) O–Ni–O), and the band
around 474 cm−1 was observed due to the asymmetric stretching of
Li–O in LiO6 octahedral environments [37,38]. The characteristic IR
spectra confirm the formation of LiNi0.5Mn0.5O2.
3.4.2. Raman analysis
Raman scattering spectra is the complementary tool to substantiate
XRD results for layered compounds [39–41] and it is very sensitive to
the short range environment of oxygen coordination around the cations
in sub-lattice. Fig. 5(a) shows deconvoluted Raman Scattering spectra of
LiNi0.5Mn0.5O2 [sample H950]. The compound LiNi0.5Mn0.5O2 has two
Raman active modes, namely A1g and Eg. A1g vibrational active modes
have greater oscillator strength and the intensity of the A1g was expected
to be twice higher than Eg mode [42,43].
The origin of the above mentioned Raman active modes was related
to M–O stretching and O–M–O bending, as the contributions of Raman
modes were only from the motions of oxygen atoms [44]. A1g mode
means that the oxygen atoms vibrate (stretches) parallel to c-axis
in opposite directions (Fig. 5(b–i) shows the schematic vibration).
And the Eg means that the oxygen atoms vibrate (bends) parallel to
lithium and transition metal planes alternately in opposite directions
(Fig. 5(b–ii) shows the schematic vibration) [40,45]. From fig. 5(a) the
two Raman active modes A1g and Eg were found to be at 591 and
480 cm−1 respectively. These modes were due to the vibrations of
Mn–O and Ni–O respectively for layered LNMO compounds [46].
Some of the less pronounced shoulders were found to appear below
400 cm−1 due to the presence of Li2MnO3 super lattice. This could not
be observed from XRD pattern due to its negligible percentage. The
carbon nominated D and G bands at ~1300 and 1500 cm−1, respectively
were not observed in the recorded Raman scattering spectra (inset of
fig. 5(a)), indicating no carbon residuals after calcination. The observed
4 P. Senthil Kumar et al. / Solid State Ionics 267 (2014) 1–8

(a)
(i) (ii)

(b)

(c)

Fig. 3. a (i) SEM images of LiNi0.5Mn0.5O2 prepared by P123 assisted hydrothermal method calcinated at 950 °C (H950) scale: 1 μm and magnification: 10,000 (ii) HRTEM image scale:
0.5 μm (b) particle size distribution spectra (from particle size analyzer measurement) and (c) EDX spectra.

Raman active bands were found to be well agreed with the reported
values of the layered compounds [42–47].
3.5. AC impedance analysis
3.5.1. Cole–Cole and conductivity spectra analysis
Figs. 6 and 8 show the Cole–Cole and the conductivity spectra of
LiNi0.5Mn0.5O2 (H950) respectively, for the frequency range of 42 Hz
to 1 MHz taken at room temperature (303 K). In Fig. 6, neglecting the
electrode effect (Warburg component) at low frequency, the complex
plane of LiNi0.5Mn0.5O2 sample was found to have two semicircles.
This indicates that there are different polarization mechanisms within
the sample [48]. The higher frequency semicircle was due to the trans-
port of charges within the bulk region (parallel combination of bulk re-
sistance (Rb) and bulk capacitance (Cb)) and the semicircle at mid
frequency was due to the transport of charges across the grain bound-
aries (parallel combination of grain boundary resistance (Rgb) and
grain boundary capacitance (Cgb)). The linear component in the low
frequency region (Warburg diffusion) suggests the dominance of
lithium ionic conductivity rather than the electronic conductivity [49,
50]. Neglecting the Warburg components, the bulk and the grain
boundary resistances were calculated by fitting the plot using the
 P. Senthil Kumar et al. / Solid State Ionics 267 (2014) 1–8 5

Fig. 4. (a) Deconvoluted FTIR spectra of LiNi0.5Mn0.5O2 prepared by P123 assisted

hydrothermal method calcinated at 950 °C (H950) (b) Schematic diagrams for FTIR active
mode [Ref. 39].

equivalent circuit, as shown in Fgi.6. The fit values are Relec = 347 Ω, for
bulk, Rb = 10.657 KΩ, CPE-T = 3.243 × 10-10 F, CPE-P = 0.89 and for
grain boundary Rgb = 60.686 KΩ, CPE-T = 1.665 × 10−8 F and CPE-
P = 0.65. The bulk and the total conductivity values were found to be
1.36 × 10−5 S cm−1and 2.03 × 10−6 S cm−1 respectively at room tem-
perature. The conductivity values were calculated from the conductivity
formula,
 
1 1 −1
σ¼ S cm
R A

where, “R” is the resistance, “l” and “A” are the thickness
(0.1137 cm) and area (0.785 cm2) of the pellet, respectively. The bulk
and grain boundary capacitance value at room temperature was calcu-
lated at the point of maximum frequency (fmax) of the semi circle
using the relation 2πfmaxRC = 1. Here R is the diameter of the semi
circle. The corresponding bulk and grain boundary capacitance value
were found to be 9.247 × 10− 11 F (~ 92 pF) and 3.579 × 10− 10 F
(~0.36 nF) respectively. The bulk and grain boundary true capacitance
values were also calculated by using the fit values of Cole–Cole plot as
mentioned above. The true capacitance values were found to be 78 pF
and 0.37 nF, closer to the values calculated using fmax as discussed
above. The capacitance values in the order of 10− 12 F and 10− 9 F
confirms the hoping of ions through grain interior and grain boundary,
respectively [51,52].
The behavior of the real and imaginary parts (Z′ and Z″) of the
impedance with frequency for the sample LiNi0.5Mn0.5O2 at room
temperature is shown in Fig. 7. The low intense peak in high frequency
Fig. 5. (a) Deconvoluted Raman spectra of LiNi0.5Mn0.5O2 prepared by P123 assisted
hydrothermal method calcinated at 950 °C (H950) [Inset: carbon nomination D and G
bands] (b) Schematic diagrams for Raman modes (i) A1g mode and (ii) Eg mode [Ref. 39].
region was attributed to the grain interior impedance and the one at
mid frequency was related to the grain boundary impedance (indicated
by arrows in fig. 7) [53]. The real and imaginary components of the im-
pedance were gradually decreasing as the frequency increases which
was attributed to the reduction of space charge effect at higher frequen-
cies. [54]. The two plateau regions observed at two different frequency
ranges in the conductivity spectra (Fig. 8, plateau region indicated by ar-
rows) proves the presence of bulk /grain interior and grain boundary
6 P. Senthil Kumar et al. / Solid State Ionics 267 (2014) 1–8
Fig. 6. Cole–Cole spectra for the compound LiNi0.5Mn0.5O2 (H950).
effect [55], in correlation with Cole–Cole spectra and Z′/Z″ vs log fre-
quency spectra. Extended plateau regions were expected in case of
very long range diffusion of lithium ions inside the bulk of the sample
and across the grain boundaries. But in LNMO, the shortened plateau re-
gions suggest that the lithium ions in this material have short range dif-
fusion with respect to different frequencies. The bulk and grain
boundary conductivities calculated by extrapolating the mid frequency
plateau regions in the conductivity spectra to the y-axis were found to
be ~ 1.0 × 10−5 S cm− 1 and 2.87 × 10− 6 S cm−1, respectively. The
bulk conductivity value from conductivity spectra matches very well
with the bulk conductivity calculated by using Cole–Cole plot as
discussed above.
3.5.2. Dielectric spectra analysis
Fig. 9 shows the real part (ε′) and imaginary part (ε″) of the dielectric
permittivity spectra of the compound LiNi0.5Mn0.5O2 in the frequency
region of 42 Hz to 1 MHz at room temperature. At lower frequency
region the real (ε′) and imaginary part (ε″) of the permittivity was
very high and it decreases with an increase in frequency and reaches a
constant value. At higher frequencies the periodic reversal of the field
takes place so fast that the excess ionic jumps were restricted in the
field direction. This leads to the decrease in permittivity at higher
frequency.
The plot of log ω vs. log ε″ is shown in Fig. 10. The slope of the
straight line was found to be − 0.7, indicating the predominance DC
conduction nature of the sample. The deviation of the slope from unity
could be due to the space charge effects at low frequency [56]. Though
the absence of relaxation peak in the dielectric loss spectra indicates
Fig. 7. Real and imaginary parts of the impedance spectra with respect to frequency at
room temperature for the compound LiNi0.5Mn0.5O2 (H950).
Fig. 8. Conductivity spectra for the compound LiNi0.5Mn0.5O2 (H950).
the long range mobility of the lithium ions [57], its diffusivity must be
further improved as discussed in conductivity spectra. While the short
range lithium ion diffusion leads to AC conductivity, the long range dif-
fusion leads to DC conductivity. We expect an electrode to have good DC
conduction for it to have better intercalation/deintercalation properties.
3.5.3. Modulus spectra analysis
Electrical modulus spectrum was used to find the ion transport
process in mixed conductors. The electric modulus spectrum of the
compound LiNi0.5Mn0.5O2 in the frequency region of 42 Hz to 1 MHz
at room temperature is shown in Fig. 11. At lower frequencies modulus
tends towards zero. This indicates that the electrode polarization makes
a negligible contribution to M′ and the dispersion was mainly due to the
conductive relaxation [58]. Gradual variation in the modulus spectra
shows the spreading of relaxation processes over a wide angular
frequency range [59]. The dominant relaxation peak in high frequency
region was attributed to the grain interior effect and the mid frequency
low intense peak was related to the grain boundary effect (indicated by
arrows in Fig. 11) [60,61]. The relaxation time (τ) was calculated from
the modulus spectrum using the formula τ = 1/ωmax. The value of the
grain interior relaxation time was found to be 1.45 × 10− 6 s. Fig. 12
shows the frequency dependent tan δ (dielectric loss) spectra at room
temperature. The dissipation factor tan δ was found to fastly increase
with increase in frequency, which is representative of the presence of
DC conductivity. After reaching tan δmax it was found to decrease. This
behavior indicates that the system is to be represented by a parallel
RC element [62]. The comparative spectra of normalized tan δ, M″, Z″
and Y″ of the compound LiNi0.5Mn0.5O2 in the frequency region of
Fig. 9. Real and imaginary parts of dielectric permittivity spectra for the compound
LiNi0.5Mn0.5O2 (H950).
 P. Senthil Kumar et al. / Solid State Ionics 267 (2014) 1–8
Fig. 10. Log ω vs. log ε″ spectra for the compound LiNi0.5Mn0.5O2 (H950).
42 Hz to 1 MHz at room temperature is shown in Fig. 13. There was no
overlapping between the spectra Z″/Zmax″ vs. log ω, tan δ/tan δmax vs.
log ω and M″/Mmax″ vs. log ω, this indicates the presence of both
short and long range lithium ion diffusion, supported by conductivity
spectra as discussed above. The M″/Mmax″ vs. log ω and Y″ /Ymax″ vs.
log ω nearly overlap, which also suggests that the sample has both
long range and localized relaxation [63].
3.6. Four probe DC conductivity analysis
Fig. 14 shows the voltage vs. current (V/I) spectra for LiNi0.5Mn0.5O2
sample at room temperature using 4-probe DC measurement. Since the
applied voltage range (V/I) spectra shows a linear response, it indicates
that the transport appear to be within the ohmic region. The current
(I) and voltage (V) in the 4-probe DC measurements can be used to
calculate the conductivity by the expression,
σdc = (I/V) (l/a) S cm−1
Where “l” and “a” are the distance between the probes and the area
of the sample respectively. The 4-probe DC method electrical conductiv-
ity value was calculated to be 6.63 × 10−6 S cm−1, which was in the
same order as that of total conductivity value obtained from the AC
impedance analysis at room temperature. This supports the total
conductivity value of LNMO calculated using AC impedance analysis.
3.7. Transference number measurement
Ionic transference number (ti) value of LiNi0.5Mn0.5O2 (H950) was
calculated by simple and well known Wagner polarization method
[64]. By applying a steady DC potential of 500 mV across gold coated
pellet, the change in current was measured. The variation of
Fig. 11. Electrical modulus spectra for the compound LiNi0.5Mn0.5O2 (H950).
7
Fig. 12. Loss tangent spectra for the compound LiNi0.5Mn0.5O2 (H950).
conductivity as a function of time under a constant DC potential is
shown in Fig. 15. From the figure, it was found that the conductivity
values calculated from the observed current was decreasing with in-
creasing time and then gets saturated. When time, t = 0, the highest
conductivity value σ0 = 7.55 × 10−6 S cm−1 (or 0.76 × 10−5 S cm−1)
was observed due to the flow of both the charge carriers (lithium ions
and electrons). This value is mainly due to the bulk effect and the
value is very close to the bulk conductivity calculated from both the
Cole–Cole plot and the conductivity spectra. This validates our measure-
ment values. As the time increases, the exponential decrease in conduc-
tivity was attributed to the pile up of the lithium ions at the blocking
electrodes because of applied dc potential. The saturated conductivity
(σα) was observed only due to the migration of the electrons. The initial
highest conductivity (7.55 × 10−6 S cm−1) and saturated conductivity
(2.75 × 10−6 S cm−1) values were used to calculate the ionic transfer-
ence number by the relation
t i ¼ ðσ 0 −σ α Þ=σ 0 :
The ionic transference number was found to be ti = 0.64, indicating
the domination of ionic conductivity of the compound when compared
to electronic conductivity. The difference in initial and saturated
conductivity gives the value of ionic conductivity of the compound.
The corresponding ionic and electronic conductivity values were
found to be 4.80 × 10−6 S cm−1 and 2.75 × 10−6 S cm−1 respectively.
The domination of ionic conductivity in the total conductivity was in
correlation with the observed spike in Cole–Cole spectra, as discussed
in AC impedance analysis. Therefore, the above results, proves the
mixed conduction nature of LNMO, which is required for a material to
be good cathode for lithium ion battery applications.
Fig. 13. Comparative normalized spectra of M″, Z″, Y″ and tan δ for the compound
LiNi0.5Mn0.5O2 (H950).
8 P. Senthil Kumar et al. / Solid State Ionics 267 (2014) 1–8

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Fig. 15. Time dependence conductivity spectra of LiNi0.5Mn0.5O2 (H950) at room

temperature.