Journal of Power Sources 492 (2021) 229634

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Journal of Power Sources

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Design and theoretical study of novel deep eutectic solvents: The effects of
bromine and chloride anions on solvation structure and
supercapacitor performance
Di Wu a, Li Hua Xu a, Hua Jie Feng b, Yan Wu Zhu a, Xiang Ying Chen a, *, Peng Cui a, **
a
School of Chemistry and Chemical Engineering, Anhui Key Laboratory of Controllable Chemistry Reaction & Material Chemical Engineering, Hefei University of
Technology, Hefei, 230009, Anhui, PR China
b
College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, 571127, Hainan, PR China

H I G H L I G H T S

• TEAB or TEAC serves as HBA and EG as HBD, forming DES system.

• Bromine and chloride anions exert crucial effects on solvation structure.
• DES system delivers remarkable physical properties.
• Redox stability is verified by HOMO and LUMO with Gaussian09.
• DES exhibits superior capacitive performance using DES as electrolyte.

A R T I C L E I N F O A B S T R A C T

Keywords: Designing high efficiency electrolytes with wide voltage window and operating temperature range is crucial for
Deep eutectic solvent achieving high capacity and electrochemical stability of activated carbon-based supercapacitors. Here, novel
Wide operating temperature range deep eutectic solvent (DES) electrolytes utilizing tetraethylammonium bromide (TEAB) or tetraethylammonium
Theoretical simulation
chloride (TEAC) as hydrogen bond acceptor (HBA) and ethylene glycol (EG) as hydrogen bond donor (HBD) are
Hydrogen bond interaction
Supercapacitor performance
proposed to modulate the temperature dependent ion transport and desolvation within activated carbon (AC)
electrodes. Compared with conventional aqueous electrolytes, the present DES electrolytes have broad electro­
chemical stable window (up to 3.03 V), wide operating temperature range (− 40 to 115 ◦ C), considerable ionic
conductivity (8.70 mS cm− 1 at 25 ◦ C) and low viscosity (18.13 mPa s at 25 ◦ C). Significantly, theoretical sim­
ulations reveal that the highest occupied molecular orbitals (HOMO) energies of DES complexes decrease
obviously, indicating that the electron transitions become more difficult and the DES electrolytes are more stable
after the formation of hydrogen bond interactions. The AC||AC supercapacitors using DES electrolytes exhibit
expanded cell voltage (2.4 and 1.8 V at − 40 and 25 ◦ C, respectively), increased energy density of 32.2 Wh kg− 1
and impressive cycling stability (92.8% capacity retention at 1 A g− 1 after 10000 cycles).

1. Introduction
Supercapacitors are new types of energy storage devices that store
and release electric charges based on the fast and reversible ion
adsorption/desorption processes or redox reactions at the interface be­
tween electrodes and electrolyte [1,2]. Compared to traditional capac­
itors and batteries, supercapacitors have the characteristics of high
power density, ultra-long cycle life, fast charging/discharging rate, wide
operating temperature and high security [3,4]. Taking commercial
carbon-based supercapacitors as an example, the main components are
activated carbon, electrolyte and separator [5]. Furthermore, electro­
lytes have a great impact on the performance of supercapacitors and the
electrochemical stable windows (ESWs) of different types of electrolytes
are various [6]. According to the equation E=1/2 CV2, increasing

* Corresponding author.
** Corresponding author.
E-mail addresses: chenxy@hfut.edu.cn (X.Y. Chen), cuipeng@huft.edu.cn (P. Cui).

https://doi.org/10.1016/j.jpowsour.2021.229634
Received 6 December 2020; Received in revised form 28 January 2021; Accepted 8 February 2021
Available online 18 February 2021
0378-7753/© 2021 Elsevier B.V. All rights reserved.
D. Wu et al.
capacitance and expanding voltage window are the promising ways to
improve energy density [7]. Therefore, the optimal design of electrolyte
system with low viscosity, high ionic conductivity, high electrochemical
stability and wide voltage window is the essential requirement and
feasible approach to broaden the working temperature of super­
capacitors at this stage [8,9].
In most cases, the electrolytes are composed of electrolyte salts and
solvents [10]. The most representative aqueous electrolytes are H2SO4,
KOH and Na2SO4, which have small ion size, high ion conductivity
(600–800 mS cm− 1) and good wettability but suffer from low thermo­
dynamics stable voltage of H2O (1.23 V) [11,12]. The conventional
organic electrolytes are TEABF4-ACN and TEABF4-PC solutions with
high operating voltage over 2 V which are accompanied with moderate
ion conductivity (1.7–50 mS cm− 1), low ionic mobility, flammability
and toxicity [13,14]. Besides, ionic liquids (ILs) are usually formed by
Coulomb forces between organic cations and anions which are often
accompanied by hydrogen bonds at room temperature [15]. ILs can be
used as supercapacitor electrolytes due to the wide voltage window
(2–4 V), high stability and security, but the complex synthesis process,
strong water adsorption and high purification cost hinder the commer­
cial application of ILs [16]. In recent years, some important strategies for
broadening the ESWs of the electrolytes have been reported, such as
“water in salt” and super-concentrated electrolyte, which provide a 2.3
V LiMn2O4||Mo6S8 full cell [17,18]. Therefore, it is still a challenge to
design more rational and efficient electrolytes in the field of
carbon-based supercapacitors.
Recently, deep eutectic solvents (DESs) have been emerged as new
type liquids which have been extensively applied in the field of elec­
trochemistry, biotransformation, extraction and separation, gas
adsorption and nanotechnology due to low cost, simple preparation, low
volatility, nonflammability and biodegradability [19]. DESs are usually
formed by two or more components (Brønsted or Lewis acids and bases)
with a certain stoichiometric ratio through hydrogen-bond interactions
[20]. Generally, DESs can be divided into two parts: hydrogen bond
acceptor (HBA, quaternary ammonium salts and zwitterions) and
hydrogen bond donor (HBD, polyhydric alcohols, carboxylic acids,
sugars, amino acids and amides) [21]. Therein, choline chloride (ChCl)
is the most commonly studied HBA, which usually forms DESs with urea,
alcohols and carboxylic acids [22]. Previously, our group has reported a
series of ChCl-based DES electrolytes which have moderate conductivity
(6–8 mS cm− 1 at RT) and viscosity (45–93 mPa s at RT) and deliver good
supercapacitor performance [23]. The freezing point of DES is signifi­
cantly lower than that of any individual component [24]. There exists
extensive hydrogen bonding networks among the components in DES,
resulting in low mobility of free substance, low ionic conductivity (2 mS
cm− 1) and high viscosity (~100 mPa s) due to the large size of molec­
ular, small space and electrostatic or van der Waals interactions [25]. In
general, the ionic conductivity of DES increases significantly with the
decrease of viscosity when the temperature rises [26]. Due to the lack of
exploration of internal structure and mechanism of DES in super­
capacitor, it is necessary to develop electrolyte with low cost, high
electrochemical stability and ionic conductivity and broader tempera­
ture adaptability for supercapacitors [27].
In this work, we have not only designed and synthesized several
novel DES electrolytes, but also adopted theoretical calculation to pre­
dict the redox stability and hydrogen bond interaction of DES electro­
lytes with LUMO, HOMO energies and interaction energies. Specifically,
the Cl− and Br− anions exist in solvated structures by hydrogen bonds
with EG in DES electrolytes and the ion interactions in TEAB or TEAC are
weakened. The slow ion desolvation at low temperature allows the DES
electrolytes to withstand higher voltage, while the weakening of
hydrogen bond interactions in DES makes anions more likely to be
oxidized at high temperature. The AC||AC supercapacitor using DES
electrolytes delivers a high specific capacitance of 202 F g− 1 at 60 ◦ C and
92.8% capacity retention after 10000 cycles.
2
Journal of Power Sources 492 (2021) 229634
2. Experimental section
2.1. Electrolytes preparation
Briefly, the DES electrolytes were formed separately in an argon-
filled glove box by mixing TEAB or TEAC with EG with the molar ra­
tios of 1:3, 1:4 and 1:5, respectively. Then, the mixtures were heated at
70 ◦ C with continuous stirring for 30 min and kept at different set
temperatures in a vacuum drying oven to obtain homogeneous and clear
solutions. The abbreviations of DESs are listed in Table S1. In addition,
the low temperature environment of electrolyte was provided by a
DLSB-5L/40 coolant circulating pump.
2.2. Electrolytes characterizations and physical measurements
The phase changes of DES electrolytes were tested with a NETZSCH
DSC 214 instrument in the first segment from 20 to − 170 ◦ C at 5.0 ◦ C
min− 1 and from − 170 to 30 ◦ C at 10 ◦ C min− 1 in the second segment.
Fourier transform infrared spectroscopy (FTIR) was measured with a
Thermo Fisher Nicolet 6700 spectrometer in the range of 500–4000
cm− 1. Raman spectroscopy measurements were performed in the range
of 600–3800 cm− 1 using a HORIBA JOBIN YVON LabRAM HR Evolution
microscope with a 633 nm excitation laser.
The ionic conductivities of DES electrolytes were measured at set
constant temperatures (− 40–115 ◦ C) with a Leici DDS-307A conduc­
tivity meter. The activation energy of conductivity (Ea) was fitted with
Vogel-Fulcher-Tammann (VTF) equation [28]. The viscosities of DES
electrolytes were carried out with a NDJ-5S digital display rotational
viscometer. The activation energy of viscosity (Kη) was fitted with VTF
equation of viscosity [29]. The glass microfiber filters separator with a
diameter of 47 mm was used in the present work. The electrolyte uptake
and wettability of separator (σ s) experiments were carried out according
to the following equations when the separator was immersed in DES
electrolyte for 3 h.
[ ]
− Ea
σ = σ 0 T − 1/2 exp ( ) (1)
R T − Tg
Kη 1
ln η = ( ) + ln T − ln Aη (2)
T − Tg 2
m2 − m1
Electrolyte uptake = (3)
m1
d
σs = (4)
Rs × A
where σ is experimental ionic conductivity, T stands for absolute tem­
perature, Tg is the ideal glass transition temperature (GTT), σ 0, R and Aη
are fitting parameters. Here, m1 and m2 represent the mass of separator
before and after fully immersed in the DES electrolyte, respectively.
Besides, A is the geometric area of stainless steel (SS) and d refers to the
thickness of glass fiber.
2.3. Theoretical calculation
The oxidability and reducibility of the DES complexes, cation (TEA+)
and anions (Br− or Cl− ) are calculated to obtain the correlative lowest
unoccupied molecular orbitals (LUMO) and the highest occupied mo­
lecular orbitals (HOMO) energies using Gaussian 09 software package
[30]. Firstly, GaussView 6.0 was used to establish the model of TEAB,
TEAC, and EG. The lowest energy conformation of TEAB-nEG or
TEAC-nEG system was generated by CREST 2.1.0 at the GFN2-xTB
(semiempirical tight-binding based quantum chemistry level within
framework of meta-dynamics method) [31]. Then, the structural ge­
ometry optimizations were performed with the Gaussian 09 at the
B3LYP/6-31G(d) level. The equation was employed to calculate the
D. Wu et al.
interaction energy.
ΔEDES = Ecomplex − (ETEAB + nEEG )
where Ecomplex, ETEAB, and EEG represent the single point energy of the
DES complex, TEAB, and EG, respectively. Here, n is the number of EG.
Similarly, for TEAC-EG electrolyte, the single point energy of TEAC was
conducted with the same computational process to obtain ETEAC.
2.4. Electrochemical measurements
The electrochemical stable windows of DES electrolytes were
investigated by linear scanning voltammetry (LSV) at a scan rate of 1
mV s− 1 in the potential range of +3 to − 3 V, with glassy carbon as
working electrode, Pt plate as counter electrode and SCE as reference
electrode [32]. The SS||wet separator||SS system was used to evaluate
the DES electrolyte wettability to separator. The different DES electro­
lytes were assembled in AC||AC CR2023 coin cells and all the electro­
chemical tests were conducted in two-electrode system using a CHI760E
electrochemical workstation. The NEWARE battery testing system was
used to investigate the cycling performance.
3. Results and discussion
3.1. The structure and application of DES electrolytes
As is well known, the H atoms in the hydroxyl groups of EG molecule
can form hydrogen bonds with TEAB or TEAC (playing the role of HBA).
Moreover, the boiling and freezing points of EG are 197.3 and − 11.2 ◦ C,
respectively. Inspired by these principles, EG is selected as a suitable
hydrogen bond donor to form DES electrolytes with TEAB or TEAC.
Typically, the chemical structures of TEAB, TEAC and EG and the
schematic diagram of synthesis of DES electrolytes are exhibited in
Fig. 1a. The H-bonds (O–H⋯Cl or O–H⋯Br) are generated between
highly electronegative Cl− of TEAC (Br− of TEAB) and highly positive
charged H atoms (O–H) of EG. As shown in Fig. 1b, a series of digital
Fig. 1. (a) Schematic diagram of synthesis of DES electrolytes with TEAB or TEAC as HBA and EG as HBD. (b) Digital photographs of homogeneous DES electrolyte
with different molar ratios of HBA and HBD. (c) Application of DES electrolyte in AC-based supercapacitor. (d, e) The phase changes of six DES electrolytes in
DSC curves.
Journal of Power Sources 492 (2021) 229634
photographs of homogeneous and transparent DES electrolytes at room
temperature were obtained through simple mixing and heating. Inter­
(5)
estingly, the ion interactions between TEA+ cations and Cl− or Br− an­
ions are destroyed by introducing a large number of EG molecules,
meanwhile, the hydrogen bond networks among EG molecules are
reduced, leading to a significant decrease in viscosity of the DES elec­
trolytes [33]. In Fig. 1c, EG molecules form different solvation shells
with strong Lewis base anions (Cl− or Br− ) through H-bond interactions
in DES electrolytes. These DES electrolytes have the advantages of
considerable ionic conductivity (8.70 mS cm− 1), applicable viscosity
(18.13 mPa s), broad electrochemical stable window (up to 3.03 V) and
wide operating temperature range (− 40 to 115 ◦ C), which are suitable
for supercapacitor application.
Next, the phase changes of these DES electrolytes are analyzed using
DSC technology, because freezing point of the electrolyte is closely
related to the operating temperature range of supercapacitor. From the
cooling data, the heat flow values of these six DES electrolytes cannot
find any obvious change down to − 100 ◦ C due to the hydrogen inter­
action between Cl− or Br− and EG and the intermolecular hydrogen
bonding of EG is also weakened. Moreover, all the GTTs on the curves
referring to the initial temperature of the liquid-glass transition process
are − 110.2, − 109.5, − 107.4, − 113.3, − 112.3 and − 110.3 ◦ C, respec­
tively. Therefore, these DES electrolytes have remarkable operating
ability in such a wider temperature range.
3.2. The stability of DES electrolytes
The stability of DES electrolyte is predicted by the frontier molecular
orbital theory and the theoretical models of TEAB-EG and TEAC-EG
complexes were built to evaluate the reductive and oxidative behav­
iors of six DES electrolyte systems by LUMO and HOMO energies.
Among the electrolytes, the complex with the highest HOMO energy has
the strongest ability to lose electrons, leading to the most oxidative
behavior under lower cell voltage [34]. On the contrary, the complex
with the lowest LUMO energy tends to accept electrons, resulting in the
3
D. Wu et al.
most reductive behavior. Moreover, the chemical hardness (η) refers to
the energy difference between HOMO and LUMO energies, which de­
termines electron gain and loss and the transfer ability of the complexes
[35]. For the complex with a smaller η, the electron transition is much
easier and the complex is more active. Ming and co-workers have re­
ported that the solvent effect plays a significant role on the stability of
the electrolyte and a larger LUMO-HOMO energy difference of
K+-solvent-PF−6 complex indicates that the electron transfer is more
difficult and the complex is more stable [36].
Specifically, the LUMO, HOMO energies and η of the different TEAB-
EG and TEAC-EG complexes are shown in Fig. 2a. Generally, the HOMO
energy is mainly contributed by EG in TEAB-EG complexes, while the
LUMO energy is mainly derived from TEAB, which is similar to the
TEAC-EG complexes. Compared with individual TEAB and TEAC in
Fig. S6, their HOMO energies decrease significantly, indicating that
TEAB-EG and TEAC-EG complexes are difficult to be oxidized after the
formation of DES electrolytes. In detail, the DES-C14 complex has the
highest LUMO energy of 1.11 eV, the lowest HOMO energy of − 6.36 eV
and the largest η of 7.47 eV, which indicates that DES-C14 electrolyte is
the most difficult to be oxidized and reduced among other DES elec­
trolytes. DES-C13 and DES-C15 complexes have similar η (7.17 and 7.20
eV), resulting in little difference in redox stability. In addition, the
lowest LUMO energy of 0.88 eV, the highest HOMO energy of − 5.83 eV
and the smallest η (6.71 eV) of DES-B14 exhibit the worst redox stability.
Notably, the DES-B15 electrolyte shows the relatively high stability in
TEAB-EG electrolyte system. The H-bond interactions (△EDES) between
Br− in TEAB, Cl− in TEAC and H atoms in hydroxyl groups of EG in DES
complexes are depicted in Fig. 2b. It can be seen that the increase of the
proportion of EG brings about the enhancement of H-bond interactions
of O–H⋯Cl or O–H⋯Br and the ion interactions of TEA+ and Br− or Cl−
are weakened.
3.3. Characterizations and physical properties of DES electrolytes
To investigate the chemical bonds and functional groups of these DES
electrolytes, FTIR measurements were performed to analyze the in­
teractions between TEAB, TEAC and EG. As shown in the spectrum of EG
Fig. 2. (a) The LUMO, HOMO energies and the chemical hardness η of TEAB-EG and TEAC-EG complexes. (b) The interaction energies △DES of TEAB-EG and TEAC-
EG complexes.
4
Journal of Power Sources 492 (2021) 229634
in Fig. 3a, the characteristic strong and broad band at 3288 cm− 1 cor­
responds to the intermolecular O–H⋯O stretching vibration and the
bands at 2936 and 2873 cm− 1 belong to the C–H stretching [37]. Be­
sides, the bands at 1409 and 1082 cm− 1 represent O–H deformation and
C–O stretching vibration, respectively [38]. It is noteworthy that for the
TEAB-EG electrolytes, the O–H stretching in DES-B13, DES-B14 and
DES-B15 electrolytes is 3341, 3334 and 3325 cm− 1, respectively.
Compared with EG, the O–H stretching in DESs is blue-shifted signifi­
cantly and the corresponding wavenumber decreases gradually with the
increase of the molar ratio of EG. Similarly, for the spectra of TEAC-EG
electrolytes in Fig. 3b, the O–H stretching in DES-C13, DES-C14 and
DES-C15 electrolytes is 3318, 3310 and 3308 cm− 1, respectively.
Additionally, the spectra of DES-B15 and DES-C15 in the wave­
number range of 3100–3700 cm− 1 are deconvoluted in order to explore
the contribution of different forms of O–H stretching to the broad peak.
On the one hand, as it can be seen in Fig. 3c, the absorbance peaks in
DES-B15 at 3249, 3363 and around 3490 cm− 1 can be attributed to
O–H⋯Br, associated O–H⋯O–H and few free O–H stretching vibrations.
On the other hand, the deconvoluted peaks in DES-C15 at 3240, 3363
and about 3490 cm− 1 can be ascribed to O–H⋯Cl, associated O–H⋯O–H
and negligible free O–H groups which are exhibited in Fig. 3d. Based on
the analysis of other DES electrolytes in Fig. S1, it can be concluded that
the existences of O–H⋯Br or O–H⋯Cl H-bond interactions lead to the
increase of O–H bond length and the decrease of intra/intermolecular H-
bond interactions of EG, which are consistent with the report of Wang
et al. [39].
Raman spectrum is selected to supplement the FTIR results to further
understand the structures and properties of these DES electrolytes. The
spectra of pure EG, TEAB, TEAC and three DES electrolytes in the
wavenumber of 600–3800 cm− 1 are exhibited in Fig. 3e and f. The wide
and weak bands at about 3300 cm− 1 correspond to the associated O–H
stretching, which appear in pure EG and all DES electrolytes except
TEAB and TEAC. The bands at 2942 and 2882 cm− 1 are related to C–H
stretching and the bands at 868 cm− 1 are attributed to C–C–O stretching
vibrations in EG and all DES electrolytes [40]. Besides, the 675 cm− 1
could be ascribed to N–C stretching vibrations.
To evaluate the influence of physical properties of DES electrolytes
D. Wu et al.
Fig. 3. (a, b) FTIR spectra, (c, d) Deconvolution peaks of ν (O–H), (e, f) Raman spectra for TEAB-EG and TEAC-EG electrolytes.
on the electrochemical performance, the ionic conductivity and viscos­
ity of these TEAB-EG and TEAC-EG electrolytes at different temperature
were measured, as displayed in Fig. 4a and b and S2a-d. On the one
hand, the ionic conductivities of DES-B13, DES-B14 and DES-B15 elec­
trolytes at room temperature are 8.42, 8.56 and 8.70 mS cm− 1,
respectively. It can be noticed that the ionic conductivities reach 25.93,
25.75 and 24.61 mS cm− 1 when the temperature increases to 115 ◦ C.
The temperature dependence of ionic conductivity of TEAB-EG elec­
trolytes was fitted by VTF equation and the corresponding results are
presented in Fig. 4c and Table 1. There are good linear relationships
between the figures of ln (σT1/2) and 1000/(T-T0), and the values of Ea
for DES-B13, DES-B14 and DES-B15 electrolytes are 5.21, 3.72 and 4.49
kJ mol− 1, respectively [41]. As a result, the lowest Ea of DES-B14 elec­
trolyte is in good accordance with the slope of VTF plots, demonstrating
that the ionic conductivity of DES-B14 electrolyte is the least sensitive to
temperature [42].
On the other hand, the viscosities of DES-B13, DES-B14 and DES-B15
at room temperature are 25.83, 19.03 and 18.13 mPa s, respectively. On
the contrary, the viscosities of these TEAB-EG electrolytes decrease to
4.22, 3.70 and 3.08 mPa s, respectively when the temperature rises to
115 ◦ C. Moreover, the values of ln (ηT− 1/2) are well linear fitted with
1000/(T-T0) and the results of Kη are 1.42, 0.56 and 0.37 kJ mol− 1 for
TEAB-EG electrolytes in Fig. 4e. The results indicate that the DES-B13
electrolyte has the highest Kη and its viscosity is relatively more
5
Journal of Power Sources 492 (2021) 229634
sensitive to temperature, which is in line with the high slope of the DES-
B13 in VTF plots [43].
Similarly, the ionic conductivities of DES-C13, DES-C14 and DES-
C15 electrolytes at room temperature are 8.13, 8.02 and 7.82 mS
cm− 1, respectively. Besides, the viscosities of these electrolytes are
26.67, 25.21 and 18.47 mPa s, respectively. The ionic conductivity in­
creases and the viscosity decreases with the increase of temperature
which is shown in Fig. 4b. Furthermore, the values of Ea for these TEAC-
EG electrolytes are 24.07, 13.98 and 15.55 kJ mol− 1 and the values of Kη
are 4.42, 0.43 and 0.68 kJ mol− 1, as shown in Fig. 4f and Table 1.
Therefore, the relatively low Ea and Kη for DES-C14 electrolyte indicate
that its ionic conductivity and viscosity are the least sensitive to tem­
perature. Besides, the ionic conductivity and viscosity of DES-C13
electrolyte are the most sensitive to temperature due to the highest Ea
and Kη.
3.4. Electrochemical stable window and wettability of DES electrolytes
One of the important factors in evaluating the stability and practi­
cability of electrolytes is ESW which determines the thermodynamic
stability and electrochemical performance [44]. Therefore, based on
steady-state polarization method, the ESWs of these DES electrolytes
were measured by LSV at 1 mV s− 1 and the results are shown in Fig. 4g
and h. It can be noticed that the ESWs of DES-B13, DES-B14 and
D. Wu et al. Journal of Power Sources 492 (2021) 229634

Fig. 4. (a, b) ionic conductivity and viscosity of different DES electrolytes in the temperature range of − 40 to 115 ◦ C. (c, d) VTF plots of ionic conductivity. (e, f) VTF
plots of viscosity. (g, h) ESWs of various DES electrolytes measured from LSV curves at 1 mV s− 1. (i) Electrolyte uptake of DES electrolytes toward glass microfiber
separator. (j) The electrochemical impedance spectra of SS||wet separator||SS system.

Table 1
Abbreviation of DES electrolyte, ionic conductivity and viscosity at 298.15 K, ionic conductivity and MacMullin number of wet separator, Tg, activation energy of
conductivity and viscosity from VTF equation.
Electrolyte σe (mS cm− 1) ηe (mPa⋅s) σs (mS cm− 1) Tg (K) Ea (kJ mol− 1) Kη (kJ mol− 1) MacMullin number

DES-B13 8.42 25.83 0.315 162.95 5.21 1.42 26.73

DES-B14 8.56 19.03 0.350 163.65 3.72 0.56 24.46
DES-B15 8.70 18.13 0.410 165.75 4.49 0.37 21.22
DES-C13 8.13 26.67 0.319 159.85 24.07 4.42 25.49
DES-C14 8.02 25.21 0.399 160.85 13.98 0.43 20.10
DES-C15 7.82 18.47 0.346 162.85 15.55 0.68 22.60

6
D. Wu et al. Journal of Power Sources 492 (2021) 229634

DES-B15 are 2.633 V (− 1.880 to 0.753 V vs. SCE), 2.597 V (− 1.880 to respectively. As for TEAC-EG electrolytes, the conductivities of these wet
0.717 V) and 2.670 V (− 1.862 to 0.808 V), respectively. The DES-B15 separators are 0.319, 0.399 and 0.346 mS cm− 1, respectively. Further­
electrolyte exhibits the relatively wider ESW and DES-B14 has the nar­ more, the MacMullin number of DES-B15 (21.22) is the relatively low in
rowest ESW, which is in good consistent with the results of theoretical TEAB-EG system, while DES-C14 possesses a MacMullin number of
calculation. On the other side, the ESWs of DES-C13, DES-C14, DES-C15 20.10 and exhibits the best wettability to separator [47].
are 3.003 V (− 1.891 to 1.112 V), 3.03 V (− 1.915 to 1.115 V) and 3.028
V (− 1.913 to 1.115 V), respectively. Among them, the DES-C14 elec­
3.5. Electrochemical performance
trolyte has the highest redox stability which is in agreement with
HOMO-LUMO energies. The wettability is a key factor for ion migration
On the basis of the experimental and theoretical analysis of physical
in supercapacitor and the electrolyte uptake is used to characterize the
properties and stability of DES electrolytes, all electrochemical tests
wettability of these DES electrolytes to separator [45]. As shown in
using DES electrolytes were performed with AC||AC supercapacitor in
Fig. 4i, all the DES electrolyte uptakes of glass microfiber are about 10
the temperature range of − 40 to 115 ◦ C. In TEAC-EG system, the CV
times that of the weight of separator itself. The insets in Fig. 4i are the
curves of DES-C13, DES-C14 and DES-C15 electrolytes were measured at
digital photos of the wettability of DES electrolytes to separator and the
100 mV s− 1 and the corresponding results are shown in Fig. 5a–c. With
measurement for electrolyte uptake. Due to the low viscosity of these
the increase of temperature, the shapes of CV curves are closer to rect­
DES electrolytes, the DES-B15 and DES-C14 electrolytes exhibit the
angle, indicating that EDLC plays a dominate role [48]. The
relatively high electrolyte uptake, demonstrating excellent wettability
temperature-dependent cell voltages of TEAC-EG electrolyte are sepa­
to separator.
rately 1.8, 1.4 and 1 V at RT, 60 and 115 ◦ C, respectively. In addition,
Another important index for evaluating the wettability of electrolyte
DES-C14 electrolyte has the largest geometric area of CV curve at 60 ◦ C
is the impedance of the wet separator. In the inserted picture of Fig. 4j,
that provides the highest specific capacitance.
the results obtained from this “sandwich-type” measurement are straight
Furthermore, the GCD measurements of TEAC-EG electrolytes at
which two stainless steels to clamp the wet separator with DES elec­
different temperature were carried out at 1 A g− 1, which are revealed in
trolyte lines, and these fundamentally describe the behavior of the
Fig. 5 d-f. Notably, the cell voltages of GCD tests are 1.8, 1.4 and 1 V,
electric double layer at the interface between the DES electrolytes and
respectively, which correspond with CV results. Due to the highest vis­
stainless steel. Moreover, the intercepts of these straight lines with X axis
cosity at RT, the CE of DES-C13 electrolyte is only 53% and it increases
represent the ohmic impedance of wet separators filled with DES elec­
to 71% at 60 ◦ C because the Ea and Kη of DES-C13 electrolyte (24.07 and
trolytes [46]. The conductivity of wet separator (σs) is determined by the
4.42 kJ mol− 1) is the most sensitive to temperature. In contrast, the CE
conductivity of electrolyte (σe) and the wettability of electrolyte to
of DES-C14 electrolyte at different temperature is similar (~60%), and
separator, which is closely related to the DES electrolyte used. As listed
its sensitivities of ionic conductivity (13.98 kJ mol− 1) and viscosity
in Table 1, the wet separator with DES-B13, DES-B14 and DES-B15
(0.43 kJ mol− 1) to temperature are relatively low. Furthermore, the pore
shows the conductivity of 0.315, 0.350 and 0.410 mS cm− 1,
size of AC is less than 2 nm and the contact between DES electrolyte and

Fig. 5. The electrochemical measurements were conducted in two-electrode system using DES electrolytes in the temperature range of RT to 115 ◦ C: (a, b, c) CV
curves at 100 mV s− 1; (d, e, f) GCD curves at 1 A g− 1; (g, h, i) Nyquist plots.

7
D. Wu et al.
AC is not sufficient, consequently leading to the inefficient ion diffusion.
More importantly, DES-C14 electrolyte delivers the longest discharge
time and largest integral area of discharge process at 60 ◦ C and its
specific capacitance is calculated to be 202 F g− 1 at 1 A g− 1 based on
single electrode. By comparison, the specific capacitances of DES-C13
and DES-C15 electrolytes are 142 and 154 F g− 1, respectively.
To elucidate the kinetic of ion transport between DES electrolyte and
AC electrode, the EIS tests were measured at RT, 60 and 115 ◦ C and the
Nyquist plots are displayed in Fig. 5g–i, respectively. Based on the
analysis with Nyquist plots, the curves in the low frequency region
present approximate diagonal lines and the equivalent series resistances
(ESR, the intercept with X axis in high frequency region) are 4.2, 5.1 and
5.3 Ω for DES-C15, DES-C14 and DES-C13, respectively [49]. It is
noticed that the values of ESR decrease to 1.5, 2.1 and 3.2 Ω at 60 ◦ C and
become even smaller when the temperature rises to 115 ◦ C, which can
be explained by the increase of ionic conductivities and decrease of
viscosities of DES electrolytes. Moreover, the plots in high frequency
region exhibit smaller semicircles, indicating lower charge transfer re­
sistances (Rct) between the DES electrolytes and electrodes [50].
Meanwhile, the plots in low frequency region gradually become nearly
vertical curves with the increase of temperature which can be linked
with the enhanced ion transports and better EDLC behaviors, and the
results are consistent with more rectangular CV curves [51].
According to the previous DSC results, the electrochemical
Fig. 6. (a, b) CV curves at 100 mV s− 1 and GCD curves at 1 A g− 1
measured at − 40 ◦ C. (c, d) Bode plots. (e, f) Specific capacitances at different current densities in
the temperature range of − 40 to 115 ◦ C.
8
Journal of Power Sources 492 (2021) 229634
performances of AC||AC supercapacitor using different DES electrolytes
have also been measured down to − 40 ◦ C. As shown in Fig. 6a, the
distorted CV curve of DES-C13 electrolyte gets shrunk in the geometric
area due to the reduced ionic conductivity and increased viscosity.
Notably, all of the cell voltage based on these DES electrolytes at − 40 ◦ C
can reach 2.4 V at 100 mV s− 1, although the CV curve of DES-C15
electrolyte exhibits a slight polarization. Besides, the GCD curves of
TEAC-EG electrolytes at − 40 ◦ C are shown in Fig. 6b. For DES-C14
electrolyte, the specific capacitance is calculated to be 80 F g− 1 from
the integral area of discharge process, which shows relatively higher
electrochemical performance at low temperature. It can be noticed that
the values of IR drop using DES-C13, DES-C14 and DES-C15 as elec­
trolytes for AC-based supercapacitor are 0.12, 0.05 and 0.09 V, respec­
tively. Here, the significant increase in the viscosity and decrease in the
conductivity of the bulk DES electrolyte at − 40 ◦ C leads to the sluggish
ion transport within AC electrodes, manifesting as a kind of loss caused
by ESR.
The Bode plots are obtained by EIS data in order to illustrate the
relationship between phase angle and frequency. Due to the relatively
excellent electrochemical performances of DES-C14 and DES-B15 elec­
trolytes, the Bode plots measured from − 40 to 115 ◦ C are depicted in
Fig. 6c and d, respectively. In the high frequency region, the phase an­
gles at different temperature are close to zero. Notably, the phase angles
increases continuously with the decrease of frequency and the faster it
D. Wu et al.
grows as the temperature rises. In the low frequency region, the phase
angles at 60 and 115 ◦ C can almost reach − 80◦ , indicating that the DES-
C14 and DES-B15 electrolytes are closer to the ideal capacitive behav­
iors (− 90◦ ) at higher temperature [52]. In addition, the time constant
(τ0) is reciprocal to the frequency (f) and the values of τ0 at different
temperature for DES-C14 electrolyte are 4.3, 1.2, 0.4 and 0.3 s, when the
phase angle is 45◦ . As for DES-B15 electrolyte, the value of τ0 is 4.7 s at
− 40 ◦ C and it reduces to 0.2 s at 115 ◦ C.
The specific capacitances in the current density range of 1–10 A g− 1
for DES-C14 and DES-B15 electrolytes calculated from the correspond­
ing discharge integral area and the actual cell voltage are shown in
Fig. 6e and f. It can be seen that the DES-C14 and DES-B15 electrolytes
achieve the highest specific capacitances at 60 ◦ C, but the cell voltage
decrease sharply at 115 ◦ C. For the DES-C14 electrolyte, it delivers a
specific capacitance of 202 F g− 1 at 1 A g− 1 and 131 F g− 1 at 10 A g− 1,
respectively. When the temperature rises to 115 C, the specific capaci­
tances for DES-C14 electrolyte are 125 F g− 1 at 1 A g− 1 and 93 F g− 1 at
10 A g− 1, which exhibits a good rate performance. In addition, a specific
capacitance of 80 F g− 1 at 1 A g− 1 can still be reached when the tem­
perature drops to − 40 ◦ C. As for DES-B15 electrolyte, the specific
capacitance at 60 ◦ C reaches 168 F g− 1 at 1 A g− 1 and decrease to 124 F
g− 1 at 10 A g− 1. Furthermore, the repeated GCD curves measured at 1 A
g− 1 are used to investigate the cycling stability of DES-C14 and DES-B15
electrolytes at RT, which are shown in Fig. 7a and b. In this process, the
initial several cycles are not symmetric, so the charge-discharge effi­
ciency is fairly low, which is mainly due to the fact that the AC elec­
trodes have not been fully infiltrated by the DES electrolytes [53].
Fig. 7. (a, b) Cycling performances of AC||AC supercapacitors; (c, d) Discharge specific capacity and coulombic efficiency along with cycle number using different
DES electrolytes; (e, f) Ragone plots at 60 ◦ C with various DES electrolytes.
9
Journal of Power Sources 492 (2021) 229634
On the one hand, the charge and discharge specific capacity of the
50th cycle can reach 36.7 and 34.0 mAh g− 1 using DES-C14 as elec­
trolyte, respectively. Due to the large specific surface area of AC, the
compatibility between DES-C14 electrolyte and AC electrodes is
improved with the continuous charge-discharge processes, and the ion
adsorption and desorption and charge transfer tend to be stable [54].
After 10000 cycles, the specific capacities maintain at 32.0 and 31.5
mAh g− 1, so the CE approaches to 98.4% and the capacity retention is
kept as 92.8% in Fig. 7c. On the other hand, for DES-B15 electrolyte, it
delivers a CE of 91.9% and capacity retention of 89.2% in Fig. 7d. The
cycling performances at 60 ◦ C are shown in Figs. S5a and b, and the
capacity retentions of DES-C14 and DES-B15 are 86% and 91%,
respectively. Energy density and power density are important indexes
for evaluating the practicability of SCs, and the Ragone plots at 60 ◦ C
and RT using different DES electrolytes are shown in Fig. 7e, f and S4 c,
d, respectively. Specifically, the AC||AC supercapacitor using DES-C14
electrolyte at 60 ◦ C delivers the relatively high energy density of 32.2
Wh kg− 1 at a power density of 0.8 kW kg− 1, which is better than the
commercial AC-based supercapacitor (~5 Wh kg− 1). Similarly, the en­
ergy density of DES-B15 electrolyte reaches 23.1 Wh kg− 1 at 0.7 kW
kg− 1.
3.6. Proposed mechanism for the supercapacitor with DES electrolytes
Extensive studies have focused on the cation-solvated structures in
supercapacitor electrolytes [55]. However, the mechanism of the
anion-solvated structures is relatively little. Indeed, the Cl− and Br−
D. Wu et al. Journal of Power Sources 492 (2021) 229634

anions exist in solvated structures with EG in DES electrolytes, which are
further proved by theoretical simulation. Note that the optimized ion
configurations and different anion-solvated DES structures are illus­
trated in Fig. 8a–d. The original distance between TEA+ and Br− is 3.7 Å
and the corresponding distance in TEAC is 3.6 Å, which are exhibited in
the schematic of ion interactions (TEA+, Br− and Cl− ). After the intro­
duction of EG to form different DES electrolytes, the distances between
TEA+ and Br− in DES-B13, DES-B14 and DES-B15 increase to 4.2, 4.3
and 4.4 Å, indicating that the electrostatic interactions between solvated
Br− and TEA+ are reduced. Additionally, as shown in Fig. S7 a-c, the
distances of O–H⋯Br in these three DES are approximately 2.3 and 2.4 Å
which are belonged to H-bond interactions [56]. Similarly, as for three
TEAC-EG electrolytes, the distances between TEA+ and Cl− increase to
4.1, 4.4 and 4.6 Å, respectively, which are owing to the existences of
H-bond interactions in solvated Cl− formed with EG and most of the
distances between O–H⋯Cl are 2.2 and 2.3 Å, as revealed in Fig. S7 d-f.
It is universally known that the transport and adsorption of ions
within the pore channels of AC are closely related to the ion size and

Fig. 8. Schematic illustration of simulated anion solvation structures of (a) TEAB-EG and (c) TEAC-EG complexes and the interaction of (b) TEA+ and Br− , (d) TEA+
and Cl− solvation structures, (e) Proposed interfacial behaviors of the TEAB-EG or TEAC-EG electrolyte on the AC electrode.

10
D. Wu et al.
pore size of AC during the charging process [57]. Based on the DFT
model analysis of pore size distribution (PSD) in Fig. S3, the pore
structure of AC is mainly composed of micropores smaller than 2 nm. In
addition, considering that the optimized ion size of TEA+ is only 6 Å, the
ion transport in the micropores smaller than 0.6 nm is hindered. As
shown in Fig. S7, the ion sizes of three solvated Br− are 8.5, 8.7 and 10.5
Å, and the values for solvated Cl− are 8.4, 11.1 and 11.8 Å, respectively.
Here, the ion transports of solvated Br− and Cl− to the pores less than
1.2 nm are accompanied by the temperature dependent ion desolvation
processes [58]. When the temperature increases, the H-bond in­
teractions between Br− /Cl− and EG and intermolecular H-bond inter­
action of EG are decreased. As a result, the ionic conductivity of the DES
electrolytes increases and the viscosity decreases. More importantly, the
Cl− and Br− ions are more likely to lose electrons and be oxidized at the
interfacial between DES electrolytes and AC, leading to the drop in the
endurable cell voltage at higher temperature [59].
The LUMO and HOMO energies of TPAB (tetrapropylammonium
bromide) and TBAB (tetrabutylammonium bromide) with EG complexes
were also simulated and the corresponding results are presented in
Figs. S8a–d. The lowest HOMO energy of − 6.16 eV and the largest η of
7.20 eV are obtained when the molar ratio of TPAB and EG is 1:4,
exhibiting the relatively high stability. Although the redox stability of
TPAB-EG (1:4) complex is similar to that of TEAB-EG (7.12 eV) and the
cell voltage can reach 1.8 V at RT, it is difficult for TPA+ to enter most of
the micropores below 0.8 nm in AC due to the large optimized ion size of
8.5 Å which is shown in Fig. S9a. Besides, the TBA+ exhibits the largest
optimized ion size of 10.3 Å. Therefore, the specific capacitances using
TPAB-EG (1:4) as electrolyte in Fig. S10 are only 43 and 68 F g− 1 at RT
and 115 ◦ C, respectively. For comparison, we list other excellent works
of AC-based supercapacitor using different electrolytes in Table S2. The
cell voltages using TEAC-EG or TEAB-EG as electrolytes can reach 1.8 V
at RT and 2.4 V at − 40 ◦ C, respectively. The present DES electrolytes
have the advantages of excellent performance, wide operating temper­
ature range and low cost.
As exhibited in Fig. 8e, during the charging process, the functional
groups on the surface of AC include –OH, –COOH, and a small quantity
of –NH2 groups in Fig. S4, which can form hydrogen bonds with Br− , Cl−
ions and –OH groups in EG. When the temperature is down to − 40 ◦ C,
the resistance of ion diffusion in DES electrolyte increase and the charge
transfer is slowed down [60]. According to the results of Gaussian
calculation, after the formation of DES with EG, the LUMO energies of
TEAB and TEAC decrease slightly which are shown in Fig. S6. However,
the HOMO energies of DES complexes decrease significantly, which the
ability to loss electron is weakened and it is less likely to be oxidized.
Moreover, the larger differences (η) between LUMO-HOMO energies
make the electron transition more difficult and the complex more stable.
Although ion desolvation still exists at low temperature, the resistance of
solvated Br− /Cl− transport from bulk DES electrolyte to the interfacial of
AC and electrolyte is increased. The H-bond interactions among solvated
Br− , Cl− and associated EG have not been weakened yet, so the DES
electrolytes can withstand higher voltage at low temperature [61].
4. Conclusions
In summary, we propose several novel DES electrolytes employing
TEAB or TEAC as HBA and EG as HBD, and the relationships among the
molar ratio of HBA/HBD, DES structure, physical property and elec­
trochemical stability are presented by adjusting the H-bond interactions
and ion interactions in DES electrolytes.
(1) Specifically, these DES electrolytes exhibit high ionic conduc­
tivity, low viscosity, broad ESW, good wettability and wide
operating temperature range.
(2) Meanwhile, the DES-C14 electrolyte possesses the lowest HOMO
energy of − 6.36 eV and highest redox stability. The ionic
11
Journal of Power Sources 492 (2021) 229634
conductivity and viscosity of DES-C14 electrolyte are relatively
less sensitive to temperature.
(3) Furthermore, the AC||AC supercapacitor using DES-C14 electro­
lyte exhibits improved EDLC performance (202 F g− 1 at 1 A g− 1
and 32.2 Wh kg− 1 at 0.8 kW kg− 1) and excellent cycling perfor­
mance (92.8% capacity retention after 10000 cycles).
CRediT authorship contribution statement
Di Wu: Investigation, Formal analysis, Writing - original draft. Li
Hua Xu: Investigation, Formal analysis, Writing - original draft. Hua Jie
Feng: Software, Validation. Xiang Ying Chen: Supervision, Writing -
review & editing. Peng Cui: Supervision, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was financially supported by Hainan Provincial Science
and Technology Project (ZDYF2019160), National Natural Science
Foundation of China (51602003), Startup Foundation for Doctors of
Anhui University (J01003211), and Key Laboratory of Photovoltaic and
Energy Conservation Materials, CAS (PECL2019KF001).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2021.229634.
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