FAMIZA BINTI ABDUL LATIF. A thesis submitted in fulfilment of the requirements for the award of the degree of Doctor of Philosophy

Transcription

1 PREPARATION AND CHARACTERIZATION OF POLY (METHYL METHACRYLATE) / 50% EPOXIDISED NATURAL RUBBER BASED SOLID ELECTROLYTES FOR LITHIUM-ION SECONDARY BATTERY FAMIZA BINTI ABDUL LATIF A thesis submitted in fulfilment of the requirements for the award of the degree of Doctor of Philosophy Faculty of Science Universiti Teknologi Malaysia JUNE 2006

2 To my beloved husband and families iii

3 iv ACKNOWLEDGEMENT In preparing this thesis, I was in contact with many people, researchers, academicians and librarians. They have contributed towards my understanding and thoughts. First and foremost, I wish to extend my deepest gratitude and profound appreciation to my main thesis supervisor, Associate Professor Dr Madzlan Aziz from the Chemistry Department, Faculty of Science, Universiti Teknologi Malaysia for his invaluable supervision. I am also very thankful to my co-supervisor, Encik Nasir Katun for his guidance and assistance. A note of thanks also goes to Encik Hanan, En Fuad, Encik Azmi, Encik Rahim, Encik Hamzah, Pn Ambiga (UNIPEM) and all the laboratory staff for their assistance in the course of my work. A special note of gratitude also goes to Dr Wan Azlina for her invaluable advice and support. Special thanks for Dr Muhd Zu Azhan Yahya and the Solid-State Group of UiTM Shah Alam for allowing me to use the facilities in the SSID lab at my convenience. Further thanks also go to En Hussien, En Omar and En Ayob from the Faculty of Mechanical Engineering, UiTM Shah Alam for the all the help and time spent. To all my fellow postgraduate students, Chee, Zatur, Ita and Huda, thanks for the support. My sincere appreciation also extends to my UiTM colleagues who had supported me. Further thanks to MOSTE and Universiti Teknologi Mara for awarding me scholarship and study leave to undertake this work. Last and not least, special thanks to my husband and families who have in more ways than one contributed to the completion of this work.

4 v ABSTRACT This research focused on the development of new thin film electrolytes based on Poly(methyl methacrylate)(pmma) / 50% epoxidised natural rubber (ENR 50) blend by solvent casting method. Lithium nitrate (LiNO 3 ), lithium triflate (LiCF 3 SO 3 ) and lithium imides (LiN(CF 3 SO 2 ) 2) salts were used as the doping material to provide lithium ion for the ionic conduction. Dimethyl carbonate (DMC), ethylene carbonate (EC) and propylene carbonate (PC) plasticizers were used to improve the physical properties and the morphology of the films. Freestanding films were obtained when PMMA was blended with 10% and 20% of ENR 50. Above these compositions, the films became brittle and bonded strongly to the glass substrate. The blend films were not homogeneous in which the phase separation can be observed in their FESEM micrographs even in the presence of plasticizers. Though the films were not homogeneous, the brittle properties of PMMA film have been improved. The DSC thermograms of these films further confirmed the in-homogeneity of the blends by exhibiting two glass transition temperatures, Tg. The infra red (IR) spectra established the PMMA-ENR 50 interactions and the polymer-salt complexation. Doped PMMA / ENR 50 films with LiNO 3 salt were observed to be unstable where by the films obtained became damp and opaque when exposed to the ambient environment. It was observed that the best salt for this PMMA / ENR 50 blend was LiCF 3 SO 3 in which the highest conductivity of 10-5 S/cm at room temperature were obtained. On the other hand, PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 electrolyte exhibited the lowest ionic conductivity of 10-7 S/cm at room temperature. The effect of plasticizers differs from one electrolyte system to another. The ionic conduction behaviour in the electrolyte systems depends on the salt and the plasticizers used. The transference number and the modulus formalism showed that the PMMA / ENR 50 blend based electrolytes were ionic conductor. The equivalent circuit for the highest conducting film from each plasticized or non-plasticized electrolyte system was determined using Autolab software. Films with 10-5 S/cm at room temperature were fabricated into LiNiCoO 2 / polymer electrolyte / mesocarbon microbeads (MCMB) cell. It was observed that these cells exhibit poor charge-discharge characteristic and can be improved.

5 vi ABSTRAK Kajian ini memfokuskan kepada penyediaan filem baru elektrolit polimer berasaskan campuran poli(metil metakrilat) (PMMA) / 50% getah terepoksida (ENR 50) dengan kaedah solvent casting. Garam litium nitrat (LiNO 3 ), litium triflat (LiCF 3 SO 3 ) dan litium imida (LiN(CF 3 SO 2 ) 2) telah digunakan sebagai dopan dalam penyediaan elektrolit polimer berasaskan PMMA / ENR 50. Dimetil karbonat, (DMC) etilena karbonat, (EC) dan propilena karbonat (PC) telah digunakan sebagai bahan pemplastik untuk membantu memperbaiki morfologi filem elektrolit. Filem elektrolit polimer ini telah berjaya dihasilkan apabila 10% dan 20% ENR 50 ditambah ke dalam campuran. Filem menjadi semakin rapuh dan sukar dipisahkan daripada acuan apabila komposisi ENR 50 dalam campuran melebihi 20%. Kesemua filem berasaskan PMMA/ ENR 50 ini adalah tidak homogen yang mana pemisahan fasa dapat dilihat dengan jelas pada permukaan filem. Malahan, ianya telah dapat dibuktikan melalui analisis permukaan menggunakan mikroskop pengimbasan elektron, FESEM. Walau bagaimanapun, penyediaan elektrolit berasaskan campuran ini diteruskan kerana kerapuhan filem PMMA telah dapat diperbaiki. Analisis pengimbas kalorimetri, DSC pula telah menunjukkan kehadiran dua suhu peralihan kaca, Tg. Daripada analisis spektrum infra merah (IR), didapati telah terbentuknya interaksi antara kedua-dua polimer dan pembentukan kompleks antara polimer dan garam. Dopan LiNO 3 memberikan filem yang paling tidak stabil yang mana filem menjadi lembab dan bertukar opak apabila didedahkan kepada sekitaran. Garam LiCF 3 SO 3 telah menunjukkan konduktiviti filem terbaik dengan nilai 10-5 S/cm pada suhu bilik manakala filem PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 pula menunjukkan nilai yang sangat rendah dengan konduktiviti tertinggi yang dapat dicapai hanyalah 10-7 S/cm. Kehadiran bahan pemplastik telah menunjukkan kesan yang berbeza-beza antara satu sistem elektrolit dengan sistem elektrolit yang lain. Modul pergerakan ion di dalam campuran polimer ini juga bergantung kepada garam dan bahan pemplastik yang digunakan. Daripada penentuan nombor angkutan dan analisis modulus didapati elektrolit polimer ini adalah konduktor ionik. Kesepadanan litar bagi kesemua sistem dengan kekonduksian ionik tertinggi telah ditentukan dengan menggunakan perisian Autolab. Filem dengan kekonduksian minima 10-5 S/cm telah digunakan sebagai elektrolit bateri sekunder dalam sel LiNiCoO 2 / elektrolit polimer / mesocarbon microbeads (MCMB). Didapati sel ini telah menunjukkan sedikit kelemahan dalam prestasi cas-discasnya dan masih boleh diperbaiki.

6 vii TABLE OF CONTENTS CHAPTER TITLE PAGE ACKNOWLEDGEMENT ABSTRACT ABSTRAK TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES LIST OF PHOTOGRAPH LIST OF SYMBOLS LIST OF ABBREVIATIONS LIST OF PUBLICATIONS iv v vi vii xviii xxiv xxxix xl xli xlii 1 INTRODUCTION 1.1 Classification of Polymer Electrolytes 1.2 Polymer Electrolytes Background 1.3 Why Polymer Electrolytes 1.4 The Characteristics of Polymer Electrolytes 1.5 Characteristic of the Doping Salt 1.6 Preparation of Polymer Electrolytes 1.7 Modification of Polymer Host 1.8 Applications of Polymer Electrolytes 1.9 Problem Statements 1.10 Objectives

7 viii 1.11 Research Scope Selection of Materials Selection of Material Characterizations Selection of Test cell 1.12 Expectations 1.13 Technical Challenge and limitations LITERATURE REVIEW 2.1 Poly(methyl methacrylate) as a Polymer Host 2.2 Epoxidised Natural Rubber 2.3 Plasticizers 2.4 Structure and Morphology 2.5 Polymer-Salt Interaction : Concepts of Ion Solvation by the Polymer 2.6 Conductivity Studies Impedance Spectroscopy 2.7 Ionic Conduction Mechanism Arrhenius Behaviour : Solid State Theory Vogel-Tammam Fulcher Equation : A Free Volume-Based Model Williams, Landel and Ferry 2.8 Dielectric Behaviour Study 2.9 Equivalent Circuit Study 2.10 Electrochemical Cell Studies Introduction Secondary Lithium Batteries Electrochemical Characteristics and Performance Criteria of Cells and Batteries

8 ix 3 RESEARCH METHODOLOGY 3.1 Samples Preparation Materials 3.2 Preparation of Polymer Stock Solution 3.3 Preparation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber film To Determine the Effect of 50% Epoxidised Natural Rubber on the Properties of PMMA To Determine the Effect of Salts on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber Blend To Determine the Effect of Plasticizer on the Conductivity of doped Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber Films 3.4 Material Characterization Scanning Electron Microscopy Differential Scanning Calorimetry Infrared Spectroscopy 3.5 Conductivity Studies 3.6 Ion Transport Characterization by Wagner s Polarization Method 3.7 Fabrication of Solid State Secondary Battery POLY(METHYL METHACRYLATE) / 50% EPOXIDISED NATURAL RUBBER BLEND 4.1 The effect of 50% Epoxidised Natural Rubber on the Formation of Freestanding Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber Films 4.2 Field Emission Scanning Electron Microscopy Study on The Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber Films

9 x 4.3 Differential Scanning Calorimetry Study on the Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber Films 4.4 Fourier Transform Infra Red Study Poly(methyl methacrylate) 50% Epoxidised Natural Rubber Interactions 4.5 Conductivity Study 4.6 Conclusion POLY(METHYL METHACRYLATE) / 50% EPOXIDISED NATURAL RUBBER / LITHIUM NITRATE BASED ELECTROLYTES 5.1 The Effect of Lithium Nitrate Salt on the Formation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films 5.2 The Effect of Plasticizer on the Formation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films 5.3 Field Emission Scanning Electron Microscopy Study The Effect of Lithium Nitrate Salt on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber Films The Effect of Dimethyl Carbonate Plasticizer on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films 5.4 Fourier Transform Infra Red Study Determination of Polymer-Salt Complexation in Un-plasticized Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films Determination of Polymer-Salt Complexation in Plasticized Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films 5.5 Conductivity Study

10 xi Concentration Dependence The Effect of Lithium Nitrate Salt on the Conductivity of Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber Films The Effect of Dimethyl Carbonate Plasticizer on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films Conductivity : Temperature Dependence The Effect of Temperature on the Conductivity of Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Nitrate Films The Effect of Temperature on the Conductivity of Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Nitrate / Dimethyl Carbonate Films 5.6 Dielectric Behaviour Study Dielectric Study for Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films Dielectric Study for Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate / Dimethyl Carbonate Films 5.7 Equivalent Circuit Determination Equivalent Circuit for Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Nitrate Films Equivalent Circuit for Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Nitrate Films 5.8 Conclusion

11 xii 6 POLY(METHYL METHACRYLATE) / 50% EPOXIDISED NATURAL RUBBER / LITHIUM TRIFLATE BASED ELECTROLYTES 6.1 The Formation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Film Based Electrolyte The Effect of Lithium Triflate Salt on the Formation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films The Effect of Plasticizer on the Formation of Poly (methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films 6.2 Field Emission Scanning Electron Microscopy Study The Effect of LiCF 3 SO 3 O 3 Salt on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber Films The Effect of Plasticizers on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films The Effect of Single Plasticizer on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films The Effect of Mix Plasticizers on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films 6.3 Fourier Transform Infra Red Study Determination of Polymer-Ion Complexation in Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Triflate Films

12 xiii Determination of Polymer-Ion Complexation in Single Plasticized Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films Determination of Polymer-Ion Complexation in Mix Plasticized Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films 6.4 Differential Scanning Calorimetry Studies of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films 6.5 Conductivity Study Concentration Dependence The Effect of Salt Concentration on The Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Films The Effect of Single Plasticizer on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Electrolytes The Effect of Mix Plasticizers on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Electrolytes Conductivity Study : Temperature Dependence The Effect of Temperature on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Electrolytes The Effect of Temperature on the Conductivity of Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber/ Lithium Triflate Films

13 xiv The Effect of Temperature on the Conductivity of Mix Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Triflate Films 6.6 Dielectric Behaviour Study Dielectric Behaviour for Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Electrolytes Dielectric Behaviour for Single Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Triflate Electrolytes Dielectric Behaviour for Mix Plasticizer System of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate Electrolytes 6.7 Transference Number 6.8 Equivalent Circuit Study 6.9 Battery Fabrication and Characterization Characterization of the Lithium Nickel Cobalt Oxide / Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate / Mesocarbon Microbeads Cell Characterization of the Lithium Nickel Cobalt Oxide / Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate / Propylene Carbonate / Mesocarbon Microbeads Cell Characterization of the Lithium Nickel Cobalt Oxide / Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Triflate / Ethylene Carbonate / Dimethyl Carbonate / Mesocarbon Microbeads Cell 6.10 Conclusion

14 xv 7 POLY(METHYL METHACRYLATE) / 50% EPOXIDISED NATURAL RUBBER / LITHIUM IMIDES BASED ELECTROLYTES The Formation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Film Based Electrolyte The Effect of Lithium Imides Salt on the Formation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films The Effect of Plasticizer on the Formation of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films 7.2 Optical Microscope Study The Effect of Lithium Imides Salt on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber Films The Effect of Plasticizers on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films The Effect of Single Plasticizer on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films The Effect of Mix Plasticizers on the Morphology of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films 7.3 Fourier Transform Infra Red Study Determination of Polymer-Ion Complexation in Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Imides Films

15 xvi Determination of Polymer-Ion Complexation in Single Plasticized Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films Determination of Polymer-Ion Complexation in Mixed Plasticized Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films 7.4 Conductivity Study Concentration Dependence The Effect of Sal Concentration on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Films The Effect of Single Plasticizer on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Electrolytes The Effect of Mix Plasticizers on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Electrolytes Conductivity Study : Temperature Dependence The Effect of Temperature on the Conductivity of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Electrolytes The Effect of Temperature on the Conductivity of Single Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Imides Films

16 xvii The Effect of Temperature on the Conductivity of Mix Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Imides Films 7.5 Dielectric Behaviour Study Dielectric Behaviour for Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Electrolytes Dielectric Behaviour for Single Plasticized Poly(methyl methacrylate)/ 50% Epoxidised Natural Rubber / Lithium Imides Electrolytes Dielectric Behaviour for Mix Plasticizer System of Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber / Lithium Imides Electrolytes 7.6 Equivalent Circuit 7.7 Conclusion CONCLUSIONS 322 REFERENCES 325

17 xviii LIST OF TABLES TABLE NO. TITLE PAGE PMMA Based Electrolytes Some Physical Properties of EC, PC and DMC plasticizers Dilution Procedure for PC and DMC T g for PMMA / ENR 50 Blend -C=O, -OCH 3, -C-O, -CH 3 Bands of PMMA and -C-O-C Band of ENR 50 Obtained from Previous Studies -C=O, -OCH 3, -CH 3, -C-O-C and C=C Bands Obtained from Present Study Average Thickness and Conductivity of Un-doped PMMA / ENR 50 Blend The Shift of C=O Band After Complexation in PMMA / ENR 50 / LiNO 3 Electrolyte The Average Conductivity Value for PMMA / ENR 50 / LiNO 3 Films at Various Amounts of Salt and Temperatures The Average Conductivities for PMMA / ENR 50 / LiNO 3 Electrolyte Films at Various Amounts of DMC and Temperatures Conductivity Relaxation Times For Various Concentration of LiNO 3 Salt in PMMA / ENR 50 Blend Conductivity Relaxation Times For Various Concentration of DMC Plasticizer in PMMA / ENR 50 / LiNO 3 Electrolytes

18 xix 5.6 The Fitted Values for the Equivalent Circuit for The Highest Conducting PMMA / ENR 50 / LiNO 3 Electrolyte, PE1N2 5.7 The Fitted Values for the Equivalent Circuit for The Highest Conducting Plasticized PMMA / ENR 50 / LiNO 3 Electrolyte, PE1ND1 Bands Shift in PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes Bands Shift in PMMA / ENR 50 / LiCF 3 SO 3 / DMC Electrolytes Bands Shift in PMMA / ENR 50 / LiCF 3 SO 3 / EC Electrolytes Bands Shift in PMMA / ENR 50 / LiCF 3 SO 3 / PC Electrolytes Bands Shift in PMMA / ENR 50 / LiCF 3 SO 3 / EC/ DMC Electrolytes Bands Shift in PMMA / ENR 50 / LiCF 3 SO 3 / EC/ PC Electrolytes Bands Shift in PMMA / ENR 50 / LiCF 3 SO 3 / PC/ DMC Electrolytes The Average Conductivity of PMMA / ENR 50 / LiCF 3 SO 3 at Various Amount of Salt and Temperatures The Average Conductivity of PMMA / ENR 50 / LiCF 3 SO 3 / DMC Electrolytes at Various Amount of DMC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiCF 3 SO 3 / EC Electrolytes at Various Amount of EC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiCF 3 SO 3 / PC Electrolytes at Various Amount of PC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiCF 3 SO 3 / EC / DMC Electrolytes at Various Amount of EC:DMC and Temperatures

19 xx The Average Conductivity of PMMA / ENR 50 / LiCF 3 SO 3 / EC / PC Electrolytes at Various Amount of EC:PC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiCF 3 SO 3 / PC / DMC Electrolytes at Various Amount of PC:DMC and Temperatures The Activation Energy, Ea for PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes The Activation Energy, Ea for PMMA / ENR 50 Blend/ LiCF 3 SO 3 / DMC Electrolytes The Activation Energy, Ea for PMMA / ENR 50 Blend/ LiCF 3 SO 3 / EC Electrolytes The Activation Energy, Ea for PMMA / ENR 50 Blend/ LiCF 3 SO 3 / PC Electrolytes The Activation Energy, Ea for PMMA / ENR 50 Blend/ LiCF 3 SO 3 / EC / DMC Electrolytes Conductivity Relaxation Times For Various Concentration of LiCF 3 SO 3 Salt in PMMA / ENR 50 Blend at Room Temperature Dielectric Constant Value for Various Concentration of Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes at 100 Hz Dielectric Loss Value for Various Concentration of Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes Dielectric Constant and Dielectric Loss at 100 Hz for Plasticized PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes at Various Temperature Conductivity Relaxation Times For Various Concentration of EC and DMC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 at Room Temperature Dielectric Constant Value for Various Concentration of Plasticizer Mixture in PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes at 100 Hz

20 xxi Dielectric Loss Value for Various Concentration of Plasticizers Mixture in PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes at 100 Hz Dielectric Constant and Dielectric Loss at 100 Hz for Plasticized PMMA / ENR 50 / LiCF 3 SO 3 Electrolytes at Various Temperature Conductivity Relaxation Times For Various Concentration of EC / PC and PC / DMC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 at Room Temperature Transference Number for the Highest Conducting Sample The Fitted Values for the Equivalent Circuit for PE1T3, PE1TP2 and PE1TE2D1 Bands Shift in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolytes Bands Shift in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / DMC Electrolytes Bands Shift in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / EC Electrolytes Bands Shift in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / PC Electrolytes Bands Shift in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / EC/ DMC Electrolytes Bands Shift in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / EC/ PC Electrolytes Bands Shift in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / PC/ DMC Electrolytes The Average Conductivity of PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 at Various Composition of Salt and Temperatures The Average Conductivity of PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / DMC Electrolytes at Various Amounts of DMC and Temperatures The Average Conductivity of PMMA / ENR 50 /

21 xxii LiN(CF 3 SO 2 ) 2 / EC Electrolytes at Various Amounts of EC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / PC Electrolytes at Various Amount of PC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / EC / DMC Electrolytes at Various Compositions of EC:DMC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / EC / PC Electrolytes at Various Compositions of EC:PC and Temperatures The Average Conductivity of PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / PC / DMC Electrolytes at Various Compositions of PC:DMC and Temperatures The Activation Energy, Ea for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolytes The Activation Energy, Ea for PMMA / ENR 50 Blend/ LiN(CF 3 SO 2 ) 2 / DMC Electrolytes The Activation Energy, Ea for PMMA / ENR 50 Blend/ LiN(CF 3 SO 2 ) 2 / EC Electrolytes The Activation Energy, Ea for PMMA / ENR 50 Blend/ LiN(CF 3 SO 2 ) 2 / EC / DMC Electrolytes Conductivity Relaxation Times For Various Concentration of LiN(CF 3 SO 2 ) 2 Salt in PMMA / ENR 50 Blend at Room Temperature Conductivity Relaxation Times For Various Concentration of LiN(CF 3 SO 2 ) 2 Salt in PMMA / ENR 50 Blend at Different Temperatures Conductivity Relaxation Times For Various Concentration of EC and DMC Plasticizer in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 at Room Temperature Conductivity Relaxation Times For EC Plasticized in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 at Elevated Temperature

22 xxiii Conductivity Relaxation Times For Various Concentration of Mix Plasticizer in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 at Elevated Temperature The Fitted Values for the Equivalent Circuit for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolyte The Fitted Values for the Equivalent Circuit for Plasticized PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolyte

23 xxiv LIST OF FIGURES FIGURE NO. TITLE PAGE 2.1 Structure of PMMA Free Radical Vinyl Polymerization of Methyl Methacrylate 1,4 cis-polyisoprene Structure of ENR 50 Structure of Crystalline PEO-NaClO 4 Schematic Representation of Polymer Spherullite DSC Scans for Pure PMAAM-co-PMMA Copolymers DSC Curve for ABS / PMMA Blend Based Electrolytes Electron Micrograph of Polymer Electrolytes Based on PVC / PMMA Surface Morphology of ENR 50 FTIR plots for PVC / PMMA / LiBF 4 / DBP Complexes Complex Impedance Plot of a Typical Polymer Electrolyte Complex Impedance Plot in Li/P(VDF-HFP)-g-PMMA Impedance Plots of Salt-Doped Modified Natural Rubber Based Gel Electrolytes Impedance Plot of PMMA-PVdF-LiCF 3 SO 3 -DMP Complex Impedance Plot and its Respective admittance Plot Complex Impedance Plot at Various Temperature Cation Transport Mechanism in PEO-Based Polymer Electrolyte

24 xxv (a) 2.22 (b) 2.22 (c) 2.23 (a) 2.23 (b) Log of σ vs. 1000/T that Obeys Arrhenius Equation in PMMA / LiN(CF 3 SO 2 ) 2 / EC / PC Systems Log of σ vs. 1000/T that Obeys VTF Equation in PVC / PMMA / LiAsF 6 / DBP Systems The Master Curve of the WLF Plots of Ionic Conductivity for Various PEO-Alkali Metal Salt Complexes The Vacancy mechanism The Interstitial Mechanism The Interstitialcy Mechanism Cationic Motion in Polymer Electrolyte Assisted by Polymer Chain Motion Cationic Motion in Polymer Electrolyte by Contribution of Ionic Cluster Dispersion of the (a) Real and (b) Imaginary Part of Dielectric for Chitosan Doped with Different Amounts of Lithium Acetate Dispersion of the (a) Real and (b) Imaginary Part of Electrical Modulus for Chitosan Doped with Different Amounts of Lithium Acetate Complex Impedance Plots and Their Respective Equivalent Circuit Equivalent Circuit Consisting of R and Q Equivalent Circuit Consisting of R, C and W Cole-Cole Plot that Contain W Element The Schematic Diagram of the Electrochemical Process in a Rocking Chair Lithium Battery A Typical Current Voltage Curve with Superimposed Cell Power as a Function of Load Current Schematic Diagram in DSC Technique Schematic DSC Plot Diagram Determination of τ from the Plot of Electrical Modulus, (M) Versus Log Frequency (f)

25 xxvi Experimental Arrangements for Measuring Ionic Transference Number by d.c Polarization Technique Normalized Current vs. Time Plot The (a) Aerial and (b) Cross-Section View of the Fabricated Cell Distribution of ENR 50 in PMMA Matrix Possible Hydrogen Bonds Between PMMA and ENR 50 Hydrogen Bonding in (a) PMMA and (b) ENR 50 Chains FESEM Micrograph for Pure PMMA FESEM Micrograph for Pure ENR 50 FESEM Micrograph for PMMA Blend with (a) 10%, (b) 20%, (c) 30%, (d) 40% and (e) 50% ENR 50 DSC Scans for (a) Pure PMMA and (b) Pure ENR 50 DSC Scans for (a) 10% ENR 50 blend and (b) 50% ENR 50 blend FTIR Spectra for (a) Pure PMMA and (b) Pure ENR 50 FTIR Spectra for (a) 10% and (b) 50% ENR 50 blend Cole-Cole Plots for (a) Pure PMMA and (b) Pure ENR 50 Films The Effect of ENR 50 on the Conductivity of PMMA / ENR 50 Blends Cole-Cole Plot for 10% ENR 50 Blend Film at Room Temperature FESEM Micrograph of 10% ENR 50 Blend Doped with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of LiNO 3 Salt FESEM Micrograph of 20% ENR 50 Blend Doped with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of LiNO 3 Salt FESEM Micrograph for Doped LiNO 3 in 10% ENR 50 Blend when Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of DMC FESEM Micrograph for Doped LiNO 3 in 20% ENR 50 Blend when Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of DMC

26 xxvii The IR Spectrum for Pure LiNO 3 Salt FTIR Spectra for (a) 10% and (b) 20% ENR 50 Blend Doped with 0.2 g LiNO 3 FTIR Spectra for (a) 10% and (b) 20% ENR 50 Blend Doped with 0.3 g LiNO 3 Polymer-Salt Complex at C=O and O-CH 3 Groups The IR Spectra for DMC Plasticizer FTIR Spectra for 0.2 g Doped LiNO 3 in (a) 10% and (b) 20% ENR 50 Plasticized with 0.3 g DMC Cole-Cole Plots for (a) PMMA, (b) ENR 50 and (c) PMMA / ENR 50 Blend Films Doped with 0.2 g of LiNO 3 Salt The Effect of LiNO 3 Salt on the Conductivity of PMMA / ENR 50 / LiNO 3 Films at Room Temperature Cole-Cole Plots for PMMA / ENR 50 / LiNO 3 Films Electrolyte when Plasticized with 0.2 g of DMC Plasticizer The Effect of DMC on the Conductivity of PMMA / ENR 50 / LiNO 3 / DMC Transport of Lithium Ion Along a Convoluted Path Illustration of Lithium Ion Trapped in ENR 50 Coil Cole-Cole Plot for the Highest Conducting Sample of PMMA / ENR 50 / LiNO 3 : PE1N2 at Various Temperatures Plot ln (σ) Vs. 1000/T for Various Amount of LiNO 3 in PMMA / ENR 50 / LiNO 3 Electrolyte Cole-Cole Plot for PMMA / ENR 50 / LiNO 3 / DMC : PE1D1 at Various Temperatures Plot ln (σ) Vs. 1000/T for Various Amount of DMC in PMMA / ENR 50 / LiNO 3 / DMC electrolyte Dielectric Constant (ε r ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 electrolytes at Room Temperature

27 xxviii Dielectric Constant (ε r ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 : PE1N2 at Different Temperatures Dielectric Loss (ε i ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 electrolytes at Room Temperature Dielectric Loss (ε i ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 : PE1N2 at Different Temperatures (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 electrolytes at Room Temperature (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 : PE1N2 at Different Temperatures (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 / DMC at Room Temperature (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for the Highest Conducting Plasticized PMMA / ENR 50 / LiNO 3 : PE1ND1 at Different Temperatures (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 /DMC at Room Temperature (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiNO 3 / DMC : PE1ND1 at Different Temperatures The Fitting Conductivity Plot for the Highest Conducting PMMA / ENR 50 / LiNO 3 Electrolyte, PE1N2 The Equivalent Circuit for the Highest Conducting PMMA / ENR 50 / LiNO 3 Electrolyte, PE1N2 The Fitting Conductivity Plot for the Highest Conducting

28 xxix Plasticized PMMA / ENR 50 / LiNO 3 Electrolyte, PE1ND1 The Equivalent Circuit for the Highest Conducting Plasticized PMMA / ENR 50 / LiNO 3 Electrolyte, PE1ND1 ENR 50 Chains in PMMA phase (a) without Plasticizer and (b) With Plasticizer FESEM Micrograph of 10% ENR 50 Films Doped with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of LiCF 3 SO 3 Salt FESEM Micrograph of 20% ENR 50 Films Doped with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of LiCF 3 SO 3 Salt FESEM Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of DMC FESEM Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of DMC FESEM Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of EC FESEM Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of EC FESEM Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of PC FESEM Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of PC FESEM Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with EC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 FESEM Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with EC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 FESEM Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :

29 xxx FESEM Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 FESEM Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 FESEM Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 The FTIR Spectrum for LiCF 3 SO 3 Salt FTIR Spectra for 10% ENR 50 Blend when Doped with (a) 0.1 g and (b) 0.3 g of LiCF 3 SO 3 Polymer-Salt Complex in PMMA FTIR Spectra for 10% ENR 50 Blend when Plasticized with (a) 0.1 g and (b) 0.3 g of DMC The FTIR Spectra for EC Plasticizer FTIR Spectra for 10% ENR 50 Blend when Plasticized with (a) 0.1 g and (b) 0.3 g of EC The FTIR Spectra for PC Plasticizer FTIR Spectra for 10% ENR 50 Blend when Plasticized with (a) 0.1 g and (b) 0.3 g of PC FTIR Spectra for EC:DMC (0.2 g:0.1 g) System in (a)10% ENR 50 Blend and (b) 20% ENR 50 Blend FTIR Spectra for EC:PC (0.2 g:0.1 g) System in (a)10% ENR 50 Blend and (b) 20% ENR 50 Blend FTIR Spectra for PC:DMC (0.2 g:0.1 g) System in (a)10% ENR 50 Blend and (b) 20% ENR 50 Blend DSC Scan for 10% ENR 50 Blend Doped with (a) 0.1 g and (b) 0.3 g LiCF 3 SO 3 Cole-Cole Plots for (a) PMMA, (b) ENR 50, (c) 10% ENR 50 Blend and (d) 20% ENR 50 Blend Films when Doped with 0.2 g of LiCF 3 SO 3 Salt The Effect of LiCF 3 SO 3 Addition in 10% and 20% ENR 50 Blend Illustration of Ion Transport in (a) Different Metal and (b) Un-homogeneous Films

30 xxxi Cole-Cole Plots for 0.2 g of LiCF 3 SO 3 Doped in 10% ENR 50 Films when Plasticized with 0.3 g of (a) DMC, (b) EC and (c) PC The Effect of (a) DMC and (b) EC Plasticizer in 10% ENR 50 Blend and (c) DMC and (d) EC Plasticizer in 20% ENR 50 Blend The Effect of PC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / PC Electrolytes Cole-Cole Plot for PMMA / ENR 50 / LiCF 3 SO 3 / EC / DMC (0.1 g:0.2 g) in (a) 10% and (b) 20% ENR 50 Blend Cole-Cole Plot for PMMA / ENR 50 / LiCF 3 SO 3 / EC / PC (0.1 g:0.2 g) in (a) 10% and (b) 20% ENR 50 Blend The Effect of EC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / EC/DMC Electrolytes The Effect of EC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / EC/PC Electrolytes Cole-Cole Plot for PMMA / ENR 50 / LiCF 3 SO 3 / PC / DMC (0.1 g:0.2 g) in (a) 10% and (b) 20% ENR 50 Blend Cole-Cole Plot for the Highest Conducting Sample of PMMA / ENR 50 / LiCF 3 SO 3 : PE1T3 at Elevated Temperature Arrhenius Plot for Different Amount of LiCF 3 SO 3 Dopant in PMMA / ENR 50 / LiCF 3 SO 3 Electrolyte Activation Energy Variations with LiCF 3 SO 3 in PMMA / ENR 50 Blend Impedance Plot for the Highest Conducting Sample of PMMA / ENR 50 / LiCF 3 SO 3 when Plasticized with 0.3 g of DMC at Elevated Temperature Arrhenius Plot for Different Amount of DMC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / DMC Electrolyte Activation Energy Variations with DMC Plasticizer in

31 xxxii PMMA / ENR 50 / LiCF 3 SO 3 / DMC Electrolyte Arrhenius Plot for Different Amount of EC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / EC Electrolyte Activation Energy Variations with EC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / EC Electrolyte Arrhenius Plot for Different Amount of PC Plasticizer in (a) 10% ENR 50 Blend and (b) 20% ENR 50 Blend Activation Energy Variations with PC Plasticizer in 10% ENR 50 Blend Arrhenius Plot for Different Amount of EC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / EC / DMC Electrolyte Activation Energy Variations with EC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / EC / DMC Electrolyte Arrhenius Plot for Different Amount of EC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / EC/ PC Electrolyte Arrhenius Plot for Different Amount of PC Plasticizer in PMMA / ENR 50 / LiCF 3 SO 3 / PC / DMC Electrolyte (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiCF 3 SO 3 at Room Temperature (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for the Highest Conducting Sample of PMMA / ENR 50 / LiCF 3 SO 3 : PE1T3 at Different Temperatures (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiCF 3 SO 3 at Room Temperature (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiCF 3 SO 3 : PE1T3 at Different Temperatures (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for Plasticized PMMA / ENR 50 / LiCF 3 SO 3 at Room Temperature

32 xxxiii Dielectric Constant (ε r ) Versus Log Frequency (log f) for the Highest Conducting Sample of PMMA / ENR 50 / LiCF 3 SO 3 plasticized with (a) DMC: PE2TD3; (b) EC: PE2TE3 and (c) PC: PE1TP2 at elevated Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for Various Concentration of (a) DMC, (b) EC and (c) PC in PMMA / ENR 50 / LiCF 3 SO 3 Electrolyte at Room Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for the Highest Conducting Sample of PMMA / ENR 50 / LiCF 3 SO 3 Plasticized with (a) DMC: PE2TD3, (b) EC:PE2TE3 and (c) PC:PE1TP2 at Elevated Temperature (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for mix plasticized PMMA / ENR 50 / LiCF 3 SO 3 at Room Temperature Dielectric Constant (ε r ) Versus Log Frequency (log f) for (a) PE1TE2D1, (b) PE1TE1P2 and (c) PE1TP1D2 at Elevated Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for Various Concentration of (a) EC:DMC, (b) EC:PC and (c) PC:DMC in PMMA / ENR 50 / LiCF 3 SO 3 Electrolyte at Room Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for (a) PE1TE2D1, (b) PE1TE1P2 and (c) PE1TP1D2 at Elevated Temperature Normalized Current Versus Time Plot for (a) PE1T3, (b) PE1TP2 and (c) PE1TE2D1 (a) The Fitting Conductivity Plot and (b) The Equivalent Circuit for PE1T3 (a) The Fitting Conductivity Plot and (b) The Equivalent Circuit for PE1TP2 (a) The Fitting Conductivity Plot and (b) The Equivalent

33 xxxiv Circuit for PE1TE2D1 The Charging Curve for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / MCMB Cell at 10 ma Charging Current The Charging Capacity Curve for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / MCMB Cell at 10 ma Charging Current The Discharge Curve for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / MCMB Cell at 10 ma The Discharge Rate for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / MCMB Cell at 10 ma The Charging Curve for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / PC / MCMB Cell at 10 ma Charging Current during (a) 1 st Cycle and (b) 2 nd Cycle The OCV Versus Time Plot for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / PC / MCMB Cell The Charging Curve for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / EC / DMC / MCMB Cell at 10 ma Charging Current The Charging Capacity Curve for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 /EC / DMC / MCMB Cell at 10 ma Charging Current The Discharge Curve for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / EC / DMC / MCMB Cell at 10 ma The Discharge Rate for LiNiCoO 2 / PMMA / ENR 50 / LiCF 3 SO 3 / EC / DMC / MCMB Cell at 10 ma Optical Micrograph for (a) Pure PMMA and (b) Pure ENR 50 Films Optical Micrograph for (a) 10% ENR 50 Blend and (b) 20% ENR 50 Blend Films Optical Micrographs for 10% ENR 50 Blend Films Doped with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of LiN(CF 3 SO 2 ) 2 Optical Micrographs for 20% ENR 50 Blend Films

34 xxxv Doped with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of LiN(CF 3 SO 2 ) 2 Optical Micrographs for 10% ENR 50 Blend Films Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of DMC Optical Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of DMC Optical Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of EC Optical Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of EC Optical Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of PC Optical Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of PC Optical Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with EC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 Optical Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with EC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 Optical Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 Optical Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 Optical Micrographs for 10% ENR 50 Blend Electrolytes Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 Optical Micrographs for 20% ENR 50 Blend Electrolytes Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1 The FTIR Spectrum for LiN(CF 3 SO 2 ) 2 Salt FTIR Spectra for 10% ENR 50 Blend when Doped with (a) 0.1 g and (b) 0.3 g of LiN(CF 3 SO 2 )

35 xxxvi Polymer-Salt Complex in PMMA FTIR Spectra for 10% ENR 50 Blend when Plasticized with (a) 0.1 g and (b) 0.3 g of DMC FTIR Spectra for 20% ENR 50 Blend when Plasticized with (a) 0.1 g and (b) 0.3 g of DMC FTIR Spectra for 10% ENR 50 Blend when Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of EC FTIR Spectra for 20% ENR 50 Blend when Plasticized with (a) 0.1 g and (b) 0.3 g of EC FTIR Spectra for 10% ENR 50 Blend when Plasticized with (a) 0.1 g, (b) 0.2 g and (c) 0.3 g of PC Proposed Interaction Between PC-Salt Complex Via Hydrogen Bonding FTIR Spectra for 10% ENR 50 Blend when Plasticized with EC:DMC (a) 0.1 g: 0.2 g and (b) 0.2 g:0.1 g FTIR Spectra for 20% ENR 50 Blend when Plasticized with EC:DMC (a) 0.1 g: 0.2 g and (b) 0.2 g:0.1 g FTIR Spectra for EC:PC (0.1 g:0.2 g) System in (a)10% ENR 50 Blend and (b) 20% ENR 50 Blend FTIR Spectra for 10% ENR 50 Blend Electrolyte when Plasticized with PC:DMC (a) 0.1 g: 0.2 g and (b) 0.2 g:0.1 g Cole-Cole Plots for (a) PMMA, (b) ENR 50, (c) 10% ENR 50 Blend and (d) 20% ENR 50 Blend Films when Doped with 0.2 g of LiN(CF 3 SO 2 ) 2 Salt The Effect of LiN(CF 3 SO 2 ) 2 Addition in 10% and 20% ENR 50 Blend Cole-Cole Plots for 0.2 g of LiN(CF 3 SO 2 ) 2 Doped in 10% ENR 50 Blend Films when Plasticized with 0.3 g of (a) DMC, (b) EC and (c) PC The Effect of Plasticizers in (a) 10% ENR 50 Blend and (b) 20% ENR 50 Blend when Doped with LiN(CF 3 SO 2 ) 2 Salt

36 xxxvii The Cole-Cole Plots for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 plasticized with (0.1 g:0.2 g) (a) EC / DMC, (b) EC / PC and (c) PC / DMC in 10% ENR 50 Blend Arrhenius Plot for Different Amount of LiN(CF 3 SO 2 ) 2 Dopant in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolyte Plot ln (σ) Vs. 1000/T for Different Amount of (a) DMC, (b) EC and (c) PC Plasticizer in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolyte Arrhenius Plot for Different Amount of EC Plasticizer in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / EC / DMC Electrolyte Arrhenius Plot for Different Amount of EC Plasticizer in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / EC / PC Electrolyte Arrhenius Plot for Different Amount of PC Plasticizer in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 / PC / DMC Electrolyte (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolytes at Room Temperature (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for the Highest Conducting Sample of PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 : PE2I3 at Different Temperatures (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolytes at Room Temperature (a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical Modulus Versus Log Frequency (log f) for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 : PE2I3 at Different Temperatures (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for Plasticized PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 at Room Temperature The Dielectric Constant (ε r ) Versus Log Frequency (log f)

37 xxxviii for the Highest Conducting Sample of Plasticized PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 with (a) DMC:PE2ID3, (b) EC: PE2IE1 and (c) PC:PE1IP2 at Elevated Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for Various Concentration of (a) DMC, (b) EC and (c) PC in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolyte at Room Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for (a) DMC:PE2ID3, (b) EC:PE2IE1 and (c) PC:PE1IP2 in Plasticized PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 at Elevated Temperature (a) Dielectric Constant (ε r ) and (b) Dielectric Loss (ε i ) Versus Log Frequency (log f) for Mix Plasticized PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 at Room Temperature The Dielectric Constant (ε r ) Versus Log Frequency (log f) for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 plasticized with (a) EC / DMC : PE1IE2D1, (b) EC / PC : PE1IE2P1 and (c) PC / DMC : PE1IP2D1 at Elevated Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for Various Concentration of (a) EC:DMC, (b) EC:PC and (c) PC:DMC in PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Electrolyte at Room Temperature The Imaginary Part of Electrical Modulus (Mi) Versus Log Frequency (log f) for PMMA / ENR 50 / LiN(CF 3 SO 2 ) 2 Plasticized with (a) EC/DMC : PE1IE2D1, (b) EC/PC : PE1IE2P1 and (c) PC/DMC : PE1IP2D1 at Elevated Temperature (a) The Fitting Conductivity Plot and (b) The Equivalent Circuit for PE2I3 (a) The Fitting Conductivity Plot and (b) The Equivalent Circuit for PE2IE3 (a) The Fitting Conductivity Plot and (b) The Equivalent Circuit for PE1IE2D