polyvinyl pyrrolidone polymer blend electrolytes

polyvinyl pyrrolidone polymer blend electrolytes

Accepted Manuscript Studies on sodium nitrate based polyethylene oxide / polyvinyl pyrrolidone polymer blend electrolytes K. Sundaramahalingam, N. Nal...

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Accepted Manuscript Studies on sodium nitrate based polyethylene oxide / polyvinyl pyrrolidone polymer blend electrolytes K. Sundaramahalingam, N. Nallamuthu, A. Manikandan, D. Vanitha, M. Muthuvinayagam PII:

S0921-4526(18)30485-X

DOI:

10.1016/j.physb.2018.08.002

Reference:

PHYSB 310989

To appear in:

Physica B: Physics of Condensed Matter

Received Date: 8 July 2018 Revised Date:

31 July 2018

Accepted Date: 1 August 2018

Please cite this article as: K. Sundaramahalingam, N. Nallamuthu, A. Manikandan, D. Vanitha, M. Muthuvinayagam, Studies on sodium nitrate based polyethylene oxide / polyvinyl pyrrolidone polymer blend electrolytes, Physica B: Physics of Condensed Matter (2018), doi: 10.1016/j.physb.2018.08.002. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT

Studies on sodium nitrate based polyethylene oxide / polyvinyl pyrrolidone polymer blend electrolytes

M. Muthuvinayagama,*

Multi-functional Materials Laboratory/ Department of Physics/ International research centre,

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a

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K. Sundaramahalingama, N. Nallamuthua, A. Manikandanb, D. Vanithaa,*,

Kalasalingam Academy of Research and Education - 626 126, Tamil Nadu, India. Department of Chemistry, Bharath Institute of Higher Education and Research (BIHER),

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b

Bharath University, Chennai 600073, Tamil Nadu, India.

*Corresponding Author: [email protected] (D. Vanitha);

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Phone number: +91 6381456553

[email protected] (M. Muthuvinayagam)

ABSTRACT

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Phone number: +91 9942066575

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Solid polymer electrolytes (SPEs) consisting of polyethylene oxide (PEO) /Polyvinyl pyrrolidone (PVP) complexed with sodium nitrate have been synthesized by solution casting technique. Structural studies were carried out using X-ray diffraction (XRD) measurements. The complex formation between the bonding of polymers and the salt was confirmed by Fourier Transform Infrared (FT-IR) spectral data. The ionic conductivity and dielectric response of the SPE systems were studied within the frequency range of 42Hz - 1 MHz at the temperature range of 303-363 K. The maximum ionic conductivity was found to be

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ACCEPTED MANUSCRIPT 6.157×10-7 S/cm at 303K for PEO (67wt %) /PVP (27wt %)/NaNO3 (6wt%). The dielectric properties were also studied using the complex dielectric permittivity spectra and complex electric modulus spectra of the SPE films. The higher dielectric permittivity was obtained due to accretion of ionic charges at lower frequencies. The surface morphology of the polymer

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blend electrolyte film complexed with sodium nitrate was studied using Scanning Electron Microscopy (SEM).

Key words: Ionic conductivity; SEM; Polymer blend Electrolyte; XRD; FTIR; Transference

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number.

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1. Introduction

The main objective in polymer research is preparation of higher ionic conducting polymer electrolyte for electrochemical applications. Solid polymer electrolytes are having the best parameters like electrical conductivity, electrochemical stability and energy density. So that,

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it has applied for many devices such as electrochromic devices, fuel cells, electrochemical cells, solid state batteries, super capacitors, fibres, etc. [1-9]. Ionic conducting polymer electrolytes are produced by dissolving ionic salts into high molecular weight polymer

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matrix. The ions are using as a charge carrier to enhance the ionic conductivity [10,11].

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Nowadays, the advanced lithium ion battery can be broadly utilized for energy storage framework because of its higher energy density [12-15]. In any case, the staggering expense, lessening of plenitude, environmental impact and

well being confinements worried to lithium materials obstruct their far reaching usage in future battery advancements [16]. In this manner, there is an urgent need for alternate energy storage system to compensate the lithium battery. Sodium (Na) ion batteries (SIB) has caught more consideration since it has lower cost, environmentally friendly, less - toxic and earth abundant materials. 2

ACCEPTED MANUSCRIPT Polyethylene oxide is one of the best polymer matrix in which ionic salts are dissolved to make ion conducting polymer electrolyte. Polyethylene oxide is exhibited as a crystalline polymer by close arrangement of monomers whereas amorphous nature has occurred after mixing salt in it. [17,18]. Sodium fluoride (NaF) salt mixed in Polyethylene

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oxide (PEO) has provided the ionic conductivity in the range of 10-7 Scm-1.

Polyvinyl-pyrrolidone has good accomplice with PEO to make high amorphous behaviour. Mechanical and thermal properties are enhanced in blend polymer system. The

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carbonyl assembly (C = O) in the side chain in PVP enables to form different complexes with metal salts. The C=O bond in PVP is more useful for the complexation of salt in the blend

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polymer system [19,20].

Polymer blending is one of the most feasible techniques to improve the conductivity of the polymer electrolytes. This technique has more advantages from other techniques because of its controlling physical parameters in the miscibility of blend polymer

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composition [21,22].

In the present work, an attempt is made to prepare and characterize PEO-PVP based blend polymer electrolyte complexed with NaNO3. The structural characterization and dielectric

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properties of the polymer blend electrolytes are discussed.

2. Preparation

The polymers PEO (Mw of 5×106) and PVP (Mw of 3.6×105) and sodium nitrate were procured from Sigma - Aldrich for the utilization as precursor materials. The weight percentages of PEO/PVP/NaNO3 were taken in the ratios (69:29:2, 68:28:4, 67:27:6, 66:26:8, 65:25:10) to prepare the blend polymer electrolytes. The suitable weight percentage of PVP, PEO and NaNO3 were dissolved in water. They were continuously stirred with mechanical blending at room temperature for 24 hours to maintain consistency and miscibility of the 3

ACCEPTED MANUSCRIPT polymers. The formed viscous solutions were transferred to polypropylene dishes and the solvent was permitted to evaporate gradually at room temperature. Four days later, the prepared electrolytes were expelled from petri dish for further analysis. Figure 1 shows the schematic representation for preparation of blend polymer using solution casting method.

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The XRD pattern of the blend polymer electrolyte was recorded using Bruker make X-Ray diffractometer having CuKα radiation (λ=1.540 Aº) with scanning rate 5º per minute in the range of 10o-80o. FTIR transmittance spectra of the films were traced using

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"SHIMADZU IR Tracer 100" spectrometer in the wave number region between 4000 cm-1 and 400 cm-1. The scanning electron microscope instrument made by Carl ZEISS EVO 18

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was used to analyse the morphological structure of the polymer electrolytes. The impedance measurements were done by HIOKI 3532-50 LCR Hi-tester within the frequency region from 42Hz to 1MHz in the temperature range of 303K-363K.

3.1 XRD Analysis

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3. Result and Discussion

Figure 2, shows the XRD pattern of pure and various composition of sodium nitrate mixed

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PEO-PVP blend polymer electrolyte. In the XRD graph, blend Polymer PEO-PVP has two

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crystalline peaks at 18o and 23o, due to involvement of PEO. These peaks are appeared due to strong interaction between the molecules in the polyether side chain of PEO polymer [23, 24]. By increasing the salt concentration, the intensity of the peak decreases up to composition of 6 Wt% of NaNO3 which indicates the increasing amorphous nature in the polymer electrolytes. For the other higher concentrations, the peak intensity is increased and also a new peak is appeared at 28.9o in XRD pattern. The newly observed XRD peak is due to the presence of sodium nitrate which is confirmed by JCPDS (89-0310) data. This is the indication of incomplete distribution of salt in the polymer matrices. The maximum 4

ACCEPTED MANUSCRIPT amorphous nature is obtained for 6wt% sodium nitrate added to the blended system, leading to the maximum conductivity of the polymer electrolyte. The amorphous nature of the blend is improved due to the intermolecular interaction between polymer blend in C–O–C group of PEO and/or C=O group of PVP of polymer blend with salt. It is more helpful to reduce the

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continuous chain of the polymer and close packing arrangement. Hence, the crystalline pattern has decreased to improve the amorphous upto the composition of 6wt% sodium nitrate.

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3.2 FTIR Analysis

The Fourier transform Infrared Spectroscopy is used to identify the functional group in the NaNO3 complexed polymer blend electrolyte. Figure 3 shows the FTIR spectrum of prepared blend polymers in different composition. The obtained broad band between the

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regions of 2913 cm-1 - 2830 cm-1 is due to the asymmetric stretching of CH2 in PEO matrix.. The miscibility of PEO and PVP is confirmed through the appearance of carbonyl groups

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(C=O) of PVP and ether oxygen groups(C-O-O) of PEO in the blend polymer matrix [25]. The inclusion of the salt with the polymer blend is observed by means of decrease in

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intensity, broadening, shifting of bands. This may be observed due to the formation of cross link between the cation and oxygen in PEO and PVP matrix. The vibrations modes of functional groups of PEO and PVP are tabulated in Table 1.

3.2.1 Confirmation of PEO The observed IR Peak at 2887 cm-1 is mainly due to the symmetric C-H stretching of PEO. A small band observed at 1334 cm-1 is attributed to the CH2 bending of PEO and the band observed at 940 cm-1 is assigned to the CH2 rocking vibrations of ethylene group of PEO [26, 5

ACCEPTED MANUSCRIPT 27]. A band observed at 838 cm-1 is due to the CH2 rocking in PVP and with some C–O stretching in PEO. A small band at 1450 cm-1 is assigned to the CH2 scissoring mode of PEO [28]

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3.2.2 PVP Confirmation

The vibrational band appeared at 2878 cm-1 is attributed to the CH stretching of PVP matrix. The band at 1272 cm-1 is assigned to the CH2 twisting or wagging of both PEO and PVP

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chains. A band at 1097 cm-1 present in the spectrum is appeared due to the stretching

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vibrations of C-N in PVP matrix [29, 30].

3.2.3 Complexation of PEO/PVP/NaNO3

A band observed at 1142 cm-1 is due to the complexation of ether oxygen with Na+ ion due to the addition of salt. The C-H bending vibration in both PEO and PVP appears at 1483cm-1

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which is shifted to 1464 cm-1, indicates the inclusion of the salt with PEO/PVP [31]. A band appears at 1360 cm-1 is attributed to asymmetric vibration of C–H in CH2 group, which indicates the amorphous nature of PEO. There are some slight changes in the peaks due to the

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increase in the concentration of sodium nitrate salt in blend polymer matrices.


3.3 SEM Analysis

The scanning electron microscope is used to identify the surface morphology of the

sodium nitrate complexed with blend polymer matrices. Figure 4 shows the scanning electron microscopical images of various wt% of sodium nitrate doped PEO-PVP solid polymer blend electrolyte. In all SEM images, there exist pores within the range of 2µm. The pores are created due to the continuous removal of solvent presence of PEO in the electrolyte system. 6

ACCEPTED MANUSCRIPT By increasing the salt concentration to the PEO-PVP system, there is no excess of salt visible in the polymer electrolyte. But some crystalline peaks appeared in the XRD pattern may be due to the porous nature of PEO.

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3.4 Ac impedance analysis 3.4.1 Cole-Cole Plot

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The cole-cole plot of various wt% of sodium nitrate doped PEO- PVP solid blend polymer electrolyte is shown in Figure 5. In cole-cole plot, there exists a semi-circle which is

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equivalent to the parallel connection of resistance and capacitance. Generally, in polymer electrolytes, the presence of immobile charge carriers and movement of ions in the polymer electrolyte are the main reason for the formation of the semi-circle [20]. The intercept of the semicircle on the X-axis is considered as the bulk resistance of the polymer electrolyte. The

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bulk conductivity is increased upto the composition of 6wt% of sodium nitrate complexed blend polymer matrices. The same result is coincided in XRD analysis. The bulk conductivity

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is calculated using the formula

σ = l/Rb A

(1)

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Here σ is the bulk conductivity, Rb means bulk resistance and A is the area of the sample. Table 2 shows the conductivity of different weight percentage NaNO3 at different temperature. The maximum bulk conductivity is obtained as 6.67×10-7 S/cm for 6wt% sodium nitrate doped PEO-PVP solid polymer electrolyte system.
Figure 6 exhibits the cole- cole plot of 6wt% sodium nitrate doped PEO-PVP solid polymer with respect to temperature. The bulk resistance of the polymer electrolyte decreases by

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ACCEPTED MANUSCRIPT increasing the temperature. As a result, the increasing conductivity is obtained for higher temperature due to increasing mobilisation of ions.


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3.4.2 Conductance spectra

The variation of conductivity with respect to frequency is the characteristic response

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of polymer blend electrolytes. Figure 7 demonstrates the variation of conductivity at various temperatures of PEO/PVP blend polymer electrolyte doped with 6 wt% NaNO3. In the

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conductivity spectra, there exist two distinct regions: low frequency dispersion region, plateau region. The plateau region at low frequencies is related to long range of hopping ions. [37]. The dc conductivity can be calculated by extending the curve towards the low frequency in the y (logσ) axis. At high frequencies, the increment of conductivity is observed due to the

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forward and backward movement of ions simultaneously, thereby increasing the movement of ions attributed to the universal power law behaviour of the polymer electrolytes.


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3.4.3 Temperature-dependent ionic conductivity analysis

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The temperature-dependent ionic conductivity plots are shown in Figure 8. The relation between the dc conductivity and the temperature is explained by Arrhenius model and it is given by the equation:

σdc(T)=σ0exp(−Ea / kBT)

- (1)

According to Arrhenius plot, movement of ions in polymer electrolytes depends on the segmental motion. While increasing the temperature, the increment of electrical conductivity is obtained due to the segmental motion of polymer, local structural relaxation and also hopping mechanism between the coordination sites [32-36]. 8

ACCEPTED MANUSCRIPT By increasing the temperature, the chain flexibility also increases due to the decrease in viscosity, thereby increases the conductivity. The increase in conductivity with temperature can also be interpreted by increasing the free space and also facilitates the flow of ions in the polymer electrolytes.

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3.4.4 Concentration Dependence of Conductivity

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The Figure 9 gives the variation of dc conductivity as a function of composition in terms of salt concentration in PEO/PVP blend at various temperatures. From the figure 9, it is also

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observed that the conductivity increases by increasing the salt concentration and reaches maximum value and then decreases. Primarily, the increment in the ionic conductivity is due to the increase in ionic carrier concentration. The ions move through the formed free space in polymer matrix. Polymer segmental motion with higher amplitude is fully supported by ion

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movement in polymer matrix. In amorphous regions, the segmental motion is higher than the crystalline regions. The amorphous nature can be obtained due to the increase in flexibility of polymer backbone. Above 6wt% of salt concentration, due to the addition of NaNO3, the

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increase in crystallinity decreases conductivity as confirmed by XRD. Table 3 shows the

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activation energy of prepared solid polymer electrolyte.


3.4.5 Dielectric Analysis

Dielectric studies provide an ability to store electrical energy in the materials. The dielectric permittivity is the parameter calculated through impedance data. The equation explains the dielectric loss and dielectric spectra of Polymer electrolytes.

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ACCEPTED MANUSCRIPT ε' (ω) =

- (2)

ε'' (ω) =

- (3)

Where ε′′ is the imaginary permittivity and ε′ is the real permittivity, ω is the angular

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frequency, z′ represents the real impedance, z′′ represents the imaginary impedance, and Co represents the vacuum capacitance.

Figure 10a and b gives the variation of dielectric constant and dielectric permittivity with

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frequency at different temperatures for 6wt% sodium nitrate complexed PEO-PVP blend polymer matrix. The high dielectric constant at low frequency region may be due to the

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accumulation of charges in the electrode and electrolyte interface, thereby blocking the transport of charges and space charge polarization is developed in this region [28-42]. At high frequencies, the dielectric constant is totally independent of frequency. This may be due to the rapid occurrence of the periodic reversal of electric field where the charge carriers are

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arranged in the field direction.

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3.4.6 Tangent Analysis

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The dielectric relaxation behaviour of the polymer electrolyte realizes vital bits of knowledge into ionic transport movement. The dielectric relaxation of the polymer electrolyte can be given as a component of frequency and it can be characterized by the condition tan δ = ε"/ε'. The absorption peak is depicted by the relation ωτ=1 where τ is the relaxation time and ω is the angular frequency of the applied field. As the temperature increases, the relaxation peak moves to high frequency side indicating that the charge carriers are thermally activated to

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ACCEPTED MANUSCRIPT long range movement [43]. The presence of peaks for different temperature in the spectrum shows the existence of relaxing dipoles in the polymer electrolyte.


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3.4.7 Transference number

The transport number of the polymer electrolytes has been estimated by utilizing wagner polarization procedure at a constant connected voltage (10 mV) over the sample. The figure

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12 denotes the variation of polarization current as a function of time. The transference number is used to find out whether the conductivity is obtained due to ions or electrons. The

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contribution of ions and electrons for conduction can be estimated from the variation of polarization current as a function of time for all the polymer blend electrolytes. For all the polymer electrolytes, the current increases sharply with respect to time. Then the current attains eventually a saturation value and remains constant as a function of time. The high

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value of the initial current is obtained due to the contribution of both ions and electrons. The saturation final current is due to the mobility of the electrons. The transference number has been estimated and presented in table 4. The transference number obtained for all the

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polymer blend electrolytes is in the range of 0.91-0.96.


4. Conclusion

Solid polymer electrolytes using pure PEO/PVP and different wt% NaNO3 are

prepared by solution casting technique. From X-ray analysis, it is confirmed that the crystalline peak appeared for PEO decreases with increasing the concentration of sodium nitrate upto 6wt% NaNO3, which indicates the increase in amorphous nature. Meanwhile the crystallinity observed above 6wt% NaNO3 is due to the irregular distribution of sodium 11

ACCEPTED MANUSCRIPT nitrate salt in polymer blend matrices. FTIR spectroscopic analysis shows the presence of certain characteristic bands of PEO and PVP polymer matrices and there is an occurrence of shifting of band with the increase in the salt concentration. Impedance analysis shows the increase in the conductivity with increase in both temperature and the sodium nitrate

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concentration of blend polymer electrolytes. The polymer electrolyte PEO/PVP/6wt% sodium nitrate has showed the higher conductivity of 6.67×10-7 Scm-1. From the dielectric studies, it is clear that the dielectric constant and dielectric loss decreases monotonically with increasing

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frequency. This may be attributed to the relation between electric dipoles and field variations formed in polymer matrices. In tangent plot, the loss tangent peaks move towards the higher

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frequency by increasing the temperature, which leads to the decrease in the relaxation time. The transference number obtained for all the polymer blend electrolytes is in the range of 0.91-0.96. From this, it is confirmed that the conductivity is mainly due to ions. Thus, the

Acknowledgement

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prepared polymer electrolytes can be used for electrochemical storage devices applications.

Author KS thanks the vice chancellor and Management of Kalasalingam Academy of

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Research and Education for providing URF fund to the research.

References: [1]

S.K. Shahenoor Basha, G. Sunita Sundari, K. Vijay Kumar, K. Veera Bhadra Reddy and M.C. Rao, Electrical conduction behaviour of pvp based composite polymer electrolytes Rasayan J. Chem. 10(1) (2017) 279-285.

[2]

M. Jaipal Reddy, J. Siva Kumar, U.V. Subba Rao and P. P. Chu, Structural and ionic conductivity of PEO blend PEG solid polymer electrolyte, Solid State Ionics. 177 (2006) 253-256. 12

ACCEPTED MANUSCRIPT [3]

K. Naresh Kumar, T. Sreekanth, M. Jaipal Reddy and U.V. Subba Rao, Study of transport and electrochemical cell characteristics of PVP:NaClO3 polymer electrolyte system, J. Power Sources. 101 (2001) 130-133.

[4]

Narasimharao Maragani, K. VijayaKumar and N. KrishnaJyothi, AC conductivity and

RI PT

thermal studies of PAN-Naf doped gel polymer electrolytes for solid state battery applications, Rasayan J.Chem. 10 (2017) 665-672. [5]

J. Leveneur, A. Rajan, J. McDonald-Wharry, M. JooL,

Guen, K. Pickering, J.

Surface

and

10.1016/j.surfcoat.2018.04.006. [6]

Coatings

Technology

2018

In

Press

DOI:

M AN U

implantations,

SC

Kennedy, Structural and chemical changes of cellulose fibres under low energy ion

Marsilea Adela Booth, Jérôme Leveneur, Alexsandro Santos Costa, John Kennedy, and Jadranka Travas-Sejdic, Tailoring the conductivity of polypyrrole films using low-energy platinum ion implantation, J. Phys. Chem. C, 116 (14), (2012) 8236–

[7]

TE D

8242.

K. Thanigai Arul, E. Manikandan, P.P. Murmu, J. Kennedy, M. Henini, Enhanced magnetic

properties

of

polymer-magnetic

nanostructures

synthesized

by

N.M.Strickland,

S.C.Wimbush,

P.Kluth,

P.Mota

Santiago,

M.C.Ridgway,

AC C

[8]

EP

ultrasonication, J. Alloys Compds. 720 (2017) 395- 400.

J.V.Kennedy, N.J.Long, Effect of annealing high-dose heavy-ion irradiated hightemperature superconductor wires, Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 409 (2017) 351355.

[9]

S.Khamlich, Z.Abdullaeva, J.V.Kennedy, M.Maaza, High performance symmetric supercapacitor based on zinc hydroxychloride nanosheets and 3D graphene-nickel foam composite, Appl. Surf. Sci., 405 (2017) 329-336. 13

ACCEPTED MANUSCRIPT [10]

M. Morita, F. Araki, N. Yoshimoto, M. Ishikawa, H. Tsutsumi, Ionic conductance of polymeric electrolytes containing lithium salts mixed with rare earth salts, Solid State Ionics. 136-137(2000) 1167-1173.

[11]

K. Vignarooban, R. Kushagra, A. Elango, P. Badami, Mellander B.-E, Xu X, T G

RI PT

Tucker, C Nam, A M Kannan, Current trends and future challenges of electrolytes for sodium-ion batteries, Int. J. Hydrog. Energy. 41 (2016) 2829-2846. [12]

Lizhen Long, Shuanjin Wang, Min Xiao and Yuezhong Meng, Polymer electrolytes

[13]

SC

for lithium polymer batteries , J. Mater. Chem. A, 4 (2016) 10038-10069.

J. Shahitha Parveen and S.S.M. Abdul Majeed, Poly (ethylene oxide)/Polyurethane

M AN U

based gel polymer electrolytes for lithium batteries, International Journal of Scientific & Engineering Research 4, 2013. [14]

M.A. Morsi,Sherif A. El-Khodary, A. Rajeh, Enhancement of the optical, thermal and electrical properties of PEO/PAM:Li polymer electrolyte films doped with Ag

[15]

TE D

nanoparticles, Physica B 539 (2018) 88-96.

P. Tamilselvi, M. Hema, Conductivity studies of LiCF3SO3 doped PVA: PVdF blend polymer electrolyte, Physica B (2014) 53-57. A. Karmakar, A.Ghosh, Dielectric permittivity and electric modulus of polyethylene

EP

[16]

[17]

AC C

oxide (PEO)–LiClO4 composite electrolytes, Curr. Appl. Phys. 12 (2012) 539- 543. D.E. Fenton, J.M. Parker and P.V. Wright, Complexes of alkali metal ions with poly(ethylene oxide), Polymer. 14 (1973) 589.

[18]

K.K. Kiran, M. Ravi, Y. Pavani, S. Bhavani, A.K. Sharma, V.V.R. Narasimha Rao, Investigations on the effect of complexation of NaF salt with polymer blend (PEO/PVP) electrolytes on ionic conductivity and optical energy band gaps, Physica B 406 (2011) 1706-1712.

14

ACCEPTED MANUSCRIPT [19]

G. Zardalidis, E. Ioannou, S. Pispas and G. Floudas, Relating structure, viscoelasticity and local mobility to conductivity in PEO/LiTf electrolytes, Macromolecules. 46 (2013) 2705-2714.

[20]

K. K. Kiran, M. Ravi, Y. Pavani, S. Bhavani, A. K. Sharma, V. V. R. Narasimha Rao,

RI PT

Investigations on PEO/PVP/NaBr complexed polymer blend electrolytes for electrochemical cell applications, J. Memb. Sci. 454 (2014)200-211. [21]

Mohammed Saleem Khan, Abdul Shankoor, Jan Nisar, Conductance study of

SC

poly(ethylene oxide)- and poly(propylene oxide)-based polyelectrolytes, Ionics. 16 (2010) 539-542.

S. Rajendran, O. Mahendran, R. Kannan,Lithium ion conduction in plasticized

M AN U

[22]

PMMA–PVdF polymer blend electrolytes, Mater. Chem. Phys., 74(2002) 52-57. [23]

R. C. Agrawal, S. A. Hashmi, Electrochemical cell performance studies on all-solidstate battery using nano-composite polymer electrolyte membrane, Ionics 13 (2007)

[24]

TE D

295-298.

X. Yang, L. Zhang, F. Zhang, T. Zhang, Y. Huang, Y. Chen, A high-performance allsolid-state supercapacitor with graphene-doped carbon material electrodes and a

H.K. Koduru, L. Marino, F. Scarpelli, A.G. Petrov, Y.G. Marinov, G.B.

AC C

[25]

EP

graphene oxide-doped ion gel electrolyte, Carbon. 72 (2014) 381-386.

Hadjichristov, M.T. Iliev, N. Scaramuzza,Structural and dielectric properties of NaIO4 – Complexed PEO/PVP blended solid polymer electrolytes, Curr. Appl. Phys. 17(11) (2017) 1518-1531.

[26]

Noor Sam, A. Ahmad, I.A. Talib, M.Y.A. Rahman, Morphology, chemical interaction, and conductivity of a PEO-ENR50 based on solid polymer electrolyte, Ionics. 16 (2010) 161–170.

15

ACCEPTED MANUSCRIPT [27]

S.

Rajendran,

R.

Kannan,

O.

Mahendran,Ionic

conductivity

studies

in

poly(methylmethacrylate)–polyethlene oxide hybrid polymer electrolytes with lithium salts, J. Power Sources, 96 (2001) 406–410. [28]

B.L. Papke, M.A. Ratner, D.F. Shriver,Vibrational Spectroscopic Determination of

Electrochem Soc. 129 (1982) 1434– 1438. [29]

RI PT

Structure and Ion Pairing in Complexes of Poly(ethylene oxide) with Lithium SaltsJ.

Ch V SubbaReddy, A. P Ji, Q. Y Zhu, L. Q Mai, W. Chen.Preparation and

SC

characterization of (PVP + NaClO4) electrolytes for battery applications, Eur. Phys. J. E 19 (2006)471–476.

C.S. Ramya, S. Selvasekarapandian, G. HiranKumar, T. Savitha, P.C. Angelo,

M AN U

[30]

Investigation on dielectric relaxations of PVP–NH4SCN polymer electrolyte, J.NonCryst Solids 354 (2008) 1494–1502. [31]

K.Naveenkumar, B.H. Rudramadevi, S. Buddhudu, Energy transfer based

TE D

photoluminescence spectra of Dy3+, Sm3+: PEO&PVP polymer films, Indian J. Pure Appl. Phys., 52(2014) 588-596. [32]

N.M. Zain, A.K. Arof, Structural and electrical properties of poly(ethylene oxide)-

G.P. Simon, Z. Shen, Y.B. Cheng, Saturation ratio of poly(ethylene oxide) to silicate

AC C

[33]

EP

cadmium sulphate complexes, Mater. Sci. Eng. B 52 (1998) 40-46.

in melt intercalated nanocomposites, Eur. Polym. J. 39 (2003) 1917-1924.

[34]

B.L. Papke, M.A. Ratner, D.F. Shriver, Vibrational spectroscopic determination of structure and ion pairing in complexes of poly(ethylene oxide) with lithium Salts J. Electrochem Soc. 129 (1982) 1434– 1438.

[35]

S. Arup Dey, S. Karan, S.K.De, Effect of nanofillers on thermal and transport properties of potassium iodide–polyethylene oxide solid polymer electrolyte, Solid State Commun. 149 (2009) 1282-1287. 16

ACCEPTED MANUSCRIPT [36]

Sireerat Intarakamhang, Thesis adviser: Asst.prof. Visit Vao-Soongnern, ISBN 974533-520-7, 54(2005).

[37]

L. P. Teo, M. H. Buraidah, A. F. M. Nor, S. R. Majid,Conductivity and dielectric studies of Li2SnO3, Ionics18 (2012) 655-665. A.M Abo El Ata, S.M Atia and T.M Meaz, AC conductivity and dielectric behavior of CoAlxFe2−xO4, Solid State Sci., 6 (2004) 61-69.

[39]

RI PT

[38]

Dev K. Mahato, Alo Dutta , T.P. Sinha, Dielectric relaxation and ac conductivity of

[40]

SC

double perovskite oxide Ho2ZnZrO6, Physica B, 406 (2011) 2703-2707.

N. A Hegab, A .E Bekheet, M .A Afifi, L. A Wahaba and H A Shehata, Effect Of Cd

Res. 3 (2007) 71-82. [41]

M AN U

addition on the AC Conductivity and dielectric properties of Ge70Te30 films J. Ovonic

C.R Mariappan and G .Govindaraj, AC conductivity, dielectric studies and conductivity scaling of NASICON materials, Mater. Sci. Engi. B, 94 (2002) 82-88. E. G. El-Metwally, M. Fadel, A.M Shakra and M.A Afifi, AC conductivity and

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[42]

dielectric properties of Se70Ge30-xMx {x = 0 & 5 and M = Ag, Cd or Pb} amorphous films, J. Optoelect. Advanced Mater. 10 (2008)1320-1327. N. Kulshrestha, B. Chatterjee and P. N. Gupta, Structural, thermal, electrical, and

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[43]

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dielectric properties of synthesized nanocomposite solid polymer electrolytes, High Perf. Polym. 26(6) (2014)677–688.

Figure Captions

Figure 1. Schematic representation of PEO/PVP/ Sodium nitrate solid polymer matrices in different composition. Figure 2. XRD Pattern of NaNO3 doped PEO- PVP solid polymer electrolytes, at different compositions. 17

ACCEPTED MANUSCRIPT Figure 3. FTIR spectra of NaNO3 doped PEO- PVP blend polymer at different composition. Figure 4. SEM images of pure PEO/PVP and various wt% NaNO3 polymer electrolytes. Figure 5: Cole-Cole plot for pure and various wt% of NaNO3 doped PEO/PVP solid polymer electrolyte.

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Figure 6: Cole-Cole Plot for 6 wt% of NaNO3 doped PEO/PVP solid polymer electrolyte, at different temperatures.

Figure 7. Frequency dependence conductance spectra for PEO/PVP/ 6wt% NaNO3, at various

SC

temperatures.

electrolytes at different temperatures.

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Figure 8. Bulk conductivity of Pure and various wt% of NaNO3 doped solid polymer

Figure 9. Variation of activation energy and conductivity at different wt% NaNO3 doped PEO/PVP solid polymer electrolytes.

Figure 10 a: Dielectric constant for PEO/PVP/6wt% NaNO3 at various temperatures.

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Figure 10 b: Dielectric loss for PEO/PVP/6wt% NaNO3 at various Temperatures. Figure 11: Tangent analysis of PEO/PVP/6wt% NaNO3 at different Temperatures. Figure 12. Transference number studies of Pure PEO/PVP and different weight percentage of

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NaNO3 doped PEO/PVP polymer matrices.

18

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PEO

PVP

References

Symmetric C-H Stretching

2887

~2900

[23,20]

C-H bending of CH2

1485

1463

[9]

CH2 Wagging

-

1438

CH2 bending

1340

-

CH2 Symmetric twisting

1238

1278

C-C Stretching

-

1149

C-O-C (Symm & Asym) stretching s

1096

-

[25]

-

[27]

C-O

Stretching

with

some

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Asymmetric rocking

CH2 957

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Vibrational Modes

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Table 1. Vibrational modes of PEO/PVP polymer electrolytes.

CH2 rocking in PVP and with some C-O 843

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stretching in PEO

843

[21]

[24]

[25]

[26]

[27]

ACCEPTED MANUSCRIPT Table. 2 Conductivity of PEO/PVP with various wt% NaNO3 polymer electrolytes with different Temperature.

333K

343K

1.01×10-9

1.38×10-09

PEO/PVP/2wt% NaNO3

1.65×10-9

PEO/PVP/4wt% NaNO3

3.2×10-09

1.63×10-08

2.41×10-08

4.19×10-08

9.9×10-08

3.13×10-09

2.18×10-08

3.89×10-07

6.75×10-07

1.61×10-06

5.03×10-06

6.19×10-9

1.54×10-08

6.39×10-08

1.25×10-06

1.99×10-06

3.76×10-06

8.73×10-06

PEO/PVP/6wt% NaNO3

6.67×10-7

1.69×10-06

5.04×10-06

1.45×10-05

3.17×10-05

5×10-05

PEO/PVP/8wt% NaNO3

5.03×10-7

6.00×10-07

PEO/PVP/10wt% NaNO3

3.34×10-7

4.81×10-07

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353K

363K

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PEO/PVP/0wt% NaNO3

323K

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313K

1.95×10-05

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303K

1.40×10-06

5.20×10-06

9.19×10-06

1.63×10-05

3.52×10-05

1.26×10-06

5.58×10-06

8.28×10-06

2×10-05

3.68×10-05

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Concentration

ACCEPTED MANUSCRIPT Table 3. Activation energy of Pure PEO/PVP blend polymer and NaNO3 mixed in different composition of blend polymer.

Composition

Activation energy 0.91

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Pure PEO/PVP/0wt% Sodium nitrate PEO/PVP/ 2wt% Sodium nitrate

0.85

PEO/PVP/ 4wt% Sodium nitrate

0.81

PEO/PVP/ 6wt% Sodium nitrate

0.65

0.68

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PEO/PVP/ 8wt% Sodium nitrate

0.75

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PEO/PVP/ 10wt% Sodium nitrate

Table 4. Transference numbers of Pure and NaNO3 doped PEO/PVP blend polymer

Transference Number

PEO/PVP/0wt% Sodium nitrate

0.95

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Composition

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electrolyte.

PEO/PVP/2wt% NaNO3

0.91

PEO/PVP/4wt% NaNO3

0.93

PEO/PVP/6wt% NaNO3

0.96

PEO/PVP/8wt% NaNO3

0.95

PEO/PVP/10wt% NaNO3

0.93

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Figures

Figure 1. Schematic representation of PEO/PVP/ Sodium nitrate solid polymer matrices

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in different composition.

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Figure 2. XRD Pattern of NaNO3 doped PEO- PVP solid polymer electrolytes, at different Compositions.

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Figure 3. FTIR Spectra of NaNO3 doped PEO- PVP blend polymer at different composition.

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Figure 4. SEM Images of pure PEO/PVP and various wt% NaNO3 polymer electrolytes.

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Figure 5: Cole-Cole plot for pure and various wt% of NaNO3 doped PEO/PVP solid polymer electrolyte.

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Figure 6: Cole-Cole Plot for 6 wt% of NaNO3 electrolyte, at different temperatures.

doped PEO/PVP solid polymer

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Figure 7. Frequency dependence conductance spectra for PEO/PVP/ 6wt% NaNO3, at

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various temperatures.

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Figure 8. Bulk conductivity of Pure and various wt% of NaNO3 doped solid polymer electrolytes at different temperatures.

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Figure 9. Variation of activation energy and conductivity at different wt%

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NaNO3 doped PEO/PVP solid polymer electrolytes.

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a

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b

Figure 10. (a) Dielectric Constant for PEO/PVP/6wt% NaNO3 at various temperatures, (b) Dielectric Loss for PEO/PVP/6wt% NaNO3 at various Temperatures.

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Figure 11: Tangent Analysis of PEO/PVP/6wt% NaNO3 at different Temperatures.

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Figure 12. Transference number studies of Pure PEO/PVP and different weight

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percentage of NaNO3 doped PEO/PVP polymer matrices.