Electromechanical engineering in SnO2 nanoparticle tethered hybrid ionic liquid

Debalina Deb and Subhratanu Bhattacharya

Citation: AIP Conference Proceedings 1832, 040008 (2017); doi: 10.1063/1.4980210

View online: http://dx.doi.org/10.1063/1.4980210
View Table of Contents: http://aip.scitation.org/toc/apc/1832/1
Published by the American Institute of Physics
 Electromechanical Engineering in SnO2 Nanoparticle
Tethered Hybrid Ionic Liquid
Debalina Deb* and Subhratanu Bhattacharya

Department of Physics, University of Kalyani, Kalyani, Nadia, West Bengal, Pin-741235, India
*(Email: debalinadeb03@gmail.com

Abstract. Challenge of developing electrolytes comprising synergic properties of high mechanical strength with superior
electrical and electrochemical properties has so far been unmet towards the application of secondary storage devices. In
this research, we have engineered the electromechanical properties of 2-(trimethylamino) ethyl methacrylate
bis(trifluoromethylsulfonyl) imide [TMEM]TFSI ionic liquid by tethering silane modified SnO2 nanoparticles within it.
Different percentages of tethering are employed to achieve improved ionic conductivity, better discharge/ charging ratio
(40%) along with gel like mechanical properties. Our findings appear to provide an optimal solution towards the future
prospects in application in a number of areas, notably in energy-related technologies.
Keywords: LMBs, NHIL, SnO2, Electro-mechanical, Galvanostatic charge-discharge
PACS: 81.05.-t, 81.07.Oj, 81.07.Pr

INTRODUCTION characterizations of different nanoscale hybrid ionic

In recent years, to meet growing needs for electronic
devices, as well as to accommodate growing interest
in hybrid and fully electric vehicles the demand for
rechargeable batteries has increased tremendously.
The current research aims to come up with batteries
with improved energy storage capacity, charge/
discharge cycling stability, higher power densities,
and lower initial and lifecycle costs. To this end, in
recent years, secondary lithium metal batteries
(LMBs) have received attention where metallic
lithium serves as the anode. Though these might be
a potential alternative to lithium-ion batteries yet
there are serious problems associated with dendrite-
induced short circuits. One approach to address this
problem involve stabilization Li anode surface using
electrolyte additives or hybrid ionic liquid
nanostructures or by using a high modulus separator.
In this aspect room temperature ionic liquids have
received intensive scientific interest as electrolytes
for LMBs for their ability to provide leakage free,
flexible and safer systems. But the gel electrolyte
systems have consistently underperformed owing to
their low conductivity, poor mechanical modulus and
high cost.
In this direction, followed by the seminal work by
Archer et.al. A number of groups have contributed
considerably, including the synthesis
DAE Solid State Physics Symposium 2016
AIP Conf. Proc. 1832, 040008-1–040008-3; doi: 10.1063/1.4980210
Published by AIP Publishing. 978-0-7354-1500-3/$30.00
liquids containing a high volume fraction of different
functionalized nanoparticles (such as SiO2 1, ZrO2 2
etc.). The effects of structural and compositional
variations on the molecular dynamics and bulk
properties are still sketchy and needs systematic
investigation to address the open questions on
relationship between NHILs structure, the local and
collective molecular dynamics and the macroscopic
properties which are roadblocks towards optimized
design of NHILs. Herein we report on hybrid
electrolytes created by tethering 8-10nm SnO2
nanoparticles. We show that the mechanical and
electrochemical properties of the resultant SnO2-IL-
TFSI hybrid electrolytes can be facilely tuned by
varying the amount of SnO2 tethering maintaining its
Newtonian nature. All of these qualities promote its
promise as IL in typical LMBs.
EXPERIMENTAL
Synthesis Procedure of SnO2 Nanoparticle Core
and SnO2 Nanoparticle Hybrid Ionic Liquid:
5 mM SnCl4.2H2O and 5 mM oxalic acid were
individually dissolved in 60 ml deionized water with
continuous stirring for 1 hour. The precipitation was
collected, washed and subsequently dried at 600C

040008-1
followed by calcination at 6000C with 2 hours
soaking time. The ionic liquid [TMEM]TFSI
hereafter synthesized and grafted with SnO2
nanocore using the following scheme:
Scheme 1: Synthesis of SnO2-[TMEM]TFSI NHIL
RESULTS & DISCUSSIONS:
Transmission electron micrograph of the SnO2-NHIL
(Figure 1(a)), obtained from JEOL JEM-2100, 200
kV HR-TEM, confirms the uniform dispersion of the
nanoparticles within the IL matrix.
X-ray diffraction pattern (Rigaku Miniflex 600)
(Figure 1(b)) shows consistency with rutile-type
tetragonal structure (space group: P42mnm) of SnO2
nanoparticles.
FIGURE 1: (a) Transmission electron microscope image
of SnO2-NHIL; (b) XRD of SnO2 nanoparticles.
Mechanical Properties:
Figure 2 depicts the viscosity of Pure IL and NHIL
as a function of shear rate with various
concentrations of doped SnO2 nanoparticles, at room
temperature obtained from an advanced air bearing
rheometer, model Bohlin Gemini 2 (Malvern
Instruments, UK) with parallel plate geometry.
Evidently, the crosslinking nanoparticle suspensions
enhance the mechanical strength by several orders.
The data reveals that upto 2 wt% concentration of
silane modified SnO2 dispersion, the viscosity is
independent of shear rate which means that it
040008-2
behaves like newtonian fluids. Further increase of the
concentration of SnO2 (5 wt%) (not shown in the
figure), the viscosity shows significant shear rate
dependency, which may be attributed to the possible
aggregation of the nanoparticles within the NHIL
matrix.
Electrical and Electrochemical Properties:
Cyclic voltammogram (CV) of both 1% and 2%
SnO2-NHIL within a potential window of -4 to +4
volt at scan rate 50mV/sec obtained from CH
instrument model 608 are shown in Figure 4(a). The
CVs are observed to be symmetrical in positive and
negative applied voltage without any current peak
indicating the absence of any redox couples in the
entire range of voltage sweep.
As evident from Figure 4(a), maximum cathodic and
anodic current in the CV of 2% SnO2-NHIL (9.0ȝA)
is greater than that of 1% SnO2 dispersions (6.4ȝA)
by around 40%. This increase in current value is
attributed to high surface area of nanoparticles
enabling increased electron transfer between the
grafted nanoparticles and ionic liquids due to ionic
coupling between mobile and immobile phase (nano
tehthered) of IL through hopping channels.4
FIGURE 2. Viscosity as a function of shear rate for the
pure & SnO2-NHIL. Inset shows the photographs of the
NHILs viz. (a) Pure Ionic liquid; (b) Grafted With 1.0% ;
(c) Grafted With 2.0% SnO2. Electrolyte used for
subsequent electrochemical and mechanical
characterization.
Galvanostatic charge -discharge test:
Figure 4(c) VKRZV WKH GHSHQGHQFH RI VSHFL¿F
capacitance (SC) of both 1% and 2% SnO2-NHIL as
a function of current density, calculated using the
equation:
Specific capacitance (SC) = I/ (sA) (1)
Where I is the applied current, s is the scan rate and
A is the area of electrode material.
The charge discharge curve(Figure 4(b)) reveals that
with the incorporation of SnO2 grafting, the ratio of
the discharging time with respect to charging time
is increasing, i.e. nanoparticle tethering modify the
discharge capacity of the electrolyte. Comparative
studies of these charge-discharge test revealed that
specific capacity of 2% SnO2-NHIL (3.14 Fm-2) is
greater than 1% SnO2-NHIL (2.32 Fm-2).
The maximum energy density for 2% SnO2-NHIL is
obtained as 100.55 watt.sec.m-2 and for 1% SnO2-
NHIL is 74.09 watt.sec.m-2, is calculated from:
Energy Density (ED) = (CV2) / 2 (2)
FIGURE 3. (a) Cyclic voltammograms of 1% and 2%
SnO2-NHIL at scan rate 50mV/sec; (b) Galvanostatic
charge/discharge curves for Pure IL and 1%,2% SnO2-
NHILs at a specific current density 10ȝAcm-2: (c) Specific
capacitance for 1% and 2% SnO2-NHIL as a function of
scan rate.
Electrochemical impedance:
FIGURE 4. (a) Ac impedance data of 1% and 2% SnO2-
NHIL showing Nyquist plot variation; (b) Comparison of
room temperature frequency dependent Ionic conductivity
with 1% and 2% SnO2-NHIL.
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Frequency dependent electrochemical impedance
behavior of both 1% and 2% SnO2-NHIL is shown
as the Nyquist plot in Figure 4(a) showing the
dependence of imaginary part (-Z’) impedance with
real part (Z´´) of impedance.The equivalent series
resistance (ESR) obtained from the Nyquist plot are
2262 ȍ cm-2 (for 1%) and 1167 ȍ cm-2 (for 2%).
The similar pattern of ESR indicates similar ion
mobility in both concentrations of SnO2 grafting.
Figure 4(b) clearly shows significant enhancement of
conductance with increasing concentration SnO2
grafting.
CONCLUSIONS
[TMEM][TFSI] IL based NHILs have been
successfully synthesized by tethering TMPS
modified SnO2 nanoparticle within it. The NHIL
shows superior mechanical properties with
Newtonian fluid like characteristics up to 2 wt% of
SnO2 nanoparticle dispersion. The electrochemical,
electrical, galvanostatic studies reveal a significant
increase in conductance with increasing
concentration of surface modified SnO2 dispersion in
ionic liquids. Furthermore, significant (34%)
increase in the value of SC with 40% improvement
in discharge to charging time ratio have also been
achieved for the NHIL. This makes these materials
as potential candidates for electrolytic application in
secondary energy storage devices.
ACKNOWLEDGMENTS
The financial support through the Council of
Scientific & Industrial Research (Scheme number:
03(1327)/14/EMR-II) is sincerely acknowledged.
The authors also thank the DST-FIST scheme of
Department of Physics, University of Kalyani for
providing instrumental facility.
REFERENCES
1. Shuang Wang, Ben Hsia, John P. Alper, Carlo
Carraro, Zhe Wang, Roya Maboudian; Journal
of Power Sources 301 (2016) 299-305.
2. Surya S. Moganty, N. Jayaprakash, Jennifer L.
Nugent, J. Shen, and Lynden A. Archer;
Angew. Chem. 2010, 122, 9344 –9347.
3. Alexandra Wittmar• David Ruiz-Abad,
Mathias Ulbricht ; J Nanopart Res (2012)
14:651.
4. Wei Yu , Xinbing Jiang , Shujiang Ding, Ben
Q. Li; Journal of Power Sources 256 (2014)
440-448.