Journal of Molecular Liquids 366 (2022) 120245

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Ionic liquid derived novel deep eutectic solvents as low viscous

electrolytes for energy storage
Sambita Choudhury, Upasana Mahanta, R. Prasanna Venkatesh, Tamal Banerjee ⇑
Department of Chemical Engineering, Indian Institute of Technology Guwahati, India

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

Article history: This work investigates a newly emerging class of solvents to be used as alternatives to or complementar-
Received 20 May 2022 ily with ionic liquid (IL) electrolytes. Three novel deep eutectic solvents (DESs) comprised of the hydrogen
Revised 24 August 2022 bond donors (HBDs), namely N-Methylacetamide (NMAc) and formamide, were formulated with three
Accepted 28 August 2022
variants of the methyl imidazolium-based ionic liquids (ILs) as hydrogen bond acceptors (HBAs). ILs con-
Available online 5 September 2022
sisting of 1-butyl-3-methyl imidazolium ([BMIM]) cation with anions namely methanesulphonate
([MeSO3]), bis(trifluoromethylsulfonyl)imide ([Tf2N]), and hexafluorophosphate ([PF6]) were used as
Keywords:
hydrogen bond acceptors. Initially, the eutectic points of the DESs were estimated using a quantum
Deep eutectic solvents
Ionic liquids
chemical-based thermodynamic model, namely Conductor like Screening Model-Segment Activity
Electrolytes Coefficient (COSMO-SAC). The calculated melting points of the DESs were determined to be markedly
Electrochemical stable potential window lower than those of both the constituent components. Further, physical and chemical characterization
Viscosity was done on the synthesized DESs. The viscosities (<20 cp) were found to be significantly lower than
Ionic conductivity those of conventionally used pure room temperature ILs, and ionic conductivities (>5 mS/cm) were found
to be appreciably higher than those of the corresponding constituent ILs. Thermogravimetric analysis
revealed negligible mass loss up to 80–100 °C. Linear scan voltammetry (LSV) was employed to deter-
mine the electrochemical stable potential window (ESPW) of the solvents with a glassy carbon (GC) elec-
trode. LSV provided electrochemical stabilities in the range of 3.8–4 V for all three studied deep eutectic
solvents, comparable to pure ILs and far higher than the potential windows of mixtures of ILs and organic
solvents, a blend commonly used as electrolytes.
Ó 2022 Elsevier B.V. All rights reserved.

1. Introduction ities [3–6]. Furthermore, room temperature ionic liquids (RTILs)

In modern organic synthesis, apart from the attention to effec-
tiveness, the development of environment friendly and economic
solvents is of paramount importance as well [1]. Volatility,
flammability and emission of toxic fumes are some of the safety
concerns related to the formerly conventionally used organic sol-
vents. Furthermore, in various industrial applications, there is a
risk of performance degradation in the usage of these solvents
due to the complex purification processes [2]. Consequently, it
was deemed crucial to find appropriate alternatives. Over the past
few years, ionic liquids (ILs) have been recognized as potential
replacements to organic solvents and are being used in various
industrial and research processes including in electrochemical
energy storage due to the non-flammability, higher thermal and
chemical stability; and their comparatively higher ionic conductiv-
⇑ Corresponding author at: Dept. of Chemical Engineering, IIT Guwahati, Assam
781039, India.
E-mail address: tamalb@iitg.ac.in (T. Banerjee).
are very promising electrolytes owing to their wide electrochemi-
cal stable potential window (ESPW), in the range of 3–6 V [7,8].
However, their major drawback and performance limitation stems
from their higher viscosities caused by the relatively smaller aver-
age radii of the voids than radii of the ions [9]. This limitation is
usually overcome by the dilution with organic solvents like ace-
tonitrile, butyronitrile, and benzonitrile which has been reported
to appreciably lower the viscosity and consequently, increase the
ionic conductivities of RTILs [7,10]. However, the ESPW is compro-
mised with the addition of organic solvents [11,12].
Deep Eutectic solvents (DESs) constitute a newly emerging class
of solvents with their attractive physicochemical properties. A DES
is defined as an eutectic mixture of a hydrogen bond acceptor
(HBA) and a hydrogen bond donor (HBD), which when mixed in
a certain mole ratio, are associated through hydrogen bonding
[13].The new phase thus formed is characterized by a lower freez-
ing point as compared to the constituent compounds [14]. Conven-
tionally, a quaternary ammonium salt would be mixed as the HBA
with a suitable HBD such as alcohols, amides, carboxylic acids and

https://doi.org/10.1016/j.molliq.2022.120245
0167-7322/Ó 2022 Elsevier B.V. All rights reserved.
S. Choudhury, U. Mahanta, R. Prasanna Venkatesh et al.
glycols to form DESs [15]. The donor forms complexes with the
acceptor’s halide ion. Although the options aren’t restricted to it,
the most commonly used quaternary ammonium salt in literature
is choline chloride. Depending on the hydrogen bond donors and
acceptors used, DESs are classified into four distinct categories
[16]:
Type I DES: Cat+X-zMClx where M = Zn, Sn, Fe, Al, Ga.
Type II DES: Cat+X-MClx
yH2O where M = Cr, Co, Cu, Ni, Fe.
Type III DES: Cat+X-zRZ where Z = CONH2, COOH, OH.
Type IV DES: MClx + RZ = MCl+x-1. RZ + MClx+1where M = Al, Zn
and Z = CONH2, OH.
There are, however, drawbacks to using a DES due to the limi-
tations of reduced ion conductance and higher viscosity of most
quaternary ammonium salt based DESs [13,17]. To overcome this
limitation, the conventional HBAs were replaced with alkali metal
salts in the DESs. These solvents showed significant reduction in
viscosity and an increase in ionic conductivity [9,18,19]. Despite
the favourable characteristics, most DESs are not appropriate alter-
natives to IL electrolytes for energy storage owing to their inferior
electrochemical stable potential window in comparison to most
RTILs. For example, lithium bis(trifluoromethanesulfonyl)imide
was used as an HBA to form a DES with formamide with ionic con-
ductivity comparable to those of RTILs, however the operating
potential window was at a maximum of 2.2 V [18].
In order to retain the desirable properties of ILs while aiming to
reduce the viscosity, this work investigates and reports the synthe-
sis and characterization of three novel ionic liquid based DESs. IL
based DESs have demonstrated significant potential in various
fields of applications. A 1-methylimidazole-based IL was used for
DES synthesis in combination with organic acids namely propanoic
acid and nitric acid for extractive desulphurization of fuel [20]. A
DES comprised of protonated tryptophan salt and urea resulted
in enhanced oil recovery from carbonate-asphalt rocks when com-
pared to a pure IL, namely 1-ethyl-3-methylimidazolium tetrafluo-
roborate([EMIM][BF4]) [21]. A combination of 1-butyl-3-methyl
imidazolium methanesulphonate ([BMIM][MeSO3]) with urea is
also suitable for ammonia absorption [22]. The same DES of
[BMIM][MeSO3] with urea has been used in thermal dehydrogena-
tion of ethylene diamine-bis-borane (EDAB) [23]. Three different
ILs, namely, 1,8-diazabicyclo- [5,4,0]undec-7-ene imidazole
([HDBU][Im]), 1,8- diazabicyclo[5,4,0]undec-7-ene indole
([HDBU][Ind]), and 1,8-diazabicyclo[5,4,0]undec-7-ene 1,2,4-
triazole ([HDBU]- [Triz]) have been combined with ethylene glycol
to synthesize deep eutectic solvents for CO2 capture and recovery
[24]. DESs using protic ILs like imidazolium nitrate ([Im][NO3]),
1-methylimidazolium nitrate ([Mim][NO3]) and 1,2-
dimethylimidazolium nitrate ([Mmim][NO3]) have been used with
ethylene glycol as hydrogen bond donor for efficient absorption of
ammonia [25]. Choline hydroxide and amino acids (glycine, ala-
nine, serine and lysine) have been reported to form deep eutectic
solvents and aid in the separation of Cu(II) ions as an extractant
[26]. Highly efficient dissolution of xylan has been reported using
DESs synthesized employing thiourea (TU), N-methylthiourea
(NMTU), glycerol (Gly) and ethylene glycol (EG) as the HBDs and
four ILs [i.e., 1-butyl-3-methylimidazolium chloride ([BMIM]Cl),
1-ethyl-3-methylimidazolium chloride ([EMIM]Cl), 1-hexyl-3-
methylimidazolium chloride ([HMIM]Cl), 1-allyl-3-
methylimidazolium chloride ([AMIM]Cl)] as the HBAs [27].
Although ionic liquid based DESs have been recently used in a vari-
ety of different fields, the research into their potential as elec-
trolytes for supercapacitors is still in its rudimentary stage.
Literature suggests that [BMIM][MeSO3] tends to form hydro-
gen bond with HBDs [28]. [BMIM][MeSO3] has also been used to
synthesize DESs for usage in supercapacitors as an electrolyte
[29]. With this in mind, [BMIM][MeSO3] has been chosen as a
hydrogen bond acceptor to form a DES with a suitable donor in this
2
Journal of Molecular Liquids 366 (2022) 120245
work. 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)i
mide or [BMIM][Tf2N] has already been reported as a suitable elec-
trolyte for supercapacitors [12]. In this work, [BMIM][Tf2N] has
been investigated as an HBA to form a DES with better physico-
chemical as well as electrochemical properties as compared to
the pure IL. Another potential HBA investigated in this work is 1-
butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6])
which was previously used in the preparation of biopolymer elec-
trolyte systems [30]. N-Methylacetamide (NMAc) and formamide
have been chosen as the HBD because of the ease of availability,
their reported usage in DES synthesis and their low cost [18,29].
All three novel DESs investigated in this work belong to Type III.
2. Evaluation of eutectic temperature and composition
DESs are synthesized by heating and continuously stirring the
hydrogen bond donor and hydrogen bond acceptor, taken at a
specific molar ratio, at an elevated temperature until a clear liquid
is obtained [31]. The prepared DES is subsequently cooled in order
to evaluate the fusion temperature of the mixture. For new DESs,
the synthesis usually an iterative procedure until the appropriate
HBA: HBD ratio is determined. It is at this ratio that the corre-
sponding fusion temperature satisfies the requisites of a eutectic
mixture by definition. This process, however, is uneconomical
regarding the use of chemicals and resources. Therefore, alterna-
tive theoretical approaches can be used. In this work, the eutectic
composition of DES and the corresponding melting temperature
are predicted by Conductor like Screening Model-Segment Activity
Coefficient (COSMO-SAC) approach [32,33]. Reported literature
suggested agreement between predicted data from COSMO-SAC
and experimental findings [34,35]. COSMO-SAC predicts the eutec-
tic composition and temperature using the notion of mutual solu-
bility dependence on temperature, applying the solid–liquid
equilibrium (SLE) theory (Equation (1)) [36]. This model has been
comprehensively discussed in reported literature [37]. The prereq-
uisites to applying the COSMO-SAC model are the heat of fusion
(DHfus) and freezing point or melting point (Tm) data of each con-
stituent material, which are outlined in Table 1. Initially, the two
components are assumed to be mixing together to form an ‘ideal’
mixture (i.e. csolute ¼ 1). Using the values of melting temperatures
and heats of fusion, the molar composition of the solution is thus
calculated using Equation (1). This data is then used by the
COSMO-SAC model to predict the activity coefficients of the com-
ponents in a ‘real’ mixture. The csolute values thus predicted, are
once again used in Equation (1) to calculate the molar composition
and melting point of the ‘real’ deep eutectic mixture.
DHfus 1 1
lnðcsolute xsolute Þ ¼ ð  Þ ð1Þ
RT m T T m
where, xsolute and csolute represent the mole fraction and activity coef-
ficient respectively.
Initially, Gauss View 5.0 software was used to draw the molec-
ular structures of the compounds. Gaussian 09 was then used for
geometry optimization using density functional theory (B3LYP)
and 6-311G* basis set. This was followed by generation of the
COSMO-SAC input files (Fig. 1) using Gaussian 09 by the BVP86/
Table 1
Melting points and heats of fusion data of the HBAs and HBDs.
Component Tm(K) D Hfus (kJ/mol)
[BMIM][MeSO3] 347.65 12.864 [38]
[BMIM][Tf2N] 270.15 20.9 [39]
[BMIM][PF6] 266.27 19.91 [40]
NMAc 303.72 10.107 [41]
Formamide 275.85 7.98 [42]
S. Choudhury, U. Mahanta, R. Prasanna Venkatesh et al.
Fig. 1. COSMO files of Hydrogen bond acceptors (HBAs) and Hydrogen bond donors (HBDs) generated using Gaussian 09 package.
TZVP/DFT theory [36].Standard parameters namely cut off for
hydrogen-bond interaction (=0.0084 e/ Å2),hydrogen-bond interac-
tion constant [= 75,006 kcal Å4/(mol e2)], segmental surface area
(=6.32 Å2) and constant for misfit energy interaction [=
8419 kcal Å4/ (mol e2)], were considered for activity coefficient cal-
culation [36]. Ultimately, mole fraction of the solute was deter-
mined with variation of temperature using Equation (1). The
evaluated values are reported in the subsequent sections.
In the input COSMO files for SLE calculations (Fig. 1) the red,
yellow, blue and green colours of COSMO cavities represent elec-
tronegative, partially electronegative, electropositive and partially
electropositive zones respectively. Additionally, the brown and
dark blue colours denote the stronger electronegative and elec-
tropositive regions. From the COSMO files we can conclude that
all of the five compounds selected for this work have both hydro-
gen bond donor and acceptor sites. It can be noticed that NMAc and
formamide have considerable regions in red or brown and in green,
signifying the strong electronegative atoms and the partially posi-
tive hydrogen atoms respectively. This makes them suitable candi-
dates for donating hydrogen bonds.
This can also be demonstrated from the probability distribution
of surface screening charges (sigma profiles) obtained from
COSMO-SAC calculation. As it can be seen in Fig. 2, the compounds
have a considerable number of hydrogen bond donors and accep-
Fig. 2. Distribution of surface screening charge obtained from COSMO-SAC
calculations.
3
Journal of Molecular Liquids 366 (2022) 120245
tors based on their hydrogen bond cut off (±0.0084 eÅ2) indicating
they are soluble within itself as well as in the solution. The area
under the curve for formamide and NMAc in the hydrogen bond
donor region is higher than that of [BMIM][MeSO3] and [BMIM]
[Tf2N]. This corresponds to a higher tendency of donating hydrogen
bonds in the above-mentioned solvents, making them hydrogen
bond donors and a comparatively lesser tendency in the ionic liq-
uids, thereby making them hydrogen bond acceptors. It can also be
seen that formamide exhibits the highest probability of donating a
hydrogen bond. However, [BMIM][PF6] possesses nearly an equiv-
alent distribution in hydrogen bond donor region as compared to
the HBDs. Furthermore, in the hydrogen bond acceptor region
[BMIM][MeSO3] and [BMIM][Tf2N] exhibit the highest probabilities
of accepting a hydrogen bond. However, for all five compounds
most of the surface charges belong to the non-polar region.
3. Experimental details
3.1. Chemicals
[BMIM][MeSO3] (purity  95%, mp 75–80 °C), [BMIM][Tf2N]
(purity  98%) [BMIM][PF6] (purity  97%), NMAc (purity  99%,
mp 26–28 °C), formamide (99.5%) and spherical glassy carbon
(GC) powder (2–12 lm, 99.5% trace metal basis) were acquired
from Sigma Aldrich. Thermo Fischer Scientific India Pvt. Ltd. pro-
vided the Karl Fischer reagent (526 KFR).
3.2. Preparation of the deep eutectic solvents
Appropriate amounts were weighed and mixed together in
accordance with the molar ratio determined from COSMO-SAC
computations. The mixture thus formed was continuously stirred
using a magnetic stirrer at 70 °C and 500 rpm until a clear liquid
was formed [31]. To remove any residual volatile impurities and
water vapour, the DESs were vacuum dried at 80 °C.
3.3. Physicochemical characterization of the deep eutectic solvents
Lower viscosity of DESs is desirable for applications in various
fields, and for electrolytic applications higher ionic conductivity
is desirable. Water content significantly affects the electrochemical
properties as well. Thermal stability and density are important
parameters to be considered while exploring the applications in
S. Choudhury, U. Mahanta, R. Prasanna Venkatesh et al. Journal of Molecular Liquids 366 (2022) 120245

various fields. Hence, all these properties were appropriately mea-

sured. All measurements were taken repeatedly.
Anton-PaarDMATM4500 M density meter (accuracy: ± 0.00005
g/cm3) was used to measure the densities of the studied solvents.
Densities were measured at regular intervals of temperature in
the range of 10–60 °C. Viscosity was measured in the temperature
range of 10–60 °C using Anton Paar Physica Rheometer (MCR30) at
a shear rate of 1000 s1. Ionic conductivity of DESs was measured
using Economy Conductivity Portable meter (ECCON603PLUSK,
accuracy: 0.1mS/cm) at 25 °C.
The presence of water of the formulated DESs was measured by
Karl Fischer Titration (KFT) method using Metrohm 787 KF Titrino
with Karl Fischer reagent (526 KFR). The analysis was repeated
three times for each sample and the average weight % of water
has been reported. Additionally, thermogravimetric analysis
(TGA) was carried out in the temperature range of 30–400 °C at a
heating rate of 10 °C per minute under nitrogen atmosphere for
all the synthesized DESs.

3.4. Linear scan voltammetry

Linear scan voltammetry (LSV) is a characterization technique

used to determine the reduction (cathodic) and oxidation (anodic)
limits of an electrolyte. LSV was performed with GC electrode for
all three solvents. In order to prepare the GC electrode, GC powder
was mixed with paraffin wax in a weight ratio of 5:3. The mixture
was then uniformly heated at 60 °C, moulded into a regular shape
and a Cu wire was inserted into middle of the mould. This elec-
trode was subsequently cooled to room temperature [43]. Target-
ing applications in supercapacitors, the ESPW was determined
using LSV method at a scan rate of 10 mV/s.

4. Results and discussion

4.1. Insights from solid liquid equilibrium study

The solubility data as a function of temperature calculated using

COSMO-SAC model are reported in Fig. 3. The melting points of
hydrogen bond acceptors and hydrogen bond donors are repre-
sented by TA and TB respectively. A significant reduction in melting
temperature as compared to the donor and acceptor groups is
observed for all three DESs. The ideal eutectic point has been calcu-
lated considering activity coefficient equals to unity and has been
plotted in the figure. The eutectic temperature at real conditions
is slightly lower than that in ideal state. An observable depression
in melting point is desirable in order to name the mixture as a DES
[14].
The determined molar ratio and the melting points of the three
formulated DESs are given in Table 2.

Fig. 3. SLE data from COSMO-SAC calculations of a) [BMIM][Tf2N] + NMAc, b)

4.2. Physical characterization of DES [BMIM][PF6] + NMAc and c)[BMIM][MeSO3] + Formamide.

4.2.1. Density
Table 2
Densities of the prepared deep eutectic solvents were measured Molar ratio and melting points (Tm) of DES from COSMO-SAC.
at different temperatures and plotted (Fig. 4). The densities of all
three DESs are slightly higher than that of water and the values Deep Eutectic Solvents Molar ratio (HBA:HBD) Tm (K)

decrease with increasing temperature, which is a typical behaviour [BMIM][Tf2N] + NMAc 1:1 255.7
of liquids. The density of [BMIM][Tf2N] + NMAc is found to be the [BMIM][PF6] + NMAc 4:5 249.5
[BMIM][MeSO3] + Formamide 1:3 259.3
highest amongst the three followed by [BMIM][PF6] + NMAc and
[BMIM][MeSO3] + Formamide respectively. The formulated sol-
vents possess marginally higher density than the respective donors
[44,45]. This behaviour is in accordance with the hole theory of liq- addition of the hydrogen bond acceptors, thereby resulting in a
uids [46]. The theory explains that hydrogen bond donors are com- more compact structure, leading to an increase in density.
posed of holes and the radius of the hole decreases with the
4
S. Choudhury, U. Mahanta, R. Prasanna Venkatesh et al.
Fig. 4. Density as a function of temperature.
4.2.1.1. Viscosity. The viscosity was measured as described in sec-
tion 3 (Fig. 5a). It has been observed that the viscosities of all the
synthesized DESs exponentially decrease with increase in temper-
ature. In order to compare the flow behaviour and to determine the
change in viscosity after the formation of DES, viscosities of
Fig. 5. a) Viscosity as a function of temperature and b) Viscosity of DESs and
reported solvents at 293.15 K.
5
Journal of Molecular Liquids 366 (2022) 120245
[BMIM][Tf2N] and [BMIM][PF6] as acquired from Sigma Aldrich
were measured at 293.15 K. The viscosity of a [BMIM][MeSO3]
based DES, i.e. [BMIM][MeSO3] + NMAc [29] was used as a refer-
ence for comparison. These values are plotted in Fig. 5b.
The viscosity values were observed to be in the range of 4–40
cp. The dynamic viscosities of both [BMIM][PF6] + NMAc and
[BMIM][Tf2N] + NMAc are significantly lower than the constituent
RTILs in their pure form. Moreover, observed viscosity for the
[BMIM][MeSO3] + formamide DES is slightly lower as compared
to a reported [BMIM][MeSO3] based DES [29] and markedly lower
than those of some commonly used BMIM cation containing ionic
liquids [47]. Literature reports that the viscosities of RTILs is most
commonly reduced by diluting with organic solvents like propy-
lene carbonate and acetonitrile [10]. However, a simply adding sol-
vents adversely affects the mixture’s properties, especially in
electrochemistry, by significantly reducing the operating potential
windows of the electrolytes [12]. This drawback faced in the usage
of highly viscous ILs can be diminished by replacing them with
ionic liquid based DESs like the ones discussed in this study.
The viscosities of the studied DESs change appreciably as a
function of temperature. The change in viscosity ƞ with tempera-
ture can be explained using Equation (2) [31].
En
ln g ¼ ln g0 þ ð2Þ
RT
Here, g0 is a constant and En is the energy for activation of vis-
cous flow. Fig. 6 shows that the viscosities of the formulated DESs
obey Equation (2) with fairly well (r > 0.981).
4.2.1.2. Ionic conductivity. The ionic conductivities of the formu-
lated DESs were measured at 298.15 K and compared with some
reported solvents (Fig. 7). The conductivities of [BMIM][Tf2-
N] + NMAc and ([BMIM][PF6]) + NMAc were compared with those
of their corresponding hydrogen bond acceptors, namely [BMIM]
[Tf2N][12]and [BMIM][PF6][48]. [BMIM][MeSO3] + formamide
was compared with [BMIM][MeSO3] + NMAc since the HBA is a
solid at room temperatures. All the formulated DESs possess appre-
ciably higher ionic conductivity as compared to the pure HBAs. It
should also be noted that [BMIM][MeSO3] forms a more conductive
DES with formamide as compared to NMAc [29]. The latter proba-
bly offers stronger hydrogen bonding interaction to the HBA than
formamide and hence, the ions of the HBA can’t diffuse easily,
thereby resulting in lower ionic conductivity. The slightly lower
viscosity of [BMIM][MeSO3] + formamide might also facilitate bet-
ter ion diffusion in the solvent.
Fig. 6. Log viscosity vs reciprocal of temperature for the formulated DESs.
S. Choudhury, U. Mahanta, R. Prasanna Venkatesh et al. Journal of Molecular Liquids 366 (2022) 120245

Fig. 7. Ionic conductivity of the studied DESs and comparison with some reported
RTILs and DESs at 298.15 K.

4.2.1.3. Water content. The water content was evaluated using Karl
Fischer Titration and the average values are given in Table 3. The
water present in [BMIM][Tf2N] + NMA is the lowest and that of
[BMIM][MeSO3] + formamide is the highest. Water content is influ-
enced by not only the hydrophilic nature of an HBA or HBD but also
on atmospheric conditions during synthesis.

4.3. Thermogravimetric analysis

The thermal stability estimation was done within a particular

range of temperature (30–400 °C) for all three systems at 10 °C
per minute rise in temperature under nitrogen atmosphere. It is
be observed that there is insignificant mass loss for all the DES sys-
tems up to 360–370 K (Fig. 8a), and that signifies the maximum
limit for their corresponding operational temperature range. Since
a DES is composed of two non-reacting compounds, in the TGA plot
two distinct mass degradation slopes can be seen. From the DTG
plot (Fig. 8b), it can be seen that the second onset temperature
for decomposition, which correspond to the decomposition of the
HBA, is higher than 550 K for all three DESs. Both the first and
the second peaks of DTG plot, corresponding to the maximum mass
losses, appear at different temperatures for each HBA and HBD.
([BMIM][Tf2N]) + NMAc and ([BMIM][PF6]) + NMAc did not
degrade fully within 673.15 K, which was the maximum tempera-
ture maintained for the TGA study.
4.4. Determination of electrochemical stable potential window
Aiming at electrochemical applications, the electrochemical
stable potential window (ESPW) was determined using LSV with
GC electrode at 10 mV/s scan rate. LSV is a useful characterisation
technique to determine the reduction(cathodic) and the oxidation
(anodic) limits of an electrolyte. Cathodic stability for all three
DESs is observed to be at approximately 2 V and the anodic limit
can be marked in the range of 1.8 – 2 V (Fig. 9a). Therefore the
Table 3
Water content in the studied DESs using Karl Fischer Titration.
Deep Eutectic Solvents Water content (weight %)
[BMIM][Tf2N] + NMAc 0.6
[BMIM][PF6] + NMAc 1.04
[BMIM][MeSO3] + formamide 3.36
Fig. 8. a) % mass loss and b) derivative of % mass loss with temperature variation.
resulting values of ESPW of [BMIM][MeSO3] + formamide,
[BMIM][Tf2N] + NMAc and [BMIM][PF6] + NMAc are 4 V, 3.8 V
and 3.9 V respectively.
The electrochemical stabilities of the studied DESs have been
compared to those of a few reported electrolytes [29,49]
(Fig. 9b). It is noteworthy that the ESPW for [BMIM][PF6] increases
when it is in a deep eutectic mixture with NMAc. For [BMIM][Tf2N]
the ESPW decreases slightly with the addition of hydrogen bond
donors, however, it is still significantly higher than that of a mix-
ture of the ionic liquid with an organic solvent [12]. This illustrates
that ionic liquid based DESs are a potential alternative in the field
of electrochemistry, to both RTILs and their mixtures with organic
solvents, for the reduction in viscosity and increase in conductivity
without a large reduction in the ESPW.
It should be noted that a solvent’s purity largely affects its elec-
trochemical stability [50]. Since all the chemicals were used with-
out any further purification except vacuum drying, wider potential
window may be obtained with higher purity of the mixture com-
ponents. Since different characterization techniques are performed
on the DESs for different applications, for the consistent compar-
ison, we have compared the properties of the solvents in this work
to a few IL based DESs reported in literature and the pure ILs used.
These solvents were used as electrolytes in supercapacitors. The
results of the review are tabulated in Table 4.
A crucial factor in the operation of the supercapacitor is the
reduced graphene oxide (RGO) interfacial behavior. The arrange-

6
S. Choudhury, U. Mahanta, R. Prasanna Venkatesh et al. Journal of Molecular Liquids 366 (2022) 120245

tems with carbon allotropes, all-atomic classical molecular dynam-

ics (MD) simulations with explicitly included polarization may be
performed in future work. However indirectly, the ion-ion interac-
tion can be inferred from their values of ionic conductivities (>5
mS/cm) (Fig. 7) which were higher than those of the corresponding
constituent ILs. Further Linear scan voltammetry (LSV) values also
determines the electrochemical stable potential window (ESPW) of
the solvents where a glassy carbon (GC) electrode (Fig. 9). This
gives an indirect manner to formulate the number of charge carri-
ers on to the surface of RGO. LSV provided electrochemical stabil-
ities in the range of 3.8–4 V for all three studied deep eutectic
solvents. This is higher than the potential windows of mixtures
of ILs and organic solvents and hence has a significant potential.

5. Conclusion

COSMO-SAC computation confirmed the formation of the deep

Fig. 9. a) LSV at 10 mV/s with glassy carbon electrode and b) Comparison of ESPW
of the studied DESs with some reported solvents.
Table 4
Comparative study of the synthesized DESs with literature.
eutectic solvents, we desired to investigate and also predicted the
eutectic points, thereby reducing the trouble of going through the
repetitive experimentation. The studied DESs offer thermal stabil-
ity up to 80–100 °C. It should be noted that conventional IL and
organic solvent mixtures mostly employ acetonitrile as the solvent
which has a boiling point of 82 °C. This makes it practically impos-
sible to use these as solvents or electrolytes at higher tempera-
tures, which can easily be attained with the DESs developed in
this work. The fact that the DESs are made at the eutectic compo-
sition facilitates low temperature usage as well, for example in
space technology. Viscosities of all the formulated and studied
DESs were found to be markedly lower than those of conventional
RTILs, indicating their advantages over the latter as electrolytes.
The ionic conductivity values were also higher than or comparable
to those of conventionally used neat RTILs. The electrochemical
stable potential windows obtained, while lower than some com-
monly used ILs, are still much higher than RTIL and organic solvent
mixtures.
Given the large number of possible DESs that can be formulated
with various constituent HBAs and HBDs, more ionic liquid based
deep eutectic solvents may further be explored with the motive
to understand how various HBAs and HBDs affect the resultant
properties. With the knowledge of dissociation potential of various
constituent chemicals DESs with higher ESPW may be obtained.

Deep Eutectic Solvents Viscosity Ionic ESPW

(mPa s) conductivity (V) Data availability
(mS cm1)
[BMIM][Tf2N] + NMAc 18.5 6.4 3.8
No data was used for the research described in the article.
[BMIM][PF6] + NMAc 25.2 5.9 3.9
[BMIM][MeSO3] + Formamide 13.2 5.2 4.0 Declaration of Competing Interest
[BMIM][MeSO3] + Ethylene Glycol 18.3 4.2 3.8
[29]
[BMIM][MeSO3] + NMAc [29] 20.7 2.7 3.8 The authors declare that they have no known competing finan-
[BMIM][Tf2N] 46.9 2.76 [12] 5.07 [49] cial interests or personal relationships that could have appeared
[BMIM][PF6] 149 0.146 [48] 1.67 [49] to influence the work reported in this paper.

ment of ions, including the BMIM cation and [MeSO3], [Tf2N], and
[PF6] ions, may allow the HBD molecules to be structured close
to an atomically thin surface called the RGO interface (electrode
in our study), which has a significant impact on the interfacial
physicochemical characteristics of electrolytes as well as the speci-
fic capacitance of supercapacitors. The overall performance of the
supercapacitor may be significantly impacted by the adsorption
of extra charge carriers on the opposite side of the eventually thin
material, which may be affected by the adsorption of ions on one
side of the material. These occurrences are still not fully under-
stood. This phenomenon shall also be influenced by RGO electrode
porosity. To accurately describe electrolytes at interfaces in sys-
Acknowledgement
The authors highly acknowledge Vikram Sarabhai Space Centre
(VSSC, ISRO), Thiruvananthapuram for its financial assistance to
this work vide ISRO/RES/3/745/17-18.
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