Applied Surface Science 449 (2018) 435–444

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Applied Surface Science

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Full Length Article

Electrochemical performances of LiNi1−x Mnx PO4 (x = 0.05–0.2) olivine

cathode materials for high voltage rechargeable lithium ion batteries
S. Karthikprabhu a , K. Karuppasamy b,∗ , Dhanasekaran Vikraman b , K. Prasanna c ,
T. Maiyalagan d , A. Nichelson e , A. Kathalingam f , Hyun-Seok Kim b,∗
a
K. Ramakrishnan College of Technology, Trichy, Samayapuram, 621 112, Tamil Nadu, India
b
Division of Electronics and Electrical Engineering, Dongguk University-Seoul, Seoul 04620, Republic of Korea
c
Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, P.O. Box 49, DK-4000 Roskilde, Denmark
d
SRM Research Institute, Department of Chemistry, SRM University, SRM Nagar, Potheri, Kattankulathur 603 203, India
e
St. Mother Theresa Engineering College, Vagaikulam, Mudivaithanenthal Post, Thoothukudi 628 102, Tamil Nadu, India
f
Millimeter-Wave Innovation Technology (MINT) Research Center, Dongguk University-Seoul, Seoul 04620, Republic of Korea

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

Article history: This study demonstrated to synthesis of carbon-free lithium nickel phosphate (LiNiPO4 ) and its ana-
Received 27 October 2017 logue of manganese doped LiNi1−x Mnx PO4 (x = 0.05–0.2) cathode materials by a facile polyol method
Received in revised form 4 December 2017 and their suitability for use in high voltage lithium ion batteries (LIBs). The physicochemical proper-
Accepted 7 December 2017
ties were analyzed using X-ray diffraction, Fourier transform infra-red, Raman, field emission scanning
Available online 12 December 2017
electron microscopy (FE-SEM), energy dispersive analysis by X-ray (EDX), and electrochemical studies.
FE-SEM showed that the spherical shape particles were uniformly distributed on the surface and EDX con-
Keywords:
firmed the presence of all the elements in the LiNi1−x Mnx PO4 nanostructure. Substitution of Mn dopants
Cyclic voltammetry
Olivine cathode materials
with LiNiPO4 significantly improved the electrical and electrochemical performances for LiNi1−x Mnx PO4
Polyol method (x = 0.05–0.2) cathodes. The highly conducting LiNi1−x Mnx PO4 (x = 0.1) cathode exhibited initial discharge
High voltage capacity of 94.2 mA h g−1 at C/4 rate, and 62% capacity retention after 100 cycles between 2.8 and 5.6 V.
Charge-discharge These features promote LiNi1−x Mnx PO4 as a suitable cathode material for high voltage LIBs.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Olivine structured LiMPO4 (M = Ni, Co and etc.) phosphate cath-
ode materials are gaining a great deal of attention recently due
to their high safety, capacity, and structural and thermal stabil-
ities for practical energy storage devices including lithium ion
batteries (LIBs) and supercapacitor and photonic materials etc.
[1–8]. Thereby, extensive researches have been focused towards
the direction of enhancement of the energy density of practical
LIBs by finding substitutes to the state of the art active and inac-
tive materials [9–11]. Thus, the scientific community’s attention
has been focused on high voltage cathodes, charged to electrode
potentials beyond 4.2–4.3 V vs. Li/Li+ [9,12]. In particular, LiFePO4
cathodes, an olivine phosphate material, have been widely stud-
ied and optimized for energy storage systems due to its low capital
∗ Corresponding authors.
E-mail addresses: karuppasamyiitb@gmail.com (K. Karuppasamy),
hyunseokk@dongguk.edu (H.-S. Kim).
cost, eco-friendly nature, high safety, and good cyclability [13,14].
However its low energy density and low operating potential (3.45 V
vs Li/Li+ ) restricts its applications to small volume and powerful
compact LIB devices [15,16]. To overcome these shortcomings, and
develop better LIB cathodes, researchers have focused on a series
of other cost-effective abundant transition metals as dopants, such
as Ni, Mn, and Co in the LiMPO4 (M = Ni, Mn, and Co) structure,
which has been shown to produce high voltage plateaus (5.1, 4.1,
and 4.7 V, respectively) compared to other transition rare earth
elements [17–20].
The major drawback of LiMPO4 olivine structure material is
its low electronic and ionic conductivity, which restricts applica-
tions in LIBs [21,22]. The relatively poor electronic conductivities
in LiMPO4 olivine cathodes may be due to defect association effects,
which have significant influence on migration properties of cath-
ode materials [23,24]. Intensive studies and numerous efforts have
been made to overcome this drawback for high voltage LiMPO4
materials, including reducing particle size from micro to nano-size,
lattice doping, carbon coating, modified chemical routes and etc.
[25–31]. Nanometer sized particles deliver better electrical prop-

https://doi.org/10.1016/j.apsusc.2017.12.060
0169-4332/© 2017 Elsevier B.V. All rights reserved.
436 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444
erties with subsequent improved LIB performance due to its high
surface area and inherent reduction of diffusion lengths for lithium
ions [32,33].
Recent research works have elaborately investigated the alter-
natives for commercial available cathode materials (LiFePO4 and
LiCoO2 ), which are still the main cathode material in the lithium ion
market [34–36]. Despite their advantages and commercial avail-
ability, relatively little work has been done on Ni based olivine
phosphates cathodes since basic material features are not fully
understood [37,38]. Therefore, it is important to identify the major
issues with regard to the synthesis of LiNiPO4 as a cathode and their
electrochemical and cycling performances for LIBs.
Electrical properties of LiNiPO4 and their composite nanostruc-
tures have been compared previously [26,39–41], and electrical
conductivity of carbon coated LiNiPO4 showed 2–3 orders higher
than that of bare LiNiPO4 [41]. Polyol synthesized nanostructured
LiMnPO4 has been shown to have improved electronic conductiv-
ity and electrochemical performance [42]. Electrical conductivity
of LiNiPO4 synthesized by the Pechini type polymer precursor
method has also been reported previously [43], and their con-
ductivity was increasing with 10% doping of Cu2+ , Mg2+ , Zn2+ ,
and Al3+ [44,45]. The specific capacity was also improved by
LiNi1-y Mgy PO4 doped graphite carbon foam LiNi1-y Mgy PO4 com-
posites [46]. Electrical conductivity of LiNiPO4 was increased by
doping with Zn2+ using the polyol method [47,48]. Ornek et al have
reported the superior electrochemical and cycling performances
for LiNiPO4 which synthesized by solvo-thermal assisted method
[12,20,49].
In this article, we have made an attempt to prepare pure
and a series of Mn doped carbon-free LiNiPO4 cathodes using
the polyol technique, and studied the effects of Mn doping
Fig. 1. Polyol synthesis of LiNi1−x Mnx PO4 cathode materials.
percentage on structural, electrical, electrochemical, and cycling
properties of LiNi1−x Mnx PO4 (x = 0.05–0.2) cathode materials. The
LiNi1−x Mnx PO4 cathode materials exhibited smaller polarization
curve and improved ionic and electrical conductivities. Charge-
discharge capacity was also studied.
2. Experimental
2.1. Polyol synthesis of LiNi1−x Mnx PO4 particles
The Mn doped LiNiPO4 samples, i.e., LiNi1−x Mnx PO4 (x = 0.05,
0.10, 0.15, 0.20) were prepared by a facile polyol method that
yielded the desired product at lower reaction temperature. Lithium
acetate (CH3 COOLi·2H2 O, Himedia, 99.9% Purity), nickel acetate
(CH3 COONi·4H2 O, Himedia, 99.9% Purity), ortho phosphoric acid
(H3 PO4 , Merck), manganese acetate (C4 H6 MnO4 ·4H2 O, Himedia,
99.9% Purity) were used as the source materials. The polyol medium
included 1, 2-propane-diol and ethylene glycol. All precursor mate-
rials were dried under vacuum at 70 ◦ C for approximately 12 h prior
to use.
Fig. 1 shows the polyol synthesis of LiNi1−x Mnx PO4 . The sto-
ichiometric amount of precursor materials (acetate salts of Ni,
Mn, and Li) were stirred separately in the polyol medium at
ambient temperature. Then, the three precursor solutions and
ortho phosphoric acid were transferred into a round bottom flask
equipped with condenser unit. The resultant solution was sub-
jected to a condensation reaction at 240 ◦ C. The light greenish
yellow precipitate was separated by continuous centrifugation
and washed thrice with acetone to remove remaining organic
residues. Then dried under vacuum at 150 ◦ C for 15 h to remove
physically adsorbed water. Finally, LiNi1−x Mnx PO4 nanoparticles
 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444 437

Fig. 2. (a) XRD patterns, (b) FT-IR spectra, and (c) laser Raman spectra of LiNi1−x Mnx PO4 (x = 0.05–0.2).

were obtained by calcination at 650 ◦ C for 4 h. The calcinated Table 1

Calculated lattice parameters for pure and Mn doped LiNiPO4 .
LiNi1−x Mnx PO4 samples were kept under vacuum to avoid mois-
ture contamination. Sample a (nm) b (nm) c (nm)

Pure LiNiPO4 1.052 0.5858 0.4685

2.2. Material characterization
X-ray diffraction analysis of prepared LiNi1−x Mnx PO4 samples
were performed using a XPERT-PRO X ray diffractometer PW
3050/60 (with Cu K␣ radiation) at 2␪ with 0.05◦ step over 10◦ –80◦
at room temperature. Morphology of the prepared powders was
identified by scanning electron microscopy (SEM) (JEOL-6390,
computer controlled). Infrared spectra were recorded between
1200–350 cm−1 with 1 cm−1 signal resolution (JASCO FTIR-4100;
Fourier transform infrared spectrometer). Raman spectra were
recorded by laser confocal Raman spectroscopy using RENISHAW
Raman microscope with 715 nm line Argon laser source. Particle
size was measured from the intensity weighted distributions by
Malvern instrument at 25 ◦ C. Electrochemical impedance measure-
ment, an alternative to the scalable solution method [50,51], was
analyzed using a Biologic Electrochemical Workstation SP-300 on
assembled batteries at open potential with the frequency range of
7 MHz–1 Hz at 10 mV amplitude. Cyclic voltammetry studies were
performed using an Ivium Technologies electrochemical worksta-
tion in the scan range 2.8–5.6 V using a R2032 coin cell containing
LiNi1−x Mnx PO4 /1M LiTFSI/ Li. Charge-discharge analysis was car-
ried out for the R2032 coin cell assembled by sandwiching the
commercial electrolyte (1 M LiTFSI in EC/PC) between the prepared
LiNi1−x Mnx PO4 cathode foil and lithium metal anode using an Arbin
battery cycler. The coin cell was cycled between the cut-off voltage
of 4.1 and 5.6 V for three different current rates (C-rates) at room
temperature.
2.3. Cell assembly
The LiNi1−x Mnx PO4 electrode was fabricated by coating an
N-methyl pyrrolidine (Sigma Aldrich) (NMP) based slurry of
LiNi1−x Mnx PO4 , binder poly vinylidene fluoride (PVdF) (Sigma
Aldrich), super-P carbon and KS-6 carbon (85:8:3.5:3.5) onto a cop-
per foil. To ensure better electric contact between LiNi1−x Mnx PO4
particles and the current collector, super-P and KS-6 carbon mix-
ture was used. The positive electrode was dried under vacuum for
12 h at 120 ◦ C. After roll pressing electrode thickness was about
30 ␮m. The LiNi1−x Mnx PO4 slurry coating should be uniform and
the thickness of first electrode was almost equal to the thick-
LiNi0.95 Mn0.05 PO4 1.047 0.5857 0.4681
LiNi0.90 Mn0.10 PO4 1.052 0.5863 0.4679
LiNi0.85 Mn0.15 PO4 1.064 0.5865 0.4686
LiNi0.80 Mn0.20 PO4 1.070 0.5877 0.4686
ness of second (anode). 1M LiTFSI in EC/DMC (50/50) was used as
the electrolyte. Finally, the Li/1M LiTFSI/ LiNi1−x Mnx PO4 coin cell
was assembled by sandwiching the LiTFSI electrolyte between the
lithium and LiNi1−x Mnx PO4 electrodes.
3. Results and discussions
3.1. Physicochemical properties
Fig. 2(a) shows the X-ray diffraction (XRD) patterns of LiNiPO4
doped with different Mn2+ concentrations at ambient temperature.
The XRD spectra show that the doped LiNiPO4 samples have the
olivine structure indexed by the orthorhombic pnma space group.
The XRD pattern of undoped LiNiPO4 (Fig. S1(a)) is highly coincided
with the standard reference pattern (JCPDS #81-1528). Doped sam-
ples peaks are shifted to higher 2␪ value compared to undoped
sample result, which indicating the influence of lattice shift due to
doping. Similar results are also obtained for Mn2+ doped LiCoPO4
[52].
The ionic radius of Mn2+ (82 pm) is almost comparable with that
of Ni2+ (85 pm), which caused the peak shifts in the XRD pattern and
changes in lattice parameters. The calculated lattice parameters
values are shown in Table 1, and confirm that insertion of transition
metals does not collapse the LiNiPO4 core lattice structure.
Variations in sample structure and chemical bonding due to
the incorporation doping element were identified from FTIR spec-
troscopy. Fig. S1(b) shows FTIR spectrum of pure LiNiPO4 . The band
at 469 cm−1 is attributed to Li O vibrations. The stretching mode
of the NiO6 distorted octahedra is observed at 652 cm−1 , consis-
tent with the previous reported results [53]. The higher frequency
vibrational bands located around 1159, 1096, 1062, and 960 cm−1
are attributed to intramolecular stretching (1 and 3 ) motions of
each tetrahedral PO4 3- anion and it has correlated to other PO4 3-
ions in the unit cell. These vibrational bands are agreed well with
previous reports [54,55].
438 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444
Fig. 3. Deconvoluted Raman spectra (900–980 cm−1 ) for (a) LiNi0.95 Mn0.05 PO4 , (b) LiNi0.90 Mn0.10 PO4 , (c) LiNi0.85 Mn0.15 PO4 and (d) LiNi0.80 Mn0.20 PO4 .
Fig. 2(b) shows FTIR spectra for Mn2+ doped LiNiPO4 samples.
The fundamental vibration of PO4 3− band for the doped materials
(LiNi1-x Mnx PO4 ) is exhibited in the range of 969–981 cm−1 (bare
LiNiPO4 : ∼961 cm−1 ). The band between 200 and 500 cm−1 cor-
responds to lithium and nickel cation translational motions. The
detailed vibrational modes are listed in Table S1. The most of the
dominant bands corresponding to 1 , 3 , and 4 modes wavenum-
bers are increased with doping percentage of Mn2+ which proves
that both P O and M O (Ni or Li) bonding is strengthened with the
substitution of Ni by Mn2+ [56]. Thus, Mn2+ doping does not produce
a significant change in the compound structure which is evident
from the observation of characteristic vibrational bands related to
olivine structure and it has consistent with the XRD results.
Figs. S1(c) and 2(c) show laser Raman spectra for undoped and
Mn doped LiNiPO4 , respectively, at ambient temperature. The Mn
atom in Mn2+ doped samples prefers to replace Ni2+ site, since the
ionic radii of Mn2+ and Ni2+ are similar (82 and 85 pm, respec-
tively), than the Li+ site. The observed Raman bands and their mode
of vibrations are tabulated in Table S2. Fig. 3 shows the decon-
voluted Raman spectra of a characteristic olivine ␯1 (PO4 ) band.
The FWHM increases with increase of Mn2+ doping which further
strengthens our claim of Mn2+ occupies Ni2+ sites. The Raman band
at 944–945 cm−1 corresponds to the orthorhombic olivine phase,
and the other two Raman peaks between 937 and 963 cm−1 are
assigned to the bending, Eg , and stretching, A1g , mode of vibration,
respectively.
The lower and higher magnification FE-SEM images of
LiNi0.90 Mn0.10 PO4 as shown in Fig. 4(a) and (b), respectively. FE-
SEM images are revealed the homogeneous particle distribution
spherical shaped grains with agglomeration particles with similar
shape irrespective of doping. For the comparison, the pure LiNiPO4
surface morphology images are provided in the supplementary
information Fig. S1(e and f). The improved surface morphology for
LiNi0.90 Mn0.10 PO4 is very important to achieve high capacity and
good cyclability of the cathode materials which is discussed in later.
The presence of various elements in the LiNi0.90 Mn0.10 PO4 sample
was confirmed by EDX, as shown in Fig. 4(c).
Fig. 4(d) shows the particle size distribution of Mn doped
LiNiPO4 . Average particle diameter (Z average “d”) is estimated at
252 nm. Table S3 shows particle size distributions for pure LiNiPO4
and LiNi0.90 Mn0.10 PO4 samples. The particle size is enhanced due
to insertion of Mn metal atoms compared with pure LiNiPO4 .
For undoped LiNiPO4 , ∼56.6% of particles is exhibited in range of
200–300 nm diameter (Fig.S1(d)). In the case of LiNi0.90 Mn0.10 PO4 ,
the diameters of the particles are increased considerably due to the
Mn doping in LiNiPO4 as evident from Fig. 4(d) and Table S3.
3.2. Electrical properties
Fig. 5(a) shows the Cole-Cole plot for different concentrations of
Mn doped LiNiPO4 samples at ambient temperature. Fig. S2 shows
the Cole-Cole plot of un-doped LiNiPO4 . LiNi0.9 Mn0.1 PO4 has low
bulk resistance compared with pure LiNiPO4 and other Mn con-
centrations, such as 0.05, 0.15 and 0.20, doped LiNiPO4 (Fig. 5a and
its inset). The semicircle alone is observed for almost all samples.
Bulk resistance, Rb , and capacitance were calculated using Z view
software, and the corresponding equivalent circuit is shown in inset
of Fig. 5(a). The equivalent circuit represents the parallel combina-
tion of resistance and capacitance in the prepared samples. The
migration of lithium ions in the bulk LiNiPO4 is represented by
the resistor and the immobile lithium ions become polarized by
applying the AC field which is represented by the capacitor. The
semicircle is observed at high frequency due to the parallel combi-
nation of ionic migration and bulk polarization. Capacitance is on
the order of pico Farad, which indicates that the ion conduction
process occurs through the bulk nature of the material. The center
of the semicircle lies below the real axis for all samples i.e., the
depressed semicircle means the distribution of relaxation times
deviate from ideal Debye behavior [57–59]. Conductivity can be
expressed as
 1  L
b = × , (1)
Rb A
 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444
Fig. 4. (a, b) SEM images, (c) EDX spectrum, and (d) particle size distribution graph for high conducting LiNi0.9 Mn0.1 PO4 sample.
where ␴b is the bulk conductivity of the sample, and L and A are
the thickness and area of the sample, respectively. Fig. 5(b) shows
the conductance spectra of Mn doped LiNiPO4 , and their calculated
conductivity values are tabulated in supporting information Table
S4.
Fig. 5(c) shows the variation of DC conductivity with respect to
Mn concentrations. The conductivity of LiNi1−x Mnx PO4 is increased
with increase of Mn concentration up to (x = 0.1), then it has
decreased significantly. The enhanced conductivity of Mn doped
LiNiPO4 is due to introduction of disordered lattices in the LiNiPO4
matrix system. The Mn doped LiNiPO4 matrix structure pro-
vides vacant sites which favor for higher ion hopping rate, and
hence enhanced the conductivity effectively. Similar results were
observed for rare earth and metal doped LiFePO4 [60]. The variation
of grain sizes due to doping of Mn with LiNiPO4 is created the cation
vacancies during charge compensation which may increase the
channel size for Li+ diffusion and to lead the increment of electrical
conductivity [50,51,61]. The LiNi0.9 Mn0.1 PO4 sample is exhibited
with the maximum conductivity compared with other samples.
The observation of decreased conductivity for higher Mn concen-
trations doped LiNiPO4 is due to decrease the available space for ion
movement with the excess Mn atom in order to block the lithium
ion migration, which is significantly contribute the conductivity
[62].
Fig. 5(d) shows the variations of dielectric constant for various
concentration of Mn doped LiNiPO4 . Dielectric constant magnitude
is high for LiNi0.9 Mn0.1 PO4 among all the samples. Due to Mn dop-
ing, the number of free charge carriers increases with in the LiNiPO4
439
which in turn to increase the ions migration and conductivity as dis-
cussed earlier. In addition, the dielectric loss is directly related to
the material conductivity [63]. The dielectric constant is also high
for LiNi0.9 Mn0.1 PO4 (Fig. 5e), which is consistent with the conduc-
tivity result.
3.3. Electrochemical properties
The electrochemical properties of our LiNiPO4 and
LiNi0.90 Mn0.10 PO4 comprised coin cell (Li/1M LiTFSI/ LiNiPO4
or LiNi0.90 Mn0.10 PO4 ) electrodes were tested by cyclic voltam-
metry (CV) at room temperature. Fig. 6(a) shows the CV curves
for pristine LiNiPO4 and LiNi0.90 Mn0.10 PO4 in the potential range
2.5–5.5 V. The CV profile of pristine LiNiPO4 consists of redox
peaks at 4.54 and 4.50 V, which is due to the reversible two-phase
nature of NiPO4 , and hence it is electrochemically active in the
fixed potential range. The Mn doped LiNiPO4 electrode exhibits
substantial redox peaks at 3.84, 4.64, 4.58, and 3.56 V, which
suggest that anodic oxidation and cathodic reductions are facile at
electrode-electrolyte interfaces. The LiNi0.90 Mn0.10 PO4 electrode
cell exhibits higher redox intensity peaks compared to un-doped
LiNiPO4 , which confirms faster lithium ion diffusion, and hence
improved electrode reaction reversibility inside the host lattice
[12,49]. The observed results indicated that the dopant element
has a key role for improvement of lithium ion diffusion kinetics
and electrochemical performance.
Fig. 6(b) shows electrode stability of LiNi0.90 Mn0.10 PO4 com-
prised coin cell electrode which assessed by continuous CV cycling
440 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444

Fig. 5. (a) Cole-Cole impedance spectra, (b) conductance spectra, (c) conductivity spectra, (d) dielectric constant spectra, and (e) dielectric loss spectra for LiNi1−x Mnx PO4
(x = 0.05–0.2).

at 5 mV s−1 scan rate. The peaks current values are increased where R and T are the gas constant and temperature (298 K), respec-
with increase of number of cycles for both Mn2+ and Ni2+ , which tively; F is the Faraday constant (96,845 C mol−1 ); RT/(1 − ˛)nF =
is attributed to the stripping of metals from the electrode. The 0.62 for the prepared electrode material which calculated from the
reversibility as well as stability nature of LiNi0.90 Mn0.10 PO4 com- linear slope for high conducting LiNi0.9 Mn0.1 PO4 ; k = 4.06 × 10−9
prised coin cell electrode was confirmed by different scan rates at is the heterogeneous electron transfer rate constant, determined
5–25 mV s−1 performed CV curves, as shown in Fig. 6(c) and their from Eq. (2); n = 1.97 (∼2), indicating the redox reaction which
current vs. logarithmic plot is given in Fig. 6(d). From the Fig. 6(c), involves the two electron transfer as follows,
oxidation and reduction current values are increased significantly
NiPO4 → Ni2+ + PO4 + 2e− ∼
= 4.54V (oxidation), (3)
with slight shift their position as increase of scan rates, which is
consistent with Laviron’s theory [64,65], Ni 2+
+ PO4 + 2e → NiPO4 ∼
−
= 4.50V (reduction), (4)
Ni0.095 Mn0.05 PO4 → 2+
Ni0.095 + Mn2+
0.05
+ 2e + PO4 ∼
−
= (4.54&4.64 for Mn &Ni), (5)
and
E = E 0 − (RT ⁄(1 − ˛)nF)ln(v(1 − ˛)nF/RTk) (2) 2+
Ni0.095 + Mn2+
0.05
+ 2e− + PO4 → Ni0.095 Mn0.05 PO4 ∼
= (3.56&4.58 for Mn &Ni). (6)
 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444
Fig. 6. Electrochemical studies: (a) Cyclic voltammograms of LiNiPO4 and LiNi0.9 Mn0.1 PO4 , (b) Different cycles performed cyclic voltammograms for LiNi0.9 Mn0.1 PO4 , (c)
Different scan rates performed cyclic voltammograms for LiNi0.9 Mn0.1 PO4 , and (d) Current versus logarithmic scan rate for LiNi0.9 Mn0.1 PO4 .
These results are strongly support reversibility of the elec-
trodes with given electrolyte and provided a path to exploit
LiNi0.90 Mn0.10 PO4 as an active material for LIBs, and strengthen
the galvanostatic charge-discharge analysis which discussed in the
following section.
3.4. Battery cycling studies
To validate the CV results as well as investigate coin cell
performance using synthesized electrodes, we performed the
galvanostatic charge-discharge process using 4.2–5.7 V potential
range. Fig. 7(a) shows the second cycle charge-discharge profiles of
LiNiPO4 and LiNi0.90 Mn0.10 PO4 samples at 0.1 C rate. We chose the
LiNi0.90 Mn0.10 PO4 sample to compare with pristine LiNiPO4 since it
provides the high electronic conductivity at ambient temperature
as discussed in the earlier section. The potential difference between
the charge and discharge curve is significantly reduced after Mn
doping into LiNiPO4 due to the enhanced electronic conductivity.
The cell exhibited initial discharge capacity at 75.6 mA h g−1 and
94.2 mA h g−1 at 0.1 C-rate for LiNiPO4 and LiNi0.90 Mn0.10 PO4 sam-
ples, respectively, which suggests that Mn doping with LiNiPO4
significantly enhances battery performance through lithium ion
diffusion kinetics. Fig. 7(b) shows the charge-discharge behavior
of LiNi0.90 Mn0.10 PO4 at different current density rates. Discharge
capacity abruptly decreases to 70.4 and 39.3 mA h g−1 at 0.5 and
1.0 C rate, which is approximately 57–23% of the theoretical capac-
ity of the active material LiNiPO4 (167 mA h g−1 ) [20,66].
The observed electrode reversibility was 93%, 91%, and 88%
for 0.1, 0.5, and 1 C rate, respectively. With continuous cycling of
the LiNi0.90 Mn0.10 PO4 coin cell at 0.1 C-rate, the discharge capac-
ity is gradually decreased, and the cell finally delivers discharge
capacity of 56.9 mA h g−1 on the 100th cycle, as shown in Fig. 7(c)
and (e). This capacity fade may due to the formation of a solid
electrolyte interface layer over the electrode-electrolyte interfaces
441
during the continuous cycling [20,67,68]. Furthermore, the Cole-
Cole impedance plot is revealed the increment of bulk resistance
after continuous cycling performance for LiNi0.90 Mn0.10 PO4 coin
cell electrode as shown in Fig. 7d. The columbic efficiency of the
first cycle is 93.29% (inset of Fig. 7f) and it has increased steadily
with cycling to maximum efficiency of 94.12% in the 100th cycle.
The observed low columbic efficiency for the initial cycles can be
attributed to the formation of a solid electrolyte interface layer,
which is reversibly, consumed the lithium ions in the electrolyte.
These results are strongly consistent with the previously reported
outcomes [69–71]. The LiNi0.90 Mn0.10 PO4 electrode exhibits the
highest discharge capacity (94.2 mA h g−1 at 0.1 C rate), which sug-
gests that LiNi0.95 Mn0.05 PO4 would be a good alternative with a
combination lithium anode for LIBs.
4. Conclusions
This study successfully synthesized carbon free pure and Mn
doped LiNiPO4 , i.e., LiNi1−x Mnx PO4 (x = 0.05–0.2), cathode mate-
rials using a polyol method in ethylene glycol 1, 2-propane-diol
medium. The Mn2+ dopant was efficaciously incorporated into
the LiNiPO4 lattice, and fortified LiNiPO4 structural stability by
enhancing ionic transfer efficiency. LiNi0.90 Mn0.10 PO4 showed a
maximum conductivity of 5.48 × 10−8 S cm−1 at ambient temper-
ature. Cyclic-voltammetry analysis of LiNi0.90 Mn0.10 PO4 suggested
that lithium intercalation and de-intercalation was possible at the
electrode-electrolyte interfaces. The LiNi0.90 Mn0.10 PO4 electrode
also exhibited maximum discharge capacity of 94.2 mA h g−1 at
0.1 C-rate, which is superior performance than the earlier literature
studies. The excellent contribution of Mn with LiNiPO4 , particularly
LiNi0.90 Mn0.10 PO4 , to electrochemical and charge-discharge perfor-
mance provides a promising candidate along with lithium anode
and electrolyte for high voltage LIBs.
442 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444

Fig. 7. Battery performance: Charge-discharge curves for (a) bare LiNiPO4 and LiNi0.9 Mn0.1 PO4 at 0.1 C rate, (b) LiNi0.9 Mn0.1 PO4 at different C-rates, (c) LiNi0.9 Mn0.1 PO4 at
different cycle rates; (d) Cole-Cole impedance plot recorded for LiNi0.90 Mn0.10 PO4 before and after cycling; (e) Rate capability for LiNi0.90 Mn0.10 PO4 at different C-rates; (f)
Capacity retention for LiNi0.90 Mn0.10 PO4 at 0.1 C-rate.

Acknowledgements Appendix A. Supplementary data

This work was supported by the Basic Science Research Program Supplementary material related to this article can be found, in
through the National Research Foundation of Korea (NRF) funded the online version, at doi:https://doi.org/10.1016/j.apsusc.2017.12.
by the Ministry of Education (No. 2017R1D1A1A09000823) and the 060
research program of Dongguk University in 2017.
 S. Karthikprabhu et al. / Applied Surface Science 449 (2018) 435–444
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