Ionics
DOI 10.1007/s11581-016-1709-y
ORIGINAL PAPER
Influence of supporting electrolytes on the structure
of electrodeposited SnO2 thin films for energy storage applications
D. Vasanth Raj 1,2 & N. Ponpandian 1 & C. Viswanathan 1
Received: 26 November 2015 / Revised: 14 March 2016 / Accepted: 10 April 2016
# Springer-Verlag Berlin Heidelberg 2016
Abstract Different SnO2 nanostructures (SnO2Ns) were
directly electrodeposited on the surface of anodized cop-
per (Cu) substrates via the potentiostatic electrodeposi-
tion method with addition of supporting electrolytes.
The effects of the supporting electrolytes and the electro-
deposition parameters on the evolution of nanostructures
and on the electrochemical properties of the SnO2Ns
were systematically investigated using field emission
scanning electron microscope (FESEM) and electrochem-
ical methods including cyclic voltammetry (CV) and
chronoamperometry (CA). The results confirmed that
SnO2Ns exhibit alloying/de-alloying reactions with Li+
ions versus Ag/AgCl in aqueous electrolyte solution
(LiOH·H2O and Li2CO3). The super capacitor perfor-
mance of the SnO 2 Ns was investigated in 0.5-M
Na2SO4 aqueous solution, and the highest specific capac-
itance of 110 Fg−1 at a scan rate of 5 mV s−1 was ob-
tained for SnO2 microspheres made up of nanocubes.
Our study shows that supporting electrolytes and electro-
deposition parameters play the significant role in the
growth of SnO2Ns and its electrochemical properties.
Keywords Nanostructures . Electrodeposition . FESEM .
Cyclic voltammetry . Chronoamperometry
* C. Viswanathan
viswanathan@buc.edu.in
1
Department of Nanoscience and Technology, Bharathiar University,
Coimbatore 641046, Tamil Nadu, India
2
Department of Physics, PSG College of Technology, Coimbatore 04,
India
Introduction
Development of electric and hybrid electric vehicles is one of
the probable substitutes to reduce the emission of CO2 gas
from the vehicles using fossil fuels. Lithium-ion batteries with
aqueous solution electrolyte afford many advantages such as
easy performance, low cost, safety, environmental friendly
and no precise cell assembly conditions and application to-
wards improvement of electric and hybrid electric vehicles
[1–4]. An aqueous rechargeable lithium-ion battery
(ARLBs) is composed of anode, cathode and aqueous lithium
salts as electrolyte. The choice of suitable electrode materials
and electrolyte solution is a key factor for the performance of
the aqueous battery cell. Extensive efforts have been paid
upon the improvement of anode material. It is reported that
electrode made up of nanoparticles of metal oxide (MO,
where M is Co, Ni, Mn, Cu, Sn or Fe) demonstrates high
electrochemical capacities, good capacity retention and high
discharging rates [5–7]. SnO2 is regarded as one of the most
promising candidates for anode material in non-aqueous lith-
ium batteries, owing to its high (theoretically) gravimetric
lithium storage capacity of 782 mAh g−1 which is more than
twice as that of the currently commercialized graphite
(372 mAh g−1) and low potential of lithium-ion intercalation
[8–11]. However, lithium alloying and de-alloying properties
of SnO2 in aqueous electrolyte solutions are not often studied.
Study of the electrochemical behaviour of materials in aque-
ous electrolytes is of intense interest in recent research study.
We have reported the influence of deposition voltage and
electrochemical performance of nanostructured SnO2 thin
films in different aqueous electrolyte solutions in our preced-
ing work [12].
In our study, we reviewed the influence of supporting elec-
trolyte on morphology of electrodeposited SnO2 thin films by
two-electrode cell set-up. Here, we studied the morphological

and electrochemical properties of electrodeposited SnO2 films
with the support of two different electrolyte solutions. The
effects of supporting electrolytes on potentiostatic deposition
of SnO2 films were investigated in detail by introducing urea
and ammonium acetate into SnCl2·2H2O electrolyte, respec-
tively. Supporting electrolyte was an electrolyte solution,
whose constituents were not electro active in the range of
applied potentials being studied and whose ionic strength
was much larger than the concentration of an electro-active
substance to be dissolved in it and also it was an inert or
inactive electrolyte. It was used to increase the conductivity
of the solution, to eliminate the transport of electro-active
species by ion migration in the electric field and to maintain
the constant ionic strength and constant pH [13]. The
supporting electrolyte composition is known to be strongly
affecting the electrochemical properties of electrodes. The ef-
fect was usually attributed to geometrical dimensions of the
metal ion taking part in the electrode process as the counter-
ion [14].
It reveals that the chemical nature of introduced supporting
electrolytes plays a significant role in acting on the growth of
SnO2 films. The typical concentration of the electrolyte solu-
tion is 25 mM L−1. Two different morphologies of micro-
spheres made up of nanocubes and microcubes have been
obtained over copper (Cu) substrates. The structural, morpho-
logical and chemical bonding of the microstructures was ana-
lyzed by X-ray diffraction (XRD), FE-SEM and Fourier trans-
form infrared (FTIR) analysis. Redox behaviour of the SnO2
electrode at different scan rates from 5 to 100 mV s−1 was
investigated in aqueous LiOH·H2O, Li2CO3, LiNO3 and
Li2CO3 electrolyte solution. The capacitance characteristic
of the electrode was investigated in Na2SO4 electrolyte
solution.
Experimental
Materials and methods
Anodization is an electrolytic process used for protection or
decoration of metal surfaces. It also increases the thickness of
natural oxide layer on the surface of metals and provides better
adhesion. Copper foil with thickness of 0.1 mm and surface
area of 2 × 2 cm2 was used as the substrate. It was ultrasoni-
cally cleaned in acetone and 0.1-M HCl aqueous solution and
finally with de-ionized water to remove surface impurities.
Well-cleaned copper substrate was used as an anode, and plat-
inum wire had been chosen as a cathode during anodization.
Finally, copper substrate was anodized by 0.1-M aqueous
H2SO4 solution by applying 5 V for 30 min. The solutions
for electrodeposition were composed of 25 mM SnCl2·2H2O
and 75 mM of conc. HNO3 with 20 mM of urea and ammo-
nium acetate. Oxygen is blown into the mixed solutions for
Ionics
1 h to oxidize the stannous ion (Sn2+) into the stannic ion
(Sn4+). The cell for deposition was a two-electrode cell, in
which a platinum wire was used as counter electrode with
separation from the working electrode Cu by 1 cm. The ex-
posed area of the working electrode is 2 × 2 cm2. For the
deposition conducted at a desired temperature, the cell was
first maintained in a water bath to allow it to reach the stable
desired temperature (85 °C), and then, the experiment was
started once the Cu electrode was immersed into the solution.
The deposition voltage and time had been optimized, and
different SnO2 morphologies were achieved. A constant volt-
age of 3 and 4.2 V was applied to the substrates for different
deposition times of 2 and 3 min using a potentiostat. After
electrodeposition, the deposits were washed and immersed
in de-ionized water to remove the chloride contaminants and
dried in air at ambient conditions for subsequent analyses.
Supporting electrolytes having the great influence on the
structure of SnO2, in our case addition of urea resulted micro-
spheres and ammonium acetate induced the formation of
microcubes. Electrodeposition was carried out using a Bio-
Logic Science Instruments (Model SP-50) by a constant
potentiostat method. FTIR spectra of the samples were record-
ed on a BRUKER TENSOR 27 FTIR spectrophotometer in
ATR mode. Raman spectroscopy (Horiba Jobin Yvon) with
Ar laser was used to determine the bonding nature of the SnO2
nanostructures. The crystal structures of the electrodeposited
film were characterized by PANalytical X-ray diffractometer
with Cu-Kα radiation (λ = 1.5406 Å). The morphological
properties were studied by using field emission scanning elec-
tron microscope (FESEM) (JSM-7000F).
The electrochemical performances of the SnO2Ns were
measured at room temperatures using three-electrode cells
with platinum wire as the counter electrode and Ag/AgCl as
the reference electrode. The as-prepared thin films were used
as the working electrodes. The electrolytes were 0.1 M LiOH·
H2O, Li2CO3, Li2SO4 and LiNO3. The potential range for
cyclic voltammetry (CV) measurements was −0.8 to 0.6 V at
a scan rate of 20 mV s−1. Super capacitance properties were
analyzed in 0.5 M of Na2SO4 electrolyte solution at a scan rate
from 5 to 100 mV s−1. The chronoamperometry measure-
ments were taken at a constant voltage of +0.07 and 0.08 V,
and the current change was monitored for 60 s at room tem-
perature. All electrochemical measurements were controlled
via a Bio-Logic Science Instruments (Model-SP-50)
potentiostat-galvanostat.
Results and discussion
Growth mechanism of SnO2 nanostructures
At the beginning of the reaction, the SnO2 particles nucleated
on the surface of the Cu substrate. Then, the supporting
Ionics
electrolytes acted as stabilizer, it prevented the aggregation of
the products, and it also acts as a shape controller to assist the
formation of orthorhombic SnO2 crystals. When a small
amount of supporting electrolytes (CH 4 N 2 O and
CH3COONH4) was added to the reaction system, the interac-
tion strength was enhanced between the anions NO −3 ,
CH3COO− and SnO2 particles, and it was adsorbed to the
particle surface via the van der Waals interaction. The interac-
tion strength was greatly enhanced, and it could efficiently
lower the surface energies. As the reaction proceeds, the or-
thorhombic particles have grown along the different directions
with different growth rates due to their different surface ener-
gies. The adsorption and de-sorption of protons on the differ-
ent facets of SnO2 determine the crystal growth direction
which results in different microstructures.
FESEM analysis
The morphology of SnO2 microspheres electrochemically de-
posited at 3 Vat a deposition time of 2 min over a Cu substrate
is shown in Fig. 1a, b. It clearly shows the sample consisting
of a large number of hierarchical microspheres. Moreover, the
high-magnification FESEM image in Fig. 1c reveals that the
outer surface of the film looks like coarse hierarchical spheres
and consists of many small SnO2 nanocubes with an average
size of about 200 nm. It should be emphasized that these small
nanocubes aggregate to form the sphere-like structure. The
addition of low concentration of supporting electrolyte
CH4N2O played a fundamental role in the formation of mi-
crospheres. The low concentration of CH4N2O could reduce
the nucleation and growth rate of crystals but increase the self-
attachment interaction, resulting in the formation of hierarchi-
cal microstructure. The existence of urea could generate car-
bonate as well as hydroxide species in aqueous solutions;
therefore, the nucleation and growth rate were controlled.
FESEM images of the as-electrodeposited film at 4.2 Vand
3 min in the presence of CH3COONH4 as supporting electro-
lyte are shown in Fig. 2. As can be seen from Fig. 2a, the
electrodeposited film consists of uniformly distributed irregu-
lar crystals, some of them presenting cubic segment. Both the
average size of the crystals and the average size of the spaces
Fig. 1 FESEM micrographs of
SnO2 microspheres (a). b Lower
magnification. c Higher
magnification
between the crystals are about 1.5 μm. In addition to the larger
microcubes, there are also smaller cubes. Growth of two types
of cubes bigger (length of each side 1.5 μm) and smaller
(length of each side 0.8 μm) was obtained for the electrode-
posited SnO2. It is obvious that the addition of 25 mm of
supporting electrolyte can gives rise to the microcubes. The
CH3COO− ions and Sn4+ ions would diffuse, nucleate, grow
and aggregate and finally form the SnO2 microcubes. The
crystals grown have curved and imperfect faces, irregular
shape, corners and rough surface which can be seen from
Fig. 2c [15]. The difference between the formation of SnO2
microspheres and microcubes was due to the involvement of
NO−3 , CH3COO− ions which were a stabilizer and shape
controller.
Structural analysis
Figure 3a shows the FTIR spectrum of prepared SnO2 micro-
spheres. The bands at 3441 and 3323 cm−1 are due to O–H
vibrations of absorbed water [16]. The observed low-intensity
peak around 1645 cm−1 is due to the small amount of adsorbed
water. The characteristic peak at 980 cm−1 is attributed to
surface oxygen molecules (Sn–O). The bands observed at
907 and 843 cm−1 are due to Sn–OH vibrations [17]. The
peaks that present lower than 800 cm−1 are attributed to the
SnO2 phase. The phonon modes at 588 and 524 cm−1 are
correlated to Sn–O bonds [18]. Figure 3b gives the Raman
spectrum of SnO2 microspheres. The vibration mode at
628 cm−1 can be attributed to the Alg symmetric Sn–O
stretching mode in nanocrystalline SnO2. The Raman peaks
located at 228 and 308 cm−1 correspond to IR-active Eu2 TO
mode [19]. Alg mode represents the vibration of oxygen atoms
perpendicular to the c-axis where Sn atoms are at rest. The
XRD pattern of the SnO2 microspheres is shown in Fig. 3c.
The sharp peaks observed in the XRD pattern indicate the well
crystalline nature of the sample. All the observed diffraction
peaks can be systematically indexed to the orthorhombic
phase of SnO2 (JCPDS Card No.78-1063) and SnO (JCPDS
Card No.77-2296). The major reflections are indexed to SnO2
phase. The reflections at (020), (021) and (023) plane corre-
spond to SnO phase present along with SnO2 which indicates

Fig. 2 FESEM micrographs of
SnO2 microcubes (a). b Lower
magnification. c Higher
magnification
a preferred orientation. The average crystallite size calculated
from the Scherer formula was found to be 40 nm. Relatively
higher intensity of diffraction peaks of nanostructure demon-
strates the higher crystallinity.
Figure 4a shows the FTIR spectra of SnO2
microcubes. It is well known that the low wave number
region of 400–800 cm−1 depicts the lattice vibration of
SnO2. The bands, observed at 579 cm−1, are typical for
Fig. 3 a FTIR spectra. b Raman spectra. c XRD patterns of SnO2 microspheres
Ionics
the Sn–O vibration. The characteristic peak at 989 cm−1
is attributed to surface oxygen molecules (Sn–O). The
bands observed at 907 and 834 cm−1 are due to Sn–OH
vibrations. Similarly, the peaks at 3450 and 3304 cm−1
correspond to the OH stretching mode. Figure 4b shows
the Raman spectrum of SnO 2 microcubes. There are
three Raman peaks observed from the spectrum. The
peak at 472 cm−1 can be attributed to Eg vibrational
Ionics

Fig. 4 a FTIR spectra. b Raman spectra. c XRD patterns of SnO2 microcubes

mode, and the high intense peak at 631 cm−1 can be exhibit high crystallinity and the film constitutes highly
attributed to the A1g symmetric Sn–O stretching mode oriented nanoparticles.
in nanocrystalline SnO2 and the peak at 772 cm−1 can
be assigned to the B2g vibrational mode. These Raman
bands are in agreement with previous Raman studies and Electrochemical properties
confirm the high crystalline nature of the SnO 2
nanocrystals. The XRD pattern of the SnO2 microcubes The electrochemical reaction mechanism of SnO2Ns with lith-
is shown in Fig. 4c, which exhibits varied intense peaks ium ion in non-aqueous electrolyte solution has been proposed
that are easily distinguishable. The indexed peaks are in with the following reaction conditions:
agreement with the reported value of SnO2 (JCPDS # SnO2 þ 4Liþ þ 4e− →2Li2 O þ Sn ð1Þ
78–1063). No characteristic peaks of impurities, such as
tin metal and residues from supporting electrolytes, are xLiþ þ xe− þ Sn↔Lix Sn ð2Þ
observed. The average crystallite size was calculated
from the Scherer formula and was found to be 46 nm. The irreversible process in Eq. (1) results in metallic tin
XRD analysis reveals that both the microstructures dispersed in Li2O matrix, and the alloying and de-alloying

process of Li and Sn in Eq. (2) provides the reversible capacity
of the material. The chemical and electrochemical processes
of electrodes in aqueous solutions are much more complicated
than those in non-aqueous solutions. The first reduction peak
appearing in CV of SnO2 corresponds to the irreversible re-
duction reaction of SnO2 into metallic Sn in non-aqueous
solution. In case of aqueous solution, the reduction of SnO2
into metallic Sn observed reversibly in multiple cycles.
Lithium alloying/de-alloying reactions with SnO2 were
studied by cyclic voltammetry. Figure 5a, b show the first
15-cycle voltammetric curves of the SnO2 microspheres with
a scanning rate of 5 mV s−1 in LiOH·H2O and Li2CO3 solution
in the potential range of −0.8 to 0.6 V. In the first cycle, there
are three cathodic peaks located at 0.40, −0.44 and −0.78 V,
respectively, in LiOH·H2O electrolyte solution and 0.5, −0.14
Fig. 5 Cyclic voltammogram of SnO2 microspheres in a LiOH·H2O and
b Li2CO3 aqueous solution
Ionics
and −0.80 in Li2CO3 electrolyte solution. The peak at 0.40 and
0.5 V can be assigned to the reduction of SnO2. Another two
cathodic peaks at −0.44/−0.78 and −0.14/−0.80 V are related
to the alloying of Li ion with Sn. Meanwhile, two anodic
peaks are located near −0.32/−0.07 and 0.07 V, corresponding
to the de-alloying of lithium ion with Sn. The anodic peak
extending towards 0.6 V indicates oxygen gas evolution.
Further CV cycles represent the reversible process of the
alloying and de-alloying of Li ion with Sn. The Li-ion alloys
and de-alloys with the Sn between the potential windows of
0.6 to −0.8 V. The gas evolution which affects the storage
capacity of the cell can be suppressed within this potential
window. The current density of the electrode increases with
the increasing number of cycles. The CV measurements of the
SnO2 electrode demonstrate that the Li+ ion alloys and de-
alloys with SnO2 nanostructures. Figure 6a, b exhibits cyclic
Fig. 6 Cyclic voltammogram of SnO2 microspheres in a LiNO3 and b
Li2SO4 aqueous solution
Ionics
voltammogram of SnO2 microsphere in LiNO3 and Li2SO4
electrolyte solution. No well-resolved redox appeared in the
above electrolyte solution, indicating improper alloying and
de-alloying reaction of SnO2 with Li+ ions. The O2 gas evo-
lution occurs at 0.2 V in the above two electrolyte solutions
which limits the working potential of SnO2 electrode in the
LiNO3 and Li2SO4 solutions. Pseudocapacitance-like behav-
iour is observed instead of alloying and de-alloying reactions.
The CVs of SnO2 microcubes for 15 continuous cycles at
20 mV s−1 in both LiOH·H2O and Li2CO3 electrolyte solution
are shown in Fig. 7a, b. There are oxidation and reduction
peaks in the potential range of −0.8 to 0.6 V. The currents
increase with increasing the cycle time, which indicates that
the activity of the electrode material becomes higher during
the cycling process. The peak potentials have no shifting to-
wards positive and negative potential. The first reduction is
associated with decomposition of SnO2; an alloying peak of
Fig. 7 Cyclic voltammogram of SnO2 microcubes in a LiOH·H2O and b
Li2CO3
the Sn with Li+ ion is observed at second and further reduction
peaks. The presences of oxidation peaks indicate the de-
alloying reaction. Here, the SnO2 microcubes exhibit revers-
ible alloying and de-alloying in both LiOH·H2O and Li2CO3
electrolytes. Figure 8a, b shows the CVs of SnO2 microcubes
at different scan rates. In general, the peak potentials of the
ideal reversible electrode will not change with the variation of
the scanning rate. As can be seen, the potentials of oxidation
peaks shift towards positive and those of reduction peaks shift
towards negative with increasing the scanning rate. Figure 9a,
b show the CV curves of SnO2 microcubes in 0.1 M of LiNO3
and Li2SO4 electrolyte solution at a scan rate of 20 mV s−1.
SnO2 microcubes exhibit an oxidation peak at −0.16/0.08 V
and reduction peaks at 0.06/−0.43 V, indicating alloying and
de-alloying reactions of SnO2 with Li+ ions in LiNO3 electro-
lyte solution. The microcubes exhibit narrow curve in Li2SO4
Fig. 8 Cyclic voltammogram of SnO2 microcubes: a CV curves in
LiOH·H2O at different scan rates. b CV curves in Li2CO3 at different
scan rates

Fig. 9 Cyclic voltammogram of SnO2 microcubes in a LiNO3 and b
Li2SO4 aqueous solution
solution, and no redox peaks are appeared. It may be due to
the solvation of lithium ions in aqueous solutions.
Pseudocapacitance properties of SnO2 microspheres
are elucidated by CV curves in Na2SO4 solution. Figure
10a shows the CV curve for the SnO2 microsphere in
0.5 M of Na2SO4 electrolyte with different scan rates
from 5 to 100 mV s−1. It clearly shows that the pair of
redox peaks appears for the SnO2 microspheres. The oc-
currence of redox peaks implies that the charge storage
mechanism is mainly based on redox reaction. The CV
curves confirm that the redox current increases with the
increase of scan rate, and the anodic and cathodic peaks
shift towards positive and negative potential, respective-
ly. The potential difference (ΔEp) between the anodic
and cathodic peaks is found to be 0.31 V, representing
a well-reversible intercalation/de-intercalation during the
electrochemical process. The specific capacitance (Fg−1)
Ionics
Fig. 10 Cyclic voltammogram of SnO2 microspheres in a Na2SO4
aqueous solution and b dependence of specific capacitance as a
function of scan rate
was calculated from the CV curves according to the fol-
lowing equation:
I
C sp ¼ ð3Þ
S*m
where I is the current density (A), S is the scan rate
(mV s−1), and m is the mass of the electrode active material.
A maximum specific capacitance of 110 Fg−1 was obtained
for the SnO2 microspheres at a lower scan rate of 5 mV s−1.
Similarly, a specific capacitance of approximately 22 Fg−1
was obtained at a high scan rate of 100 mV s−1 for the same
material. Figure 11a shows the typical CV curves of SnO2
microcube electrode at various scan rates in 0.5 M of
Na2SO4 electrolyte solution. The specific mass of SnO2 was
0.05 mg. It is clear from Fig. 11a that there are no redox peaks
Ionics

in the range between −0.6 and 0.2 V. The CV curves exhibit

close to rectangle shape. The CVs are rectangle and symmet-
rical even at a high scan rate of 100 mV s−1, indicating good
reactivity and reversibility. A large magnitude of current in
CV could not be attributed to double-layer processes, but the
rectangular shape indicates the accumulation of charges.
Super capacitance values were calculated using the current,
scan rate of CV and weight of the material. Figure 11b shows
the variation of super capacitance with the scan rate of CV for
SnO2 microcubes, to a specific mass value of 0.05 mg. A
maximum SC value of 42.8 Fg−1 was obtained at a CV scan
rate of 5 mV s−1 and decreases to 7.57 Fg−1 at higher scan rate
of 100 mV s−1.
The stability and activity of SnO 2 electrode under
continuous operating conditions were examined by
chronoamperometric measurements. Figure 12a, b ex-
hibits chronoamperometry curves of SnO2 microspheres

Fig. 12 Chronoamperometry of a SnO2 microspheres and b SnO2

microcubes

and microcubes. Initially, the working electrode was bi-

Fig. 11 Cyclic voltammogram of SnO2 microcubes in a Na2SO4
aqueous solution and b dependence of specific capacitance as a
function of scan rate
ased anodically at −0.07 V (microspheres) and −0.08 V
(microcubes) versus an Ag/AgCl reference electrode for
60 s to allow lithium ion to react with SnO2. Later, the
polari ty was sw itched im mediately to +0.07 V
(microspheres) and +0.08 V (microcubes) to initiate re-
versible reaction and the current changes were plotted
with respect to time. A gradual decrease in current den-
sity per unit time was observed, which is an indication of
propitious electrode activity and high stability [20] and
likely indicates the availability of activation sites in
SnO2 microspheres to react with lithium ions. The elec-
trode charged up to 0.85 mA (microspheres) and
0.016 mA (microcubes) and discharged gradually, which
indicates the good electrode activity. A gradual decrease
in current density per unit time was observed. The elec-
trochemical properties of the SnO2 electrodes with mi-
crospheres and microcube morphologies were

characterized by evaluating the lithium-ion alloying/de-
alloying properties in different aqueous electrolyte
solutions.
Figures 5 and 7 show that both SnO2 electrodes undergo
alloying and de-alloying reactions in LiOH·H2O and Li2CO3
which was confirmed by the existence of anodic and cathodic
peaks. However, the SnO2 electrode with the microsphere
morphology exhibited a significantly higher current density
than the electrode with the microcube morphology. Because
these microspheres are composed of small nanocubes of aver-
age size 200 nm, this nanocube structure of SnO2 gave a high
surface to volume ratio which provides more activation sites
to react with lithium ion when compared with microcube elec-
trodes. Comparison of chronoamperometry analysis indicated
that the microsphere electrode charged up to 0.85 mA, which
is higher than microcube electrode. In both CV and
chronoamperometry (CA) analyses, SnO2 microspheres ex-
hibit a slightly higher current than SnO2 microcubes, which
may be attributed to their different morphologies. It is well
known that the composition and the surface area of the elec-
trode dramatically affect the lithium intercalation rate and ca-
pacitance. SnO2 microspheres present a larger surface area
due to the aggregation of nanocube morphology which could
be the reason for its higher capacitance, as demonstrated. All
the results above obtained from the electrochemical investiga-
tion indicate that the electrochemical properties are related to
the crystal structure, composition and morphology of the elec-
trode material. The obtained well-crystallized SnO2 micro-
spheres in this work with high aspect ratio and surface area
are favourable for reducing the diffusion distance of the solid-
state lithium ion.
Conclusion
Nanostructured SnO2 thin films with two different morphol-
ogies were prepared by introducing supporting electrolytes
and well characterized by FESEM, XRD, FTIR and Raman
analysis. SnO2Ns like microspheres and microcubes were
electrodeposited on anodized copper substrates by altering
the deposition voltage and time. Addition of supporting elec-
trolytes drastically alters the morphology, but there is no
change in the crystalline phase. SnO2Ns showed reversible
alloying and de-alloying reactions with lithium ions in
LiOH·H2O and Li2CO3 electrolyte solutions, and it corre-
sponds to battery behaviour of an electrode. It also exhibits
capacitance behaviour in LiNO3 and Li2SO4 electrolyte solu-
tions. The capacitance behaviour was confirmed by cyclic
voltammetry analysis of the electrodes in Na2SO4 solution.
From the above results, SnO2 microspheres exhibit highest
capacitance of 110 Fg−1 at a scan rate of 5 mV s−1. The elec-
trodes may be used for the assembly of efficient and cost-
effective aqueous lithium-ion batteries.
Ionics
Acknowledgments The authors are sincerely ackowledged University
Grants Commission (UGC), Govt. of India (UGC-MRP F.NO.37-101/
2009 (SR) dt: 19.12.09) for providing financial assistance. The authors
sincerly admit their thanks to DST-PURSE for providing FESEM facility.
References
1. Scrosati B (1995) Challenge of portable power. Nature 373:557–558
2. Li W, Dahn JR, Wright DW (1994) Rechargeable lithium batteries
with aqueous electrolytes. Science 264:1115–1118
3. Alias N, Mohamad AA (2015) Advances of aqueous rechargeable
lithium-ion battery: a review. J Power Sources 274:237–251
4. Wang GJ, Zhao NH, Yang LC, Wu YP, Wu HQ, Holze R (2007)
Characteristics of an aqueous rechargeable lithium battery (ARLB).
Electrochim Acta 52:4911–4915
5. Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM (2000)
Nano-sized transition-metal oxides as negative-electrode materials
for lithium-ion batteries. Nature 407:496–499
6. Wang Y, Zhang YF, Liu HR, Yu SJ, Qin QZ (2003) Nanocrystalline
NiO thin film anode with MgO coating for Li-ion batteries.
Electrochim Acta 48:4253–4259
7. Wu MS, Chiang PC (2006) Electrochemically deposited nanowires
of manganese oxide as an anode material for lithium-ion batteries.
Electrochem Commun 8:383–388
8. Liang Y, Fan J, Xia X, Jia Z (2007) Synthesis and characterization
of SnO2 nano-single crystals as anode materials for lithium-ion
batteries. Mater Lett 61:4370–4373
9. Xu M, Zhao M, Wang F, Guan W, Yang S, Song X (2010) Facile
synthesis and electrochemical properties of porous SnO2 micro-
tubes as anode material for lithium-ion battery. Mater Lett 64:
921–923
10. Yu Y, Gu L, Dhanabalan A, Chen CH, Wang C (2009) Three-
dimensional porous amorphous SnO2 thin films as anodes for Li-
ion batteries. Electrochim Acta 54:7227–7230
11. Reddy MV, Tse LY, Bruce WKZ, Chowdari BVR (2015) Low
temperature molten salt preparation of nano-SnO2 as anode for
lithium-ion batteries. Mater Lett 138:231–234
12. Vasanth Raj D, Ponpandian N, Mangalaraj D, Viswanathan C (2014)
Electrochemical behavior of nanostructured SnO2 thin films in aque-
ous electrolyte solutions. Mater Sci Semicond Process 26:55–61
13. Wang J (2006) Analytical electrochemistry. Wiley-VCH, Weinheim
14. Ivanov VD, Alieva AR (2000) Electrochemical behavior of elec-
trode modified with a cobalt hexacyanoferrate film: effect of the
supporting electrolyte cation. Russ J Electrochem 36:852–860
15. Zhu M, Chen P, Liu M (2011) Sunlight-driven plasmonic
photocatalysts based on Ag/AgCl nanostructures synthesized via
an oil-in-water medium: enhanced catalytic performance by mor-
phology selection. J Mater Chem 21:16413–16419
16. Popescu DA, Verduraz FB (2001) Infrared studies on SnO2 and Pd/
SnO2. Catal Today 70:139–154
17. Hadia NMA, Ryabtsev SV, Seredin PV, Domashevskaya EP (2010)
Effect of the temperatures on structural and optical properties of tin
oxide (SnOx) powder. Physica B 405:313–317
18. Shi L, Lin H (2010) Facile fabrication and optical property of hol-
low SnO2 spheres and their application in water treatment.
Langmuir 26:18718–18722
19. Lupan O, Chow L, Chai G, Heinrich H, Park S, Schulte A (2009)
Synthesis of one-dimensional SnO2 nanorods via a hydrothermal
technique. Phys E 41:533–536
20. Jayashree RS, Spendelow JS, Yeom J, Rastogi C, Shannon MA,
Kenis PJA (2005) Characterization and application of electrodepos-
ited Pt, Pt/Pd, and Pd catalyst structures for direct formic acid micro
fuel cells. Electrochim Acta 50:4674–4682