Small polaron hopping conduction mechanism in LiFePO4 glass and crystal

Azeem Banday, and Sevi Murugavel

Citation: Journal of Applied Physics 121, 045111 (2017);

View online: https://doi.org/10.1063/1.4974948
View Table of Contents: http://aip.scitation.org/toc/jap/121/4
Published by the American Institute of Physics

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 JOURNAL OF APPLIED PHYSICS 121, 045111 (2017)

Small polaron hopping conduction mechanism in LiFePO4 glass and crystal

Azeem Banday and Sevi Murugavela)
Department of Physics & Astrophysics, University of Delhi, Delhi 110007, India
(Received 17 October 2016; accepted 13 January 2017; published online 31 January 2017)
The optimization of a cathode material is the most important criterion of lithium ion battery
technology, which decides the power density. In order to improve the rate capability, a cathode
material must possess high electronic and ionic conductivities. Therefore, it is important to
understand the charge transport mechanism in such an advanced cathode material in its intrinsic
state before modifying it by various means. In this work, we report the thermal, structural, and
electrical conductivity studies on lithium iron phosphate, LiFePO4, both in its polycrystalline
(LFPC) and glassy (LFPG) counterpart states. The vibrational spectroscopic measurements reveal
the characteristic vibrational modes, which are the intrinsic part of LFPC, whereas in LFPG, the
phonon modes become broader and overlap with each other due to the lattice disorder. The
electrical conductivity measurements reveal that LFPG exhibits a higher polaronic conductivity of
1.6 orders than the LFPC sample. The temperature dependent dc conductivity has been analyzed
with the Mott model of polarons and reveals the origin of enhanced polaronic conductivity in
LFPG. Based on the analysis, the enhanced polaronic conductivity in LFPG has been attributed to
the combined effect of reduced hopping length, decreased activation energy, and enhanced polaron
concentration. Published by AIP Publishing. [http://dx.doi.org/10.1063/1.4974948]

I. INTRODUCTION
Lithium iron phosphate (LFP) is considered to be one
of the most promising cathode materials for next generation
rechargeable lithium ion batteries (LiBs).1 LFP has a high
theoretical specific capacity (170 mAh/g) and operating
potential (3.5 vs Liþ/Li) in addition to various other advan-
tages including excellent electrochemical properties, low
cost, eco-friendliness, and extreme thermal and structural
stability due to the strong PO4 covalent bonding.2 However,
its usefulness as a potential cathode material in current lith-
ium ion batteries is limited by its intrinsic poor electronic
and ionic conductivities. Several strategies have been made
to overcome these inherent limitations in LFP such as car-
bon coating, doping with supervalent cations, and reduction
in particle size.3–7 Although carbon coating and/or doping
with aliovalent cations lead to an adequate enhancement in
the electronic conductivity at the expense of its energy den-
sity depending on the nature of electrochemically inactive
additives.7
The chemical structure of polycrystalline LFP is classi-
fied into olivine family (also known as triphylite) having a
distorted hcp framework with lithium and iron ions coexist-
ing in octahedral sites and phosphorous in tetrahedral sites.8
The layers of FeO6 octahedra are corner-shared in the bc
plane, and linear chains of LiO6 octahedra are edge-shared in
a direction parallel to the b-axis. These chains are bridged by
edge shared and corner shared phosphate tetrahedra, creating
a stable three-dimensional structure. Importantly, the alkali
cation arrangement in LFP differs from the layered and spi-
nel structures, where the alkali ions are considered to follow
one dimensional paths. The ability of LFP as an electrode
a)
Author to whom correspondence should be addressed. Electronic mail:
murug@physics.du.ac.in
material has prompted many reports and debates on its physi-
cal properties including the nature of ionic and electronic
conductivities.
More commonly, an electron transport in transition
metal oxides is described by the small polaron model in
which the excess charge carriers are coupled with distortions
of nearby ions. In LFP, the active redox center is the transi-
tion metal ion with the Fe2þ state that becomes the Fe3þ state
upon removal of a lithium ion and an associated electron.
Hence, the excess charge carriers are localized holes, and the
subsequent deformation induced in the surrounding oxygen
ions can be regarded as a pseudo particle called small hole-
polaron. Further, the formed small polarons are coupled with
lattice ions, and consequently, they are linked to phonons.
Therefore, small polaron transport in solids is associated
with the strength of localization and coupled nature of pho-
nons. The transfer of these small polarons from an occupied
to a neighboring unoccupied site can be thermally activated
by a hopping or tunneling process depending on the tempera-
ture region considered.
Significant progress has been made in recent decades
with respect to microscopic level understanding of the
polaron mobility in LFP both theoretically and experimen-
tally. Ab initio methods on the olivine phosphate structure
reveal the migration barrier associated with small hole-
polarons and its link with lithium ion vacancy, i.e., coupled
nature of movement.9 Subsequently, the first-principle den-
sity functional theory reveals the polaron formation and its
migration energy within the framework of the GGA þ U
method in different olivine phosphate compounds. It predicts
that a lithium vacancy and an analogous hole-polaron form
the complex owing to lattice distortion and Coulomb interac-
tion between them.10 Recently, the influence of the polaron
concentration on charge transport by comparing lithiated and

0021-8979/2017/121(4)/045111/9/$30.00 121, 045111-1 Published by AIP Publishing.

045111-2 A. Banday and S. Murugavel
de-lithiated phases of the olivine phosphate structure has
been shown experimenatlly.11 In the case of the lithiated
phase, the concentration of polarons is determined by lithium
vacancies, which have low formation energy, whereas in the
de-lithiated phase, the polaron concentration is determined
by oxygen vacancies. In comparison with the lithiated phase,
the formation energy of oxygen vacancy is significantly
larger than that of lithium ion vacancy. Based on these ideas
and energy consideration, one would expect more number of
lithium vacancies in the disordered potential landscape, i.e.,
in the glassy state of LFP than the ordered landscape (poly-
crystalline LFP). In this work, we report the detailed thermal,
structural, and electrical conductivity measurements on stoi-
chiometric polycrystalline LFP and its corresponding glassy
state.
We confirmed the absence of any impurity phase in as
synthesized polycrystalline LFP by high resolution XRD and
spectroscopic investigations. The obtained LFP glass has
been found to exhibit the characteristic glass transition and
crystallization temperature. The spectroscopic investigations
reveal the characteristic vibrational modes in the polycrystal-
line state, whereas in its glassy state, the modes become fea-
tureless with broad bands due to the localized nature of
vibrational phonons. The electrical conductivity study
reveals that the polaronic conductivity in glassy LFP is
higher than the polycrystalline counterpart. The temperature
dependent electrical conductivity clearly shows that the
small polaronic behavior is responsible in intermediate and
high temperature regions. The analysis of temperature
dependent conductivity by using the Mott model of polaronic
conduction suggests the origin of enhanced polaronic con-
ductivity in glassy LFP.
II. EXPERIMENTAL
Stoichiometric polycrystalline LiFePO4 (hereafter referred
as LFPC) was synthesized by a single step solid state route
using precursors lithium carbonate (Li2CO3) (Sigma Aldrich,
99.997%), iron (II), oxalate dehydrate (FeC2O4.2H2O) (Sigma
Aldrich, >99.99%), and ammonium di-hydrogen phosphate
(NH4H2PO4) (Sigma Aldrich, 99.999%). The precursors in
appropriate amounts were weighed, vigorously mixed, and
ground in an agate mortar and pestle for 4 h. The mixture was
transferred into an alumina boat and then kept in a furnace. The
temperature of the furnace was raised slowly at the rate of 5 K/
min up to 1023 K and maintained at this temperature for 6 h
under reducing conditions (N2 with 10% H2). Subsequently, the
furnace was then cooled down to room temperature, thereby
giving the final product with average particle size in the micron
range. As obtained LFPC sample was analyzed by various tech-
niques to confirm the phase purity. Based on the high resolution
XRD and vibrational spectroscopic investigations, we ascertain
the absence of any parasitic phases.
Glassy lithium iron phosphate (LFPG) was prepared by
the standard melt quenching technique. An appropriate molar
ratio of precursors lithium carbonate (Li2CO3) (Sigma
Aldrich, 99.997%), Iron (III) oxide (Fe2O3) (Sigma Aldrich,
 99%), and ammonium di-hydrogen phosphate (NH4H2PO4)
(Sigma Aldrich, 99.999%) was used. The weighed amount of
J. Appl. Phys. 121, 045111 (2017)
all the precursors is thoroughly mixed and ground in an agate
mortar and pestle. The mixture was transferred into a platinum
crucible, kept in an electric furnace, and heated up to 1553 K.
In order to obtain the homogeneous glass, the melt was held at
this temperature for half an hour and then rapidly poured out
onto a stainless steel plate held under atmospheric conditions
and immediately pressed by another stainless steel plate. The
average thickness of the samples thus obtained was 1 mm.
Furthermore, in order to avoid the lithium loss, we have lim-
ited the melt duration (dwell time) held at high temperatures.
Additionally, we have carried out ICP-AES analysis on the
LFPG sample and estimated the content of individual oxides,
and it has been observed that the loss of lithium content is less
than 0.5%.
The thermal study on the as-prepared glass sample was
performed by using a high temperature Differential Scanning
Calorimeter (DSC) (SDT Q600 simultaneous TGA/DSC, TA
instruments). The DSC measurements were carried on the
grounded glass sample under a nitrogen atmosphere with a
heating rate of 10 K/ min and from room temperature to
923 K. X-ray diffraction (XRD) analysis on both the samples
was performed by using a Rigaku MINIFLEX II diffractom-
eter with a Cu Ka1 radiation source (k ¼ 1.5406 Å) and with
a step size of 0.02 and at a scan rate of 1 min–1. Rietveld
refinement analysis was carried out on the LFPC sample
using TOPAS software, and the refinement was done by tak-
ing into account the initial cell parameters and atomic posi-
tions reported in the literature.12 Furthermore, the various
structural species present in both LFPC and LFPG were
obtained with the help of Raman and Fourier Transform
Infra-Red Spectroscopy (FTIR) spectroscopic studies. FTIR
absorption spectroscopy (Perkin Elmer FTIR spectrometer,
Spectrum RXI-Mid IR) was carried out on powdered sam-
ples vacuum pressed to translucent discs with a spectral reso-
lution of 4 cm–1. The pellets were made by mixing the
sample and KBr with the ratio of 1:100.
The room temperature Raman spectra of both LFPC and
LFPG samples were recorded in the 180 back scattering geom-
etry, using a 514 nm excitation of an air-cooled Argon Ion laser
(RenishawInViaReflex Micro Raman Spectrometer). The spec-
trometer was fitted with a single monochromator with a Peltier-
cooled CCD (RenishawInVia Reflex). The spectral resolution
of the instrument was better than 1 cm1, and the incident
power was adjusted to 3 mW for both the samples. The electri-
cal conductivity measurements were done by using a
Novocontrol a-S high-resolution broad band dielectric analyzer
in a frequency range from 10 mHz to 1 MHz and at different
temperatures between 153 and 673 K. The electrical conductiv-
ity measurements were carried out on the pellets of 13 mm
diameter and 1 mm thickness in the case of LFPC and for
LFPG case on samples with average diameter 8 mm and aver-
age thickness 0.8 mm. On both sides, the specimens were sput-
tered with silver electrodes prior to conductivity measurements.
III. RESULTS AND DISCUSSION
A. Thermal analysis
In Figure 1, we illustrate the DSC scan for the LFPG
sample, which exhibits the characteristic endothermic and
045111-3 A. Banday and S. Murugavel
FIG. 1. The DSC scan of the LFPG sample at a scanning rate of 10 K/min.
Glass transition (Tg ¼ 758 K) and crystallization temperature (Tc ¼ 813 K)
are marked in the figure.
exothermic transitions at 758 and 813 K, respectively. The
observed transitions are related to the glass transition tem-
perature (Tg) and crystallization temperature (Tc), and they
are in agreement with earlier reported results.13 The differ-
ence between the Tg and Tc reflects the thermal stability of
the LFPG sample. Furthermore, the observed single glass
transition temperature in LFPG indicates the homogeneity of
the glass sample without any secondary phases.
B. XRD studies
The XRD patterns of both LFPC and LFPG samples are
shown in Figure 2(a). The LFPG sample shows the characteris-
tic broad hump at 2h angle between 15 and 35 in the diffrac-
tion pattern. On the other hand, the diffraction pattern on the
LFPC sample shows the characteristic peaks, and they are
assigned to the stoichiometric LFP crystal with an orthorhombic
structure and space group Pnma (JCPDS-NO. 83–2092). The
XRD pattern clearly indicates that the obtained LFP polycrystal-
line sample is free from any impurity phases, and all the Bragg
reflections are indexed to the orthorhombic olivine-type struc-
ture of LFPC. Further, we have carried out Rietveld-refinement
FIG. 2. (a) Room temperature XRD pattern of LFPG and LFPC samples, showing, respectively, the amorphous and crystalline nature of as prepared samples.
The peaks are assigned to the LiFePO4 crystal with an orthorhombic structure. (JCPDS file No.: 83-2092) (b) Experimental X-ray powder diffraction pattern
(red open circles) of the LiFePO4 sample compared to the Rietveld refine profile (continuous blue lines) and the difference curve (bottom curve) taken at room
temperature. The vertical markers (blue) below the diffraction pattern indicate positions of possible Bragg reflections.
J. Appl. Phys. 121, 045111 (2017)
analysis on the LFPC diffraction pattern using TOPAS software,
and it is represented in Figure 2(b). The extracted cell parame-
ters are found to be a ¼ 10.3109 6 0.08 Å, b ¼ 5.9973 6 0.06 Å,
and c ¼ 4.6929 6 0.08 Å, and cell volume is 291.8 6 0.1Å3.
The estimated cell parameters are in agreement with the earlier
reports, and it corresponds to the orthorhombic structure.12,14 In
addition to the cell parameters, we have estimated the lithium

vacancy ðVLi Þ and anti-site defect ðFe•Li Þ concentrations on the
LFP crystal, and they were found to be 2.21% and 3.08%,
respectively.
C. FTIR studies
The vibrational characteristic properties of LFPC and
LFPG have been studied by FTIR spectroscopy as shown in
Figure 3, which is an effective tool for probing the various
structural units present. Additionally, it also complements the
XRD pattern in terms of the existence of any parasitic phases
in the amorphous form. In LFPC, we observe distinct absorp-
tion bands, which are characteristic to the nature of vibrational
modes belonging to the olivine phosphate structure. The
assignments of various vibrational modes to respective struc-
tural species have been reported and discussed13,15–17 recently.
We briefly discuss the important vibrational bands and more
specifically those related to transition metal ion and oxygen
ions.
In LFP, the layers of iron octahedra are corner-shared in
the bc plane, h110i, and the linear chains of LiO6 octahedra
are edge-shared in a direction parallel to the b-axis, h010i. A
stable three dimensional network structure has been formed
by the linear chains, where they are bridged by edge and
corner-shared phosphate tetrahedral units. Hence, the vibra-
tional spectrum is mainly dominated by the fundamental
vibrations of PO43 anions, which are assumed to separate
into many other components due to the correlation effect
induced by the coupling with Fe-O units in the structure.
Typically, the vibrational bands originate from the internal
vibrations ( 1- 4) of PO43 units, which concern the dis-
placement of oxygen atoms of the tetrahedral and lie at high
frequencies (above 800 cm–1). The bands in the range of 450
to 600 cm1 are due to the bending modes ( 2 and  4), which
045111-4 A. Banday and S. Murugavel
involve mainly O-P-O symmetric and anti-symmetric bend-
ing. The band at around 548 cm1 is due to the translational
vibration of Li within the PO43 cage. The bands at
638 cm1 and 645 cm1 are corresponding to the contribu-
tions of FeO6. On the other hand, the bands in the range
900–1200 cm1 are due to the stretching modes ( 1 and  3)
involving symmetric and anti-symmetric modes of the P-O
bonds. It is important to mention that we do not observe any
other bands corresponding to other phosphate ion complexes.
By comparing the FTIR spectrum of LFPC with LFPG, we
find that the characteristic bands become featureless but
coincident and lie somewhat at similar positions. However, it
can be seen that the peak intensities are not very prominent
and visible in vitreous samples, and these broad peaks are
quite obvious in glassy structures. In contrast to LFPC, the
FTIR spectra of LFPG exhibit two broad bands centered in
high and low frequency regions, and these bands consist of
several other vibrational modes, which are localized in
nature due to the lattice disorder. In Figure 3(b), we illustrate
the de-convoluted FTIR spectra of LFPG, which shows a
good resemblance between the FTIR spectra of glassy and
polycrystalline LFP samples and confirms that the character-
istic vibrational modes are retained.
D. Raman studies
In Figure 4(a), we depict the Raman spectra of both
LFPC and LFPG samples. In olivine LFPC, most intense
Raman bands are observable in the region 900–1200 cm1,
while many weak peaks can be seen in the low frequency
region. The olivine structure belongs to the spectroscopic
group D16
2h with the primitive cell being centro-symmetric
J. Appl. Phys. 121, 045111 (2017)
FIG. 3. (a) Fourier Transform Infra-Red
(FTIR) absorption spectra of LFPG and
LFPC samples recorded at room tem-
perature, showing good resemblance
between the bands of both the samples.
(b) The deconvoluted FTIR spectra of
LFPG (400–750 cm1) depicting bands,
which are envelops of those observable
in LFPC.
with a formula unit cell. Li, Fe, and P atoms are distributed
on 4a, 4c, and 4c positions (Wyckoff notations), respec-
tively. Since the structure of the phospho-olivines is built
upon LiO6 and MO6 octahedral linked to PO43 tetrahedral
anions, the local cation environment can be analyzed with
the factor group and the molecular vibrational modes.18
The Raman spectroscopic studies of LFPC have already
been reported and discussed in the literature.16,19–24 In the
present study, the LFPC sample exhibits a high intensity
peak located at 950 cm1 and is ascribed to symmetric P-O
stretching vibrational modes. Two weak intensity bands at
998 cm1 and 1070 cm1 are ascribed to anti-symmetric
vibrational modes. The vibrational bands at around 570,
590, and 630 cm1 are attributed to Fe-O stretching modes,
and bands at 400 and 450 cm1 are belonging to Fe-O-P
bending modes. The vibrational bands corresponding to
these iron octahedral units are playing an important role in
the polaron transport phenomenon. Below 400 cm1, the
external optical modes are observable, which are due to
vibrations of the lattice as a whole, and they are mainly due
to translational motion of PO43 and Fe2þ ions.21 The band
around 300 cm1 corresponds to the motion of lithium ions,
but it gives very weak contributions to these vibrations. In
order to obtain a quantitative estimation of various struc-
tural species in the LFPG, it is necessary to use the decon-
volution procedure with the aim of separating individual
vibrational modes from the composite line envelope. In
Figure 4(b), we illustrate the de-convoluted Raman spectra
of LFPG, which clearly depicts characteristic bands that are
observable in the LFPC with a good concurrence between
the spectral frequencies.
FIG. 4. (a) Raman spectra of LFPC
and LFPG samples recorded at room
temperature, showing a visible differ-
ence in the peak intensities. (b) The
deconvoluted Raman Spectra of LFPG
(540–800 cm1) depicting bands, which
are envelops of those observable in
LFPC.
045111-5 A. Banday and S. Murugavel
E. Broad band electrical conductivity spectroscopic
study
The frequency dependent electrical conductivity spectra
of both LFPC and LFPG samples at different temperatures
are shown in Figure 5. The observed frequency dependent
conductivity behavior is typical of most polaron conducting
crystals and glasses.25–28 At low frequencies and relatively
higher temperatures, the measured conductivity becomes
independent of frequency and is called dc conductivity. On
the other hand, at higher frequencies and comparatively
lower temperature, the conductivity becomes frequency
dependent above the characteristic or cross over frequency
( *), defined by r0 ( *) ¼ 2rdc, which increases with an
increase in temperature.29,30 It can be said that the dc con-
ductivity and the characteristic frequency are thermally acti-
vated processes with the same activation energy. It is worth
to mention that the measured polaronic conductivity in
LFPC and LFPG samples are exclusively due to the bulk
part, thereby neglecting the contribution (if any) of grain
boundaries as evidenced by a single semi-circle in the
Nyquist plot. Due to very high impedance at low tempera-
tures, electrical conductivity measurements were limited at
273 K and 153 K, respectively, for LFPC and LFPG samples.
We ascertain that the measured conductivity at low frequen-
cies is exclusively due to polarons, which has been con-
firmed by independent ionic conductivity measurement on
these samples. We have also carried out lithium ion conduc-
tivity measurements using the electron blocking electrode
geometry, i.e., Cu/LiI/LFP/LiI/Cu, and compared with the
Cu/Ag/LFP/Ag/Cu electrode geometry. Interestingly, the
measured ionic conductivity is much higher than (order of
107 S/cm) the polaronic conductivity at 303 K. Therefore,
we suggest that the presented dc conductivity results in this
work are exclusively due to the polarons, and the ionic con-
tributions can be neglected.
The measured dc conductivity values of LFPC are in
accordance with the earlier reports31–33 while they differ
FIG. 5. The real part of the frequency dependent conductivity spectra of (a) LFPC and (b) LFPG measured at various temperatures.
J. Appl. Phys. 121, 045111 (2017)
from few others.4,34 This discrepancy could be due to various
reasons such as carbon content, metallic impurity phases,
synthesis procedure, and lithium vacancy related contribu-
tions. However, it should be noted that in our samples, the
amount of carbon content is far below the detection limit of
Raman spectroscopy or it may be less than the ppm level.
Therefore, the measured dc conductivity exclusively arises
from the contributions of small polarons, and it is an intrinsic
property of the LFPC and LFPG samples. Remarkably, the
measured dc conductivity of the LFPG sample is roughly
1.64 times higher than the corresponding polycrystalline
counterpart. The obtained dc conductivity values of LFPG
are in agreement with the literature report.13 Typically,
polaron conducting glasses are found to exhibit lower electri-
cal conductivity than the corresponding polycrystalline
state.35 However, the situation in the case of LFPG is differ-
ent, and its origin would be discussed in detail by analyzing
the temperature dependent dc conductivity data using the
Mott model of polaronic conduction. In Figure 6, we illus-
trate the measured dc conductivity of both LFPG and LFPC
over a wide range of temperatures. Clearly, the temperature
dependent dc conductivity data of LFPC show the typical
polaronic type behavior with different activation energies
depending on the temperature region. We separate the dis-
tinct regions where the slope gets changed, and it is fitted
with the Mott model of polaronic conduction at temperatures
above room temperature. In the case of LFPG, we could
extend the temperature range down to 153 K (due to low
impedance), where the observed behavior resembles the vari-
able range hopping (VRH) mechanism. In the following, we
discuss each region in detail on the underlying polaronic
conduction mechanism.
1. High and intermediate temperature regimes
Mott theoretically devised a model for hopping conduc-
tion in non-crystalline solids in terms of phonon assisted
hopping of small polarons between the localized states.36
045111-6 A. Banday and S. Murugavel J. Appl. Phys. 121, 045111 (2017)

obtained Debye temperature for the LFPC sample is in

FIG. 6. Arrhenius plots of the dc conductivity of LFPC and LFPG samples
measured over a wide range of temperatures. The symbols represent experi-
mental data points, while the solid line corresponds to the fitting of tempera-
ture dependent dc conductivity with Mott’s Equation (1) at high and
intermediate temperatures. The best parameter fit, R2, lies in the range
0.9983–0.9989, and the error factor of least square fit (Chi2) lies in the range
4.3681  1013–9.4109  1014 in the case of high temperature. Similarly, for
the intermediate temperatures, R2 and Chi2 lie in the range 0.9962–0.9971 and
1.5212  1013–2.3068  1014, respectively.
The dc conductivity of nearest neighbor hopping in the non-
adiabatic regime or at high temperature (T > hD/2) is given
by
 2    iron containing crystals and glasses.33,41 Furthermore, it is
e c ð1  c Þ Ea
rdc ¼ tph  expð2aRÞexp  ; (1)
kB TR kB T
where  ph is the longitudinal optical phonon frequency, R is
the distance between two neighboring Fe ions, a is the inverse
localization length of the s-like wave function that is assumed
to describe the localized state at each transition metal ion, hD
is the Debye temperature, and “c” is the ratio of the concentra-
tion of polaronic sites (Fe3þ) over the total amount of Fe ions
in the matrix. Ea is the activation energy for the hopping con-
duction. In Figure 6, we illustrate experimental data fitted
with Equation (1). Clearly, we find distinct slopes with tem-
perature exhibiting the positive curvature. We are able to iden-
tify three different regions namely (i) high temperature (Ht),
(ii) intermediate temperature (It), and (iii) low temperature
regions (Lt). Further, we identify half of the Debye tempera-
ture, hD, at which the crossover takes place from intermediate
temperature to high temperature by defining
htph ¼ khD ; (2)
where  ph is the longitudinal optical phonon frequency, h
is Planck’s constant, and k is Boltzmann’s constant. The
TABLE I. Summary of Mott’s parameters for LFPC and LFPG samples extracted by using Equation (1) along with obtained dc conductivity data at 313 K. hD is
the Debye temperature,  ph is the optical phonon frequency, R is the polaron hopping length, EaLt is the low temperature activation energy, EaIt is the intermediate
temperature activation energy, EaHt is the high temperature activation energy, C is the fraction of concentration of polarons, and rdc is the dc polaronic conductivity.
agreement with the earlier simulation results37 while the hD
value for LFPG is also close to the reported literature
value.38 The hD is a fundamental quantity, which character-
izes the vibrational spectrum of a polycrystalline material,
and attempts have been made to use these concepts in ana-
lyzing the behavior of amorphous materials like glasses. The
obtained Debye temperature for LFPG is significantly
smaller than the LFPC, which indicates that there is a
decrease in the vibrational energy spectrum for the LFP
glass. The experimental dc conductivity data have been fitted
by the Mott equation in high and intermediate temperature
regions and give a very good fitting with the best parameter
fit, where R2 (R is the fitting approximation) lies in the range
of 0.9962–0.9989. The estimated values of the Debye tem-
perature along with the various other physical parameters
derived from the Mott equation are given in the Table I.
In LFPC, the polaron hopping takes place within the bc
plane because the inter-planer hopping distance (5.5 Å) is
larger than the intra-planer distance (3.8 Å).39,40 Hence, the
intra-planer distance corresponds to the typical hopping
length, i.e., distance between two neighboring Fe sites. We
found from our analysis that the polaron hopping length is
3.78 Å for LFPC, and the average hopping length is 2.65 Å
for LFPG due to the lattice disorder. However, it is interest-
ing to note that the intermediate temperature activation
energy values are comparable with the reported results of
worthwhile to mention that the estimated values are in agree-
ment with some of the reports in the literature and differ
from some others. The discrepancy between our and earlier
works could be due to various factors like purity of the sam-
ple and the temperature window used for the conductivity
measurements. In the present work, we have covered a wide
temperature range between high and low temperatures and
extending to the sub-hertz region of the frequency window,
where the estimated dc conductivity shows well defined pla-
teau, and it removes any uncertainties in the estimated val-
ues. Therefore, we infer that the assessed values are intrinsic
properties of our LFPC and LFPG samples. It is interesting
to note that the activation energies of LFPG are significantly
lower than that of LFPC, which emphasizes that the energy
barrier involved for polaron hopping in the glass network is
smaller than the crystal.
Remarkably, we find that the polaron concentration esti-
mated from the Mott fitting analysis substantiates the differ-
ence between the dc conductivities of LFPG and LFPC
samples. It is interesting to note that the concentration of
polaronic sites in LFPG is nearly an order of magnitude
higher than the LFPC. More commonly, in the case of LFPC,

Sample hD (K)  p (Hz) R (Å) EaLt (eV) EaIt (eV) EaHt (eV) C rdc at 313 K (S/cm)
2
LFPC 579 1.20  10 13
3.78 … 0.62 0.78 4  10 2.3  1010
LFPG 396 0.82  1013 2.65 0.28 0.46 0.67 1  101 8.7  109
045111-7 A. Banday and S. Murugavel J. Appl. Phys. 121, 045111 (2017)

the active redox center is the transition metal ion with the where the constants A and B are defined as
Fe2þ state, which becomes Fe3þ upon removal of lithium ion
and an associated electron. Thus, the excess charge carriers A ¼ vph e2 NðEF ÞR2 ; (4)
are localized holes, and the corresponding contraction of sur- " #14
rounding oxygen ions is together known as small hole polar- a3
B ¼ B0 ; (5)
ons. Hence, the source of Fe3þ centers is considered to be kN ðEF Þ
lithium vacancies generated during the synthesis and by the
surface energy kinetics. The recent theoretical studies reveal where Bo is a constant and has different values for different
that the formation energy of lithium vacancy is 0.22 eV, treatments,45 a is the inverse localization length, N(EF) is the
which is much lower than the formation energy of other density of states at the Fermi level, and R is the hopping dis-
types of defect present in the LFP.11,42 Due to the low forma- tance given by the following relation:
tion energy, the occurrence of lithium vacancy in LFPG  14
becomes more probable than the corresponding LFPC. 3
R¼ : (6)
Among the various factors contributing to polaronic conduc- 2paN ðEF ÞkT
tion in transition metal phosphates, the polaron concentration
is more relevant and is proportional to lithium vacancies in Using the above equations, we get
LFP. The estimated concentration of polarons, c, is slightly hBi

larger than the earlier reported values on LFPC.10,33 To the 1
rdc T 2 ¼ C:e
1
T4
; (7)
best of our knowledge, the c value for LFPG has not been
reported earlier in the literature. The disparity between the where C is a constant given by
different values of c could be due to differences in prepara-

1
tion conditions used during the synthesis process and temper- 3N ðEF Þ 2
2
ature range of measured values. Furthermore, it is C ¼ ph e : (8)
2pak
worthwhile to mention that the polaron transport in solids is
closely related to a certain type of phonon mode with spe- In Figure 7, we represent a plot of log rdc T1/2 vs T1/4 where
cific phonon energy. These phonons are typically longitudi- the present experimental data have been fitted with Mott and
nal optically (LO) active phonons with the frequency range Greaves’s model [Equation (7)]. It is found that the rdc T1/2
of 1013–1014 Hz. In LFPC, the observed vibrational mode at vs T1/4 plot gives a linear fit in the low temperature region,
570, 590, and 630 cm1corresponds to the Fe-O stretching which is suggestive of the presence of variable range hopping.
mode, which contributes to the polaronic conduction, where The values of a and R are in agreement with previously
the two iron sites involved in the polaron transport have a estimated values at the intermediate temperature regime, and
common bridging oxygen atom. It is interesting to note that the value of N(EF) obtained as such is equal to 6.97
the deconvoluted Raman bands on LFPG result in similar  1021 eV1cm3 and is quite reasonable with those obtained
peak positions (with chi square value of one) and corre- from polaron conducting glasses.46
spondingly similar phonon frequency ( ph) values in LFPC The real part of frequency dependent conductivity has
and LFPG. been analyzed by using various formalisms in the literature
and in different classes of materials, which provide important
2. Low temperature regime
Low temperature conductivity measurements were con-
fined to the LFPG sample because of the high impedance in
the LFPC sample. Mott and Davis43 suggested that when aR
 1, the hopping of charge carriers is described by the near-
est neighbor hopping and when aR 1 or at sufficiently low
temperatures, hopping may preferentially occur beyond the
nearest neighbor by the variable range hopping (VRH) pro-
cess. It is clear from Figure 6 that the estimated dc conduc-
tivity values below 223 K have a distinct slope from the
high/intermediate temperature regions. We ascribe the low
temperature behavior to be the signature of VRH and discuss
it in detail in terms of the theoretical model developed by
Mott and Greaves. The theoretical models proposed by
Mott43 and Greaves44 are generally used to explain the 3D
VRH in bulk disordered semiconductors. Based on Mott’s
VRH model, the temperature dependent dc conductivity is
FIG. 7. A plot of log (rdc .T1/2) vs T1/4 for LFPG at low temperatures where
given by
the symbols represent the present experimental data points, and the solid
  line corresponds to the fitting in the low temperature region, fitted with Mott
B and Greaves’ model given by Equation (7). The best parameter fit (R2) is
rdc ¼ A exp  1 ; (3)
T4 0.9987, and the error factor of least square fit (Chi2) is 3.6425  1013.
045111-8 A. Banday and S. Murugavel
information on the charge transport in various length
scales.47 In this context, we used the empirical Jonscher rela-
tion to describe the observed frequency dependent conduc-
tivity behavior and is given by48
"  s #
t the charge carrier performing a hopping event in homoge-
rðtÞ ¼ rdc 1 þ
; (9)
t neous potential landscape.47 On the other hand, the relatively
where the exponent s is independent over a range of tempera-
tures and t* is the characteristic frequency at which the dis-
persive conductivity changes into the dc conductivity. It is a
general trend that in different ion and polaron conducting
glasses and crystals, the exponent appears to increase with
decreasing temperatures, and it approaches the value of unity
at sufficiently low temperatures.48 In Figure 8, we illustrate
the real part of the frequency dependent conductivity spectra
at 313 K fitted with the Jonscher relation, and the exponent
value is found to be 0.94 6 0.01 in the LFPC sample and
0.65 6 0.005 in the LFPG sample, respectively. Similarly,
we have fitted all the experimental conductivity isotherms of
both LFPC and LFPG samples and found that the exponent
does not vary with temperature at high and intermediate tem-
peratures. On the other hand, in LFPG, we found that there is
a significant increase (approaching unity) in the exponent
values at very low temperatures, which could be ascribed to
nearly constant loss behavior.49
More commonly, the Jonscher exponent (0 < s < 1) is
often used to describe the dispersive region of conductivity
spectra and is the result of localized hopping motions of
mobile charge carriers. The ac conductivity measurement,
rðtÞ, generally shows a frequency dispersion region, i.e., a
dependence on the angular frequency, t. Exploring this dis-
persive behavior provides an opportunity to gain insight into
the details of charge carrier migratory processes, in particu-
lar, the interaction of the migrating polarons with other
FIG. 8. The real part of the frequency dependent conductivity spectra of
LFPC and LFPG samples measured at 313 K. The symbols represent experi-
mental data points, while the solid line corresponds to the fitting done with
the Jonscher relation given in Equation (9). The best parameter fit, R2, lies
in the range 0.99957–0.99972, and the error factor of least square fit (Chi2)
lies in the range 7.2085  1012–3.1086  1013 for LFPC and the corre-
sponding values of 0.99974–0.99983 and 8.8107  1013–8.4171  1014
for LFPG, respectively.
J. Appl. Phys. 121, 045111 (2017)
charge carrier in the structure. The magnitude of the expo-
nent directly implies the strength of the localized motions,
which is found to be larger at low temperatures and at high
frequencies. In addition, it has been suggested that the mag-
nitude of the exponent indicates effective dimensionality of
smaller exponent value of LFPG indicates that the charge
carrier motion becomes less localized in character. The mini-
mal localized nature of polarons can be understood by the
smaller energy barrier between the active redox sites. In the
case of LFPC, the large value of the exponent could be
attributed to the strong Coulomb interaction between the
polarons influenced by the lithium vacancy.
IV. CONCLUSIONS
A comparison between olivine structured LFPC and
their amorphous analogs is drawn for the first time.
Characterization by various analytical techniques confirmed
the phase purity of the as prepared samples, which is neces-
sary for understanding the microscopic charge transport
mechanism. The polaronic conductivity of glassy samples
(LFPG) is found to be 1.64 orders of magnitude higher than
that of LFPC. The conductivity enhancement in LFPG has
been attributed to the increased concentration of polarons
due to the large concentration of lithium vacancies.
Furthermore, the temperature dependent dc conductivity has
been explained by using the Mott model of polaronic con-
duction in the intermediate and high temperature regions. In
the case of LFPG, we find variable range hopping conduc-
tion, and it has been explained on the basis of the model pro-
posed by Mott and Greeves. The extracted Mott parameters
support the origin of enhanced polaronic conductivity in the
LFPG sample. The estimated Jonscher exponent value for
LFPC and LFPG indicates the dimensionality and nature of
polaron transport.
ACKNOWLEDGMENTS
A.B. thanks UGC for financial support. We also thank
the Department of Science and Technology (DST), India,
and R&D Scheme of Delhi University for the financial
support. We also acknowledge M.Tech Nano Science lab
and USIC, University of Delhi, for providing various
characterization facilities during the course this work.
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