International Journal of Energy Research

Development of Dielectric LiMnPO4 and Cr doped LiMnPO4

Cathode Materials

Journal: International Journal of Energy Research

Manuscript ID Draft

Wiley - Manuscript type: Research Article

Date Submitted by the

n/a
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Author:

Complete List of Authors: Bibi , Sidra ; Quaid-i-Azam University

Ahmad, Awais; The University of Lahore, Department of Chemistry
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Khan, Safia; Quaid-i-Azam University

Al-Kahtani, Abdullah A.

Keywords: LiMnPO4, Sol-gel method, Cathode Material, Dielectric materials

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3 Development of Dielectric LiMnPO4 and Cr doped LiMnPO4 Cathode Materials
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6 Sidra Bibi*1,2, Azeem Khan*2,, Safia Khan1, Awais Ahmad*3,Syed Sakhawat Shah1, Muhammad Sidiq1,
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8 Azhar Iqbal2, Abdullah A. Al-Kahtan4
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1 Department of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan.
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12 2 Department
13 of Chemistry, Gomal University Dera Ismail Khan, Pakistan.
14 3 Department of Chemistry, The University of Lahore, Lahore 54590 Pakistan.
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16 4 Chemistry Department, College of Science, King Saud University, Riyadh 11451,
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18 Saudi Arabia.
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Abstract: Lithium manganese phosphate (LiMnPO4) and a series of chromium doped lithium
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22 manganese phosphate with variation in Cr content LiCrxMn1-xPO4 (x= 0.03, 0.06, 0.1) were prepared
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24 via conventional sol-gel method and their dielectric properties have been explored as a function of
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26 frequency. The structure and morphology were investigated by X-ray diffraction technique, Fourier
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transformed infrared spectroscopy and scanning electron microscopy characterization techniques. The
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29 influence of frequency upon electrical conductivity as well as di-electric properties of the as-
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31 synthesized LiCrxMn1-xPO4 materials have been analyzed by dielectric parameters and AC
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33 conductivity using impedance analyzer. It was observed that dielectric constant increased with
34 frequency at lower chromium concentration while at higher chromium contents, the dielectric constant
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36 was decreased with increasing frequency. Hence, the composition with highest Cr content (i.e. x=0.1)
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38 is proved as best material for various applications owing to its lowest AC-conductivity and lowest
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dielectric loss. Therefore, it is revealed that chromium doping is quite advantageous for performance
41 of LiMnPO4 in device applications as Cr doped LiMnPO4 unveiled improved dielectric loss.
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44 Keywords: LiMnPO4; Sol-gel method; Microwave devices; Dielectric materials
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1. Introduction
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Lithium ion batteries are extensively applied in multiple portable electronic devices mainly laptops,
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10 mobile phones, digital cameras while their successful implication in smart tools and automotive
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12 engineering is rigorously influenced by fundamental safety limitations of recent cathode materials.
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14 Consequently, the dielectric olivine LiMPO4 (M=metal) materials have attained a huge consideration
15 owing to enhanced electrochemical property, improved thermal stability, cost effectiveness, and
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17 environmental safety [1]. Dielectric are the materials exhibiting the aptitude to store energy in response
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19 to an applied external electric field. There is no solitary and conventional method that can characterize
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the materials for the dielectric measurement running over entire frequency band. Hence, there’s always
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22 an uncertainty associated with dielectric measurements while characterizing the materials [2].
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24 However, innovation in tunable dielectric materials for developing advance electronic devices has
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26 attained considerable significance in radars and satellite and spacecraft communications, medical
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diathermy, remote sensing, cancer treatment, particle accelerators, radio astronomy and spectroscopy
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29 [3-6]. Lithium metal phosphates LiMPO4 (M = Fe, Mn, Co and Ni) are emerging as most suitable
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31 candidates due to high energy capacity, nontoxicity, low cost, high electrochemical and thermal
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33 stabilities [7-10]. Low dielectric losses of LiMPO4 materials have presented them as a suitable and
34 prospective candidate in electric field tunable device applications [11-13]. The electrical properties of
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36 nano-crystalline lithium metal phosphate materials depend on synthesis scheme, annealing

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38 atmosphere, concentration and nature of dopant [14, 15]. LiMPO4 exhibit low electronic conductivity
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(10-10 to 10-9 S cm-1) at room temperature and high electrical resistivity [16, 17]. Owing to low ionic
41 conductivity and high resistivity LiMPO4 can be deliberated as appropriate substitute for application
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43 in microwave devices [18]. The dielectric properties and resistivity of LiMPO4 can be enhanced by
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45 monitoring the sintering temperature, phosphate composition and by introducing small amount of a
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suitable dopant [19, 20].
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48 Moreover, LiMPO4 has recently attained considerable attention as probable materials because of its
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50 lower toxicity, ease of availability, and admirable chemical as well as thermal stability [21, 22]. In this
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52 way, LiMnPO4 is widely utilized as basic material in microwave devices as it offers a high voltage of
53 about 4.1 V for operation, which is thought to be the highest limit reachable to most electrolytes [23].
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55 To enhance the device performance, one tactic to improve the AC conductivity and decrease the
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57 dielectric loss is through cation doping into LiMPO4 [24, 25]. Moreover, the determination of
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frequency dependent dielectric properties and A.C. conductivity of LiMnPO4 materials has been a
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60 focus of many scientists and several models have been anticipated to explicate the experimental output

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[13, 26]. LiMnPO4 appears to be an appropriate candidate as it exhibits excellent theoretical capacity
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8 (170 mAh g−1), high operating voltage of vs. Li+/Li, and commendable thermal stability, and which is
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10 similar like commercially available materials. Moreover, doped LiMPO4 are being currently
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12 introduced for their exceptional physio-chemical possessions, together with plentiful applications as
13 gas sensors, capacitors and catalysts [27].
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15 Herein, Cr doped LiMnPO4 materials with low and high molar ratios were prepared by conventional
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17 sol gel method and the consequence of Cr doping upon dielectric performance and electrical
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conductivity was revisited in the present work to clarify the effect of Cr doping. Our AC conductivity
20 and dielectric measurements demonstrate that the performance of LiMnPO4 could be significantly
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22 improved by Cr doping. Doping of the selected samples was carried out with Cr3+ ions in order to
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24 enhance the structural stability and also to assess the influence of the substituent (Cr3+) on the electrical
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and dielectric properties of LiCrxMn1-xPO4. Measurements are made to study the effect of frequency
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27 on dielectric parameters and AC conductivity.
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30 2. Materials and Methods
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32 2.1. Materials
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34 All the chemicals including chromium chloride [CrCl3] (99%), lithium nitrate [LiNO3] (99.99% pure),
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36 manganese acetate tetra hydrate [Mn(CH3COO)2. 4H2O] (99%), ammonium dihydrogen phosphate
37 [NH4H2PO4] (99.99%) and citric acid [C6H8O7] (99.5%) were obtained from Sigma Aldrich and were
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39 used as received without further treatments and purification. Aqueous ammonia (25%) is obtained
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41 from Fisher Chemicals.
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2.2. Synthesis method
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Nanosized pure LiMnPO4 and LiMn1-xCrxPO4 (x= 0.00, 0.03, 0.06, 0.1) were prepared following the
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47 conventional single step sol-gel method [28-30]. Synthesis involved the stoichiometric molar amounts
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49 of constituents including LiNO3, NH4H2PO4, Mn(CH3COO)2. 4H2O and CrCl3 dissolved in 150 ml of
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51 de-ionized water under continues stirring and heating at 80 oC until a clear solution was obtained.
52 Besides, the precipitating agent i.e. aqueous ammonia was added dropwise from burette until pH 6 was
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54 achieved. Moreover, in order to avoid agglomeration in proposed dielectric materials, C6H8O7 was
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56 added as chelating agent. This homogenous mixture kept on heating till the formation of pinkish-white
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gel which was subsequently dried in oven at 120 oC for 5 h to make it moisture free followed by
59 annealing at 700 °C in furnace. The product obtained was in cluster form which undergone grinding
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in agate mortar to make it a fine powder which was further subjected to characterization.

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19 Figure 1. Synthesis scheme for LiCrMnPO4.
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21 3. Results and discussion
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23 Structural properties like surface morphology, grain size, extent of porosity and crystallite nature of
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25 the LiMnPO4 materials are investigated from X-ray diffraction (XRD) analysis. Nature and
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27 significance of bonding is observed by fourier transformed infrared (FTIR) spectroscopy. Further
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structural studies are performed by scanning electron microscopy (SEM) that produced micrographs
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30 revealing the shape of material surface.
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32 3.1. X-Ray diffraction studies

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35 The phase purity and structural integrity of as-prepared dielectric materials were studied through
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36 powder X-ray diffraction technique using X´Pert PRO PANalytical diffractometer, Malvern, UK.
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38 Herein, samples have been characterized under scan rate of 0.4°/min between 10°–85° 2-theta window.
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40 Moreover, crystal structure of pure LiMnPO4 has already been reported as shown in Figure 2, and is
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termed as orthorhombic [31].
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55 Figure 2. Orthorhombic crystal structure of LiMnPO4 [26]
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XRD patterns of the pure LiMnPO4 and doped LiCrxMn1-xPO4 (x= 0.03, 0.06, 0.1) materials are shown
60 in Figure. 3. The olivine structured crystalline veracity of LiMnPO4 and LiCrxMn1-xPO4 has been

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recognized to exhibit an ordered arrangement indexed by orthorhombic symmetry. X-ray patterns
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8 displayed the strong diffraction peaks at 29° and 35° which is indication of a defined crystal
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10 morphology [32]. The peaks at 29° and 35° exhibiting hkl values of 021 and 131 correspond to Cr
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12 addition where their intensity increased with adding Cr content [33, 34]. XRD displayed no separate
13 peaks or peak shifts which refer that chromium is efficaciously doped in the LiMnPO4 structure and
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15 no structural segregation was observed. 2-theta values of these samples were in good agreement with
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17 standard pattern of LiMnPO4 corresponding to (JCPDS) card 33-0803 [29]. The decrease in unit-cell
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volume verified the prosperous doping of Cr3+ in LiMnPO4, as the doped cation has a smaller radius
20 than Mn2+ ion [35, 36].
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36 Figure 3. XRD patterns for LiMnPO4 and LiCrMnPO4 composites.

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39 Average crystallite size (Davg) of as synthesized composites is calculated by using the Debye-Scherrer
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41 equation [35].
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Davg = k λ / β sin θ (1)
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44 Where λ denotes the X-Ray wavelength which is 1.54 Å, 𝛽 corresponds to full wavelength at half
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46 maximum (FWHM), k is the Scherrer constant and depends upon shape of the crystal and size
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48 distribution. For nano-crystallite size, k value is 0.94 and 𝜃 is termed as the Bragg’s angle. Lattice
49 constant calculated by Equation. 2 [36].
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51 1/d2 = h2/a2 + k2/b2 + l2/c2 (2)
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53 Where “a” corresponds to unit cell length, hkl are Miller indices constants and “d” represents the inter-
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planer spacing. Moreover, the cell volume is calculated by Equation. 3 [37].
56 Vcell = a×b×c (3)
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58 Theoretical X-ray density of the synthesized sample can be calculated by the Equation. 4 [38].
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60 ρx = 8M/Na3 (4)
Measured bulk density “ρm” of the material can be calculated with the help of Equation. 5 [39].

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8 ρm = m/(πr2d) (5)
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10 Where m is the mass and r is the radius of the pallet. Actual porosity of the material can be calculated
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12 by applying Equation. 6 [38].
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15 P = 1- ρm / ρx (6)
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Where ρm is the measured density and ρx is the XRAY density. Specific surface area of the LiMnPO4
21 can be calculated by the Equation. 7 [40-42].
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S = 6000/ D ρm (7)
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26 D is the crystallite size and ρm is the measured density. All the calculated parameters obtained from
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XRD analysis are tabulated in Table 1.
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31 Table 1. Structural parameters estimated from XRD patterns
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Cr Molar Ratio X=0.00 X=0.03 X=0.06 X=0.1
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36 Davg (nm) 9.5 9.9 8.0 7.5

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38 a=6.08 a=6.12 a=6.09 a=6.09
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40 Lattice constant (Α˚) b=10.4 b=10.5 b=10.44 b=10.4
41 c=4.79 c=4.81 c=4.80 c=4.80
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43 Cell Volume (Å3) 302.88 309.09 305.1 304.01
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45 x-ray density ρx (g/cm3) 3.46 3.45 4.50 4.61
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Material density ρm
2.51 2.43 2.51 2.71
48 (g/cm3)
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50 Porosity p (fraction) 0.433 0.530 0.371 0.328
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Table 1 represents the variation in crystallite size, lattice constants and porosity of material with
56 increase in chromium content in the as-synthesized materials. Davg lies within the range of 7.5 nm - 10
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58 nm. Smaller the crystallite size greater will be the electrical potential for electronic devices therefore,
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60 in accordance with XRD analysis LiCr0.1MnPO4 appeared as the optimum composition exhibiting the
most commendable electrical properties. Lattice parameters including cell volume, lattice constant,

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measured density, X-ray density and porosity are also arranged in Table 1. Peak shift in XRD analysis
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8 detected at peak having hkl value 020 was credited to the Cr doping. As for Cr3+, the ionic radius (0.64
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10 Αᵒ) is smaller than that of Mn2+ (0.70 Aᵒ) thus, the increase in Cr contents let the lattice to contract and
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12 decrease in Davg was observed. The lattice parameters (a, b and c) and lattice volume (V) reduced with
13 increase in Cr doping, which is also related with the smaller ionic radius of the optimum composition.
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15 It is perceived that Davg, a and p have gone a decrease with increase in chromium content which
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17 referred the Cr (x=0.1) as the most suitable composition for dielectric applications.
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10.0
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Average crystallite size (Davg)

21 9.5
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Lattice Parameters A
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8.4 7.5
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29 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11

30 Concentration of Cr Concentration of Chromium

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Figure 4. Variation of lattice parameters (a) and average crystallite size (b) with Cr concentration.
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33 The ionic radius of Cr (0.64Αᵒ) is smaller than Mn (0.70Aᵒ). Moreover, the lattice parameters of
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35 LiCrxMn1-xPO4 (x = 0.00, 0.03, 0.06, 0.1) lie in range of LiMnPO4 [43] and LiCrPO4 [44], and also the
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37 cell parameters decrease with chromium content signifying that the lattice parameters of LiCrxMn1-
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xPO4 follow the Vegard's law [45]. Although, from figure 4 (a & b), the lattice parameters seemed to
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40 be constant and that somehow display the linearity of Vegard’s law, however the contraction of ionic
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42 radii can be clearly witnessed from Davg thereby with increasing the Cr concentration, the lattice
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44 contracted.
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46 3.2. FTIR spectra analysis
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48 FTIR spectra of the proposed dielectric materials were taken at room temperature with the Perkin
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50 Elmer FTIR Spectrometer Spectrum 2000, Cambridgeshire, UK. Materials were mixed with KBr, then
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52 ground to smooth powders and pressed into a disk [46]. All measurements were taken in range of 400-
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4000 cm-1. Comparative FTIR analysis of synthesized LiCrxMn1-xPO4 (x = 0.00, 0.03, 0.06, 0.1) is
55 shown in the Figure. 5. The bands appeared between region of 400-1400 cm-1 are the characteristic of
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57 PO4-3 ions in free state experiencing tetrahedral geometry (Td) [47]. There are four components of
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59 internal vibrations of PO4-3 ions i.e. first is the antisymmetric stretching mode ν3 between 1000-1150
60 cm-1, second is the symmetric PO4-3 stretching around 968 cm-1 v1, third is the symmetric bending ν2

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around 474 cm-1 and fourth is the antisymmetric bending v4 between 650 cm-1-530 cm-1 [48]. Low
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8 energy bands at 343, 453 and 492 cm-1 corresponds to bending mode ν2 and lattice LiMnPO4 vibrations.
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26 Figure 5. FTIR spectra for LiMnPO4 and LiCrMnPO4 composites
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31 SEM analysis was performed for the as-proposed dielectric materials using TESCAN (Brno,
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33 Czech Republic) MAIA3. Surface properties of the proposed dielectric materials LiMnPO4 and
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LiCrxMn1-xPO4 depending upon the Cr content are presented by SEM micrographs in Figure. 6
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36 (a –c) at 5 µm. The images of all samples showed crystalline microaggregates composed of
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38 sub-microparticles which are in accordance with SEM of pure LiMnPO4 at 5 µm [49]. Sintering
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40 and calcining environments perform an imperative role in structural and surface properties of
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structured LiCrxMn1-xPO4 phase. Irregular plate-like structures can be observed resembling to
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43 the reported data [50, 51]. The addition of Cr appeared as it didn’t alter the morphology of
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45 LiMnPO4 phase. SEM micrographs revealed the construction of plate like particles upon whom
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47 further coarse particles are developed. Hence, chromium doping hasn’t influence the surface
48 structure of LiMnPO4.
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24 Figure 6. SEM micrographs for pure LiMnPO4 (a), LiCrxMn1-xPO4 (b) 0.03, (c) 0.06 and (d) 0.1 molar
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26 ratio at 5 µm.
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28 3.4. Dielectric properties
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30 Electrical significance of materials can be described by their dielectric properties as a function of
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32 frequency using impedance phase analyzer (HP 4149A). Also, dielectric permittivity/constant of the
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34 LiCrxMn1-xPO4 compositions was observed to decrease with increase in frequency. Dielectric
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constant/permittivity is linked with the capacitance of material that is actually the capacity to store
37 energy when an electric field is applied [52]. Permittivity shows how easily a material can be polarized
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39 on applying the electric field. It can be seen from Figure. 7 that the decrease in dielectric constant (ɛ‫)׳‬
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41 is faster at lower frequencies while a frequency independent response is exhibited at higher frequency
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region. This behavior corresponds to the applied field which supports the electron hopping between
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44 multiple sites in the sample. Also, high dielectric constant values at low frequency region owe to the
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46 mobile electrons following the oscillating electric field which fill-up the space between electrode and
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48 electrolyte [53, 54]. It is also attributed to the involvement of multi component of polarizability via
49 deformational (electronic and ionic) and relaxation (orientation and interfacial) polarization [12]. But,
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51 this electron flow becomes hindered at high frequency which consequently cause first decrease in
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53 dielectric constant then it became constant and no further influence of electric field observed on
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dielectric constant [55]. Probability of electron hopping increases with increase in ion separation.
56 Electrons could follow the applied field more effectively at lower frequencies due to large polarization
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58 and hence greater dielectric constant is achieved. While at high frequencies, hopping couldn’t follow
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60 the applied field actively and charge polarization could take place more prominently therefore low
dielectric constant is measured [56].

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Furthermore, the effect of chromium concentration on dielectric constant at lower frequency region
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8 can also be investigated from Figure. 7 (a). It is seen that dielectric constant decreased with increase
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10 in Cr content in LiMnCrPO4 material which referred to decreased polarization and migration of ions
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12 [57]. Similar trend was observed in Figure. 7 (b) for reviewing dielectric loss (ἕ) with electric field at
13 low frequency region because higher energy is the demand for electron transfer so loss is high Electron
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15 flow became slow and constant at high frequency region therefore dielectric loss became constant.
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17 Moreover, lower the dielectric loss, more effective is a dielectric material. Hence, Cr content with the
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maximum molar ratio (i.e. x=0.1) is said to be the best dielectric material among its series facilitating
20 its integration in devices.
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23 (a) 80 (b)
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Dielectric Constant

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Dielectric loss

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28 20
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29 15 LMP 30
30 LCr(0.03)MP
LCr(0.06)MP LMP
10 20
31 LCr(0.1)MP LCr(0.03)MP
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32 5 10 LCr(0.1)MP

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34 13.5 15.0 16.5 18.0 19.5 21.0 13.5 15.0 16.5 18.0 19.5 21.0
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38 Figure 7. (a) Dielectric constant (έ) and (b) dielectric loss (ἕ) of synthesized
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39 LiCrxMn1-xPO4 materials.
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42 Moreover, some important electrical parameters are estimated to assign electrical significance of Cr
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44 doped LiMnPO4 materials. Capacitance of the material was calculated by Equation. 8.
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46 C = ɛ ɛ‫ ׳‬A/d (8)
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48 Where A represents the area of plates, d corresponds to plate thickness and ɛ represents the permittivity
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50 constant/dielectric constant (8.85 10-12 Fm-1) while C is the capacitance of plates. The values of ɛ‫ ׳‬have
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52 been intended by using Equation. 8 which was obtained from the LCR-meter.
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While dielectric loss factor (tan 𝛿) in Equation. 9 also observed by LCR-meter was used to calculate
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55 dielectric loss.
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57 ɛ‫ = ׳׳‬ɛ‫ ׳‬tan 𝛿 (9)
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3.5. AC Conductivity (σAC)
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Unlike dielectric properties, AC conductivity exhibits a directly proportional relation to the frequency.
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10 LiMNPO4 material possesses a frequency independent conductivity at low frequency region but
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12 presented a dispersive phenomenon at higher frequencies [58]. Dependence of σAC upon frequency at
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14 room temperature can be observed from Figure. 8 which gives the evidence of increase in σAC with
15 increase in frequency. Polaron hopping model can describe the nature of conduction, dielectric
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17 properties and extent of AC conductivity resulting from the output of analyzer employing LiMnPO4
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19 and LiCrMnPO4 materials [59].
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21 -1
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LCr(0.03)MP
23 LCr(0.06)MP
24 LCr(0.1)MP
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AC Conductivity (S/cm)

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0.0
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36 ln f (Hz)
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39 Figure 8. AC Conductivity variation with frequency using LiCrxMn1-xPO4

40 materials.
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43 Additionally, AC conductivity was calculated from Equation. 11 [60].
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45 σac = 2 π f ɛͦ έ tan δ (11)
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49 Here f corresponds to the applied frequency, ɛͦ denotes the permittivity of free space (ɛͦ=8.854×10 −12
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51 F m −1) and δ is representing the loss factor. The effect of chromium concentration upon AC
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53 conductivity measurements can be observed from Figure. 8. It is clear that increase in dopant
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concentration in LiCrxMn1-xPO4 will cause a successive increase in AC conductivity at high frequency
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56 region which is accredited to migration as well as the polarization of ions. Therefore, dielectric
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58 dispersion witnessed via frequency variation endorses the electrical charge hopping mechanism which
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60 governs the charge transport as well as relaxation phenomenon in active material. Estimated values of

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dielectric permittivity (έ), dielectric loss (ἕ) and AC conductivity (σac) for as-synthesized LiCrxMn1-
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8 xPO4 materials are enlisted in Table 2.
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12 Table. 2. Calculated values for Dielectric constant (έ), Dielectric loss
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(ἕ) and AC conductivity of LiCrxMn1-xPO4 materials at 1MHz.
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17 Parameters
18 Xcr = 0.00 Xcr = 0.03 Xcr = 0.06 Xcr = 0.1
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23 12.284 36.0615 8.8401 8.4471
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27 ɛ” 3.0482 75.6794 2.9514 3.0458
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σAC
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34 (∼10− 9 S 1.69 4.21 1.64 1.63
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36 cm− 1)
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It is assessed from the experimental results that doping of chromium in LiMnPO4 enhanced its intrinsic
42 physiochemical properties. Dielectric characteristics become modified as the addition of Cr increased
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44 the thermal and chemical stability of LiMnPO4 and dielectric constant/permittivity value seemed
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46 greater than pure LMP. After certain frequency limit, both dielectric constant and dielectric loss
47 become constant and no further influence of varying frequency was observed. As a material exhibiting
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49 a high dielectric constant can tolerate a high frequency electric field. Therefore, it can be an indication
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51 that such materials could be of great strength over a wide range of frequency.
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53
54 Dielectric loss (ɛ″) is associated with the relative permittivity and a measure of the loss of energy in
55 dielectric materials via slow polarization currents, conduction, and some dissipative phenomena. It is
56
57 also perceived that dielectric loss exhibited a sudden decline with increase of frequency. The
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59 accessibility of free charge carriers within the material cause such drop in dielectric loss. It decreases
60
with increasing frequency and then reaches a constant value at higher frequencies.

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Moreover, talking about AC conductivity, the increase in σAC has been observed which is more
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8 significant at high frequency region in accordance with the hoping model. The conduction could be
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10 occurred due to the electron hopping between two contiguous sites in the orthorhombic lattice as well
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12 as a transition between Cr2+⇔Cr3+ ions or Mn2+⇔Mn+ might took place. The vacancies might be
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created at the Mn-site as Cr content rises. These vacancies cause the thermal dissociation of oxygen,
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15 which subsequently increases the number of electrons and hence this increase in hopping process could
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17 enhance the conductivity.
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20 Generally, relaxation phenomenon in dielectric materials seems to be associated with frequency
21 influenced orientation polarization. At low frequency region, the permanent dipoles arrange them
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23 along the field and contribute to the cumulative polarization of a dielectric material. However,
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variation in field is robust for the dipoles to align themselves at higher frequency, accordingly their
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26
27
involvement to dielectric permittivity and polarization becomes negligible. Hereafter, dielectric
28 permittivity decreased with increase in frequency.
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29
30
31 Comparative picture of dielectric constant, dielectric loss and AC conductivity for as-synthesized
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33 dielectric materials and reported materials is given in Table 3. Herein, we can analyze the effectiveness
34 of our as-synthesized dielectric materials with reported materials. It is perceived that the σac value is
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36 enhanced by the order of 10-5 by the addition of Cr into LiMnPO4 lattice comparative to pure LiMnPO4
37
38 and also, the dielectric constant/permittivity is increased [65]. The ac conductivity of the as-
iew

39
40
synthesized material is found to be 1.63 × 10–7 which is higher than the previously described values
41 for different dopants in LLiMnPO4 [61-63]. The prepared dielectric material exhibits higher
42
43 conductivity and consequently, has greater potential for Li ion batteries at room temperature.
44
45 Table 3. Comparative analysis of dielectric parameters
46
47
48 Dielectric
49 AC conductivity
50 Materials constant References
51 σAC ( S cm− 1)
52
ɛ’
53
54
55
LiCaPO4 2⋅21 × 10–8 [61]
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57
58
LiNiPO4 1.15×10–7 [61]
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60
LiNiPO4 8.89 × 10−9 [62]

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LiNiPO4 5.3 [63]
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9
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LiMgPO4 6.96 [64]
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12
13
LiMnPO4 5.1 × 10−12 <10 [65]
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15
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LiCrMnPO4 1.63 × 10–7 8.4 This work
17
18
19
4. Conclusion
20
21
Cr-doped LiCrxMn1-xPO4 (x = 0.00, 0.03, 0.06, 0.1) were prepared employing a single step sol-gel
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23 technique. XRD pattern revealed that Cr+3 is successfully incorporated into the Mn+2 lattice and further
24
referred the crystalline structure of the as-synthesized samples. SEM micrographs revealed the plate
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27 like structure of material and also elucidated that Cr+3 didn’t affect the morphology of LiMnPO4 phase.
28 FT-IR spectra expressed one broad peak and weak side-bands across the phosphate stretching region
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30 corresponding to Cr-doped LiMnPO4 as compared to well defined peaks observed for un-doped
31
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32 LiMnPO4. Unit cell volume was decreased due to Cr+3 doping. The dielectric constant and dielectric
33
34
loss decreased with increasing frequency. High concentration of chromium in LiCrxMn1-xPO4 is highly
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suggested for devices applications because low concentration of chromium (x= 0.03) increases the AC
36
37 conductivity of the material. These observations are in accordance with the correlated barrier hopping
38
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39 (CBH) model. The low value of ε' and ε" at high frequencies suggested that the as-prepared materials
40
possess enhanced dielectric properties therefore, suitable for battery applications.
41
42
43 Author’s Contribution: Bibi, S. and Khan, A. envisioned the research scheme. Khan, A. is the
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45 supervisor of Bibi, s. Bibi, S. performed the experimental part. Ahmed, A. performed the
46
47 characterization analysis. Bibi, S. and Khan, S. wrote the manuscript. Shah, S.S. and Sidiq, M. edited
48 the manuscript and did the proof read. Iqbal, A. co-supervise the experimental process. Algarni, T.S
49
50 did the data analysis and did the proofread. All authors have read and agreed to the recent version of
51
52 the manuscript.
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54
55
Acknowledgement: Researchers Supporting Project Number (RSP-2020/266) King Saud University,
56 Riyadh, Saudi Arabia.
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58
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60

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