Electrochimica Acta 319 (2019) 753e765

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Lithium-polymer battery with ionic liquid tethered nanoparticles

incorporated P(VDF-HFP) nanocomposite gel polymer electrolyte
Pallab Bose, Debalina Deb, Subhratanu Bhattacharya*
Department of Physics, University of Kalyani, Kalyani, Nadia, 741235, West Bengal, India

a r t i c l e i n f o a b s t r a c t

Article history: We demonstrate the electrochemical performance of a lithium-polymer battery comprising P(VDF-HFP)
Received 25 March 2019 nanocomposite membrane based gel polymer electrolytes (GPE). The nanocomposite membranes are
Received in revised form prepared by incorporating ionic liquid functionalized ZnS nanoparticles on to P(VDF-HFP) copolymer.
1 July 2019
Soaking the membranes into lithium salt dissolved liquid organic solvents transform them into GPEs.
Accepted 3 July 2019
Increasing the nanoparticles content gradually improves the porosity and the solvent uptake capacity of
Available online 9 July 2019
the membrane. The optimized membrane with 64% porosity shows highest electrolyte uptake ability of
89% to form a flame-retardant GPE endowing a maximum ionic conductivity of 3.3 mS cm
1 at ambient
Keywords:
Lithium-polymer battery
temperature along with an excellent lithium ion transfer number of 0.62. The cell comprising the
P(VDF-HFP) optimized GPE with LiFePO4 cathode and Li metal anode shows outstanding electrochemical perfor-
Nanocomposite membranes mance at ambient temperature, delivering a discharge capacity of ~161 mAh/g at C/10 rate and able to
Gel polymer electrolyte retain its 89% after 50 cycles. The study suggests that conjoining ionic liquid tethered nanoparticles with
Safety insulating polymers provides a promising way to produce efficient active polymer membranes based
high-performance GPEs, enabling safer, high energy density, lithium-polymer batteries.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction promising electrolyte candidates due to their light weight and

The general issues with current lithium-ion battery (LIB) tech-
nology are their low energy density. Using lithium metal anode
comprising a remarkably high theoretical capacity of 3860 mAh g
1
and the lowest negative electrochemical potential (
3.040 V vs. the
standard hydrogen electrode) is an attractive way to increase en-
ergy density [1]. Electrolyte plays a critical role affecting the per-
formance of LIBs [2]. Traditionally used carbonated electrolytes
hinder the application of lithium metal in LIBs due to several safety
issues such as leakage, electrode corrosion, flammability and the
inevitable growth of lithium dendrite during repeated Li deposi-
tion/dissolution processes [3].
All solid-state batteries without using the liquid electrolytes
have several inherent advantages, namely complete suppression of
leakage and reduced flammability. They also allow for the imple-
mentation of advanced, high energy density, rechargeable battery
architectures comprising lithium metal as the anode. In this
concern, solid polymer electrolyte has long been appreciated as
* Corresponding author.
E-mail address: subhratanu1@gmail.com (S. Bhattacharya).
flexibility. However, poor ionic conductivity hinders the application
of polymer electrolytes.
The incorporation of ceramic nanoparticles, such as TiO2 [4],
SiO2 [5], Al2O3 [6], Fe2O3 [7], ZrO2 [8] etc. in polymer electrolytes
was shown to improve ionic conductivity, and mechanical and
electrochemical properties of the polymer electrolyte. The
improvement in ionic conductivity in composite electrolytes (CPEs)
with inert fillers has been ascribed to the plasticization effect of
nanoparticles, hindering crystallization in polymers.
Embedding ceramic garnet-type Li7La3Zr2O12 (LLZO) in cross-
linked polymer matrixes has been recently observed as a promising
strategy to improve the cyclability of the lithium metal batteries [9].
Another recently demonstrated solid polymer electrolyte loaded
with metal organic framework has also shown enhanced compat-
ibility with Li metal anode [10].
Gel polymer electrolyte (GPE) in a state between liquid and
solid, formed by immersing the polymer matrix membrane in the
liquid electrolyte, function as both electrolytes as well as separators
in a lithium battery [11]. GPEs are advantageous as compared to
solid polymer electrolytes as they possess the desirable properties
of a polymer, i.e. reduction in leakage, mechanical stability and
cohesiveness along with high ionic conductivity and diffusive

https://doi.org/10.1016/j.electacta.2019.07.013
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
754 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765
properties of liquid electrolytes. Additionally, as the liquid elec-
trolyte remains encapsulated in the polymer pores, GPEs can also
suppress the growth of dendritic Li in the electrolytes and thereby
minimise the thermal abuse conditions due to short-circuiting
[12e14].
Several GPEs based on various host polymer matrices such as
poly (ethylene oxide) (PEO) [15,16], poly (methyl methacrylate)
(PMMA) [17,18], polyacrylonitrile (PAN) [19,20] and poly (vinyli-
dene fluoride) (PVDF) [21,22] or its hexafluoropropylene copolymer
(P(VDF-HFP)) [16,23e28] have been developed. Among them, GPEs
based on P(VDF-HFP) membranes have attained extensive research
interest, owing to their better solvent trapping ability in presence of
amorphous hexafluoropropylene unit on the flexible backbone of
the crystalline PVDF [16,23e28].
To further improve the lithium ion transfer in GPEs various
strategies have been put forward, which include in situ polymeri-
zation method [15], crosslinking [29], co-polymerization [30] and
replacing the insulating polymer matrix with the ‘active’ one con-
taining either polar elements or ionic liquids within the skeleton
[27,31e34]. Among those methods, implementation of ‘active’
polymer matrix in GPEs is the most popular one as in that case the
matrix itself also contributes to the ion conductivity of the system.
Recent report has shown that room temperature ionic liquid added
cross linked active polymer matrix can be applicable as electrolyte
with high-energy cathode materials also [35].
Meanwhile, porous structures in polymer matrix plays an
important role in GPE because they are responsible for the uptake
of liquid electrolytes [24]. However, it is worthy to mention that too
large pores are detrimental for battery performance as they often
induce internal short circuit. Thus, ‘active’ polymer membrane
comprising regular sized porosity is ideal for GPEs and several
approaches such as breath-figure preparation method [24],
controlled phase inversion [36,37] and embedding inorganic
nanoparticles [38,39] and coating with other polymer matrices
have been carried out to obtain the same.
The study described in the manuscript deals with the prepara-
tion and optimization of a class of P(VDF-HFP) copolymer based
porous and ‘active’ nanocomposite membrane based GPEs for the
application as a separator as well as an electrolyte in lithium bat-
tery. The ‘active’ nanocomposite membranes were prepared by
blending the copolymer with ionic liquid functionalized nano-
particles, referred earlier as the nanoscale hybrid ionic fluid (NHIF)
[40e43]. In earlier reports of NHIFs, only ceramic or oxide nano-
particles were used as the core. In this study, a non-ceramic or non-
oxide core (ZnS) tethered NHIF material has been prepared and
used. ZnS nanoparticle is found to be equally efficient as that of
oxide nanoparticles to hold the ionic liquid chains at its surfaces.
The nanocomposite membranes thus formed, exhibit unique
porous architecture, and the porosity gradually increases with
increasing the extent of NHIF. These flame redundant GPEs are
optimized according to their solvent uptake capacity and ionic
conductivity. The best-conducting GPE shows and electrochemical
stability window of ~5.4 V vs (Li/Liþ) and considerably higher
lithium ion transference number. The GPE, when applied in a cell
with LiFePO4 cathode and lithium metal anode, shows outstanding
stability and rate capability as compared to pure P(VDF-HFP) based
GPE to establish itself as a safer electrolyte for high energy density
lithium batteries.
2. Experimental section
In this study, 1-methyl 3-propyl (trimethoxysilyl) imidazolium
bis(trifluoromethyl-sulfonyl)imide ([mpImSi(OMe)3][TFSI]) ionic
liquid chains are grafted to the surfaces of pre-synthesized ZnS
nanoparticles to prepared the ZnS-NHIF. The main advantage of
using the ZnS nanoparticles as the core is in the preparation
method. While the preparation of ceramic core nanoparticles such
as SiO2 or Al2O3 requires high-temperature sintering (1000  C),
ZnS nanoparticles can be synthesized by a simple wet chemical
technique with a moderately warm experimental condition, as
described below.
2.1. Synthesis of ZnS nanoparticles and ZnS-NHIF
Synthesis of ZnS nanoparticles followed the earlier report [44].
Typically, zinc acetate dihydrate [Zn(CH3COO)2, 2H2O] (Sigma-
Aldrich) (5 mmol) and thioureas [CH4N2S] (Sigma-Aldrich)
(25 mmol) were dissolved in deionised water at room temperature.
The mixture was refluxed 12 h at 80  C temperature. The resultant
turbid white precipitation was washed several times with water
and ethyl alcohol and dried in an oven at 100  C to obtain ZnS
nanoparticles.
The surface functionalization of the nanoparticles by ionic liquid
species was done according to the procedure reported elsewhere
[40e42] (Scheme 1). In a typical method, an equimolar amount of
1-methylimidazole 98.0% (Sigma Aldrich) and (3-chloropropyl)
trimethoxysilane 97% (Sigma Aldrich) were added in dime-
thylformamide (DMF) solvent, and the mixture was refluxed at
110  C under a nitrogen atmosphere for three days. The reaction
had been monitored continuously by thin Layer chromatography
(TLC) and final pale yellowish, viscous 1-methyl 3-propyl (trime-
thoxysilyl) imidazolium chloride ([mpImSi(OMe)3][Cl]) ionic liquid
was purified via TLC and liquid extraction in di-ethyl ether followed
by solvent evaporation. To tether the ionic liquid on the surface of
ZnS core, excess amount (1.5 wt%) [mpImSi(OMe)3][Cl] is allowed
to react with the aqueous solution of ZnS nanoparticles under
stirring at 80  C for 12 h. The resulting hydrophilic ZnS-[mpIm-
Si(OMe)3]- [Cl] NHIF was converted to hydrophobic by exchanging
the Cl anion by bis(trifluoromethyl-sulfonyl)imide (TFSI). For
anion-exchange reaction, the ZnS-[mpImSi(OMe)3][Cl]was reacted
with excess amount of aqueous solution of lithium bis(tri-
fluoromethylsulfonyl)imide (LiTFSI) salt (97%, Sigma-Aldrich) un-
der vigorous stirring at room temperature. After 1 h, the resulting
hydrophobic ZnS-[mpImSi(OMe)3][TFSI] NHIF was deposited at the
bottom of the container as separate layer. The NHIF was collected
after repeated washing with distilled water, dried under vacuum at
100  C and kept in an Argon filled a glove box for further use.
1
H NMR (inset of Scheme 1) (400 MHz, DMSO d6):
d (ppm) ¼ 8.99 (1 H, brs), 7.73 (1 H, brs), 7.59 (1 H, brs), 4.05 (3 H, s),
3.85 (3 H, s), 2.06 (8 H, s), 1.70 (2 H, brs), 0.48 (2 H, brs).
To confirm the tethering of NHIF to the ZnS nanoparticles and to
find out the grafting density, pure 1-methyl 3-propyl (trimethox-
ysilyl) imidazolium bis(trifluoromethyl-sulfonyl)imide [mpIm-
Si(OMe)3][TFSI] ionic liquid was also prepared following a similar
procedure (Scheme 2). 1H NMR (inset of Scheme 2) (400 MHz,
DMSO d6): d (ppm) ¼ 8.74 (1 H, brs), 7.5 (1 H, brs), 7.31 (1 H, brs),
3.81 (2 H, s), 3.63 (3 H, s), 3.14 (6 H, s), 1.83 (3 H, s), 1.50 (2 H, brs),
0.23 (2 H, brs).
From the 1H spectra, successful tethering of ionic liquid chains to
the surface of ZnS nanoparticles can be confirmed from the dif-
ference in peak positions corresponding to the methyl peaks of 3-
OMe group. In particular, the noticeably broader NMR lines for
the NHIF as compared to that of the pure ionic liquid is consistent
with earlier report [45]. In the spectrum of pure [mpImSi(OMe)3]
[TFSI] two peaks (d ¼ 3.63 and 3.14) has been appeared for the
same. While, after tethering on the surface of ZnS, the peak cor-
responding to the methyl unit attached to the nitrogen is combined
with one methyl peak of 3-OMe group (d ¼ 4.05e3.85). On the
other hand, one methylene group of silane tail has been merged
with the peak corresponding to two methyl unit of 3-OMe groups
 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765 755

Scheme 1. Synthesis scheme of ZnS-NHIF along with corresponding 1H NMR.

Scheme 2. Synthesis scheme of pure ionic liquid with silane tail and corresponding 1H NMR.

(d ¼ 2.05). Other peaks also shift simultaneously towards higher
value of d.
2.2. Preparation of polymer nanocomposite membranes and gel
polymer electrolytes
The polymer nanocomposite membranes were prepared by a
simple solvent casting method. Poly (vinylidene fluoride-co-
hexafluoropropylene) (P(VDF-HFP)) (average mol. wt. 455 000,
Sigma-Aldrich) was dried at 100  C under vacuum for 24 h. It has
been observed earlier that using high molecular weight P(VDF-
HFP) allows incorporating higher concentration of liquid plasti-
cizers such as ionic liquids in the membrane without hampering
the free-standing film forming ability [46]. As a typical preparation
procedure, P(VDF-HFP) (0.5 g) was dissolved in 10 ml acetone at
50  C. Then, x wt% of the dried ZnS-NHIF (x ¼ 15, 30, 40 and 50) pre-
756 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765
dispersed in acetone was added dropwise to the mixture. After
complete dissociation of polymer, the mixture was cooled to room
temperature and was stirred for 24 h followed by ultra-sonication
for 30 m to ensure homogeneity. The final homogeneous solu-
tions were poured into glass petri-dish to cast different nano-
composite membranes. The membranes were dried at 70  C under
vacuum overnight for removing the solvent and were stored in an
argon-filled glove box. Five membranes including pure P(VDF-HFP)
were prepared accordingly and are classified as shown in Table 1.
The gel polymer electrolytes (GPEs) were prepared by
immersing the nanocomposite membrane into 1 M LiTFSI salt dis-
solved mixture of ethylene carbonate (EC) and dimethyl carbonate
(DMC), (EC: DMC ratio 1:1 by volume) for 2 h. LiTFSI salt was chosen
to improve the safety of the electrolyte [47]. Therefore, five GPEs
were prepared in this method and are labelled as PVNHXLi, with
X ¼ 0, 15, 30, 40 and 50, respectively (Table 1).
2.3. Characterizations and measurements
The purity and successful formation of the synthesized NHIF
was confirmed by 1H nuclear magnetic resonance (NMR) in DMSO-
D6 solvent using a Bruker Avance-400 MHz NMR Spectrometer.
The X-ray diffraction (XRD) study of the synthesized ZnS
nanoparticles was carried out with Rigaku Miniflex 600 X-ray
diffractometer with Cu Ka radiation (l ¼ 0.154 nm) generated at
40 kV and 20 mA, in the 2q range between 10 and 90 at a scanning
rate of 0.25 /min.
The homogeneous dispersion of ZnS nanoparticles into the NHIF
and polymer matrix was confirmed using transmission electron
microscopy (TEM) (JEOL JEM-2100, 200 kV). A field emission
scanning electron microscope (FE-SEM Supra 55 (Germany) with
Air Lock) was used to investigate the morphology of the as-
prepared nanocomposite membranes.
Thermogravimetric analysis (TGA) of the synthesized NHIF
along with pure ionic liquid was performed within a temperature
range from room temperature to 600  C using a Netzsch TG 209 F3
Tarsus system at a heating rate 10  C/min under nitrogen envi-
ronment. The thermal stability of the GPEs was also obtained from
the same.
Fourier transform infrared spectra of the membranes were
conducted on a Shimadzu IR affinity 1S FT-IR spectrometer,
equipped with a single-reflection diamond attenuated total
reflection Fourier transform infrared (ATR-FTIR) sampling module.
The spectra were acquired using 64 scans and 4 cm-1 resolution
within a spectral range of 4000e400 cm-1, at room temperature.
The degree of crystallinity, glass transition and a melting tran-
sition of GPEs were studied using differential scanning calorimetry
(DSC) technique. The DSC data were obtained between
100 and
250  C employing Netzsch DSC 214, Polyma differential scanning
calorimeter under a nitrogen atmosphere. Before measurement,
both the temperature and enthalpy of the DSC were auto-calibrated
by pure indium. In a typical experiment ~15e20 mg GPE sample,
encapsulate in a concuvaus aluminium crucible covered by a lid,
was preheated to 90  C at a rate of 10  C min
1 and kept there
Table 1
Different as prepared nanocomposite membranes and GPEs with corresponding percentage of different components.
P(VDF-HFP) ZnS-NHIF (wt%) Nanocomposite membrane
(wt%)
100 0 PVNH0
85 15 PVNH15
70 30 PVNH30
60 40 PVNH40
50 50 PVNH50
isothermally for 10 min to eliminate any previous thermal history.
Then, it was cooled at a rate of 10  C/min to
100  C. The DSC re-
sults presented in the manuscript were collected from the second
heating-cooling cycle.
The temperature dependent ionic conductivity of different GPEs
was evaluated by impedance spectroscopy over the frequency
range of 42 Hz to 8 MHz with an amplitude of 5 mV in the tem-
perature range from
20  C to 100  C using a Hioki LCR meter
model IM3536 under dynamic vacuum. The GPEs were sandwiched
between symmetric stainless steel (SS) electrodes in a sample
holder, and a Eurotherm temperature controller with temperature
constancy of ±0.1  C controlled the temperature.
Electrochemical stability window (ESW) of the highest con-
ducting GPE was obtained by linear swipe voltammetry (LSV) of Li/
GPE/SS cell, with an electrochemical analyser (CH Instruments,
model 608E) in a voltage range between
0.5 V and 6.0 V, at a scan
rate of 1 mV/s.
Using Bruce method, the lithium ion transference numbers (t þ Li
)
of different GPEs were evaluated at room temperature. In this
experiment, combined chronoamperometry and electrochemical
impedance spectroscopy measurement were carried out on a
symmetric 2032 type lithium coin cell comprising GPE as both
separator and electrolyte (Li/GPE/Li) using an electrochemical
analyser (Bio-Logic, model VMP3). All the symmetric cells were
assembled in an argon filled glovebox (Mbraun, Labmaster).
Charge-discharge cycling tests (in terms of specific capacity,
cyclic stability, and rate capability) of different 2032-type coin cells
in a combination of Li/GPE/LiFePO4 were tested at room tempera-
ture using a Neware battery testing system (BTS-3000N) in the
potential range between 2.5 V and 4.1 V at different current rates.
The 2032-type coin cell batteries were assembled in an argon filled
glovebox (Mbraun, Labmaster). The LiFePO4 cathode was prepared
by LiFePO4 powder (MTI Corporation, USA) (active material), acet-
ylene black (electron-conductive additive) and PVDF (binder) with
a weight percent of 80:10:10 in N-methyl-2-pyrrolidone (NMP)
solvent. The resulting viscous slurry was coated on the aluminium
foil current collector and dried at 100  C. The loading of the active
material was ca. 2.5e3.0 mg cm
2.
3. Results and discussions
3.1. Characteristics of ZnS nanoparticles and ZnS-NHIF
The X-ray diffraction spectrum of the synthesized ZnS nano-
particles is shown in Fig. 1(a). The crystalline peaks observed at 2q
values of 28.91⁰, 48.09⁰, 57.08⁰, 70.38⁰ and 77.8⁰ correspond to the
(111), (220), (311), (400), (331) and (420) crystalline planes of the
cubic ZnS (JCPDS No. 05e0566). From the highest intensity peak
(2q ¼ 28.91⁰) and using the Scherrer's formula, 〈d〉 ¼
0:94l=d cos q(d, l and q are the full width of the half maxima, X-ray
wavelength and angle of diffraction, respectively) the average di-
ameters of the crystalline nanoparticles are estimated as ~3.1 nm.
Fig. 1(b) depicts the depicts the transmission electron micro-
scopy (TEM) of the as-prepared NHIF. Limited aggregation within
Soaked in Gel polymer electrolyte
1(M) LiTFSI in (1:1, v/v) EC/DMC PVNH0Li
PVNH15Li
PVNH30Li
PVNH40Li
PVNH50Li
 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765
Fig. 1. (a) XRD of ZnS nanoparticles, (b)-(c) TEM micrographs of ZnS-NHIF at different magnification along with SAED pattern, (d) TGA profile for ZnS-NHIF and un-tethered ionic
liquid.
the ZnS nanoparticles indicates the effectiveness of the adopted
procedure to functionalize the nanoparticles. The size distribution
of the ZnS NPs in NHIF lies within 3.5e5 nm which is in close
agreement to that estimated from XRD analysis. The clear lattice
fringes with a lattice spacing of 0.31 nm correspond to the (111)
reflecting plane of cubic ZnS (Fig. 1(c)). The selected area electron
diffraction (SAED) (inset) shows the ring patterns due to diffraction
from the crystal planes of polycrystalline ZnS nanoparticles.
Fig. 1(d) depicts the temperature dependent mass loss profile for
ZnS-NHIF and pure [mpImSi(OMe)3][TFSI] ionic liquid obtained
from the thermogravimetric analysis (TGA). As can be observed, the
thermal stability of NHIF slightly better than that of pure ionic
liquid. This is attributed to the grafting of ionic liquid chains to the
surfaces of the ZnS nanoparticles. From the TGA plots the grafting
density of ionic liquid chains can be obtained using the formula
ð1
Mnano Þ%
Mnano % NA rnano rnano
X
¼ (1)
6MW
Mnano is the TGA estimated residual mass percent of the nano-
particles that remains after the complete dissociation of the teth-
ered ionic liquid chains with molecular weight MW. NA, rnano and
rnano are the Avogadro number, radius and density of the ZnS
nanoparticles. Using the method and considering the size of the
nanoparticles from the TEM analysis the grafting density (S) are
estimated as ~2.8 chains/nm2.
3.2. Morphology of the membranes
The pore structure of the polymer membrane plays the key role
in the soaking and holding of liquid electrolyte and thereby
757
significantly affects the electrochemical performance of a GPE.
Fig. 2(a)e(e) show the FE-SEM images of different nanocomposite
membranes along with that of pure P(VDF-HFP). Each of the
membranes including the pure polymer exhibit a porous structure.
The number of pores and their size increase with increasing NHIF
concentration in the matrix. For PVNH50 membrane the pore size
becomes more than ~10 mm, resembling the possible coalescence of
small pores.
Fig. 2(f) display the dispersion of ZnS-NHIF in a representative
nanocomposite membrane (PVNH40) which shows non-uniform
distribution of the nanoparticles forming local aggregations.
3.3. Thermophysical characteristics of the gel polymer electrolyte
(GPEs)
3.3.1. Thermal stability
The thermal stability of electrolyte is an important parameter
regarding the safety of batteries. Fig. 3(a) shows the thermogravi-
metric (TG) curve for different GPEs. The TGA profiles for P(VDF-
HFP) is also included in figure. P(VDF-HFP) decompose in a single
step at ~455  C, but each of the GPEs shows multi-step degradation.
Apart from the evaporation of EC/DMC solvent around 150  C, each
of the GPEs shows a substantial mass loss between 230 and 330  C.
This is attributed to either the decomposition of complex formed
between P(VDF-HFP) and Li- salt or that of the LiTFSI salt (~300  C)
[46]. The TGA profiles indicate that although the thermal stability of
the GPEs decreases with increasing NHIF content, it is good enough
for a lithium battery application even at the highest concentration
of NHIF used in the study (PVNH50Li).
758 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765

Fig. 2. (a)-(e) FE-SEM images of the different polymer nanocomposite membranes along with the pure polymer. (f) Dispersion of ZnS-NHIF in a representative polymer nano-
composite membrane.

3.3.2. Ionepolymer interaction
The ion-polymer interactions in different electrolyte soaked
membranes are analysed from the corresponding FT-IR spectral
features as depicted in Fig. 3(b), between 400 and 1600 cm
1. The
spectrum of pure polymer based GPE contains exclusive bands at
976, 796, 764 615, 532 and 488 cm
1, corresponding to a- PVDF
only [48e51]. The bands observed near 513 and 570 cm
1 corre-
spond to the CF3 asymmetric bending mode of LiTFSI salt. The
spectra of nanocomposite GPEs contain absorption bands near and
600-618 cm
1 corresponding to Zn-O-Si symmetric stretching vi-
bration, Si-O stretching and CH2 and CH3 scissoring vibration of
ZnS-NHIF [52]. Similarly, the vibrations observed at 740, 789, and in
the region 1050e1150 cm
1 correspond to the overlapping of
symmetric bending mode of -CF3, combination of CeS and SeN
stretching mode, asymmetric SeNeS stretching mode and
CeSO2eN bonding mode of ZnS-NHIF and LiTFSI, [46,52]. The bands
at 654 cm
1 and 1573 cm
1 resemble the CeH vibrational mode of
cyclic methylimidazolium group and the interaction between CeC
and CeN bending mode of ZnS-NHIF [52]. With the increase of
ZnSeNHIF the intensity of the a-bands weaken (disappear above
PVNH15Li) and some new bands exclusive to electroactive g-PVDF
at 431, 482, 509, 811, 839 and 1234 cm
1 appear. It may be antici-
pated from the structure of the ZnS-NHIF (as shown in Scheme 1)
that when the ionic liquid chains get tethered via hydrogen
bonding between the e(OMe)3 group of the silane tail and the
surface charge of ZnS, the Si-O bond attached to the other side get
weaken due to charge separation, leaving Si partially positive.
When the NHIF has been incorporated within the P(VDF-HFP) in
the solution state, that Si-O dipole interacts with >CF2 dipole. At
low concentration, the interaction is feeble but with increasing
NHIF content, the interaction become stronger. The observed
change in conformation of P(VDF-HFP) can be attributed to such a
 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765
Fig. 3. (a) TGA curves of GPEs with different NHIF concentrations. TGA profiles for pure polymer is also included. (b) FT-IR spectra of different GPEs. (c) heating and a cooling scan of
different GPEs. (d) Crystallization and melting enthalpy along with the degree of crystallinity for different GPEs as a function of NHIF content.
strong dipole-dipole interaction. In each of the electrolytes, the
bands at 1332 and 1354 cm
1 correspond to the CeSO2eN bonding
mode and asymmetric SO2 stretching mode of LiTFSI [46]. Due to
poor soaking ability of pure P(VDF-HFP) membrane, the intensity of
the bands associated with LiTFSI appear very feeble in the spectrum
of PVNH0Li, which improves significantly with the increase of NHIF
content in the GPEs. The appearance of new bands near
1050e1110 cm
1 in the spectra accompanying with a gradual shift
in CFeCHeCF bending vibration (878 cm
1) towards the higher
wavelength further designate such strong interactions.
3.3.3. Differential scanning calorimetry (DSC)
DSC thermograms of different GPEs are shown in Fig. 3(c). Each
of the GPEs shows a single melting and crystallization peaks, which
gradually shift towards lower temperatures with increasing NHIF
content. Thus, in the presence of NHIF, both crystallization and
melting transitions delay. The enthalpy value, i.e. the area under the
curve corresponding to either melting (DHm) or crystallization
(DHc) transition, decreases with increasing fraction of NHIF into the
GPEs (Fig. 3(d) (left axis). This is in line to our recent study where
NHIF was found to exert a stronger effect in melt-crystallization of
P(VDF-HFP) than that of individual ionic liquid or nanoparticles
[40].
The absolute crystallinity fraction XC is estimated as [53].
DHm
XC ¼  100%
ð1
xÞDH0m
where DH 0m is the extrapolated enthalpy corresponding to the
melting of 100% crystalline PVDF [104.7 J/g] [54] and x is the weight
fraction of NHIF in the nanocomposites. The degree of crystallinity
(Xc) decreases from 23% to 7% for 50 wt% NHIF incorporation in the
GPE (Fig. 3(d), right axis). Thus, ZnS-NHIF in the membranes not
759
only improves the porosity, but it also effectively improves the
amorphous regions in the GPEs. It has been reported earlier that the
amorphous regions of polymer matrix are advantageous for ion
conduction [55]. Therefore, higher NHIF containing GPEs with more
amorphous regions, could have a promising high ionic conduction.
3.4. Porosity and electrolyte uptake
The porosity of pure copolymer and NHIF incorporated nano-
composite membranes were further compared by measuring the
pore size using simple n-butanol adsorption method used by
several researchers [16,24,25]. In that method, weighed mem-
branes were immersed in n-butanol for 2 h. Then, the membrane
surface was dried by filter paper and weighed again. Porosity was
calculated according to the following equation
ðMw
Md Þ=rn
Porosity ð%Þ ¼   100 % (3)
ðMw
Md Þ=rn þ Md rp
where Mw and Md correspond to the weights of the wet and dry
membranes, and rn and rp designate the densities of n-butanol and
polymer, respectively. Fig. 4(a) compares the porosity trend of
different membranes as a function of the wt% of NHIF as obtained
from the n-butanol method using Eq. (3). As can be observed, NHIF
incorporation in the polymer matrix generates substantially higher
(2) porosity, and a maximum porosity of 64% can be observed in
PVNH40 membrane as compared to 29% porosity for the pure
copolymer membrane. It is important to notice that for PVNH50
membrane, the porosity percentage obtained from the butanol
adsorption method is in contrast to the feature appears in FE-SEM
micrograph. This may be ascribed to the reduction in the quantity
of butanol that being held by the membrane due to large pores in
the membranes observed in FE-SEM micrograph.
760 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765

Fig. 4. (a) Porosity and (b) liquid electrolyte uptake percentage as a function of NHIF content in membranes. Electrolyte uptake as a function of time is shown at the inset of (b).

The gel polymer electrolytes were obtained by impregnating the content in the membranes shows good agreement with the trend
porous nanocomposite membranes in 1 M LiTFSI salt dissolved EC/ exhibits by the porosity (Fig. 4(a)). While the PVNH40Li GPE con-
DMC electrolyte. The amount of liquid electrolyte uptake is esti- tains ~89% liquid electrolyte, PVNH50 membrane could absorb only
mated using Eq. (4) as ~72% electrolyte.

Wa
Wb
uptakeð%Þ ¼  100 % (4)
Wb 3.5. Ion conductivity

where Wa and Wb are the mass of the membrane after and before
soaking of liquid electrolyte respectively. Fig. 4(b) compares the
soaking performance of the membranes as a function of the wt% of
NHIF. The electrolyte uptake percentage with time for different
membranes is also compared at the inset. As observed, each of the
membranes including pure polymer shows similar electrolyte up-
take characteristics, i.e. initially absorbs the electrolyte rapidly and
gets saturated within 30 min. It is worthy to mention that the
variation of the electrolyte uptake percentage with the NHIF
High ionic conductivity is a major parameter for an electrolyte
for the used in lithium-ion batteries. Fig. 5(a) displays the tem-
perature variation of real part of ac conductivity spectra obtained
from the impedance spectroscopy measurement for a representa-
tive GPE. The compositional variation of the conductivity spectra at
room temperature (30  C) is shown in Fig. 5(b). As observed, ac
conductivity shows a thermally activated nature and with
increasing NHIF content it gradually improves. The conductivity
spectra were analysed using an equivalent circuit (inset of Fig. 5(a))

Fig. 5. (a) Temperature and (b) compositional variation of frequency dependent real part of the complex conductivity. Solid lines are best fits according to the equivalent circuit as
shown at the inset. (c) Inverse temperature variation of DC conductivity (sdc ) for different GPEs evaluated from the fitting of ac conductivity spectra. Solid lines are best fits to VFT
equations. (d) Comparison of electrochemical stability window of highest conducting GPE and pure P(VDF-HFP) based GPE vs (Li/Liþ).
 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765 761

Table 2
Variation of VFT parameters obtained from the fitting of temperature dependent ion sdc ¼ s0 exp ð
Ea =kB ðT
T0 ÞÞ (5)
conductivity data.

Samples s0 [S cm
1] ±0.03 Ea [eV] ±0.002 T0 [K] ±2.0 where Ea is the activation energy for ion conduction and T0 is the
equilibrium glass transition temperature whose value is usually
PVNH0Li 0.42 0.087 203.0
PVNH15Li 0.55 0.071 196.2
considered as 30  C lower than the thermodynamic glass transition
PVNH30Li 0.61 0.055 183.9 temperature (Tg). The solid lines in Fig. 5 correspond to the best fits
PVNH40Li 0.65 0.044 174.3 of the conductivity data according to Eq. (5) with the fitting pa-
PVNH50Li 0.58 0.052 187.2 rameters as shown in Table 2.
The value of both Ea and T0 gradually reduces with increasing
concentration of NHIF up to PVNH40Li above which the trend
contraries. Thus, NHIF in polymer matrix enables to soak a higher
to obtain the DC conductivity [56e58]. Fig. 5(c) shows the inverse amount of liquid electrolyte and provides better-disordered
temperature variation of DC conductivity of different GPEs. It can be network structure for ion conduction. Consequently, with
observed that the conductivity increases with increasing temper- increasing NHIF content in the membrane, the conductivity of GPE
ature and follows a non-Arrhenius type thermally activated pro- gradually improves with lower activation energy.
cess. Analogous to ac conductivity, DC conductivity of GPE also
improves with the increase of NHIF content within the matrix. The
3.6. Electrochemical stability
highest conductivity at room temperature (30  C) is found to be
3.3  10
3 S cm
1 for PVNH40Li, which is almost an order of
The electrochemical stability of PVNH40Li GPE has been
magnitude higher than that of the pure polymer based GPE
compared with PVNH0Li by linear swipe voltammetry (LSV). In
(PVNH0Li) (2.6  10
4 S cm
1). However, for PVNH50Li the trend
Fig. 5(d), the LSV curves of two cells between
0.5 V and 6.0 V
reverses. It is well accepted earlier that for good electrochemical
(versus Li/Liþ) at a constant scan rate 1 mV/s are presented. The
performances of lithium battery, in terms of capacity and stability,
onset voltage at which the current starts to increase from its con-
an electrolyte with conductivity value  1 mS cm
1 is required [59].
stant value can be considered as the upper limit of GPE. For
Thus, the conductivity achieved by the GPE is well above the stip-
PVNH40Li, near onset voltage at 5.2 V the anodic current start
ulated value.
raising which is related to the oxidation of the TFSI anion present in
Observed non-linear temperature variation can be suitably
the GPE. Similarly, the cathodic current observed at about 0.20 V is
explained by the VogeleFulchereTammann (VFT) equations [60]
related to the decomposition of the ionic liquid cation. Electro-
expressed as
chemical deposition of lithium metal may also occurs at that

Fig. 6. Flammability test of (a)e(b) PVNH0Li and (c)-(d) PVNH40Li GPE.

762 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765

potential. Therefore, electrochemical stability window of the GPE

can be considered as ~5.4 V vs Li/Liþ, which is significantly higher
than that of the PVNH0Li GPE (~4.2 V).

3.7. Flame retardant property

The flame retardation property of GPEs is analysed to ensure

their applicability in abusive conditions of the battery such as in
thermal runaway. The liquid electrolyte used in this study is 1.0 M
LiTFSI in EC/DMC (1:1, w/w), which is highly flammable. It ignites
easily and combusts violently. Fig. 6(a)e(d) compare the results of
the flammability test of two GPEs viz. PVNH0Li and PVNH40Li,
respectively. They are being exposed in oxidant flame, ignited by a
lighter. The PVNH0Li GPE burns quickly when the flame of the
lighter is applied to it for 3 s (Fig. 6(a)). After the flame is applied for
6 s, the GPE burns violently with dripping (Fig. 6(b)). However, in a
similar condition, the PVNH40Li GPE curves without burning, as
shown in Fig. 6(c)-(d). Thus, the encapsulation of NHIF inside the
P(VDF-HFP) creates a flame retardant protective layer that prevents
direct exposure of the soaked electrolyte and thereby slows down
its dissolution. On the other hand, it may be anticipated that if
thermal runaway condition appears for the PVNH40Li containing
battery, the nanocomposite membrane will melt much earlier than
that of P(VDF-HFP) (Fig. 3(c)). Consequently, the encapsulated
flame retardant NHIF, which is thermally stable up to 400  C
(Fig. 1(d)), will be released into the highly flammable electrolyte
and will effectively suppress its combustion.

3.8. Liþ ion transference number

Apart from the substantially higher ion conductivity, high

transference number of lithium-ion (tLiþ ) is also an important cri-
terion for an electrolyte for lithium battery application. The trans-
ference number (tLiþ ) for the GPEs is estimated by the combination
of chronoamperometry and EIS analysis under an applied voltage of
10 mV following the equation proposed by Bruce and co-workers
 .  
tLiþ ¼ I S DV
I 0 R0I I 0 DV
IS RSI
whereR0I and RSI are the initial and steady-state resistances of the
passivation layers, with Is and I0 as the corresponding currents,
respectively. Fig. 7(a) and (b) display the Nyquist plots of imped-
ance before and after the chronoamperometry measurements of
two Li-symmetrical cells, comprising PVNH40Li and PVNH0Li GPEs,
respectively. Inset of the figures show the corresponding DC po-
larization currents. Using Eq. (6) and from the experimental data,
the value of tLiþ for the electrolytes are evaluated as 0.26 and 0.62,
respectively. Observed high value of transference number may be
attributed to trapping of TFSI
anion by the ZnS nanoparticles
present in the matrix. Similar immobilization of anions in presence
of nanoparticle in gel polymer electrolytes was also reported earlier
[61]. Moreover, soaking of larger amount of electrolyte due to
higher porosity also able to release a higher number of Liþ ions to
transfer, which consequently improves the value of tLiþ for
PVNH40Li such a large extent.
3.9. Electrochemical performance of the lithium-polymer battery
The room temperature (25  C) electrochemical performance of
the highest conducting GPE (PVNH40Li) is studied in 2032 coin cell
with LiFePO4 as a cathode and Li metal as the anode within an
operating voltage window from 2.5 to 4.0 V. For comparison, a
similar cell containing PVNH0Li GPE is also being studied under
identical conditions. Fig. 8(a) depicts the room temperature charge-
Fig. 7. Current-time profile of symmetrical (a) Li/PVNH0Li/Li and (b) Li/PVNH40Li/Li
cells polarized applying 10 mV DC voltage. Corresponding Nyquist impedance spectra
of the cells before and after polarization are shown at the inset.
(6) discharge profile of the Li/PVNH40Li/LiFePO4 cell recorded with
various C-rates. the electrode/electrolyte interface. Fig. 8(b) shows
the charge-discharge profiles at C/10 rate for every 10th cycles of
the battery starting from the 1st cycle, up to 50 cycles. Similar
charge-discharge profiles for the Li/PVNH0Li/LiFePO4 cell are also
shown in Fig. 8(c)-(d). The specific discharge capacity of the cell
containing PVNH40Li GPE was found to be 160.7 mAhg
1 at C/10,
146.8 mAhg
1 at C/5, 134.5 mAhg
1at C/2, 112.4 mAhg
1 at 1 C and
93.8 mAhg
1 at 2 C, respectively (the theoretical specific capacity of
LiFePO4 active material is 170.0 mAhg
1). While, PVNH0Li GPE
comprising cell shows much lower discharge capacity such as 141.2
mAhg
1 at C/10, 126.3 mAhg
1 at C/5, 106.4 mAhg
1at C/2, 85.2
mAhg
1 at 1 C and 63.6 mAhg-1 at 2 C, respectively. With a pro-
gressive increase in C-rate, both the discharged plateau and specific
capacity gradually drop for both the batteries, owing to the slow
lithium ion transport kinetics in the LiFePO4 cathode [62]. The rate
performance of the electrolyte is an essential factor towards its
practical application. The rate performance of both the cells were
analysed by charging and discharging the cells at different current
rates for 10 cycles as shown in Fig. 9(a). In the first 50 cycles, the
current rate gradually increases from 0.1C, with a consequent
decrease in the discharge capacity. The capacity drops to lowest
value at 2.0 C rate. However, for PVNH40Li, the value is substan-
tially higher (~92 mAh g
1) than that obtained from PVNH0Li cell
(~66.1 mAh g
1). For the next 50 cycles, the cells undergoes a
reverse charge-discharge operation up to C/10 rate. While,
PVNH40Li cell recovers ~99% of its initial capacity, the PVNH0Li
 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765 763

Fig. 8. Charge-discharge profiles for Li/PVNH40L/LiFePO4 cell at (a) different current rates and (b) after different cycles at C/10. (c) and (d) display similar charge-discharge profiles
for Li/PVNH0Li/LiFePO4 cell.

Fig. 9. (a) Rate performance of different cells and (b) long-term cycling performance, i.e. the capacity and Coulombic efficiency versus cycle number of the PVNH40Li cell at C/10
current rate. The inset shows the corresponding cycle variation of the charge-discharge capacity.

could recover only ~85%. Finally, the cycle performance of the
PVNH40Li cell is evaluated at C/10 current rate (Fig. 9(b)). The
Coulombic efficiency of the cell is ~99% after 50 cycles. It is able to
deliver a discharge capacity of ~142 mAh g-1 after 50 cycles (inset
of Fig. 9(b)), i.e. retains ~89% of its initial value.
4. Conclusions
In summary, a series of free-standing, porous, P(VdF-HFP)
nanocomposite membranes were prepared by blending the
copolymer with imidazolium-based ionic liquid tethered ZnS
nanoparticles, the nanoscale hybrid ionic fluid (NHIF). Corre-
sponding gel polymer electrolytes were obtained by submerging
those porous membranes in the lithium salt dissolved liquid elec-
trolyte. A large number of characterization methods confirmed that
the nanocomposite membrane based GPEs had superior perfor-
mance than that based on pure P(VdF-HFP). The 40 wt% of NHIF was
found to be optimum to develop a nanocomposite membrane
comprising 64.0% porosity with highest (89.0%) electrolyte uptake
capacity. The GPE obtained from the membrane exhibited the
highest ionic conductivity of 3.3  10
3 S cm
1 at ambient tem-
perature along with appreciable lithium ion transferability. At C/10,
the GPE containing 2032 coin cell in combination with Li/LiFePO4
electrodes delivered a discharge capacity of ~161 mAh g
1 with
~89% retention after 50 cycles in conjunction with nearly 100%
Coulombic efficiency. Thus, the present methodology is promising
in the development of high energy density lithium-polymer bat-
teries with better safety.
Acknowledgements
Authors thankfully acknowledge the DST-SERB (Govt. of India)
for the financial support under the Research Scheme No: EMR/
2014/000290 Dated 11.09.2015. The authors thankfully
764 P. Bose et al. / Electrochimica Acta 319 (2019) 753e765
acknowledge the DST-FIST scheme of the Department of Physics
and DST-PURSE-II scheme of the University of Kalyani for providing
instrumental facilities. Also, the authors express their sincere
thanks to Prof. S. Basu Majumder and Mr. Mainul Akhtar of Mate-
rials Science Centre, Indian Institute of Technology, Kharagpur for
extending kind cooperation regarding cell preparation.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.07.013.
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