A FLEXIBLE EPOXIDIZED 30% POLY(METHYL METHACRYLATE)-GRAFTED-NATURAL RUBBER POLYMER ELECTROLYTES FOR SUPERCAPACITOR

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A FLEXIBLE EPOXIDIZED 30% POLY(METHYL METHACRYLATE)-GRAFTED-NATURAL RUBBER POLYMER ELECTROLYTES FOR SUPERCAPACITOR

International Malaysia-Indonesia-Thailand ath Symposium on Innovation and Creativity sic 'EMBRACING INNOVATION AND CREATIVITY IN INDUSTRIAL REVOLUTIONS"

International Malaysia-Indonesia-Thailand ath Symposium on Innovation and Creativity sic 'EMBRACING INNOVATION AND CREATIVITY IN INDUSTRIAL REVOLUTIONS"

International Malaysia-Indonesia-Thailand ath Symposium on Innovation and Creativity sic 2021 'EMBRACING INNOVATION AND CREATIVITY IN INDUSTRIAL REVOLUTIONS

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TEAM MEMBERS

DR. KHUZAIMAH NAZIR DR. NABILAH AKEMAL MUHD ZAILANI DR. FAIEZAH HASHIM MRS. SHARIFAH NAFISAH SYED ISMAIL PROF. DR. AB MALIK MARWAN ALI

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POSSIBLE NEW INVOLVING 787 Worldwide. . First in Business Worldwide. - First in Business

https://www.cnbc.com/2013/01/08/boeing-traces-source-of-dreamliner-fire-another-787-has-problems.html

https://www.cnbc.com/2013/01/08/boeing-traces-source-of-dreamliner-fire-another-787-has-problems.html

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BOEING (BA) 75.26 A 0.92 76.5 75.0 73.5 n.o 70.5 16 Noon OO Noon 2 no NASDAQ 6 00 ALL DREAMLINERS GROUNDED 3,136 no First in Business Worldwide. First in Business World'- s Worldwide. . 0 00:10 1 04:54

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JANUARY '6.2019 FAA INVESTIGATING SIMILARITIES BETWEEN 787 BATTERIES THAT FAILED onw • fla 79 13.596 02

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BATTERIES AT THE HEART OF THE CRISIS Ektrc*yte the . Batteries can hig n•mmabte if it teaks arvi IS o A ti01ium tire can burn at up to - three US safety say thet to critkal systerns an structures. and tin s used to start he time hotter than meltir•o mint cd tho Drearr.lfrHs at 343C.

Japan Air grounds Boeing 787 after battery problem A airport worker drives a luggage transport vehicle past one ot tne company's Boeing CO's 781 Dreamliner plane (L) and a Beotng 761 at Narita international airport in Nanta. east of Tokyo. November II. 2013 REUTERS/Toru Hanai

Culprit: The Boeing 78Ts lithium battery can self heat as a resu It of temperature and pressure changes. Which may have caused this battery fire on a Dreamliner at Logan Airport. Boston on January 7

Boeing's Dreamliner batteries "inherently unsafe"—and yours may be too popular lithium-ion batteries have all it takes to create a firebomb. SEAN GALLAGHER 1/19/2013, 3:20 AM 787

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HP expands laptop battery recall due to fire and burn hazards 78,500 laptop batteries are to be recalled after eight new reports of battery packs overheating, melting, or charring. BY Campbell Kwan I March 14, 2019 - 01:34 GMT (09:34 SGT) I Topic: e in a f Hardware HP expands Take your ideas to new places.

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Business Samsung phone catches fire on Southwest plane Device was Galaxy Note 7, powered down and previously repaired after recall, report says cac News , 05, 2016 1141 AMET I Last Updated: October 6, 2016

Samsung Galaxy S6 Explodes on a Plane, Fills the Cabin with Smoke December 9, 2016 By: Bogdan Popa The Samsung Galaxy Note 7 is generally referred to as "the phone that explodes," but in the last few months, we've seen many other devices catching fire, including here Apple's iPhones and other Samsung models. It goes without saying that the bigger the number of exploding phones, the more worrying the whole thing gets, and today Samsung's getting all the attention. Again. With a different phone. A Samsung Galaxy S6 exploded onboard a China Airlines flight earlier this month, filling the cabin with smoke and causing injuries to the man who was holding it. The flight, identified as C1027, was heading to Taipei, when a Galaxy S6 burst into flames, leading to small burns to the owner, who quickly threw it to the ground. Flight attendants managed to stop the fire quite quickly, and nobody else was injured, but the cabin was filled with smoke, which obviously can't make you feel safe, especially mid-flight.

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YET ANOTHER LITHIUM BATTERY FIRE REPORTED IN FATAL TESLA CAR CRASH HOME LATEST NEWS r IRE REPORTED IN April 23, 2021: Reports of a fatal Tesla car crash that took place in Texas on April 17 say firefighters took more than four hours and 30,000 gallons of water to put out a fire caused by the lithium battery continually re-igniting.

Tesla Battery Explodes and Burns Car to a Crisp Aug 18. 2016

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WHY ALL OF THAT INCIDENTS HAPPENED?

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Leaking of LIQUID ELECTROLYTES Liquid electrolytes (LEs) = inorganic salts + low molecular weight organic solvent ADVANTAGE exhibit better ionic conductivity DISADVANTAGE highly flammable. prone to leakage from sealant can ignite or even explode when exposed to the high temperature.

LIQUID ELECTROLYTES

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WHAT WE NEED TO PROVIDE A SAFE ELECTROLYTE?

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By virtue of that incidents, the development of POLYMER ELECTROLYTES (PEs) can provide a safer way. Unlike LEs, POLYMERS do not vaporize and they decomposed at higher temperatures.

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WHAT IS POLYMER?

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polymers.bmp

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WHAT IS POLYMER ELECTROLYTES?

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PEs can be referred to any macromolecular or supramolecular nanoaggregate system characterized by a significant ionic conductivity . PEs usually acts as : separator to separate two electrodes providing excellent electronic insulation allow transport of the desired ions for energy devices.

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COMMERCIALIZATION POTENTIAL

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.10)pedto.10dns

Fuel Cell

Dye sensitize solar cell

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TYPES OF POLYMER ELECTROLYTES

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TYPES OF POLYMER ELECTROLYTES

Gel Polymer Electrolytes (GPEs)

Polymer Host + Salt

Solid Polymer Electrolytes (SPEs)

Composite Polymer Electrolytes (CPEs)

Polymer Host + Salt + Plasticizer

Polymer Host + Salt + Filler

Promising Characteristics of electolytes

Characteristic Solid Gel Liquid Ionic conductivity ( σ ) at 25 0 C (S.cm -1 ) ~10 -5 ~10 -3 - 10 -2 ~10 -3 - 10 -2 Solution leakage None None Yes Fabrication Easy Easy Difficult Discharge rate Small High High Mechanical strength Good Intermediate Low Electrode contact Poor Good Good

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POLYMER HOST

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To date, a numbers of polymers have been proposed as matrices in PEs such as : PEO PAN PVA PVC PVdF PVdF -HFP PMMA

Among them, PMMA has attracted many researchers due to its advantages

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GPE BASED ON POLY(METHYLMETHACRYLATE) (PMMA)

However

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GPE BASED ON 30% PMMA-GRAFTED NATURAL RUBBER (MG30)

Structure of MG30

However

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Epoxidation reaction

Synthesis of epoxidized MG30 by performic acid epoxidation method

OUR INNOVATION

Ctnlhe &ide (OCI) HrDROGfN Ethglerpglgcol tG)

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OBJECTIVES

To formulate the modification of MG30 with performic epoxidation method in order to decrease the C=C degradation effect of polymer host in polymer electrolyte system To improve the ionic conductivity of polymer electrolyte by by introducing EMG30 incorporating lithium tri( fluoro methanesulfonate ) (LiCF 3 SO 3 ) and ethylene carbonate (EC). To evaluate the performance of fabricated energy device (supercapacitor) using the highest conducting GPEs based on EMG30.

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ADVANTAGES OF LITHIUM TRIFLUOROMETHANESULFONATE (LiCF 3 SO 3 )

Molecular structure Advantages of LiCF 3 CO 3 : Very stable, Easy to dissociate, Delocalization of charge, Small radii

ADVANTAGES OF ETHYLENE CARBONATE

Molecular structure Advantages of EC : high dielectric constant (89.6) low viscosity (1.90 Cp ) able to dissolve inorganic salts by containing polar group increase the flexibility of polymer chain

o o

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HOW TO MAKE IT?

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METHODOLOGY

PHASE 1 Synthesis and characterization of EMG30 polymer host using performic epoxidation method

PHASE 2 Preparation and characterization of GPEs based EMG30 by using solution casting method (EMG30+LiCF 3 SO 3 +EC)

PHASE 3 Fabrication and characterization of energy device (supercapacitor) cell

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OUR FINDINGS

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Figure 1: 1 HNMR spectrum of a) MG30 and b) EMG30 .

Sample MG30 (g) Time of Reaction (hours) Formic acid Content (mol) Hydrogen Peroxide content (mol) Mol Epoxide Content (%) S1 1.0 6 0.25 0.75 54.6 S2 1.0 9 0.25 0.75 62.3 S3 1.0 12 0.25 0.75 50.0

NOVELTY 1

Appearance of new peak C-O-C

C=C bonds were reduced

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NOVELTY 2

GPEs based on EMG30 show the highest ionic conductivity 4.83x10 -3 S cm -1 at room temperature.

Figure 2. Room temperature conductivity of EMG30-LiCF 3 SO 3 electrolyte a function of LiCF 3 SO 3 concentration.

6.00E-03 5.00E-03 4.00E-03 2.00E-03 0.4 EC content (wt.%) 0.5

Figure 3. Room temperature conductivity of EMG30-LiCF 3 SO 3 +EC electrolytes

EMG30 polymer electrolytes show ONE order higher than MG30 polymer electrolytes

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NOVELTY 3

Figure 6 : (a) Cyclic voltammograms and (b) Discharge capacitance of highest conducting sample

Figure 6 : (a) Cyclic voltammograms and (b) Discharge capacitance of highest conducting sample.

Exhibit ideal box-like shape → capacitance characteristic Specific capacitance, C s = 0.470 F/g The results is higher compared to the work by Pandey et al. (2011), C s =2.6 x 10 -3 F/g [3]

Exhibit ideal box-like shape → capacitance characteristic Specific capacitance, C s = 0.470 F/g The results is 3 times higher compared to the work by Pandey et al. (2011), C s =2.6 x 10 -3 F/g [3]

Stable ≥ 100 cycles Energy density = 9.71 Wh /kg Power density = 7.49 W/kg

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PERFORMANCE OF ENERGY DEVICE (SUPERCAPACITOR CELL)

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Capacitor 105 105 104 103 102 10 10•2 Super- capacitor 10 EMC,30- LiCF3S03- EC cell Battenes Fuel Cells 102 103 Energy density (Wh/kg)

Achieve minimum requirement for energy storage devices [4]

Achieve minimum requirement for energy storage devices [4]

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PUBLICATIONS

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Effect Of Ethylene Carbonate (EC) Plasticizer on Epoxidized 30% Poly(Methyl Methacrylate)-Grafted Natural Based Polymer Electrolytes for Lithium Batteries Khuaaimah Sharifah Natisah Syed Ismaill•b'. Nabilah Akemal Muhd Zailanil'", Muhd Zu Azhan Yahya2•a and Ab Malik Marwan 'Faulty Peris Ken •Faculo• SKA' fa&ufiøh'g u im •alumy ' 'rubi my Abstrx•t. A gd 62_3 mom of mom of Is l.K-F:SOt1s .•åylere as pbsti.•izer 'resured by tanpcat're d.era•nce of ccnildiviy of tc Folyrner films is obscv.•d resub. In samples. Olitiing of tic "C—O» rno•lc of EC can EC and ccwdnati•n of l. i' on re. Li'l.i• subihty of wih oxiditi«n at tu• V of c-clb_ INTRODUCTION for to ekx-t-o•k• corixt; howeva. trey Is I init.•d o 111_ solid main foals of o f mcQunicalsubility liluid than •Eno* all CRI of plym.•t whidl e.• solvem retired in toa at which tie qlt is tie a&liticn of a Plymer [SJ_ GPLs arc bawccn ckxtnb'L•s solver •fra•

(K. Nazir et al., 2021)

Effect of ethylene carbonate (EC) plasticizer on epoxidized 30% poly(methyl methacrylate)-grafted natural based polymer electrolytes for lithium batteries Alp you MAY BE The •ff«ts Of tirn• on crosslink dersitv EPON waste/ S-c•wninq or "ua waste subst•at. 'ot tMFCl 233Z (2021b Synthesis and chatactetiutön et bw cost act".t" carbon •i" rind AD 233Z Webinar to Characterize Magnetic Vatenala Girg CRYOGENIC AIP

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Interrutional Jotrnal of Engineering & src Conductivity Studies of Epoxidized PMMA Grafted Natural Rubber I)01Rd Lithium Triflate Gel Polymer Electrolytes Muhd Zu Y*ya• , AbMAA A E A 0162.3 Of 1. IntroåJction 01 to 10 91 _ a of a of nun• 110-191 201 oi MG*O auS,• to •-10' S to & of (C —C I i• (22. Oi Of MG*O oi by '1&•••

Preparation and Characterization of Epoxidized.30% Poly(methyl Natural Rubber Polymer Electrolyte Khuzaimah Siti Fadzilah Aytb2*, Ahmad Fairoz Aziza-a, Ab Mdik Marmn Ali'•b, Muhd Zu Azhan Yahya'g •Faajny of MARA. 40450 Nam. Selmv, md Devices. MARA 40150 9.ah Ram. Selmp. I-Jriv«såi Wlaysia, 57aX) Way-sia my Juw 17.2013; Jury 18.2013; Avil 15, 20141 paymer Aistract. In this study. a freestanding thin film cotnposcd of lithium trinatc (LiTf) (30-40 polyoncthyl nx•ll.acrylalcbgrancd natural rubber W.M(i30) 54.6, 62.3 mol uv•rc prcparcd by a solvout casi texhnQuc. Thc EMG30 wcrc fou.xl irxrcasc tbc ioni• corunx•tivity of EMGNO-LiTf by ooc or&r of maynitLÄK• compared to MGYO-LiTf. Tbc highest ionic conductivity achieved was at When •10 Wt.% Of I-ill salts were introchx•cd into 62,3 % EMGYO. ionic corxiuction mechanisms in EMGJO. LiTf electrolytes obey Arlbcnius rule in which ion materiab is thermally Introd uction Polymcr clcctrolytcs (PEsi havc sparked attention to tbc 'X..ibility of application in a variety of elcctrocbcmical II perfonnancv• of fundamentally With tlk• sclN•tion Of The Of host contain a functional group with any of tbcsc heteroatom (N. O. S. or attached in d.cir stnxture, Tbcsc betcroatoms commonly a lonc pairs of electron acts as TIX is able to a With to form first polymer is polyethylene ox by claints that PEO with alkali metal salts was fonncd cvmplexcd and demonstrated significant i4Miic conductivity for possibk• application a. battery clcctrolylcs. Apparently. PEO possess ionic conductivity but it crystallize With age. Will bc hindered ionic corkiuctivily ISI Since tbcn many rcscarch has b.vn gcarcd to tind a suitable hosts to substitute PEO. To dmc. several types of polymer been devclopcd and charactcrizcd methyl 161, (PAN) 17 poly Vinyl 181 and poly vinylidcoc fluoride (PVdEi 191. AnxMig ihcm, PMMA basc•d on gcl vx»lymcr electrolyte (GPE) rceciv.•d much attcntOn 1101. PMMA many advantages such as lightweight. chemical resistance has an oxygen atom in tlK•ir I I II. PMMA side chain MMA monomer has a polar functional group that has a high atYUüty to cation ransporl. nuin drawtucks of PMMA arc its nw•chanical properties. Latif al. rcpored that modifying PMMA With rubber Was improved mechanical property but tik• film was to phasc sq»aration observations 1 121 Mudy on moditicd PMMA with NR has by Otlk•r and that PMMA — grancd.NR could improved nx•ch.nical propcnics problems poly (mclhyl nw•lhacrylatci-grancd NR a good criterion to act a polymer by having Of a pair electron, iuvc a low glass transition temperature of -62 X, soft elastomer diaracterization at nx,.m tanpøaturc good elasticity 1161, can result in flat, free-slaruiing, thin

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Ionic Conductivity Studies of Epoxidind Poly (Methyl Methacrylate)-Grafted Natural Rubber Based Gel Polymer Electrolyte for Dye Sensitized Polymer Solar Cell K. Nazir' A.F. Aziz', M,Z.A.Yahya2. A.M,M. Ali ot MGIO by •10' S SO •t 01 01 "m 01 by INTRODUCTION by W 19 n fut tie 'Otulwtivity of Pl's ashicve 10' S etna a' rsom Of only of Armani 121 'to 'Etc. are mail 01' Sovral 01' as 'Silgm.•fiyl (PMMA'. poly(vnyl PVC'. PVDI". ability to Of MGI(wl.iX. Aliet (T,SO, of (121 t•q• •alo• prswrtk•s Oi rnaa• Of polyma Ali al (71 Vape' al (Sl arnhk•nt in Of • 10' • S • . of itnic c."'kK'wity atv •ill for 'us to

Preparation and Characterization Of Poly(methyl Natural Rubber Polymer Electrolyte Khuzairnah Nazir•t•, Siti Fadzilah AYLA/ A, Ahmad Fairoz Azizxa, Ab Mdik Marv-an Alit b, Muhd Zu Azhan Yahyalg md Dev•.ces, IJnW'di MARA, 4N50 Nam, pertiunm tess:nal Wiaysia, 57000 Ku•a Müysia my Ju•» 17.2013; reseed: Juw 18, 2013; 15. 20141 Keywords Paymer Atbtraet. tn this study. a freestanding thin film composed of lithium triflate (LiTf) 0040 Wt.%) polyObcthyl natural rubber I SO. 54.6, 62.3 mol were by a casi The E MGY() wcrc tbc ionk• conductivity of EMGJO.LiTf by of con•pued to MGYO.LiTf, Tbc highest ionic achieved was at temperature When 40 Of LOT f salts were introduced into 62.3 % EMGYO, ionic conduction in EMGJO. LiTf Oik•y in Which ion tbcsc is a"istgl, polymer electrolytes due to po«ibility Of application in a Variety of dcviccs II Tbc of fundamentally associated with tlK• of polymer of poly•mcr host should contain a With any Of heteroatom O, S, or attached in structure. commonly a 10rK• Of acts as is able to fonn a with tlK• cationsto form Tbc first polymcr host used is polycthylcoc oxide (PEO) by Fenton ct al, 141, authors' claims thal PEO with alkali metal salts was fonnAl «»mplcxcd and dcmonstratcd significant ionic coruluaivity for possibk appliaion as battery clcctrolyics. Appucntly, PEO possess ionic coruluaivity bun it oystallizcs with agc. The higbcr cry.tallinc 'k.main prcs.•nt will bc hindcrcd coruluaivily I Sl. Sirwx then many research has becn gcarcd to tind a suitable polymer hosts to substitute Ibe PEO. To datc. sc•.eral types of polymer hosts been dcvclopcd and characterizcd viz poly nwlhyl nu•d.acrylatc (PMMA) 161. poly actylo nirilc WAN) 171. poly vinyl chloride (PVC' 181 and vx»ly vinylidcoc tu»ridc (PVdE' 191. Anxsng them, PMMA bascd on gcl 'x.ly•mcr clcctrolyle rcccived much attcntk»n 1101. PMMA nuny advantagcs such as lightweight, chemical rcsistaocc and lus an oxygen atom in Ibeir structure II II. PMVtA Sidc chain MMA mommcr has a polar functional group that has a high affinity to olion tansporl. Ebwevcr, tbc nuin drautu.cks of PMMA arc its pcx»r nxchanical properties. Latif ct al. rcvored that nu»difying PMMA with natural rubbcr (NRj improved mechanical property but tbc blend film was to phasc sevar.øion observations 1 121 Study on nu»ditied PMMA with NR has been by Ksurukd that PMMA -grafted-NR could improved nx•chamical propcnics problcnb | poly (mcthyl nxlhacrylatci-grancd NR (MG)O) provides a criterion to act as a by Laving of oxygen mom a lonc pair electron. have a low glass transition tcmpcrature of 4-,2X, soft clastonw•r charx•tcriuion at tanpaature good elasticity 1161. These can result in flat, freestanding, thin

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Conductivity and thermal t»haviour of poly (methyl methErylate)-grafted natural rubl»r-lithiurn triflate bas«i solid polyrner electrolytes Khuzaimah Nazir Siti Fadzilah Ayubt. Ahmad Fairoz Aziz' , Rosnah Zakaria', Muhd Zu Azhan Yahya2, Ab Malk Marwm Ali3b of Univ«sdi MARA. AMSO 9uh Nam. , '.•Wapia 'Faa.jny SCWE• Tectn•ogy. Uniwrsiti Of Tekrdo• MARA, 404Ø yuh , Keywords Potgn« Ime c«mrttvdy, Ttvm• Abstract nin films of Oncihyl methacrylaiei.graned nah.ral ruHK•r (EMGU)) .bped with lithium trifbte I t.iTf) salt wcrc prepared by using thc solution.casting technique, Of doublc into cpoxidc group Of EMG*O by I IINMR ionic carried out tlx• highest Was to be at S at tcmpcrMurv• sample with al 60wt% EMGU): 40wt% LiTf. T bennai gravimetric analysis studies st»wcd 'Ton tbc addiion of lithium .alts into EMGJO has tbc 'Obility or Intri*luetion Recently. r»lymer electrolyte based on nuxliticd rubber has attracted attention due to clastomctric properties. Varina. natural rubber viz, ENR2 SO. ENR50. MG30 and MG-49 II •71 a polyma in attractive is fk•xiblc it Wills results excellent contact tx•twcen cl«trock• and clcctrolytc in batrrics system 181. Punbermorc. natural rubber low glass Vansition Emperaturc 10-600C 19-101 Mcxliticd natural with heteroatom O in tlu•ir structure can also act a. a r»lynaic solvent am' tlx• is to higtn•r State Of Among Of in Malaysia. natural rubber or M(i.U) is tix stulied for use as host in polymer I I II. MGJO 'bows a &awhack to its durability long•tcnn u•agc, thin film based on this from 'Wing low ity to cracked Of based up 10 10' S.•mo at room temperature insufficient for application in lithium rcviurgeablc which is need up to 10" S. cm' In order to enliarKx i»nic conductivity and elccmxlk•mical st*ility of tbc electrolyk•. epoxidized. MGM) or EMG3() has been intruILK*d. EMGU) has bc€•n used a. a 1*'lynEr since it has incrcasc a polar functional group in thc Sidc chain that sl»ws high affinity lithium ions, Tbc oxygen atom in a lithium to interaction between tlK• oxygen atoms lithium Of nwtal forms a arul generate B)lymcr-salt complexes. tn aJditOn. thc oxi"ion of (C-O.C) is tv•lic•,«• to reduce tbc aging effect by unstable cari»n radicals 'R) that is easily reacq with oxygen abm nuinly at temperature. 11K•reforc. a higher staå»ility of electrolyte baw•d on EMG.U) is cxpcctcd.