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The Effect of Nanofiller on Electrical Conductivity of PVA Based Solid Polymer Electrolyte
Available online at www.sciencedirect.com
ScienceDirect Materials Today: Proceedings 15 (2019) 581–585
www.materialstoday.com/proceedings
ICMAM-2018
The Effect of Nanofiller on Electrical Conductivity of PVA Based Solid Polymer Electrolyte S.R. Jadhaoa, R.V. Joatb a
Department of Physics, VidyaBharatiMahavidyalay Amravati (M.S)-444602, India Department of Physics, VidyaBharatiMahavidyalay Amravati (M.S)-444602, India
b
Abstract The nanofiller aluminium oxide (Al2O3) dispersed with polyvinyl alcohol doped with ammonium nitrate have been prepared in different concentration using solution cast technique.The AC conductivity of prepared sample was measured with LCR meter in frequency range 20 Hz-1MHz at different temperature. It is observed that conductivity increases with increase nanofiller concentration as well as temperature. The temperature dependent conductivity shows Arrhenius behavior. © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
Keywords: Electrical conductivity, polyvinyl alcohol, solid polymer electrolyte, nanofiller
* Email- [email protected]
2214-7853 © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
582
S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
1.0 Introduction In the recent year, studies on electrical properties has been driven special attention due to their potential application in electronic and optical devices such as rechargeable batteries, supper capacitor, fuel cells, gas sensors and electro chromic display devices [1-4]. It is clearly mentioned that electrical and optical properties of polymer can be suitability modified by adding of salt, adding plasticizer to polymer electrolyte, adding inorganic filler, blending of two polymers [5-6]. It is extremely important to understand the charge transport mechanism of polymer electrolyte for practical application in microelectronics devices. There are scarce studies available electrical conduction mechanism in solid polymer electrolytes dispersed with nanofiller. This study investigates of the effect of nanofiller Al2O3on the electrical behavior of polyvinyl alcohol doped with ammonium nitrate. In the present study polyvinyl alcohol used as a host polymer. It is soluble in water and biodegradable polymer having effective film forming capacity. Also materials have high mechanical strength and high tensile strength and flexibility as well as high oxygen and aroma barrier properties so that it is used to fabricate electrochemical devices [7-8]. It is semi-crystalline material and it contain hydroxyl group attach to methane carbon which can be source of hydrogen bounding. As per literature survey ammonium salt are very good proton donor [9-11]. Also ceramic filler in polymer electrolyte improve the mechanical strength. These filler also enhance the composite polymer electrolyte transport properties without affecting its interfacial stability. The aim of the present work is to study the conductivity along with dielectric analysis of ammonium nitrate doped with polyvinyl alcohol dispersed with Al2O3of different mole concentration. 2. Experimental details: In the present study, polyvinyl alcohol (AR grade) received from S.D.fine, ammonium nitrate (AR grade) received from Merck, nanofiller aluminium oxide (AR grade), and double distilled water were used to prepare solid polymer electrolyte by solution cast technique. Appropriate quantity of polyvinyl alcohol and ammonium nitrate was dissolved separately in double distilled water. Then this solution is mixed together form homogenous solution. The different concentrations of nanofiller (0, 0.5, 1.0, 1.5, and 2.0) were mixed with 80PVA-20AN using magnetic stirrer for 10-12 hrs to form homogenous solution has been obtained. This homogenous solution then poured on petri dish. To achieve the uniform thickness the solution is placed on the pool of mercury. The solvent was allowed to evaporate slowly at room temperature for 3-4 days. The films of uniform thicknesses ranging 0.032-0.021 mm were taken for experimental studies. 3. Result and Discussion: 3.1Temperature Dependant conductivity The ionic conductivity (σ) of polymer electrolyte depends on number of charge carrier concentration n and carrier mobility μ as describe by the relation σ = n.q.μ (1) Where q represent the charge of mobile carrier Concentration of conducting species and their mobility is related with electrical conduction of polymer electrolyte. It was found that conductivity increases with increasing temperature for all concentration. The conductivity is high at higher temperature [12]. Temperature dependent conductivity obey Arrhenius equation σ=σ0exp (-Ea\KT)
(2)
Where σ0 is pre exponential factor, Ea is activation energy, K is Boltzman constant, T is absolute temperature. The increase in conductivity with temperature was interpreted as hopping mechanism between co-ordinate sites [13]. Fig 1 represent electrical conductivity related to the temperature and concentration of nanofiller in the temperature range 313-353K for 80PVA-20AN
S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
583
. Figure 1-Temparature dependent conductivity of (a) 80PVA:20AN:0Al2O3 (b) 80PVA:20AN:0.Al2O3, (c) 80PVA:20AN:1.0Al2O3,(d) 80PVA:20AN:1.5Al2O3,(e) 80PVA:20AN:2.0Al2O3
3.2 Concentration dependent conductivity The variation of conductivity as a function of concentration is shown in figure 2.
Figure 2 Variation of electrical conductivity with nanofiller concentration
It is observed that temperature dependent conductivity increases with increasing nanofiller concentration. It shows that the ceramic particle are aiding the formation of amorphous phase thereby reduces the energy barrier to segmental motion of polymer chain resulting in an enhanced ionic conductivity (14). 3.3 Frequency Dependent Conductivity The variation of AC electrical conductivity of the prepared sample was measured in the frequency LCR meter in frequency range 20 Hz-1MHz at different temperature ranging from 313K-353K The real part of complex conductivity σ (ω) is consist of two components, dc component σdc and ac component σac given by the following equation σ (ω) =σdc+σac
(3)
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S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
The variation of ac conductivity σac(ω) for particular frequency is described by universal power law σac(ω) =A(T).ωs
(4)
Where A is a constant temperature-dependant parameters. The variation of AC conductivity as a function of frequency for80PVA-20ANdispersed 2.0Al2O3concentrationsof nanofiller in the temperature range 313-353K is shown in figure 3.
with
Figure 3 Variation of AC conductivity with frequency for 80PVA-20AN-2.0Al2O3 polymer electrolyte film.
It is observed that conductivity value increases with increase in temperature. The AC conductivity obeys Jonscher’s power law. Mobile charge carriers move easily in the amorphous polymer matrix and hence the conductivity increases. 3.4 Dielectric analysis Dielectric analysis of solid polymer electrolyte is an important technique for evaluating the frequency dependent dielectric relaxation processes. Figure (4a) indicate the frequency verse dielectric constant of different concentration of nanofiller and figure (4b) indicate the frequency verse dielectric loss of different concentration of nanofiller
Figure (4a) frequency dependent dielectric constant of different concentration of nanofiller
S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
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Figure (4b) Frequency dependent dielectric loss of different concentration of nanofiller
It indicates that the value of dielectric constant and dielectric loss is high at low frequency region due to space charge effect which is contributed by the accumulation of charge carrier near the electrodes and space charge polarization (15-16) and at the higher frequencies dielectric constant and dielectric loss decreases due to the high periodic reversal of the electric field, 4. Conclusion: The solid polymer electrolytes based on polyvinyl alcohol doped with ammonium nitrate and dispersed with nanofiller aluminium oxide (Al2O3) have been prepared in different concentration using solution cast technique .Electrical conductivity has been found to be increase with increase nanofiller concentration due to mobile charge carriers move easily in the amorphous polymer matrix of solid polymer electrolytes. Temperature dependent conductivity of polymer electrolyte obeys Arrhenius behavior. Frequency dependant conductivity value increases with increase in temperature. Dielectric constant and dielectric loss is high at low frequency region and decreases with frequency for all samples. Reference: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.
S. Guinot, E. Salmon, J.F. Penneau ,J.F.Fauvarque, Electro-chim. Acta 43, ( 1998) 1163-1170. N. Vassal, E. Salmon, J. F. Fauvarque, J. Electrochem, Soc.146, (1999) 20-26. A. Lawandowski, K. Skorupska, J. Malinska, , Solid State Ionics 133, (2000)265-271. A. A. Mohamad, N. S. Mohamed, Y. Alias, A. K. Arof, J. Alloys Comp. 337 (2002) 208-213. P. W. Blom, H. F. M. Schoo, M. Matters, Appl. Phys. Lett.73 (26), (1998)3914-3916. A.Kiesow ,J.E.Morris, C.Radehaus,A.Heilmann, J.Appl. Phys.94, (2003) 6988-6990. M. Krumova ,D. lopaz , R. Benavent, C.Mijangos, J. M. Parena, , Polymer 41, (2002) 9265-9272. K .Masuda, H.Kaji, F. Hori, J PolymSci Part B, 38, (2002) 1 F.Billmeyer, Jr.Text Book ofPolymer Science Wiley Singapur(1984). S. Chandra, S A Hashim, G. Prasad,Solid State Ionic 40-41, (1990) ,651-654 R. Mishra, N.Baskaran,P. Ramakrisnan,K.J.Rao , Solid State Ionics 112, (1998) 261-273 M. Kumar, S. S. Sekhon, Eur polymer J 38, (2002)1297-1304. R.Murri, LSchiavulli, N pinto , T.Lingonzo, Journal of Non CrystallineSolid 139, (1992), 60- 66. S.Gopal,S.A.Agnihotry, V. D. Gupta, Sol.Energ.Mat.Sol.C.44, (1996) ,237-250. R.D.Armstrong , W.P.Race , J.Electroanal Chem74, (1976) 125-143. S.Ramesh,A.H.Yahya,A.K. Arof, Solid State Ionic 152-153, (2002), 291-294
ScienceDirect Materials Today: Proceedings 15 (2019) 581–585
www.materialstoday.com/proceedings
ICMAM-2018
The Effect of Nanofiller on Electrical Conductivity of PVA Based Solid Polymer Electrolyte S.R. Jadhaoa, R.V. Joatb a
Department of Physics, VidyaBharatiMahavidyalay Amravati (M.S)-444602, India Department of Physics, VidyaBharatiMahavidyalay Amravati (M.S)-444602, India
b
Abstract The nanofiller aluminium oxide (Al2O3) dispersed with polyvinyl alcohol doped with ammonium nitrate have been prepared in different concentration using solution cast technique.The AC conductivity of prepared sample was measured with LCR meter in frequency range 20 Hz-1MHz at different temperature. It is observed that conductivity increases with increase nanofiller concentration as well as temperature. The temperature dependent conductivity shows Arrhenius behavior. © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
Keywords: Electrical conductivity, polyvinyl alcohol, solid polymer electrolyte, nanofiller
* Email- [email protected]
2214-7853 © 2019 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON MULTIFUNCTIONAL ADVANCED MATERIALS (ICMAM-2018).
582
S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
1.0 Introduction In the recent year, studies on electrical properties has been driven special attention due to their potential application in electronic and optical devices such as rechargeable batteries, supper capacitor, fuel cells, gas sensors and electro chromic display devices [1-4]. It is clearly mentioned that electrical and optical properties of polymer can be suitability modified by adding of salt, adding plasticizer to polymer electrolyte, adding inorganic filler, blending of two polymers [5-6]. It is extremely important to understand the charge transport mechanism of polymer electrolyte for practical application in microelectronics devices. There are scarce studies available electrical conduction mechanism in solid polymer electrolytes dispersed with nanofiller. This study investigates of the effect of nanofiller Al2O3on the electrical behavior of polyvinyl alcohol doped with ammonium nitrate. In the present study polyvinyl alcohol used as a host polymer. It is soluble in water and biodegradable polymer having effective film forming capacity. Also materials have high mechanical strength and high tensile strength and flexibility as well as high oxygen and aroma barrier properties so that it is used to fabricate electrochemical devices [7-8]. It is semi-crystalline material and it contain hydroxyl group attach to methane carbon which can be source of hydrogen bounding. As per literature survey ammonium salt are very good proton donor [9-11]. Also ceramic filler in polymer electrolyte improve the mechanical strength. These filler also enhance the composite polymer electrolyte transport properties without affecting its interfacial stability. The aim of the present work is to study the conductivity along with dielectric analysis of ammonium nitrate doped with polyvinyl alcohol dispersed with Al2O3of different mole concentration. 2. Experimental details: In the present study, polyvinyl alcohol (AR grade) received from S.D.fine, ammonium nitrate (AR grade) received from Merck, nanofiller aluminium oxide (AR grade), and double distilled water were used to prepare solid polymer electrolyte by solution cast technique. Appropriate quantity of polyvinyl alcohol and ammonium nitrate was dissolved separately in double distilled water. Then this solution is mixed together form homogenous solution. The different concentrations of nanofiller (0, 0.5, 1.0, 1.5, and 2.0) were mixed with 80PVA-20AN using magnetic stirrer for 10-12 hrs to form homogenous solution has been obtained. This homogenous solution then poured on petri dish. To achieve the uniform thickness the solution is placed on the pool of mercury. The solvent was allowed to evaporate slowly at room temperature for 3-4 days. The films of uniform thicknesses ranging 0.032-0.021 mm were taken for experimental studies. 3. Result and Discussion: 3.1Temperature Dependant conductivity The ionic conductivity (σ) of polymer electrolyte depends on number of charge carrier concentration n and carrier mobility μ as describe by the relation σ = n.q.μ (1) Where q represent the charge of mobile carrier Concentration of conducting species and their mobility is related with electrical conduction of polymer electrolyte. It was found that conductivity increases with increasing temperature for all concentration. The conductivity is high at higher temperature [12]. Temperature dependent conductivity obey Arrhenius equation σ=σ0exp (-Ea\KT)
(2)
Where σ0 is pre exponential factor, Ea is activation energy, K is Boltzman constant, T is absolute temperature. The increase in conductivity with temperature was interpreted as hopping mechanism between co-ordinate sites [13]. Fig 1 represent electrical conductivity related to the temperature and concentration of nanofiller in the temperature range 313-353K for 80PVA-20AN
S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
583
. Figure 1-Temparature dependent conductivity of (a) 80PVA:20AN:0Al2O3 (b) 80PVA:20AN:0.Al2O3, (c) 80PVA:20AN:1.0Al2O3,(d) 80PVA:20AN:1.5Al2O3,(e) 80PVA:20AN:2.0Al2O3
3.2 Concentration dependent conductivity The variation of conductivity as a function of concentration is shown in figure 2.
Figure 2 Variation of electrical conductivity with nanofiller concentration
It is observed that temperature dependent conductivity increases with increasing nanofiller concentration. It shows that the ceramic particle are aiding the formation of amorphous phase thereby reduces the energy barrier to segmental motion of polymer chain resulting in an enhanced ionic conductivity (14). 3.3 Frequency Dependent Conductivity The variation of AC electrical conductivity of the prepared sample was measured in the frequency LCR meter in frequency range 20 Hz-1MHz at different temperature ranging from 313K-353K The real part of complex conductivity σ (ω) is consist of two components, dc component σdc and ac component σac given by the following equation σ (ω) =σdc+σac
(3)
584
S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
The variation of ac conductivity σac(ω) for particular frequency is described by universal power law σac(ω) =A(T).ωs
(4)
Where A is a constant temperature-dependant parameters. The variation of AC conductivity as a function of frequency for80PVA-20ANdispersed 2.0Al2O3concentrationsof nanofiller in the temperature range 313-353K is shown in figure 3.
with
Figure 3 Variation of AC conductivity with frequency for 80PVA-20AN-2.0Al2O3 polymer electrolyte film.
It is observed that conductivity value increases with increase in temperature. The AC conductivity obeys Jonscher’s power law. Mobile charge carriers move easily in the amorphous polymer matrix and hence the conductivity increases. 3.4 Dielectric analysis Dielectric analysis of solid polymer electrolyte is an important technique for evaluating the frequency dependent dielectric relaxation processes. Figure (4a) indicate the frequency verse dielectric constant of different concentration of nanofiller and figure (4b) indicate the frequency verse dielectric loss of different concentration of nanofiller
Figure (4a) frequency dependent dielectric constant of different concentration of nanofiller
S.R. Jadhao and R.V. Joat / Materials Today: Proceedings 15 (2019) 581–585
585
Figure (4b) Frequency dependent dielectric loss of different concentration of nanofiller
It indicates that the value of dielectric constant and dielectric loss is high at low frequency region due to space charge effect which is contributed by the accumulation of charge carrier near the electrodes and space charge polarization (15-16) and at the higher frequencies dielectric constant and dielectric loss decreases due to the high periodic reversal of the electric field, 4. Conclusion: The solid polymer electrolytes based on polyvinyl alcohol doped with ammonium nitrate and dispersed with nanofiller aluminium oxide (Al2O3) have been prepared in different concentration using solution cast technique .Electrical conductivity has been found to be increase with increase nanofiller concentration due to mobile charge carriers move easily in the amorphous polymer matrix of solid polymer electrolytes. Temperature dependent conductivity of polymer electrolyte obeys Arrhenius behavior. Frequency dependant conductivity value increases with increase in temperature. Dielectric constant and dielectric loss is high at low frequency region and decreases with frequency for all samples. Reference: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.
S. Guinot, E. Salmon, J.F. Penneau ,J.F.Fauvarque, Electro-chim. Acta 43, ( 1998) 1163-1170. N. Vassal, E. Salmon, J. F. Fauvarque, J. Electrochem, Soc.146, (1999) 20-26. A. Lawandowski, K. Skorupska, J. Malinska, , Solid State Ionics 133, (2000)265-271. A. A. Mohamad, N. S. Mohamed, Y. Alias, A. K. Arof, J. Alloys Comp. 337 (2002) 208-213. P. W. Blom, H. F. M. Schoo, M. Matters, Appl. Phys. Lett.73 (26), (1998)3914-3916. A.Kiesow ,J.E.Morris, C.Radehaus,A.Heilmann, J.Appl. Phys.94, (2003) 6988-6990. M. Krumova ,D. lopaz , R. Benavent, C.Mijangos, J. M. Parena, , Polymer 41, (2002) 9265-9272. K .Masuda, H.Kaji, F. Hori, J PolymSci Part B, 38, (2002) 1 F.Billmeyer, Jr.Text Book ofPolymer Science Wiley Singapur(1984). S. Chandra, S A Hashim, G. Prasad,Solid State Ionic 40-41, (1990) ,651-654 R. Mishra, N.Baskaran,P. Ramakrisnan,K.J.Rao , Solid State Ionics 112, (1998) 261-273 M. Kumar, S. S. Sekhon, Eur polymer J 38, (2002)1297-1304. R.Murri, LSchiavulli, N pinto , T.Lingonzo, Journal of Non CrystallineSolid 139, (1992), 60- 66. S.Gopal,S.A.Agnihotry, V. D. Gupta, Sol.Energ.Mat.Sol.C.44, (1996) ,237-250. R.D.Armstrong , W.P.Race , J.Electroanal Chem74, (1976) 125-143. S.Ramesh,A.H.Yahya,A.K. Arof, Solid State Ionic 152-153, (2002), 291-294