1 s2.0 S0378775320301506 Main

Download as pdf or txt
Download as pdf or txt
You are on page 1of 10

Journal of Power Sources 452 (2020) 227847

Contents lists available at ScienceDirect

Journal of Power Sources


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

An alternative electrolyte of deep eutectic solvent by choline chloride and


ethylene glycol for wide temperature range supercapacitors
Min Zhong a, Qian Fang Tang a, Yan Wu Zhu a, Xiang Ying Chen a, b, *, Zhong Jie Zhang c, **
a
School of Chemistry and Chemical Engineering, Anhui Key Laboratory of Controllable Chemistry Reaction & Material Chemical Engineering, Hefei University of
Technology, Hefei, Anhui, 230009, PR China
b
Anhui Province Key Laboratory of Green Manufacturing of Power Battery, TiannengBattery Group (Anhui Company), Jieshou, 236500, Anhui, PR China
c
School of Chemistry & Chemical Engineering, Anhui Province Key Laboratory of Environment-friendly Polymer Materials, Anhui University, Hefei, 230601, Anhui, PR
China

H I G H L I G H T S

� DFT calculation was used to determine the most stable DES-based electrolyte.
� Wide temperature range electrolytes were obtained by mixing ChCl and EG.
� Lower viscosity and higher conductivity were achieved by DES-1-2 under 115 � C.
� Superior energy density (50.33 Wh kg 1) was provided by DES-1-2 at 115 � C.

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

Keywords: In present work, we present a novel deep eutectic solvent electrolyte for supercapacitors simply by mixing
Wide temperature range electrolyte choline chloride and ethylene glycol. It unveils that the molar ratio of choline chloride and ethylene glycol exerts
Supercapacitors crucial effect on the viscosity, electrical conductivity and capacitive behaviors under extreme conditions
Deep eutectic solvent
( 40–115 � C). With the increase of temperature, the viscosity of electrolyte decreases along with the
Density functional theory
enhancement of electrical conductivity; similar phenomenon toward capacitive behaviors under extreme con­
ditions also occurs. The electrolyte with molar ratio of 1:2 (choline chloride:ethylene glycol) under 115 � C shows
a specific capacitance of 362 F g 1 (with energy density of 50.33 Wh kg 1), which can remain as 102 F g 1 (with
energy density of 14.13 Wh kg 1) even at 40 � C. In addition, density functional theory also confirms that the
electrolyte with molar ratio of 1:2 has larger absolute value of adsorption energy as 4.42 eV. The present deep
eutectic solvent by choline chloride and ethylene glycol can extend to other electrolytes especially for wide
temperature range supercapacitors.

1. Introduction materials including carbon materials (hierarchical porous carbons,


heteroatom-doped carbons, carbons with different morphology) [9–14],
Supercapacitor is an effective device that can store energy through a metal oxides (Co3O4, V2O5, NiO, MnO2, MnMoO4/CoMoO4 etc.)
double-layer interface between electrode material and electrolyte [1]. [15–19], conducting polymers (such as polypyrrole, polyaniline and
Due to the excellent rate performance, ultra-high power density and polythiophene) [20–22]. Actually, electrolyte also plays crucial effect on
extended lifetime, it receives extensive attention [2–5]. Nonetheless, it is the eventual capacitive behaviors of supercapacitor.
always facing a major problem with low energy density [6]. In order to Electrolytes for supercapacitor application are usually classified into
improve the energy density, it can be concentrated in two aspects: three species: aqueous solution (KOH, H2SO4, Na2SO4, KCl etc.), organic
electrode materials and electrolytes [7,8]. So far, most of the researched solution (acetonitrile, propylene carbonate, ethylene carbonate and
concerning supercapacitor are focused on the synthesis of electrode dimethyl carbonate etc.), and ionic liquid (EMIMBF4, BMI-PF6, TMPY-

* Corresponding author. School of Chemistry and Chemical Engineering, Anhui Key Laboratory of Controllable Chemistry Reaction & Material Chemical Engi­
neering, Hefei University of Technology, Hefei, Anhui, 230009, PR China.
** Corresponding author.
E-mail addresses: [email protected] (X.Y. Chen), [email protected] (Z.J. Zhang).

https://doi.org/10.1016/j.jpowsour.2020.227847
Received 18 October 2019; Received in revised form 20 January 2020; Accepted 4 February 2020
Available online 7 February 2020
0378-7753/© 2020 Elsevier B.V. All rights reserved.
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

BF4, EMI-TFSI etc.) [23–26]. However, the aqueous electrolyte has a were subjected to constant temperatures treatment before assembling
limited voltage window generally below 1 V due to the low decompo­ the batteries. More importantly, the assembled batteries also require a
sition voltage of water (1.23 V) [27]. Additionally, the organic elec­ constant temperature treatment maintaining 6 h before electrochemical
trolyte is usually highly toxic and the ionic liquid electrolyte is very testing (Keeping temperature is also necessary while measuring). The
expensive [28]. As a consequence, seeking an alternative electrolyte present DES-based electrolytes derived from ChCl and EG composites
especially with green, safe and low cost merits remains compulsory but with different molar ratios (1:1, 1:2, 1:4) are named as DES-1-1/DES-1-
competitive. Until now, the great majority of electrolytes used are only 2/DES-1-4, respectively. For the preparation of low temperature elec­
be operated at room temperature [29]. Nevertheless, some super­ trolytes, we use a cryogenic coolant circulation pump to cool them to
capacitors used in novel fields covering aerospace, electronic automo­ reach the corresponding temperatures ( 20 � C, 40 � C).
bile and military industries need to work under extreme conditions Note that the maximum temperature of 115 � C is chosen because the
including ultra-high temperature and ultra-low temperature [30–32]. limit temperature of the sealing material in the button battery is 120 � C.
Therefore, research on wide temperature range electrolytes is necessary Some material characterization methods and calculation methods are
and should be put on the agenda. also presented in the support material.
Deep eutectic solvent (DES) is an ionic liquid analogue formed by
hydrogen bond donor/acceptor at the temperature below the melting 3. Results and discussion
point of each component [33,34]. According to Abbott, the DES can be
divided into four categories: CatþX zMClx (M ¼ Zn, Sn, Fe, Al, Ga, In); 3.1. Synthetic simulation
CatþX zMClx⋅yH2O (M ¼ Cr, Co, Cu, Ni, Fe); CatþX zRZ (Z ¼ CONH2,
COOH, OH); MClx þ RZ ¼ MClþ x-1⋅RZ þ MClxþ1 (M ¼ Al, Zn; Z ¼ CONH2, As we know, DFT is a quantum mechanical method that uses particle
OH) [35]. The application of DES covers many fields (metal plating, density to study the electronic structure of multi-electron systems
material extraction, reaction medium or catalyst, material synthesis, [41–43]. In present work, for better understanding the synthesis process
electrolyte, etc.) what deserves our attention is the application of DES in of DES consisting of ChCl and EG, we thus employed DFT to simulate the
the area of energy storage [36–38]. For examples, the DES electrolyte bonding mode of DES (hydrogen bond) with different molar ratios and
consisting of N-methylacetamide and lithium bis[(trifluoromethyl)sul­ calculate the Mulliken atomic charges of each atom in the corresponding
fonyl]imide obtained a wide voltage window which make its specific system. As shown in Fig. 1a, a series of colorless, transparent and uni­
capacitance up to 380 F g 1 at 80 � C [39]. Besides, DES composed of form DES solvents were obtained by simple heat treatment (below than
choline chloride (ChCl) and ethylene glycol (EG) is more cheaper, safer, 100 � C) of the ChCl-EG compounds. Obviously, the three ratios of DES
which makes them more suitable for various fields such as extraction, solvents are indistinguishable in appearance from the recorded photos,
separation, electrolyte [40]. Considering the facts that this kind of DES but there are actually different. Thus, the theoretical calculation based
exhibits proper viscosity and electrical conductivity, it is perhaps suit­ on DFT was considered to utilize and the adsorption energy (Eads) of
able for supercapacitor application. different DES system was finally acquired through a series of processes
Herein, we synthesized a series of DES-based electrolytes for super­ such as model building, geometric optimization and theoretical calcu­
capacitors by simply mixing ChCl and EG with different molar ratios as lation [44]. The absolute values of Eads for the DES-1-1, DES-1-2 and
1:1, 1:2, 1:4. This DES-based electrolyte achieved normal operation at a DES-1-4 are 3.69, 4.42 and 4.30 eV, respectively. According to relevant
wide temperature range from 40 to 115 � C ( 40 � C, 20 � C, RT, 40 � C, literature reports, the greater the absolute value of Eads in a system is, the
60 � C, 80 � C, 100 � C, 115 � C) in the two-electrode system. Meanwhile, more stable the system is, which is closely related to the transport
the viscosity and conductivity of all DES-based electrolytes at various property (for instance, viscosity and electrical conductivity) in DES so­
temperatures were measured and compared to investigate the differ­ lution [45–47]. Therefore, DES-1-2 is relatively more stable under high
ences in electrochemical performance of electrolytes. Furthermore, temperature than DES-1-1/DES-1-4, which provides a theoretical basis
theoretical calculation based on density functional theory (DFT) was for the subsequent electrochemical performance test results [48]. The
also used to determine the most stable DES-based electrolyte system, DFT simulation results of three proportional DES structures in which the
providing a reasonable explanation for the stable presence of electrolyte components are primarily connected to each other by hydrogen bonds
at ultra-high temperature and for exhibiting excellent electrochemical (ChCl and EG are hydrogen bond acceptors and donors, respectively) are
performance. also presented in Fig. 1b–d [49].
In addition, the Mulliken atomic charges of the major atoms in the
2. Experimental section DES systems are also summarized in Table S1 (all atoms in each system
have been indexed before calculation). From Table S1, it can be seen that
2.1. Synthesis procedure for DES the Mulliken atomic charge of H15 (a hydrogen atom on the hydroxyl
group of the EG) is reduce in all DES systems while the Mulliken atomic
Firstly, by adjusting the molar ratios as 1:1, 1:2, 1:4, a certain dose of charge of Cl (chlorine atom in the ChCl) is increase, indicating that the
ChCl powder (sealed preservation, analytically pure) and EG solution hydrogen bond is formed between them [50,51]. Furthermore, the hy­
(analytically pure) were poured into a clean beaker without any addi­ droxyl group in the ChCl can also form a hydrogen bond with another
tional aqueous solution. And then, the mixture in the beaker was heated hydroxyl group on the EG Ref. [52]. For example, the hydrogen atom
by ZNCL-TS type intelligent constant temperature magnetic stirrer (H1) on the hydroxyl group of ChCl loses electron and the oxygen atom
under 80 � C until the white solid was completely dissolved. As a result, a (O3) on the other hydroxyl group of EG acquires electron in the DES-1-1
colorless, transparent and uniform liquid was obtained. Finally, we system. However, we not need to conduct an in-depth research here in
sealed the synthesized DES solution with plastic wrap. this hydrogen bond, but the hydrogen bond formed by the former should
be mainly explored because it plays a major role in
2.2. Preparation of DES-based electrolytes DES-1-1/DES-1-2/DES-1-4 [53].

A series of DES-based electrolytes with different temperatures can be 3.2. Structure characterization and transport properties
obtained via heating different molar ratios of DES solutions to the cor­
responding temperatures (RT, 40 � C, 60 � C, 80 � C, 100 � C, 115 � C). It is In order to investigate the performances of DES-based super­
worth noting that the DES-based electrolytes below 80 � C were obtained capacitors, the relevant properties (pore structure, viscosity and elec­
by cooling the synthesized DES solutions to the corresponding temper­ trical conductivity) of AC or DES-1-1/DES-1-2/DES-1-4 electrolytes
atures (RT, 40 � C, 60 � C) and the battery modules which would be used were firstly studied. For carbon-electrode materials, the principal

2
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

Fig. 1. The DES-1-1/DES-1-2/DES-1-4 samples: (a) Synthetic schematic; (b–d) Theoretical calculation based on DFT.

influence factors of supercapacitors are the porous structure (includes isothermal curve [58]. On the other hand, some oxygen-containing
macropore, mesopore, micropore) and the doping of heteroatoms (such functional groups (phenolic hydroxyl groups, carboxyl groups, lactone
as N, O, P, S etc.) [54,55]. On the one hand, the specific surface area groups, carbonyl groups) appearing on the surface of AC are favorable of
(SBET ¼ 1933 m2 g 1) and pore volume (VT ¼ 0.96 cm3 g 1) of AC were the pseudocapacitive for supercapacitors [59]. Raman result was also be
obtained by N2 adsorption-desorption test. It can be seen from the provided for the reason that graphitization degree is very important for
isothermal curve of Fig. 2a that the AC with no hysteresis loop from 0.4 AC. As shown in Fig. S1, the AC has a well degree of graphitization and
to 1.0 P/P0 exhibits a sharp rise when the relative pressure is close to can be applied as an electrode material for supercapacitors.
zero (characteristic of Type I), clearly representing that the micropore is For DES-based electrolytes, the fluidity and electrical conductivity of
dominant [56,57]. Moreover, the pore size distribution (PSD) curve in the electrolytes are critical to the performance of supercapacitors [60].
Fig. 2a has peaks at 1–2 nm (micropores) which corresponds to the More importantly, the viscosity and electrical conductivity of the

Fig. 2. (a) The isotherm and PSD curve of AC; (b–d) The viscosity and electrical conductivity of DES-1-1/DES-1-2/DES-1-4 samples at different temperatures from RT
to 115 � C.

3
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

solution will also change as the temperature increases [61]. Therefore, Fig. 3a/d/g and the sample of DES-1-2 has the largest closed area which
the viscosity and electrical conductivity of DES-1-1/2/4 at RT, 40 � C, 60 implies the best specific capacitance [62,63]. The GCD curves of three

C, 80 � C, 100 � C and 115 � C were measured and the results are shown in DES electrolytes under 1 A g 1 always maintain a symmetrical form
Fig. 2b–d. Overall, the viscosities of the three DES-based electrolytes although the temperature is rises from RT to 115 � C as shown in
decrease with increasing temperature while the electrical conductivities Fig. 3b/e/h. Meanwhile, for the same sample, the charge and discharge
of the electrolytes increase with increasing temperature. In detail, from time extend as the test temperature increases. This phenomenon can be
RT to 115 � C, the viscosity of DES-1-1 decreased from 93.31 to 34.25 cP attributed to the fact that as the temperature rises, the viscosity of the
and the corresponding electrical conductivity increased from 6.23 to electrolyte decreases and the electrical conductivity increases as the
10.35 mS cm 1. As shown in Fig. 2c, DES-1-2 has a viscosity as 9.60 cP result of the migration rate of the electrolyte ions continuously ag­
and an electrical conductivity up to 11.75 mS cm 1. However, when the grandizes [64].
amount of EG increases further, the viscosity of DES-1-4 can be as low as The Nyquist plots reveal the transport of electrolyte ions between the
10.18 cP, and the electrical conductivity can be as high as 10.79 mS electrodes, where the charge transfer resistance can be determined by
cm 1. Comparatively, DES-1-2 has a lower viscosity and a higher elec­ the semicircular diameter (Rct), and the electrolyte diffusion capacity
trical conductivity, which completely coincides with its excellent elec­ can be obtained by observing the slope of the vertical curve [65,66].
trochemical performance measuring later. Noteworthily, the sample of DES-1-2 exhibits better electrochemical
performance than DES-1-1/DES-1-4 at different working temperatures
which matches well with its excellent transport properties (the lowest
3.3. Electrochemical measurements
viscosity as 9.60 cP and the highest conductivity as 11.75 mS cm 1
under 115 � C) according to Fig. 2b–d and Fig. 3c/f/i.
Since the three prepared DES electrolytes (DES-1-1/DES-1-2/DES-1-
As shown in Fig. 4a/d/g, it can be seen that the specific capacitance
4) have excellent transport property, they are fully qualified as the
of DES-1-1/DES-1-2/DES-1-4 has a visible growing tendency from RT to
electrolytes of supercapacitors. Therefore, the related electrochemical
115 � C, and the sample of DES-1-2 shows the most outstanding specific
tests in the symmetrical two-electrode configurations (button batteries
capacitance. In detail, for DES-1-1, the capacitance can be increased
using AC as working electrode) assembled from three DES electrolytes
from 53 to 179 F g 1 (Fig. 4a) as the temperature continues to rise when
under different temperatures from RT to 115 � C were conducted, the
the current density is 1 A g 1, while the DES-1-4 is from 61 to 329 F g 1
results of the tests are shown in Fig. 3 and Fig. 4. The CV curves with the
(Fig. 4g). Interestingly, the capacitance of DES-1-2 can be as high as 362
voltage window as 2 V at 100 mV s 1 are all relatively rectangular from

Fig. 3. The DES-1-1/DES-1-2/DES-1-4 samples under different temperatures from RT to 115 � C: (a, d, g) CV curves at 100 mV s 1; (b, e, h) GCD curves under 1 A g 1
;
(c, f, i) Nyquist plots.

4
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

Fig. 4. The DES-1-1/DES-1-2/DES-1-4 samples under different temperatures from RT to 115 � C: (a, d, g) Specific capacitance; (b, e, h) Ragone plots; (c, f, i)
Cycling stability.

F g 1 (Fig. 4d) when the temperature is 115 � C, which is about twice DES-1-1/DES-1-2/DES-1-4 electrolytes still display relatively symmet­
than that of DES-1-1. Moreover, compared with the previously reported rical charge and discharge curves even operated at an ultra-high tem­
electrolytes such as lithium bis[(trifluoromethyl)sulfonyl]imide perature, and the coulombic efficiencies are quite good, which are
(LiTFSI)/N-methylacetamide (MAc) (1.5 V), LiPF6 with a mixture of 63.25%, 72.57% and 67.47%, respectively. Besides, the sample of DES-
ethylene carbonate and diethyl carbonate (1.5 V), 1 M Na2SO4 (1.6 V), 2 1-2 delivers a area specific capacitance of 320.7 mF cm 2 at 1 mA cm 2
M Li2SO4 (1.6 V) [67–70], the DES-1-2 electrolyte (2 V) delivers a higher (DES-1-1: 158.8 mF cm 2, DES-1-4: 291.1 mF cm 2, Fig. 5b), which is
voltage window which is beneficial for increasing specific capacitance. much higher than some literature data previously reported, for example,
Significantly, the energy densities of all DES electrolytes at 1 kW the 160 mF cm 2 provided by 3D porous hybrid material; 118 mF cm 2
kg 1 under 115 � C abide by the following sequence: DES-1-2 (50.33 Wh afforded by PPy/GO-CNT; 250 mF cm 2 offered by cellulose-derived
kg 1, Fig. 4e) > DES-1-4 (45.68 Wh kg 1, Fig. 4h) > DES-1-1 (24.92 Wh porous carbon (CNUY–600H); 134 mF cm 2 furnished by NiFe oxy­
kg 1, Fig. 4b), and even at a power density up to 10 kW kg 1, they can fluoride (NiFeOF) [72–75].
still provide 36.26 Wh kg 1, 31.48 Wh kg 1, 17.30 Wh kg 1, respec­ Fig. 5c displays the Bode plots obtained by EIS test data expansion,
tively. Considering the fact that the DES-based electrolyte has marvelous the relaxation time constant τ0 (which can be defined as the time at
thermal and chemical stability [71], the three electrolytes display which the electrode can be reversibly charged/discharged when the
distinguished cycle lifes at different temperatures during the 10000 efficiency exceeds 50%) is closely related to the operating frequency f0
cycle performance test. As shown in Fig. 4c/f/i, the cycle performance of (which is the frequency corresponding to the phase angle 45� ), and the
DES-1-2 (99.86% at 115 � C) is better than those of the other two formula τ0 ¼ 1/f0 can be used to express the relationship between them
DES-based electrolytes (DES-1-1: 96.42% at 115 � C, DES-1-4: 98.37% at [76,77]. Unquestionably, the DES-1-2 possesses a τ0 as 2.0 s which is
115 � C), which corresponds to the results of the previous DFT theoretical lower than that of DES-1-1 (3.7 s) or DES-1-4 (2.5 s). This suggests that
calculation (DES-1-2 has the highest absolute value of Eads as 2.34 eV). the resistance of DES-1-2 is correspondingly small due to its excellent
To further investigate the effect of the difference in the molar ratio of transport property. The frequency responses of C0 also be described as
the DES component on the electrochemical performances, the coulombic shown in Fig. 5d, this result corresponds well with Fig. 5c and insures
efficiency, areal capacitance, Bode plot as well as frequency response of the excellent electrochemical behavior of DES-1-2.
C0 for different samples were compared at the same temperature (115 Except from the high temperature working environment, many

C). It can be seen from Fig. 5a that the supercapacitors assembled by the electrochemical energy storage devices in production and life operated

5
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

1
Fig. 5. The DES-1-1/DES-1-2/DES-1-4 samples at 115 � C: (a) GCD curves under 1 A g (the inset corresponds to coulombic efficiency); (b) Areal capacitances vs.
current density; (c) Bode plots; (d) Frequency responses of C0 .

in extremely low temperature environment. Therefore, DES-1-1/DES-1- than many previously reported literature data shown in Fig. 6e [79–84].
2/DES-1-4 are also used to assemble cryogenic supercapacitors of 20 Besides, after 10,000 cycles, the DES-1-2/4 at 20 � C (DES-1-2: 90.12%,

C and 40 � C (The electrolytes of DES-1-2 and DES-1-4 at 20 � C and DES-1-2: 87.63%) have a longer lifespan than at 40 � C (DES-1-2:
40 � C are respectively represented as DES-1-2 ( 20), DES-1-2 ( 40), 86.24%, DES-1-2: 82.79%, Fig. 6f). This phenomenon may be attributed
DES-1-4 ( 20), DES-1-4 ( 40)) to investigate whether their properties to the fact that as the temperature decreases, the transport resistance of
differ significantly from those at room or high temperature. Before the the electrolyte ions between the electrode material increases, eventually
electrochemical test, the DES-1-1/DES-1-2/DES-1-4 were first placed at manifesting a shortening of the cycle life [85]. In order to further verify
the corresponding temperature to see if the electrolytes became solid, this type of electrolytes exhibiting the excellent performance in elec­
and it was found that only DES-1-1 will become solid at low tempera­ trochemical field, the GCD curve after the severe cycling is also be
tures while DES-1-2/DES-1-4 remain liquid state. Then, the viscosity and provided (as shown in Figs. S2 and S3), which further proves that the
electrical conductivity of DES-1-2/4 ( 20/40) were also measured, and DES-based electrolyte with a molar ratio of 1: 2: 2 is more outstanding.
the results are shown in Table S2, where DES-1-2 ( 20) has the largest In addition, it can be found that the specific capacitance of DES-based
electrical conductivity (1.79 mS cm 1) and minimum viscosity (146.23 electrolytes with different molar ratios still is increased as raising the
cP). Consequently, only the performances of DES-1-2/DES-1-4 on elec­ temperature. This can be attributed to the fact that when the tempera­
trochemistry have been considered, and the results are shown in Fig. 6. ture is not high, the electrolyte ions lack the power of mass transfer, and
According to the CV curves at 100 mV s 1 (Fig. 6a) and GCD curves the high temperature just replenishes a certain amount of energy for the
under 1 A g 1 (Fig. 6b), DES-1-2 ( 20) displays the larger curve area, mass transfer to proceed smoothly, thereby obtaining better specific
while DES-1-4 ( 40) is the smallest, but the curve area at low temper­ capacitance.
atures is smaller than that of RT. It may be ascribed to the high viscosity For researching how the DES-based electrolyte (DES-1-2) worked at
of the electrolyte at low temperature, resulting in a decrease in ion different temperatures ( 40–115 � C), the mechanism of prepared elec­
transport rate of the electrolyte as well as the electrical conductivity trolyte operated in a two-electrode equipment with AC as electrode
[78]. As a consequence of the reason described above, the evolution of material was reasonably interpreted and the results are shown in Fig. 7.
C00 vs. Frequency (Fig. 6c) likewise shows that the DES-1-2 ( 20) has an As is known, the DES solution can be stably presented even at ultra-high
excellent electrochemical performance showing in the τ0 of it as low as temperature due to the excellent thermal and chemical stability [86].
2.5s. Surprisingly, even the temperature as low as 40 � C, the DES-1-4 The deeper reason for this phenomenon can be traced back to the in­
still has a specific capacitance of 65 F g 1 at 1 A g 1 (DES-1-2 ( 20): ternal hydrogen bond formed between the donor (EG) and acceptor
102 F g 1, DES-1-2 ( 40): 78 F g 1, DES-1-4 ( 20): 89 F g 1 as shown in (ChCl). When the battery is operated, the unbonded hydroxyl groups in
Fig. 6d), and the corresponding rate performance are 57.67% (DES-1-2 DES-1-2 can form hydrogen bonds with the oxygen-containing func­
( 20): 77.74%, DES-1-2 ( 40): 62.31%, DES-1-4 ( 20): 61.34%). With tional groups (-COOH or –OH) on the surface of AC, which accelerates
power density from 1 to 10 kW kg 1, the energy density of each sample the transport of electrolyte ions and thus achieves high electrical con­
shows a slight change, with DES-1-2 ( 20) still maintains 10.98 Wh ductivity [87]. Meanwhile, the positive and negative electrolyte ions (as
kg 1 even at 10 kW kg 1 (14.13 Wh kg 1 at 1 kW kg 1) which is better shown in Fig. 7) in the DES-1-2 electrolyte will also transfer toward the

6
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

1 1
Fig. 6. The DES-1-2 and DES-1-4 samples under 20 � C as well as 40 � C: (a) CV curves at 100 mV s ; (b) GCD curves under 1 A g ; (c) Evolution of C00 vs.
frequency; (d) Capacitances vs. current density (e) Ragone plots; (f) Cycling stability.

Fig. 7. The working mechanism of DES-1-2 electrolyte in the two-electrode equipment with AC as electrode material.

corresponding electrode surface (there is Van der Waals force exist be­ of the electrolytes; the other is that the unbonded hydroxyl group in the
tween the two working electrodes) [88]. From the above, the reason DES solution forms hydrogen bond with an oxygen-containing func­
why the DES-based electrolytes can operate normally at the extreme tional group on the AC surface, which promotes the migration of elec­
temperature could be attributed to the following two aspects: one is that trolyte ions. The reason why this type of DES solution become an
the hydrogen bond formed inside the DES solution ensures the stability electrolyte for supercapacitors lies in the following requirements:

7
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

excellent transport properties to ensure the normal transport of elec­ References


trolyte ions; the hydroxyl functional groups in the DES system can form
hydrogen bonding with functionalities on the surface of the carbon [1] A. Gonz� alez, E. Goikolea, J.A. Barrena, R. Mysyk, Review on supercapacitors:
technologies and materials, Renew. Sustain. Energy Rev. 58 (2016) 1189–1206.
material, improving the capacitance of the electrolyte. The mechanism [2] Z. Gao, C. Bumgardner, N. Song, Y. Zhang, J. Li, X. Li, Cotton-textile-enabled
for DES-1-1 and DES-1-4 electrolyte can be deduced by analogy. flexible self-sustaining power packs via roll-to-roll fabrication, Nat. Commun. 7
(2016) 11586.
[3] X.G. Li, B.Y. Guan, S.Y. Gao, X.W. Lou, A general dual-templating approach to
4. Conclusions biomass-derived hierarchically porous heteroatom-doped carbon materials for
enhanced electrocatalytic oxygen reduction, Energy Environ. Sci. 12 (2019)
In summary, a series of novel wide temperature range DES-based 648–655.
[4] L.Z. Sheng, L.L. Jiang, T. Wei, Z. Liu, Z.J. Fan, Spatial charge storage within
electrolytes for supercapacitors were successfully obtained by employ­ honeycomb-carbon frameworks for ultrafast supercapacitors with high energy and
ing ChCl and EG as hydrogen bond acceptor and donor. The research power densities, Adv. Energy Mater. (2017) 1700668.
results of the present work are summarized as follows: [5] X.W. Yang, C. Cheng, Y.F. Wang, L. Qiu, D. Li, Liquid-mediated dense integration of
graphene materials for compact capacitive energy storage, Science 341 (2013)
534–537.
1) The DES solution was obtained by simple heat treatment of the ChCl [6] X. Fan, C. Yu, J. Yang, Z. Ling, C. Hu, M. Zhang, J. Qiu, A layered-nanospace-
and EG composites with different molar ratios as 1:1, 1:2, 1:4. This confinement strategy for the synthesis of two-dimensional porous carbon
nanosheets for high-rate performance supercapacitors, Adv. Energy Mater. 5
DES possesses excellent transport property (low viscosity, high (2015) 1401761.
electrical conductivity) and can be used as an electrolyte for super­ [7] S. Shahzad, A. Shah, E. Kowsari, F.J. Iftikhar, A. Nawab, B. Piro, M.S. Akhter, U.
capacitor. On the one hand, under the same ratio, the viscosity of A. Rana, Y.J. Zou, Ionic liquids as environmentally benign electrolytes for high-
performance supercapacitors, Global Challenges 3 (2019) 1800023.
DES decreases with increasing temperature while the electrical [8] S.Z. Wang, L.L. Li, Y.L. Shao, L. Zhang, Y.L. Li, Y.Z. Wu, X.P. Hao, Transition-metal
conductivity increases. On the other hand, the DES-1-2 electrolyte oxynitride: a facile strategy for improving electrochemical capacitor storage, Adv.
(the molar ratio of ChCl and EG is 1:2) shows superior transport Mater. (2019) 1806088.
[9] Y.P. Zhai, Y.Q. Dou, D.Y. Zhao, P.F. Fulvio, R.T. Mayes, S. Dai, Carbon materials for
property at the same temperature compared with DES-1-1 and DES-
chemical capacitive energy storage, Adv. Mater. 23 (2011) 4828–4850.
1-4. [10] S. Dutta, A. Bhaumik, K.C.W. Wu, Hierarchically porous carbon derived from
2) This DES-based electrolyte can operate normally over a wide tem­ polymers and biomass: effect of interconnected pores on energy applications,
perature range from 40 to 115 � C. The reason for such phenomenon Energy Environ. Sci. 7 (2014) 3574–3592.
[11] S.L. Huo, M.Q. Liu, L.L. Wu, M.J. Liu, M. Xua, W. Nia, Y.M. Yan, Synthesis of
could be attributed to the following two aspects: the hydrogen bond ultrathin and hierarchically porous carbon nanosheets based on interlayer-
formed inside the DES solution ensures the stability of the electro­ confined inorganic/organic coordination for high performance supercapacitors,
lytes at different temperatures ( 40 � C, 20 � C, RT, 40 � C, 60 � C, 80 J. Power Sources 414 (2019) 383–392.
[12] R. Paul, F. Du, L.M. Dai, Y. Ding, Z.L. Wang, F. Wei, A. Roy, 3D heteroatom-doped

C, 100 � C, 115 � C); the unbonded hydroxyl group in the DES solu­ carbon nanomaterials as multifunctional metal-free catalysts for integrated energy
tion forms hydrogen bond with an oxygen-containing functional devices, Adv. Mater. (2019) 1805598.
group on the AC surface, which promotes the migration of electrolyte [13] G.H. An, H. Kim, H.J. Ahn, Improved ionic diffusion through the mesoporous
carbon skin on silicon nanoparticles embedded in carbon for ultrafast lithium
ions. storage, ACS Appl. Mater. Interfaces 10 (2018) 6235–6244.
3) The theoretical calculation based on DFT can be applied to simulate [14] G.H. An, D.Y. Lee, H.J. Ahn, Tunneled mesoporous carbon nanofibers with
different molar ratios of DES architectures to determine which sys­ embedded ZnO nanoparticles for ultrafast lithium storage, ACS Appl. Mater.
Interfaces 9 (2017) 12478–12485.
tem is more stable. Among all DES-based electrolytes, the DES-1-2 [15] C.Z. Yuan, L. Yang, L.R. Hou, L.F. Shen, X.G. Zhang, X.W. Lou, Growth of ultrathin
has the highest absolute value of Eads as 4.42 eV (DES-1-1: 3.69 eV, mesoporous Co3O4 nanosheet arrays on Ni foam for high-performance
DES-1-4: 4.30 eV) indicating that the most stable structure. Simul­ electrochemical capacitors, Energy Environ. Sci. 5 (2012) 7883–7887.
[16] J.S. Bonso, A. Rahy, S.D. Perera, N. Nour, O. Seitz, Y.J. Chabal, Kenneth
taneously, the change of Mulliken atomic charges also provides a
J. Balkus Jr., J.P. Ferraris, D.J. Yang, Exfoliated graphite nanoplatelets-V2O5
theoretical basis for the subsequent mechanism explanation. nanotube composite electrodes for supercapacitors, J. Power Sources 203 (2012)
4) The electrochemical performances of DES-based electrolytes at 227–232.
different temperatures under the two-electrode devices are consis­ [17] Q.Z. Zhang, D. Zhang, Z.C. Miao, X.L. Zhang, S.L. Chou, Research progress in
MnO2-carbon based supercapacitor electrode materials, Small (2018) 1702883.
tent well with the results of transport performance and theoretical [18] L.Q. Mai, F. Yang, Y.L. Zhao, X. Xu, L. Xu, Y.Z. Luo, Hierarchical MnMoO 4/
calculation. Obviously, the DES-1-2 has higher specific capacitance, CoMoO4 heterostructured nanowires with enhanced supercapacitor performance,
energy density and cyclic stability at the same temperature due to its Nat. Commun. 381 (2011), https://doi.org/10.1038/ncomms1387.
[19] G.H. An, S.N. Cha, J.I. Sohn, Surface tailoring of zinc electrodes for energy storage
minimum viscosity, highest electrical conductivity and maximum devices with high-energy densities and long cycle life, Appl. Surf. Sci. 467‒468
absolute value of Eads. (2019) 1157–1160.
[20] M.R.A. Velez, M.E. Roberts, Redox solute doped polypyrrole for high-charge
capacity polymer electrodes, Chem. Mater. 26 (2014) 1601–1607.
Declaration of competing interest [21] P.C. Du, W.L. Wei, D. Liu, H.X. Kang, P. Liu, Fabrication of hierarchical carbon
layer encapsulated polyaniline core-shell structure nanotubes and application in
supercapacitors, Chem. Eng. J. 335 (2018) 373–383.
The authors declare that they have no known competing financial [22] G.P. Wang, L. Zhang, J.J. Zhang, A review of electrode materials for
interests or personal relationships that could have appeared to influence electrochemical supercapacitors, Chem. Soc. Rev. 41 (2012) 797–828.
[23] G.A. Snook, P. Kao, A.S. Best, Conducting-polymer-based supercapacitor devices
the work reported in this paper. and electrodes, J. Power Sources 196 (2011) 1–12.
[24] F. B�eguin, V. Presser, A. Balducci, E. Frackowiak, Carbons and electrolytes for
advanced supercapacitors, Adv. Mater. 26 (2014) 2219–2251.
Acknowledgments
[25] C. Zhong, Y.D. Deng, W.B. Hu, J.L. Qiao, L. Zhang, J.J. Zhang, A review of
electrolyte materials and compositions for electrochemical supercapacitors, Chem.
This work was financially supported by National Natural Science Soc. Rev. 44 (2015) 7484–7539.
Foundation of China (51602003), Startup Foundation for Doctors of [26] A.C. Forse, C. Merlet, J.M. Griffin, C.P. Grey, New perspectives on the charging
mechanisms of supercapacitors, J. Am. Chem. Soc. 138 (2016) 5731–5744.
Anhui University (J01003211), Key Research and Development Projects [27] M. Tian, J.W. Wu, R.H. Li, Y.L. Chen, D.H. Long, Fabricating a high-energy-density
of Anhui in 2018 (1804a09020064) and Key Laboratory of Photovoltaic supercapacitor with asymmetric aqueous redox additive electrolytes and free-
and Energy Conservation Materials, CAS (PECL2019KF001). standing activated-carbon-felt electrodes, Chem. Eng. J. 363 (2019) 183–191.
[28] A. Lewandowski, A. Olejniczak, M. Galinski, I. Stepniak, Performance of carbon-
carbon supercapacitors based on organic, aqueous and ionic liquid electrolytes,
Appendix A. Supplementary data J. Power Sources 195 (2010) 5814–5819.
[29] F. B�eguin, V. Presser, A. Balducci, E. Frackowiak, Carbons and electrolytes for
advanced supercapacitors, Phys. Chem. Chem. Phys. 9 (2007) 1774–1785.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2020.227847.

8
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

[30] K. Hung, C. Masarapu, T. Ko, B.Q. Wei, Wide-temperature range operation [58] H. Liu, D.D. Zhai, M. Wang, J.S. Liu, X.Y. Chen, Z.J. Zhang, Urea-modified phenol-
supercapacitors from nanostructured activated carbon fabric, J. Power Sources 193 formaldehyde resins for the template-assisted synthesis of nitrogen-doped carbon
(2009) 944–949. nanosheets as electrode material for supercapacitors, ChemElectroChem 6 (2019)
[31] W.L. Zhang, J. Wang, D.B. Ruan, Q. Shi, F.M. Zhang, Q.J. Ren, Z.Q. Shi, Water- 885–891.
based synthesis of spiro-(1,1)-bipyrrolidinium bis(fluorosulfonyl)imide electrolyte [59] Y.H. Liu, B. R�ety, C.M. Ghimbeu, B.S. Guillous, P.L. Taberna, P. Simon,
for high-voltage and low-temperature supercapacitor, Chem. Eng. J. 373 (2019) Understanding ageing mechanisms of porous carbons in non-aqueous electrolytes
1012–1019. for supercapacitors applications, J. Power Sources 434 (2019) 226734.
[32] L. Liu, K. Du, Z.B. He, T. Wang, X.L. Zhong, T. Ma, J.M. Yang, Y.C. He, G.B. Dong, S. [60] A. Boisset, S. Menne, J. Jacquemin, A. Balduccib, M. Anouti, Deep eutectic solvents
H. Wang, X.G. Diao, High-temperature adaptive and robust ultra-thin inorganic all- based on N-methylacetamide and a lithium salt as suitable electrolytes for lithium-
solid-state smart electrochromic energy storage devices, Nano Energy 62 (2019) ion batteries, Phys. Chem. Chem. Phys. 15 (2013) 20054–20063.
46–54. [61] J.W. Zhao, J. Zhang, W.H. Yang, B.B. Chen, Z.M. Zhao, H.Y. Qiu, S.M. Dong, X.
[33] E.L. Smith, A.P. Abbott, K.S. Ryder, Deep eutectic solvents (DESs) and their H. Zhou, G.L. Cui, L.Q. Chen, “Water-in-deep eutectic solvent” electrolytes enable
applications, Chem. Rev. 114 (2014) 11060–11082. zinc metal anodes for rechargeable aqueous batteries, Nanomater. Energy 57
[34] Q.H. Zhang, K.D.O. Vigier, S. Royer, F. J� er^
ome, Deep eutectic solvents: syntheses, (2019) 625–634.
properties and applications, Chem. Soc. Rev. 41 (2012) 7108–7146. [62] F.L. Qi, Z.X. Xia, J.T. Jin, X.D. Fu, W. Wei, S.L. Wang, G.Q. Sun, Chemical foaming
[35] J.D.M. Morales, R.J.S. Leija, A. Carranza, J.A. Pojman, F.D. Monte, G.L. B� arcenas, coupled self-etching: a multiscale processing strategy for ultrahigh-surface-area
Free-radical polymerizations of and in deep eutectic solvents: green synthesis of carbon aerogels, ACS Appl. Mater. Interfaces 10 (2018) 2819–2827.
functional materials, Prog. Polym. Sci. 78 (2018) 139–153. [63] D.P. Lia, L. Chen, L.N. Chen, Q. Sun, M. Zhu, Y.M. Zhang, Y. Liu, Z. Liang, P.C. Sia,
[36] C. Florindo, F. Lima, B.D. Ribeiro, I.M. Marrucho, Deep eutectic solvents: J. Lou, J.K. Feng, L.J. Ci, Potassium gluconate-derived N/S co-doped carbon
overcoming 21st century challenges, Curr. Opin. Green and Sustain. Chem. 18 nanosheets as superior electrode materials for supercapacitors and sodium-ion
(2019) 31–36. batteries, J. Power Sources 414 (2019) 308–316.
[37] P. Liu, J.W. Hao, L.P. Mo, Z.H. Zhang, Recent advances in the application of deep [64] Q.Y. Dou, S.L. Lei, D.W. Wang, Q.N. Zhang, D.W. Xiao, H.W. Guo, A.P. Wang,
eutectic solvents as sustainable media as well as catalysts in organic reactions, RSC H. Yang, Y.L. Li, S.Q. Shi, X.B. Yan, Safe and high-rate supercapacitors based on an
Adv. 5 (2015) 48675. “acetonitrile/water in salt” hybrid electrolyte, Energy Environ. Sci. 11 (2018)
[38] D. Carriazo, M.C. Serrano, M.C. Guti�errez, M.L. Ferrer, F.D. Monte, Deep-eutectic 3212–3219.
solvents playing multiple roles in the synthesis of polymers and related materials, [65] Z.Y. Song, H. Duan, L.C. Li, D.Z. Zhu, T.C. Cao, Y.K. Lv, W. Xiong, Z.W. Wang, M.
Chem. Soc. Rev. 41 (2012) 4996–5014. X. Liu, L.H. Gan, High-energy flexible solid-state supercapacitors based on O, N, S-
[39] W. Zaidi, L. Timperman, M. Anouti, Deep eutectic solvent based on sodium cations tridoped carbon electrodes and a 3.5 V gel-type electrolyte, Chem. Eng. J. 372
as an electrolyte for supercapacitor application, RSC Adv. 4 (2014) 45647–45652. (2019) 1216–1225.
[40] C. Ruß, B. K€onig, Low melting mixtures in organic synthesis-an alternative to ionic [66] X.R. Chen, J.W. Han, X.H. Lv, W. Lv, Z.Z. Pan, C. Luo, S.W. Zhang, Q.W. Lin, F.
liquids, Green Chem. 14 (2012) 2969–2982. Y. Kang, Q.H. Yang, Dense yet highly ion permeable graphene electrodes obtained
[41] H.C. Greenwell, S. Stackhouse, P.V. Coveney, W. Jones, A density functional theory by capillary-drying of a holey graphene oxide assembly, J. Mater. Chem. 7 (2019)
study of catalytic trans-esterification by tert-butoxide MgAl anionic clays, J. Phys. 12691–12697.
Chem. B 107 (2003) 3476–3485. [67] A. Boisset, J. Jacquemin, M. Anouti, Physical properties of a new deep eutectic
[42] S. Grimme, S. Goerigk, L. Goerigk, Effect of the damping function in dispersion solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-
corrected density functional theory, J. Comput. Chem. 32 (2011) 1456–1465. methylacetamide as superionic suitable electrolyte for lithium ion batteries and
[43] H.Y. Jin, C.X. Guo, X. Liu, J.L. Liu, A. Vasileff, Y. Jiao, Y. Zheng, S.Z. Qiao, electric double layer capacitors, Electrochim. Acta 102 (2013) 120–126.
Emerging two-dimensional nanomaterials for electrocatalysis, Chem. Rev. 118 [68] B. Wang, Y.H. Wang, Y.Y. Peng, X. Wang, J. Wang, J.B. Zhao, 3-dimensional
(2018) 6337–6408. interconnected framework of N-doped porous carbon based on sugarcane bagasse
[44] F. Sun, Z.B. Qu, J.H. Gao, H.B. Wu, F. Liu, R. Han, L.J. Wang, T. Pei, G.B. Zhao, Y. for application in supercapacitors and lithium ion batteries, J. Power Sources 390
F. Lu, In situ doping boron atoms into porous carbon nanoparticles with increased (2018) 186–196.
oxygen graft enhances both affnity and durability toward electrolyte for greatly [69] C.Y. Li, W.Z. Wu, P. Wang, W.B. Zhou, J. Wang, Y.H. Chen, L.J. Fu, Y.S. Zhu, Y.
improved supercapacitive performance, Adv. Funct. Mater. 28 (2018) 1804190. P. Wu, W. Huang, Fabricating an aqueous symmetric supercapacitor with a stable
[45] H. Liu, M. Wang, D.D. Zhai, X.Y. Chen, Z.J. Zhang, Design and theoretical study of high working voltage of 2 V by using an alkaline-acidic electrolyte, Adv. Sci.
carbon-based supercapacitors especially exhibiting superior rate capability by the (2018) 1801665.
synergistic effect of nitrogen and phosphor dopants, Carbon 155 (2019) 223–232. [70] T.Q. Lin, I.W. Chen, F.X. Liu, C.Y. Yang, H. Bi, F.F. Xu, F.Q. Huang, Nitrogen-doped
[46] D.P. Li, X.H. Ren, Q. Ai, Q. Sun, L. Zhu, Y. Liu, Z. Liang, R.Q. Peng, P.C. Si, J. Lou, J. mesoporous carbon of extraordinary capacitance for electrochemical energy
K. Feng, L.J. Ci, Facile fabrication of nitrogen doped porous carbon as superior storage, Science 350 (2015) 1508–1513.
anode material for potassium-ion batteries, Adv. Energy Mater. (2018) 1802386. [71] J.R. Zeng, J.W. Liu, S.S. Siwal, W.Q. Yang, X.Z. Fu, Q.B. Zhang, Morphological and
[47] C.V. Nguyen, S. Lee, Y.G. Chung, W.H. Chiang, K.C.W. Wu, Synergistic effect of electronic modification of 3D porous nickel microsphere arrays by cobalt and
metal-organic framework-derived boron and nitrogen heteroatom-doped three- sulfur dual synergistic modulation for overall water splitting electrolysis and
dimensional porous carbons for precious-metal-free catalytic reduction of supercapacitors, Appl. Surf. Sci. 491 (2019) 570–578.
nitroarenes, Appl. Catal. B Environ. 257 (2019) 117888. [72] S. Witomska, Z.Y. Liu, W. Czepa, A. Aliprandi, D. Pakulski, P. Pawluc, A. Ciesielski,
[48] P. Jiang, L. Chen, H.Z. Shao, S.H. Huang, Q.S. Wang, Y.B. Su, X.S. Yan, X.M. Liang, P. Samorì, Graphene oxide hybrid with sulfur-nitrogen polymer for high-
J.J. Zhang, J.W. Feng, Z.P. Liu, Methylsulfonylmethane-based deep eutectic solvent performance pseudocapacitors, J. Am. Chem. Soc. 141 (2019) 482–487.
as a new type of green electrolyte for a high-energy-density aqueous lithium-ion [73] Z.S. Lv, Y.X. Tang, Z.Q. Zhu, J.Q. Wei, W.L. Li, H.R. Xia, Y. Jiang, Z.Y. Liu, Y.F. Luo,
battery, ACS Energy Lett 4 (2019) 1419–1426. X. Ge, Y.Y. Zhang, R.H. Wang, W. Zhang, X.J. Loh, X.D. Chen, Honeycomb-lantern-
[49] C. Mukesh, R. Gupta, D.N. Srivastava, S.K. Nataraj, K. Prasad, Preparation of a inspired 3D stretchable supercapacitors with enhanced specifc areal capacitance,
natural deep eutectic solvent mediated self polymerized highly flexible transparent Adv. Mater. (2018) 1805468.
gel having super capacitive behaviour, RSC Adv. 6 (2016) 28586–28592. [74] H. Lu, L.Z. Zhuang, R.R. Gaddam, X.M. Sun, C.L. Xiao, T. Duignan, Z.H. Zhu, X.
[50] R.T. Cygan, J.J. Liang, A.G. Kalinichev, Molecular models of hydroxide, S. Zhao, Microcrystalline cellulose-derived porous carbons with defective sites for
oxyhydroxide, and clay phases and the development of a general force field, electrochemical applications, J. Mater. Chem. A published online (2019), https://
J. Phys. Chem. B 108 (2004) 1255–1266. doi.org/10.1039/c9ta05891e.
[51] K. Rado�sevi�c, M.C. Bubalo, V.G. Sr�cek, D. Grgas, T.L. Dragi�cevi�c, I. [75] K. Liang, K. Marcus, Z.Z. Yang, L. Zhou, H. Pan, Y.L. Bai, Y.G. Du, M.H. Engelhard,
R. Redovnikovi�c, Evaluation of toxicity and biodegradability of choline chloride Y. Yang, Freestanding NiFe oxyfluoride holey film with ultrahigh volumetric
based deep eutectic solvents, Ecotoxicol. Environ. Saf. 112 (2015) 46–53. capacitance for flexible asymmetric supercapacitors, Small 14 (2018) 1702295.
[52] J.R. Olles, P. Slavik, N.K. Whitelaw, D.K. Smith, Self-assembled gels formed in deep [76] D.D. Zhang, J.L. Wang, C. He, Y.Z. Wang, T.T. Guan, J.H. Zhao, J.L. Qiao, K.X. Li,
eutectic solvents: supramolecular eutectogels with high ionic conductivity, Angew. Rational surface tailoring oxygen functional groups on carbon spheres for
Chem. Int. Ed. 58 (2019) 4173–4178. capacitive mechanistic study, ACS Appl. Mater. Interfaces 11 (2019) 13214–13224.
[53] X.B. Kou, M. Anouti, Physical properties of a new deep eutectic solvent based on a [77] X.G. Liu, C.D. Ma, J.X. Li, B. Zielinska, R.J. Kalenczuk, X.C. Chen, P.K. Chu,
sulfonium ionic liquid as a suitable electrolyte for electric double layer capacitors, T. Tang, E. Mijowska, Biomass-derived robust three-dimensional porous carbon for
J. Phys. Chem. C 119 (2015) 970–979. high volumetric performance supercapacitors, J. Power Sources 412 (2019) 1–9.
[54] M. Wang, H. Liu, D.D. Zhai, X.Y. Chen, Z.J. Zhang, In-situ synthesis of highly [78] W.J. Tian, H.Y. Zhang, H.Q. Sun, M.O. Tade, S.B. Wang, Template-free synthesis of
nitrogen, sulfur co-doped carbon nanosheets from melamine-formaldehyde- N-doped carbon with pillared-layered pores as bifunctional materials for
thiourea resin with improved cycling stability and energy density for supercapacitor and environmental applications, Carbon 118 (2017) 98–105.
supercapacitors, J. Power Sources 416 (2019) 79–88. [79] Y.L. Cheng, L. Huang, X. Xiao, B. Yao, L.Y. Yuan, T.Q. Li, Flexible and crosslinked
[55] L. Ni, R.W. Wang, C.Y. Sun, B. Sun, Z.T. Zhang, Designing nanographitic domains N-doped carbon nanofiber network for high performance freestanding
in N-doped porous carbon foam for high performance supercapacitors, Carbon 139 supercapacitor electrode, Nanomater. Energy 15 (2015) 66–74.
(2018) 1152–1155. [80] Y.F. Nie, Q. Wang, X.Y. Chen, Z.J. Zhang, Nitrogen and oxygen functionalized
[56] Y. Qing, Y.T. Jiang, H. Lin, L.X. Wang, A.J. Liu, Y.L. Cao, R. Sheng, Y. Guo, C. hollow carbon materials: the capacitive enhancement by simply incorporating
W. Fan, S. Zhang, D.Z. Jia, Z.J. Fan, Boosting the supercapacitor performance of novel redox additives into H2SO4 electrolyte, J. Power Sources 320 (2016)
activated carbon by constructing overall conductive networks using graphene 140–152.
quantum dots, J. Mater. Chem. 7 (2019) 6021–6027. [81] J.Y. Qu, C. Geng, S.Y. Lv, G.H. Shao, S.Y. Ma, M.B. Wu, Nitrogen, oxygen and
[57] S.L. Huo, M.Q. Liu, L.L. Wu, M.J. Liu, M. Xu, W. Ni, Y.M. Yan, Methanesulfonic phosphorus decorated porous carbons derived from shrimp shells for
acid-assisted synthesis of N/S co-doped hierarchically porous carbon for high supercapacitors, Electrochim. Acta 176 (2015) 982–988.
performance supercapacitors, J. Power Sources 387 (2018) 81–90.

9
M. Zhong et al. Journal of Power Sources 452 (2020) 227847

[82] D. Xu, W. Hu, X.N. Sun, P. Cui, X.Y. Chen, Redox additives of Na2MoO4 and KI: [86] N.J. Fu, L.T. Li, K.J. Liu, C.K. Kim, J. Li, T. Zhu, J.H. Lia, B.K. Tang, A choline
synergistic effect and the improved capacitive performances for carbon-based chloride-acrylic acid deep eutectic solvent polymer based on Fe3O4 particles and
supercapacitors, J. Power Sources 341 (2017) 448–456. MoS2 sheets (poly(ChCl-AA DES)@Fe3O4@MoS2) with specifc recognition and
[83] X. He, R. Li, J. Qiu, K. Xie, P. Ling, M. Yu, X. Zhang, M. Zheng, Synthesis of good antibacterial properties for β-lactoglobulin in milk, Talanta 197 (2019)
mesoporous carbons for supercapacitors from coal tar pitch by coupling 567–577.
microwave-assisted KOH activation with a MgO template, Carbon 50 (2012) [87] H.Y. Wang, S.Y. Liu, Y.L. Zhao, J.J. Wang, Z.W. Yu, Insights into the hydrogen
4911–4921. bond interactions in deep eutectic solvents composed of choline chloride and
[84] Q. Wang, Y.F. Nie, X.Y. Chen, Z.H. Xiao, Z.J. Zhang, Use of pyrocatechol violet as polyols, ACS Sustain. Chem. Eng. 7 (2019) 7760–7767.
an effective redox additive for highly promoting the supercapacitor performances, [88] J.W. Lang, X. Zhang, L. Liu, B.J. Yang, J. Yang, X.B. Yan, Highly enhanced energy
J. Power Sources 323 (2016) 8–16. density of supercapacitors at extremely low temperatures, J. Power Sources 423
[85] Y. Kado, K. Imoto, Y. Soneda, N. Yoshizawa, Highly enhanced capacitance of MgO- (2019) 271–279.
templated mesoporous carbons in low temperature ionic liquids, J. Power Sources
271 (2014) 377–381.

10

You might also like