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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 2021
'EMBRACING INNOVATION
AND CREATIVITY IN
INDUSTRIAL REVOLUTIONS

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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

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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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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.

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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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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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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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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)

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

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Synthesis of epoxidized MG30 by  performic acid  epoxidation method

Ctnlhe &ide (OCI)
HrDROGfN
Ethglerpglgcol tG)

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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

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

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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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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

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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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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]

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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•

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

Scene 39

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

Scene 40

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

Scene 41

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.

Scene 42

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

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

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