1 s2.0 S0378775320301506 Main
1 s2.0 S0378775320301506 Main
1 s2.0 S0378775320301506 Main
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.
* 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.
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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.
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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
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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:
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