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Hydroxy functionalized ionic liquids as promising electrolytes for

supercapacitor study of α-Fe2O3 thin films

Article  in  Journal of Materials Science: Materials in Electronics · August 2017

DOI: 10.1007/s10854-017-6978-3

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J Mater Sci: Mater Electron
DOI 10.1007/s10854-017-6978-3

Hydroxy functionalized ionic liquids as promising electrolytes

for supercapacitor study of α-Fe2O3 thin films
Sandip K. Patil1 · Madagonda M. Vadiyar1 · Sagar C. Bhise1 · Suryakant A. Patil1 ·
Deepak V. Awale1 · Uma V. Ghorpade1,2 · Jin H. Kim2 · Anil V. Ghule3 ·
Sanjay S. Kolekar1 

Received: 17 December 2016 / Accepted: 17 April 2017

© Springer Science+Business Media New York 2017

Abstract  Herein, we are exploring hydroxy functional-
ized ionic liquids (HFILs) as electrolytes in electrochemi-
cal studies of F­ e2O3 thin films in aqueous medium. The
thin films are deposited by simple and cost effective succes-
sive ionic layer adsorption and reaction (SILAR) method at
room temperature. Four HFILs, [HEMIM][Cl], [TEHEA]
[Cl], [(EtOH)NH3][Ac] and [(EtOH)3NH][Ac] are synthe-
sized and their aqueous solutions have been studied as elec-
trolytes. Syntheses of ILs are confirmed by NMR spectra
whereas the structural and surface properties of ­Fe2O3 thin
film is determined by X-ray diffraction pattern (XRD), field
emission scanning electron microscopy (FESEM), energy-
dispersive X-ray spectroscopy (EDAX) and Brunauer–
Emmett–Teller (BET) analysis. XRD pattern confirms the
rhombohedral phase of α-Fe2O3 (hematite). Electrochemi-
cal performance of F ­ e2O3 electrode in 0.1  M HFILs is
investigated with cyclic voltammetry (CV), galavanostatic
Electronic supplementary material  The online version of this
article (doi:10.1007/s10854-017-6978-3) contains supplementary
material, which is available to authorized users.
* Jin H. Kim
jinhyeok@chonnam.ac.kr
* Sanjay S. Kolekar
sskolekar@gmail.com
1
Analytical Chemistry and Material Science Research
Laboratory, Department of Chemistry, Shivaji University,
Kolhapur, MS 416004, India
2
Department of Materials Science and Engineering
and Optoelectronics Convergence Research Centre, Chonnam
National University, 300, Yongbong‑Dong, Buk‑Gu,
Gwangju 500‑757, South Korea
3 broad scope in electrochemistry [5]. ILs own such proper-
Green Nanotechnology Laboratory, Department
of Chemistry, Shivaji University, Kolhapur, MS 416004,
India
charge/discharge (GCD) analysis and electrochemical
impedance spectroscopy (EIS). ­Fe2O3 electrode exhibited
good capacitive nature in all HFILs, however, [HEMIM]
[Cl] conferred highest specific capacitance of 124  Fg−1 at
4.0  mA  cm−2 current density amongst the studied HFILs.
Good cycle stability and up to 91% retention of capacitance
over 1000 cycles is availed with [HEMIM][Cl]. Such prom-
ising results are strongly emphasizing the possible utiliza-
tion of HFILs as environmental benign media in superca-
pacitor application.
1 Introduction
Room temperature ionic liquids (RTILs) are entirely com-
posed of ions and generally, known to be having melting
point below 100 °C [1]. Due to the unique physico-chem-
ical properties they have attracted much attention in wide
applicative fields as promising contenders. Their non-
detectable vapour pressures and distinctive solvent proper-
ties, indeed, provide the possibility for green manufactur-
ing in chemical industry [2, 3]. ILs are treated as ‘designer
molecules’ since their physical and chemical properties can
be tailored just by tuning the pairing combination of cati-
ons and anion. This unique ability to tune the properties,
often with just selection of the ions rather than covalent
modification, makes ILs attractive for wide range of appli-
cations, from materials science to electrochemistry and
from catalysis to medicinal chemistry [4]. The environmen-
tal benign nature of ILs along with wide electrochemical
window, high thermal and electrochemical stability, high
conductivity, non-volatility, non-flammability, afford them
ties essential for an electrolyte to be employed in energy
devices such as supercapacitors, solar cells, batteries, fuel

13
Vol.:(0123456789)

cells etc. In addition the problem of safety inherent with
energy devices, which is a critical issue than performance
these days, is expected to be resolved by the use of ILs
[6]. Accordingly, numbers of reports have been explored
the variety of ILs as electrolytes in supercapacitor study
with different electrode materials, for instance electrolyte/
electrode systems, [­BMIM][BF4], ­[BMIM][PF6]/activated
carbon (AC)//poly(3-methylthiophene) (pMeT) [7]; phos-
phonium ILs/AC ­[Pyrr][NO3]/carbon [8, 9]; pyridinium IL/
Nafion-doped polypyrrole ­[CMIM][HSO4]/Ru doped CuO
[10–12]; imidazolium ILs/glassy carbon [13].
Electrochemical supercapacitors are simple energy stor-
age devices with high rate charging-discharging capabilities
and high power density [14]. In extension with our previ-
ous work related to supercapacitor study, in which thiocy-
anate functionalized ILs with ­ZnFe2O4 and [MOPDMIM]
[Cl] with CuO electrode [15, 16] were explored; in present
work, we have investigated electrochemical performance
of ­Fe2O3 electrode in aqueous hydroxy functionalized ILs
(HFILs). Comparing to non-functionalized ionic liquids,
incorporation of hydroxyl group in IL moiety evolves
the physico-chemical features such as viscosity, density,
improved solubility of inorganic salts, enhanced hydrogen
bonding interactions, increasing hydrophilicity as well as
it influences the thermodynamic properties of ILs [17–21].
Some of the HFILs possess high polarity close to protic ILs
and water [22]. These advancements in physical and chemi-
cal properties of HFILs opened extensive usability, like in
solvent extraction [23], fixation of C
­ O2 [24], synthesis and
stabilization of nanoparticles [25], dehydration of fructose
or glucose to 5-hydroxymethylfurfural [26], dissolution of
heavy crude oils [27] and many more. Moreover, HFILs
are low toxic and exhibiting antimicrobial activities [28,
29]. Fascinating electrochemical properties including high
ionic conductivity and wider potential window make them
capable aspirants in electrochemistry [30–32]. Due to such
attractive properties, we have chosen HFILs as electrolytes
in this electrochemical study. The ion sizes, viscosity and
electric conductivity of electrolyte affect the electrochemi-
cal performance of electrode material [15, 33]. To investi-
gate effect of these factors on capacitance of ­Fe2O3 elec-
trode we have selected four different HFILs having different
cationic sizes, different viscosities and conductivities. We
have synthesized imidazolium; ammonium and alkanolam-
monium based four HFILs encompassing 2-hydroxyethyl
chain.
To investigate their performance, aqueous solutions
of HFILs are exploited as electrolytes in electrochemi-
cal study of F ­ e2O3 thin film as electrode. Amongst the
transition metal oxides, F ­ e2O3 is one of the most prom-
ising pseudocapacitor electrode materials with respect
to both its specific capacitance and cost effectiveness
[34]. In fact, n-type hematite (α-Fe2O3) an attractive
13
J Mater Sci: Mater Electron
environmental friendly semiconductor material largely
utilized in electrochemical capacitors because of its high
abundance, superior chemical stability, high resistance
to corrosion and non toxicity [35–39]. The thin films of
­Fe2O3 are deposited by successive ionic layer adsorp-
tion and reaction method (SILAR). This low cost and
low temperature soft chemical solution method has its
own advantages such as layer-by-layer growing mode,
simple and handy process, excellent material utilization
efficiency, ease of incorporation of composite elements
and good control over the deposition process along with
the film thickness and large-scale deposition capabil-
ity on any type of substrate [40–43]. Prepared electrode
material was subjected to structural and surface mor-
phological characterizations prior to the electrochemical
measurements.
2 Experimental
2.1 Materials and chemicals
All chemicals procured were of analytical grade and used
as received without further purification. Doubly distilled
water was used preferentially throughout the experi-
ment. 1-methylimidazole, 1-chloroethanol from Spec-
trochem Pvt. Ltd. (India), triethylamine, ethanolamine,
triethanolamine and acetic acid from s d fine chem. Ltd.
(India) were purchased for the syntheses of ionic liquids.
Whereas ferrous chloride tetrahydrate ­(FeCl2·4H2O) and
ammonia (Merck India, Ltd.) were used for the thin film
deposition on stainless steel substrates. All the solvents
used in IL synthesis were of analytical grade and used as
received.
2.2 Material characterization techniques
The NMR spectra of ILs were recorded on Bruker
300 MHz spectrometer. The structure and phase identifica-
tion of ­Fe2O3 was evaluated by XRD (Bruker, D2-Phaser
X-ray diffractometer) with Cu-Kα (λ = 1.5406 A°) radia-
tion in the range 10–80°. The surface morphology of the
­Fe2O3 thin film was characterized by field emission scan-
ning electron microscopy (FESEM) (Hitachi, S-4700).
Nitrogen adsorption–desorption isotherm was obtained
by Quantachrome Instrument (NOVA 1000e). The surface
area was calculated with the Brunauer–Emmett–Teller
(BET) and the pore size distributions were calculated by
Barrett–Joyner–Halenda (BJH) equation. The conductivi-
ties of aqueous HFILs were measured by digital conductiv-
ity bridge (Equip-tronics, EQ-664-E, India).
J Mater Sci: Mater Electron
2.3 Electrochemical characterization
A three electrode system consisting of ­Fe2O3 thin film as a
working electrode, silver/silver chloride (Ag/AgCl) as ref-
erence electrode and graphite as a counter electrode, was
constructed for electrochemical measurements. The elec-
trochemical study involving cyclic voltammetry (CV) anal-
ysis at different scan rates (10–100  mVs−1), the galvano-
static charge/discharge (GCD) study as function of varying
current densities and electrochemical impedance spectros-
copy (EIS) in the frequency range from 1  Hz to 100  kHz
was performed in 0.1 M HFIL solutions by using CHI 608E
electrochemical analyzer (CH Instruments, Inc., USA).
2.4 Synthesis of ionic liquids
2.4.1 Synthesis of [HEMIM][Cl] and [TEHEA][Cl]
These two ILs were synthesized by conventional reflux
method (Scheme S1). In a typical procedure, to 0.1  mol
1-methylimidazole, 0.15 mol of 1-chloroethanol was added
slowly with constant stirring in a round bottom flask in
presence of acetone as solvent. The reaction mixture was
refluxed at 70 °C for 24 h. Two layers were formed, out of
which upper solvent layer was discarded and remaining vis-
cous layer of IL was washed with ethyl acetate (5 × 10 mL)
followed by n-hexane. Obtained IL, 1-(2-hydroxyethyl)-
3-methylimidazolium chloride, [HEMIM][Cl] was further
dried in vacuum for 24 h. Same methodology was acquired
for synthesis of IL, N,N,N-triethyl-2-hydroxyethan-1-amin-
ium chloride [TEHEA][Cl], by using triethylamine as start-
ing reagent. Both ILs are white, low melting solid products
and dried prior to use.
2.4.2 Synthesis of [(EtOH)NH3][Ac] and [(EtOH)3NH]
[Ac]
However, these two ILs were prepared by simple neutrali-
zation reactions (Scheme S2). Equimolar amounts of etha-
nolamine or triethanolamine and acetic acid (each 0.1 mol)
were mixed together slowly under ice-cold conditions.
Reaction mixture was stirred vigorously for 3 h to get cor-
responding ILs. Obtained ILs were washed several times
with ethyl acetate (5 × 10  mL) and n-hexane. The viscous
ILs, 2-hydroxyethan-1-aminium acetate, [(EtOH)NH3][Ac]
and 2-hydroxy-N,N-bis(2-hydroxyethyl)ethan-1-aminium
acetate, [(EtOH)3NH][Ac] were well dried in vacuum for
further utilization.
2.5 Deposition of ­Fe2O3 thin films
The thin films of F
­ e2O3 were prepared by successive ionic
layer adsorption and reaction (SILAR) deposition method.
The optimized deposition method involved 30  mL of
0.1 mol L−1 ferrous chloride tetrahydrate as precursor solu-
tion having pH 10 maintained by using ammonia solution.
The well cleaned stainless steel substrate was immersed in
precursor solution for 30 s for adsorption of iron species on
surface of the substrate. The substrate was then rinsed in
double distilled water for 30 s. Thus, one SILAR cycle of
deposition was completed. 100 such deposition cycles were
repeated at room temperature to get optimum thickness.
After completion of deposition, films were dried in air and
further air annealed at 773 K for 5 h. Formed dark orange
red colored ­Fe2O3 films were subjected to structural, mor-
phological characterization and electrochemical study.
3 Results and discussion
3.1 Characterization of ILs
Synthesized ILs were characterized by 1HNMR and
13
CNMR spectroscopy (spectra included in electronic
supplementary material, Figs. S1–S8). Spectral data is as
follows,
[HEMIM][Cl]; 1HNMR data (DMSO ­ d6, 300  MHz),
δ (ppm): 2.50 (s, 2H), 3.85 (s, 3H), 4.21–4.23 (d, 2H),
5.34 (s, 1H), 7.70–7.74 (d, 2H), 9.20 (s, 1H).
13
CNMR data (DMSO ­d6, 75  MHz), δ (ppm): 36.21,
52.02, 59.93, 123.07, 123.52, 137.06.
[TEHEA][Cl]; 1HNMR data (DMSO ­d6, 300  MHz), δ
(ppm): 1.20–1.25 (t, 9H), 3.33–3.43 (m, 8H), 3.82 (s,
2H), 5.60 (s, 1H).
13
CNMR data (DMSO d­6, 75  MHz), δ (ppm): 7.70,
53.41, 55.04, 58.37.
[(EtOH)NH3][Ac]; 1HNMR data (DMSO d­ 6, 300 MHz),
δ (ppm): 1.79–1.85 (t, 3H), 2.85 (s, 2H), 3.62 (s, 2H),
6.26 (s, 3H), 7.22 (s, 1H).
13
CNMR data (DMSO ­d6, 75  MHz), δ (ppm): 22.94,
58.63, 60.68, 170.75.
[(EtOH)3NH][Ac]; 1HNMR data (DMSO d­ 6, 300 MHz),
δ (ppm): 1.86 (s, 3H), 2.58–2.62 (t, 6H), 3.45–3.48 (t,
6H), 4.94 (s, 4H).
13
CNMR data (DMSO ­d6, 75  MHz), δ (ppm): 21.70,
57.36, 59.17, 173.41.
3.2 X‑ray diffraction analysis
The XRD pattern of SILAR deposited F ­e2O3 thin film
annealed at 773 K is shown in Fig. 1. The pattern showed
prominent peaks at 2θ angles 24.24°, 33.26°, 35.72°,
40.98°, 49.58°, 54.22°, 57.68°, 62.58°, 64.14°, 69.76° and
72.08° corresponding to (012), (104), (110), (113), (024),
(116), (122), (214), (300), (208) and (119) orientations
13
 J Mater Sci: Mater Electron

respectively. The peaks due to stainless steel substrate are

marked by asterisk. XRD peaks in the pattern confirm the
rhombohedral phase of α-Fe2O3 (hematite) in accordance
with Joint Committee on Powder Diffraction Standards
(JCPDS) card number 024-0072 (a = 5.038 Å, c = 13.77 Å).
The intense and narrow diffraction peaks indicate the purity
with well defined crystalline structure of iron oxide.

3.3 FESEM and EDAX analysis

Figure 2a–c demonstrates the FESEM images of the α-Fe2O3

thin film at different magnifications. The surface of thin film
displayed agglomerated nanograins like morphology [44].
The agglomeration may arised due to the thickness of film.
Smaller primary particles have a large surface free energy
and therefore, tend to agglomerate faster and grow into larger
grains [36]. The surface morphological study demonstrated
the crack less and homogeneous deposition of ­Fe2O3 thin
Fig. 1  The XRD pattern of SILAR deposited ­
Fe2O3 thin film
annealed at 773 K film. Growth of depositing material at surface of thin film has

Fig.  2  a–c FESEM images of the F

­ e2O3 thin film at different magnifications displaying nanograins like morphology, d energy-dispersive X-ray
spectroscopy (EDAX) spectrum of α-Fe2O3 thin film

13
J Mater Sci: Mater Electron
much impact on its performance [45]. The Energy-dispersive
X-ray spectroscopy (EDAX) spectrum of α-Fe2O3 exhibited
the presence of Fe and O elements which confirms the forma-
tion of iron oxide, Fig. 2d.
3.4 BET analysis
The surface area and porous nature of α-Fe2O3 was esti-
mated by Nitrogen adsorption–desorption isotherm
(Fig. 3). The specific surface area was derived by using the
Brunauer–Emmett–Teller (BET) method from the adsorption
isotherm in P/P0 range of 0.05–0.3. The isotherm of F ­ e2O3
appears to be class IV with H3 type hysteresis in the P/P0
range of 0.1–0.9 [46, 47]. Barreett–Joyner–Halenda (BJH)
curves from desorption branch of isotherms exhibits pore
size distribution with average pore diameter of 4.6  nm and
the obtained BET surface area is 17.34 m2 g−1 indicating the
occurrence of nanostructure.
3.5 Electrochemical studies of α‑Fe2O3 with aqueous
HFILs
Synthesized HFILs were studied as aqueous electrolytes to
assess the electrochemical performance of α-Fe2O3 thin film
as an electrode. The electrochemical study was conceded in
four HFILs; [HEMIM][Cl], [TEHEA][Cl], [(EtOH)NH3][Ac]
and [(EtOH)3NH][Ac] as electrolytes in aqueous media. The
concentration of each IL taken was 0.1 M in the electrochem-
ical cell constructed with three electrode system as follows
[48],
SS/α − Fe2 O3 ∕0.1M HFIL/Ag/AgCl/G
Fig. 3  Nitrogen adsorption–desorption isotherm of ­Fe2O3 with pore
size distribution (inset)
The CV curves obtained for α-Fe2O3 electrode with HFIL
electrolytes at different scan rates (10–100 mVs−1) within the
potential window of 1.2 V are shown in Fig. 4. The shapes
of CV curves are found varied with the electrolytes. Some-
what identical shapes observed with analogous ILs, such as,
[HEMIM][Cl] and [TEHEA][Cl] or [(EtOH)NH3][Ac] and
[(EtOH)3NH][Ac]. The slight deviations seen in CV curve
shapes with increasing scan rates are emphasizing the capaci-
tive behaviour of electrode. The shapes of these curves are
deviated from the ideal rectangular shape perceived with
electric double layer capacitors (EDLCs), suggesting the
capacitance characteristic of α-Fe2O3 is due to the pseudoca-
pacitance behaviour. This is due to a low contact resistance
of ion migration, which indicates excellent capacitive features
[16, 49–51]. The capacitance of the α-Fe2O3 is ascribed to
redox conversions in oxidation state of iron as ­Fe3+ to ­Fe2+
and vice versa. The diversity in CV curve shapes acquired
with HFILs is may be due to the differences in the size of
cations and anions as well as their physico-chemical proper-
ties. The α-Fe2O3 electrode exhibited small redox peaks in all
the electrolytes except the ILs containing acetate (Ac) anions,
especially, [(EtOH)3NH][Ac] shows exceptionally fine shape
of CV curves which provides obvious redox peaks with sym-
metrical orientation.
Figure  5 shows the galavanostatic charge–discharge
(GCD) curves of α-Fe2O3 thin films with HFIL electrolytes
at different current densities. The nature of GCD curves also
supports the capacitive behaviour of α-Fe2O3 in HFIL elec-
trolytes [38]. From the GCD analysis the specific capacitance
­(Csp) of α-Fe2O3 is calculated by using following equations
[15, 52],
C = (I ⋅ Δt)∕ΔV (1)
Csp = C∕m (2)
where, I is the constant discharge current, Δt is the dis-
charge time, ΔV is the voltage range, m is the active mass
of the working electrode, and Csp is the specific capaci-
tance. Derived specific capacitances of α-Fe2O3 in 0.1  M
HFILs at various current densities are presented in Table 1.
A common tendency of reduction in capacitance with rise
in current density is observed in all electrolytes, Fig.  6a.
It was mainly due to the incremental IR drop and lacking
of active material involved in the redox reactions at higher
current densities [53]. [HEMIM][Cl] exhibited highest
specific capacitance of 124 ­Fg−1 at 4.0 mA  cm−2 current
density whereas [(EtOH)3NH][Ac] shown lowest (48 F ­ g−1
−2
at 1.1  mA  cm ) amongst the HFILs. The energy density
(E) and power density (P) for α-Fe2O3/0.1 M HFIL electro-
chemical systems are derived by using following formulae
[54],
Csp × ΔV 2
E= (3)
7.2
13

Fig. 4  Cyclic Voltammetry (CV) curves of α-Fe2O3 electrode with 0.1  M HFIL electrolytes at different scan rates; 10, 20, 40, 60, 80,
100 mVs−1 within the potential window of 1.2 V
3.6 × E
P= (4)
Δt
where, E is the energy density, P is the power density, Csp is
the specific capacitance, ∆V is the potential window and ∆t
is the discharging time. The energy density of the system is
found decreasing with increase in power density (Fig. 6b).
Further, to investigate the electrochemical behaviour of
α-Fe2O3, electrochemical impedance spectroscopic (EIS)
study was performed (Fig.  7). The impedance spectrum
comprises two regions, semicircle in the high frequency
region and a slanting line in the low frequency region. The
intercept of the semicircle on the real axis at high frequency
represents the solution resistance (­ Rs) while the diameter of
the semicircle corresponds to the charge transfer resistance
­(Rct) [55]. A semicircle in the high-frequency region and
a sloping line in the low-frequency region, confirms the
supercapacitor behaviour of α-Fe2O3 [56, 57]. EIS spectra
reveal the good capacitance nature of α-Fe2O3 with studied
HFIL electrolytes. The R ­ s and ­Rct values provided by the
13
J Mater Sci: Mater Electron
Nyquist plot are as shown in Table 2. The solution resist-
ance are in order [HEMIM][Cl] < [TEHEA][Cl] < [(EtOH)
NH3][Ac] < [(EtOH)3NH][Ac] whereas, expectedly, lesser
charge transfer resistance is also observed with [HEMIM]
[Cl] amid the HFILs.
Electric conductivity and viscosity of electrolyte solu-
tion are crucial factors in any electrochemical system.
Generally, ILs are known for good conductivity but their
highly viscous character creates barrier in charge transport
in electrolytic systems and consequently decreases the elec-
trochemical performance of electrode. Indeed, the high vis-
cosity hinders their applications in energy devices [58]. In
present case, the observed lower R­ s and R
­ ct values indicate
the high electrical conductivity and faster charge-transfer
capability of 0.1  M [HEMIM][Cl] compared with that of
other HFIL electrolytes. In general, imidazolium ionic liq-
uids are known for good ionic conductivity compared to
other types of ionic liquids and therefore they can provide
better electrochemical performance [33]. Measured electri-
cal conductivity and the viscosities of 0.1  M solutions of
J Mater Sci: Mater Electron

Fig. 5  Galavanostatic charge–discharge (GCD) curves of α-Fe2O3 thin films with 0.1 M HFIL electrolytes at different current densities

Table 1  Specific capacitance ­(Csp), power density (P) and energy HFILs (Table 2) clearly establish that [HEMIM][Cl] is the
density (E) of α-Fe2O3 thin films in 0.1 M HFIL electrolytes at differ- superior electrolyte over other studied HFILs. The high-
ent current densities derived from GCD curves
est specific capacitance of α-Fe2O3 electrode in 0.1  M
Sr. no. HFIL Current Csp P E [HEMIM][Cl] can be attributed to its high electrical con-
density (F g−1) (kW kg−1) (Wh kg−1) ductivity and low viscosity which consequently fascinate
(mA cm−2)
the charge transport.
1 [HEMIM][Cl] 4.0 124 3.4 24.8 For comparison purpose, the electrochemical perfor-
4.5 107 3.9 21.4 mance of α-Fe2O3 was checked in 0.1  M ­Na2SO3, which
5.0 76 4.3 15.1 is one of the conventional electrolytes for iron oxide thin
6.0 49 5.1 9.7 films used in supercapacitor. The non-rectangular shapes
2 [TEHEA][Cl] 4.0 54 3.4 10.9 as well as deviations with increasing scan rates in shapes
4.5 42 3.9 8.4 of CV curves obtained within potential window of 1.2  V
5.0 32 4.3 6.4 uphold the pseudocapacitance behaviour of α-Fe2O3 elec-
6.0 22 5.1 4.4 trode, Fig. 8a. The specific capacitance of α-Fe2O3 in 0.1 M
3 [(EtOH)NH3] 2.0 57 1.7 11.5 ­Na2SO3, derived from GCD analysis, Fig. 8b, is found to be
[Ac] 3.0 41 2.6 8.1 63 Fg−1 at current density of 0.5 mA cm−2 which is lower
3.5 26 3.0 5.3 than that is obtained with 0.1 M [HEMIM][Cl].
4.0 20 3.4 3.9 Cycle stability and retention of capacitance of electrode
4 [(EtOH)3NH] 1.1 48 0.9 9.5 is essential part in practical applications of supercapaci-
[Ac] 1.5 23 1.3 4.5 tors. The cycle stability of α-Fe2O3 in 0.1 M [HEMIM][Cl]
2.0 19 1.7 3.7 was tested upto 1000 cycles and counter checked with that
2.5 17 2.1 3.3 of 0.1  M N ­ a2SO3. Upto 91% retention of capacitance is

13
 J Mater Sci: Mater Electron

Fig.  6  a Graph of Specific capacitance (­Fg−1) vs. current density (mA  cm−2), b ragone plot of energy density (Wh  kg−1) vs. power density
(kW kg−1) of α-Fe2O3 thin films with 0.1 M HFIL electrolytes

Fig. 7  Nyquist plots from Electrochemical Impedance Spectroscopic (EIS) study of α-Fe2O3 thin films in 0.1 M HFIL electrolytes

observed with 0.1  M [HEMIM][Cl] which is comparably
better than in 0.1 M N
­ a2SO3 (84% retention), Fig. 9.
The electrochemical performance of α-Fe2O3 in 0.1 M
[HEMIM][Cl] is very promising compared to different
electrolytes investigated in various literature reports
(Table 3). The study reveals the potential of current elec-
trochemical system in supercapacitor application.

13
J Mater Sci: Mater Electron

Table 2  Electrical conductivity Sr. no. HFIL Conductivity of Viscosity of 0.1 M solu- Rs (ohm) Rct (ohm)
(σ), viscosity (η), solution 0.1 M solution tion at RT (mPa.s)
resistance ­(Rs) and charge (mS cm−1)
transfer resistance (­ Rct) of 0.1 M
HFIL electrolytes 1 [HEMIM][Cl] 7.69 0.95 2.67 10.05
2 [TEHEA][Cl] 6.93 0.97 3.22 13.14
3 [(EtOH)NH3][Ac] 4.43 1.02 4.59 28.47
4 [(EtOH)3NH][Ac] 3.50 1.03 5.61 26.13

Fig.  8  a Cyclic voltammetry (CV) and b galavanostatic charge–discharge (GCD) analysis of α-Fe2O3 thin film in 0.1 M N
­ a2SO3 electrolyte

Table 3  Comparison of electrochemical performance of α-Fe2O3

electrode with different electrolytes
Sr. no. Electrolyte Current Specific Reference
density/scan capaci-
rate tance
(F g−1)

1 1 M ­Li2SO4 0.75 A ­g−1 116 [59]

2 1 M LiOH 1 mV ­s−1 102 [60]
3 1 M NaOH 5 mV ­s−1 4.9 [61]
1 M ­Na2SO3 5 mV ­s−1 48
4 1 M KOH 1 A ­g−1 118 [62]
1 A ­g−1 145 [37]
5 1 M ­Na2SO3 1 A ­g−1 127 [63]
6 1 M ­NEt4BF4/pro- 20 mV ­s−1 47 [64]
pylene carbonate
7 0.1 M [HEMIM] 4 mA ­cm−2 124 Present work
[Cl]
Fig. 9  Cycle stability study of α-Fe2O3 in 0.1 M [HEMIM][Cl] and
0.1 M ­Na2SO3 electrolytes over 1000 cycles

SILAR deposited α-Fe2O3 (hematite) thin film has agglom-

4 Conclusion
Four hydroxy functionalized ionic liquids have been inves-
tigated as electrolytes in electrochemical study of iron
oxide. The structural and surface studies demonstrate the
erated nano-grains like surface morphology with fine pore
size distribution. It exhibited good capacitive nature in
0.1 M HFILs, revealed by cyclic voltammetry analysis. The
specific capacitance of α-Fe2O3 electrode is derived from
galavanostatic charge/discharge studies at different current

13

densities. 0.1  M [HEMIM][Cl] furnished highest specific
capacitance of 124 F ­ g−1 at 4.0  mA c­ m−2 current density
within 1.2 V potential window amongst the studied HFILs.
The high capacitance of [HEMIM][Cl] electrolyte can be
attributed to least solution and charge transfer resistance
availed due to its good electrical conductivity and low vis-
cosity in aqueous medium. Adequate cycle stability with
good capacitance retention of α-Fe2O3 electrode empha-
size the convenient appliance of [HEMIM][Cl] in superca-
pacitor. In conclusion, we are proposing an environmental
benign hydroxy functionalized IL with moderate concen-
tration as an electrolyte in supercapacitor application.
Acknowledgements  The authors SKP, MMV under the UGC-BSR
Meritorious Students fellowship and SCB under RGNF are thankful
to the University Grants Commission (UGC) for financial support and
DST-FIST, Department of Chemistry, Shivaji University, Kolhapur.
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