Structural and Morphological Studies of Nano Composite Polymer Gel Electrolyte having SiO2

VIVA-Tech International Journal for Research and Innovation Volume 1, Issue 4 (2021)
ISSN(Online): 2581-7280
VIVA Institute of Technology
9th
National Conference onRole of Engineers in Nation Building – 2021 (NCRENB-2021)
14
www.viva-technology.org/New/IJRI
Structural and Morphological Studies of Nano Composite
Polymer Gel Electrolyte having SiO2
Manju R. Mishra1
,S.k Tripathi2
1.Department of Humanities & Sciences, Viva Institute of Technology, Mumbai University, Maharashtra, , India
2.Department of Physics, Mahatma Gandhi Central University, Patna, India
Abstract: In today’s society, we stand before a change in energy scarcity. As our civilization grows, many
countries in thedeveloping world seek to have the standard of living that has been exclusive to a few nations, so
their arises a need in thedevelopment of technology that is compatible enough with the resources provided by
nature in order to have sustainabledevelopment to all class of the society. In order to overcomethe prevailing
challenges of huge energy crises in near future, there is an urgent need for the development of electrical
vehiclesor hybrid electrical vehicles with low CO2 emissions using renewable energy sources. In view of the
above, electrochemicalcapacitors can fulfil the requirements to some extent.Preparation of nano composite
polymer gel electrolyte is the best optional product to overcome these problems. When fillers are added or
dispersed to the polymer gel electrolyte, amorphous or porous nature of electrolyte increases which enhances
the liquid absorbing quality of polymer and helps in removing the drawbacks of polymer gel electrolytes such as
leakage, poor mechanical and thermal stability etc. In this work dispersion of SiO2 nano filler is done in the
[PVdF (HFP)-PC-Mg (ClO4)2] for the synthesis of nano composite PGE [PVdF (HFP)-PC-MgClO4- SiO2].
Optimization and characterization was carried out by using various techniques.
Keywords -Compatible, Electrochemical capacitor, Depletion, Renewable resources, sustainable
I. INTRODUCTION
Now a day’s rechargeable batteries and supercapacitors having different types of solid state electrolytes are
fabricated which are having different compositions, such as polymer blend electrolyte, polymer composite
electrolyte, polymer gel electrolyte, ionic liquid-base polymer gel electrolyte etc., Almost all the electrolytes
shows high conductivity equivalent to that of liquid electrolyte i.e. ~10-4
Scm-1
, but they deal with some serious
problems which restrict their suitability for practical objectives. Poor dimensional stability, less thermal stability
and low range of power window are some basic problems which has to be remove from these polymer
electrolytes to make it efficient for its use in modern age highly sensitive technical inventions for eg. Fuel cells,
Sensors, Electrochromic tool etc. [1-4]. Preparation of nano composite polymer gel electrolyte is the best
optional product to overcome these problems. Nano science is the new and emerging field which attracted the
attentions of global scientist and research fraternity because it is clear till now that nano size of the materials can
do the miracle in electrical as well as electronics field due to its exceptionally unique chemical, physical, and
mechanical properties such as: high interfacial energy, exceptionally large aspect ratios, high degree of disorder,
high ionic transport [5].When such fillers are added or dispersed to the polymer gel electrolyte, amorphous or
porous nature of electrolyte increases (to many fold as compared to normal composite electrolytes) which
enhances the liquid absorbing quality of polymer and helps in removing the drawbacks of polymer gel
electrolytes such as leakage, poor mechanical and thermal stability etc. [6-7].Type of nano filler which is used to
prepare the composite polymer gel electrolyte, contributes important part to modify structural configuration at
microscopic level for the electrolytic system which further enhances theproperties such as polarization,

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15
ionization and mobility of charge carriers, they have direct impact on ionic conduction and other phenomenon of
good polymer gel electrolyte.
In this paper dispersion of SiO2 nano filler is done in the [PVdF (HFP)-PC-Mg (ClO4)2] arrangement for the
synthesis of nano composite PGE [PVdF (HFP)-PC-MgClO4- SiO2]. Optimization and characterization of the
NCPGE having SiO2 was carried out by using various techniques.
2. METHODOLOGY
2.1 Synthesis and optimization of nano PGE
NCPG electrolytic complex was synthesised by the chemical combination of poly vinylidene fluoride-co-hexa
fluoro propylene as base polymer mixture, magnesium perchlorate Mg (ClO4)2 as salt, SiO2 (<50 nm) as nano
filler (all obtained from Sigma-Aldrich), Propylene carbonate (PC) as solvent and tetrahydrofuran (THF) as
volatile intermediate solvent. The nano composite polymer gel electrolyte PVdF (HFP)-PC-Mg (ClO4)2 - SiO2
has been developed by utilizing Standard “solution cast-techniques”. When nano particle of SiO2 filler was
added in polymer gel electrolyte, it enhances the porous and amorphous nature of the system which in turn,
increases the captivation capacity of liquified system and minimise the leakage problem of device. In the present
work nano particle of SiO2 is used as filler for optimized polymer gel electrolyte, [PVdF (HFP)-PC-Mg (ClO4)2]
to prepare nano composite polymer gel electrolyte [PVdF (HFP)-PC-Mg (ClO4)2- SiO2].[8-10] Hence the final
optimized composition for nano composite polymer gel electrolyte is [PVdF (HFP)] (15 wt %)-[{ PC-Mg
(ClO4)2} (0.3M)]-nano SiO2 (12wt %). ionic conductivity at this composition was determined as ~5.72x10-3
Scm-
1
.
2.2 Instrumentation used in the present studies
XRD impression of the synthesized material was explained with Bruker D8 Advance diffractometer with Cu-Kα
radiation over the Bragg angle (2θ) range of 10-60°. The scan rate was fixed at 5°/ min. The superficial texture
analysis was demonstrated by applying SEM technique (JEOL JXA - 8100 EPMA).Fourier transform infrared
(FTIR) spectral examinations of the polymeric systems were performed by Bruker vertex 70 spectrophotometer.
3. Results & Discussions
3.1 Structural and morphological properties
3.1.1 X- ray diffraction Studies
In the figure 1. plot (a) explains the XRD pattern of the Mg (ClO4)2 ionic salt which shows the predominant
peaks at 2θ = 13.0, 17.5, 21.1, 22.7, 26.2, 28.0, 31.3, 34.4, 43.7, 51.3 and 56.9, which shows the pure crystalline
nature of ionic salt. Figure 1(b). Signify the scattering pattern of polymer mixture peaks observed at 2θ = 18.4,
29.3, and 38.9 due to semi-crystalline nature having mixed characteristics of crystalline as well as amorphous
regions. Figure 1(c). shows the stage when liquid electrolyte is adsorb by polymer electrolyte PVdF(HFP)- PC
solution, we can clearly observed that some peaks of ~ 38.9 get disappeared, which was due to the increasing
amorphous nature of [PVdF(HFP)(15wt%)-{PC-Mg(ClO4)2}(0.3M)] PGE. Figure1 (d) shows the peaks, when
nano SiO2 filler was mixed with optimized gel polymer electrolytes, some diffraction of PVdF (HFP) at peaks
(~2θ = 29.3 and 38.9) are disappeared. This also confirms the complete interaction of filler and polymer gel
electrolyte resulting into homogeneous mixture of nano polymer gel electrolyte. This makes the system more
amorphous and flexible in nature, which is the cause of modification in ionic transportation. [11-12].
XRD method is helpful in calculating various structural parameters such as crystal size, scherrer length (l), d-
spacing, relative peak intensity of pure salt, pure polymers, PGE, NPGE. All these parameters are given in
tabular form:

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Fig: 1. XRD impression of : (a) Mg(ClO4)2 (b) PVdF(HFP) film (c) [PVdF(HFP)](15wt%)-[PC-
Mg(ClO4)2]{0.3M} polymeric system and its composite film with (d) 12wt% of SiO2
nanoparticles.
Table 1(a): X-ray diffraction data of pure Mg (ClO4)2, pure PVdF (HFP) film, [PVdF (HFP)]
(15wt %) - [PC-Mg (ClO4)2]{0.3M} polymer electrolytes and nano gel polymer electrolytes
Sample 2θ(deg) Θ D l(Aᵒ) Intensity
Mg(ClO4)2 13.0 6.5 6.76 0.17 100
Pure PVdF(HFP) 38.9 19.4 2.30 0.63 100
PGE 20.3 10.1 4.36 0.09 100
PGE-SiO2 (12wt%) 20.3 10.18 4.4 0.11 100
PGE-SiO2 (16wt%) 20.2 10.15 4.4 0.10 100
Table 1(b): Detail studies of XRD technique:
Sample 2θ (deg.) Θ D l((Aᵒ) Intensity
Mg(ClO4)2 13.0 6.5 6.76 0.17 100
26.2 13.1 3.39 1.09 38.4
31.3 15.6 2.85 1.02 28.2
34.4 17.2 2.59 1.03 16.2
43.7 21.8 2.06 0.78 9.8
Pure PVdF(HFP) 18.4 9.2 0.78 0.11 44.4
38.9 19.4 2.30 0.63 100
57.1 28.5 1.60 0.87 14.1
PGE 20.3 10.1 4.36 0.09 100
29.7 14.8 3.00 0.64 51.2
44.5 22.2 2.03 0.67 43.3

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PGE- SiO2 (12wt%) 20.3 10.18 4.4 0.11 100
PGE-SiO2 (16wt%) 20.2 10.15 4.4 0.10 100
3.1.2 Scanning electron microscopy studies
Fig.2.express the morphological arrangement of polymer electrolyte and nano polymer gel electrolyte at
microscopic level. For this purpose (SEM) scanning electron microscope is used which can show the high
resolution images that can give us the idea about atomic and molecular distribution throughout the system.
Figure 2(a) indicates the uniform distribution of small pores of polymer gel electrolyte which is attributed to the
random and irregular nature of the gel polymer electrolyte while figure 2 (b)& 2(c) indicate complete interaction
between polymer gel electrolyte and fillers, which are visible in the form of homogenous and uniform
distribution of small pores connected to the polymeric chain (at different magnifying levels) , due to which the
polymer gel electrolyte can able to adsorb more amount of liquid electrolyte which will result into two
advantages first due to this mechanism ionic conductivity increases and second the leakage tendency decreases.
(a) (b) (c)
Fig:2. SEM images of [PVdF (HFP)](15wt%)-[PC-Mg(ClO4)2]{0.3M}-SiO2(12wt%) polymer gel
electrolytes system with different magnification.
3.1.3 Fourier transform infrared spectroscopy studies
The internal microscopic and molecular structure of amorphous region, organic molecules and their interactions
with the functional groups in polymeric system, can be detected with the help of vibrational peaks of electrolytic
system, appearing in FTIR spectra. Figure 3 (a-e) shows the FTIR spectra for polymer (PVdF (HFP), [(PVdF-
HFP)-PC-Mg (ClO4)2 and optimized NCPG electrolytes with different wt. % of SiO2 as fillers.
Various absorption peaks are observed in the FTIR spectra which can be explained and assigned to different
characteristics vibration bands, functional groups and interactions of salt, plasticizer or solvent, polymer and
nano filler in the nano gel polymer electrolytes etc.
Figure (a) shows the plot of pure polymer (PVdF(HFP) in which many peaks can be seen at the wavenumber
3024 and 2984 /cm is on account of asymmetric and symmetric stretching vibration, indicates the crystalline as
well as amorphous nature of polymer, assigned by CH2. Fig: (b) The appearance of peak at wave number 1787,
874, 840, 758 and 490 cm-1
, corresponds to the presence of vinylidene group and appears due to the presence of
-CF=-CF2- group, assigned to the CH2 rocking of the vinylidene band, -CF2 shows asymmetric stretching, CH2
wagging vibration and CF2 scissoring vibration of the vinyl group, respectively , which explains that the
crystalline phase is present in the polymer. [13].
Fig:(c) Further, when liquid electrolytes was added to the polymer materials some new vibration peak are
observed at wave numbers 1631, 1553, 1484, 1389, 776, 711 and 627 cm-1
. The wavenumber 1631 and 1553/cm
was attributed to the C=O stretching vibration of plasticizer (PC). The wavenumber 1484 and 1389/ cmwas
assigned to bending vibration of -CH3 of plasticizer. The vibration peaks at wave number 776 and 711 cm-1
represents the C-Cl stretching vibration. The peak at wave number 627cm-1
is assigned to the vibration of ClO-
4
ions. The interaction vibration of ionic pairs between Mg and ClO-
4 is observed at the peak of wave number
1119 to 1078 cm-1
.

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The vibration peaks of 3024, 2984, 1787, 874, 840 and 490 cm-1
are shifted to 2993,
2926, 1792, 877, 838 and 476 /cm in the nano composite polymer gel electrolytes. The shuffling of peaks in the
IR spectra of PVdF (HFP)-PC-Mg(ClO4)2- SiO2, nano composite polymer gel electrolytes is due to the
homogeneous mixing and interaction of constituents in the complex system. Figure 3(d&e) shows the identical
pattern.
Fig:3. FTIR Spectral impression of: (a) Pure Mg(ClO4)2 (b) pure PVdF-HFP film (c)
[PVdF(HFP)](15wt%)-[PC-Mg(ClO4)2]{0.3M} polymer films containing SiO2 nanoparticles (d)
8wt% (e) 12wt%.
Table 2: Designation of specific FTIR zones of pure PVdF (HFP), gel polymer electrolytes with
different concentration filler in nano gel polymer electrolytes
Band
Assignment
(Cm-1)
PVdF(HFP) film [PVdF(HFP)-PC-Mg(ClO4)2 4wt%
SiO2
12wt%
SiO2
- 3406 3404 3396
CH2 Asym.
Stret.
3024 2989 2993 2986
CH2 Sym. Stret. 2984 2926 2926 2926
-CF=-CF2- 1787 1792 1787 1789
C=O stret. Vib. - 1631 1649 1631

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of plasticizer - 1553 1553
-CH3 bending
vib.
- 1484 1486 1486
- 1456 1456
CH2 group - 1389 1394 1384
1354 1360 1354
-CF2 Sym. Stret. - 1184 1179 1179
1119 1119 1119
1078 - -
1052 1046 1052
- - 950
CH2 Rocking
αPhase
874 878 877 877
CH2 Asym.
Stret & CF2
Asym. Stret. β
Phase
840 839 838 838
C-Cl Stret. - 776 781 780
CH2 wagging
vib.
758 - - -
C-Cl Stret. - 711 715 712
ClO-
4 - 627 626 627
CF2 scissoring
vib α Phase
490 481 476 480
IV Conclusion:
From the detail studies of various characterization technique, it was clear that the nano composite polymer gel
electrolyte [PVdF (HFP) (15%)-PC-Mg (ClO4)2(0.3M)-SiO2 (12wt %)] which was synthesised in present
chapter was efficient and compatible to the other electrolyte that are already in use for the fabrication of
electrochemical devices such as supercapacitors.
Illustrating all demonstrated data the summarised points can be written as:
✓ The “standard solution cast “procedure was capitalised for the preparation of electrolytic complex
system.
✓ The maximum value for ionic conduction of optimized nano composite polymer gel electrolyte was
calculated as 5.72 x10-3
Scm-1
at room temperature.
✓ The surface morphology and topography image has been obtained from scanning electron microscopy,
which shows the porous texture and hence supports the electrical conductivity throughout the polymeric
network.
✓ The FTIR method clearly gives the idea about complete homogeneous mixing of all the constituents’
electrolyte, polymer, and nano materials which results into the synthesis of nano composite polymer gel
electrolyte having very good flexibility as well as good mechanical stability.
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[2] Gray, F. M. (1991), Solution, Polymer&Electrolytes: Fundamentals and Technological Application, VCH
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K.
[5] Nagasubramanian, G., and Stefano, S. D. (1990), Journal. of Electrochemical Society., vol. 137, no. 12, pp.
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Structural and Morphological Studies of Nano Composite Polymer Gel Electrolyte having SiO2