Article

Cite This: ACS Appl. Energy Mater. 2019, 2, 5835−5842 www.acsaem.org

A Low-Cost Zn-Based Aqueous Supercapacitor with High Energy

Density
Liang He,†,§ Yu Liu,†,§ Chunyang Li,† Dezhi Yang,† Weigang Wang,† Wenqi Yan,† Weibin Zhou,†
Zhixian Wu,† Lili Wang,† Qinghong Huang,† Yusong Zhu,† Yuhui Chen,† Lijun Fu,*,†,‡
Xianhua Hou,*,‡ and Yuping Wu*,†,‡
†
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Energy Science and Engineering and Institute of
Advanced Materials, Nanjing Tech University, No. 30, Puzhu Road (S), Nanjing, Jiangsu 211800, China
‡
South China Normal University, No. 55, West Zhongshan Road, Tianhe District, Guangzhou, Guangdong 510631, China
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*
S Supporting Information
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ABSTRACT: Low-cost supercapacitors with high energy densities have attracted great research attention, since it would
broaden the application of capacitors. Increasing the capacitance is one principle to obtain a high energy density of a
supercapacitor. In this study, a low cost aqueous Zn-based hybrid supercapacitor (AZHS) with high energy density is achieved
using an actived carbon derived from corncob (denoted as ACC) as the positive electrode, zinc metal as the negative electrode,
and the 2 M ZnSO4 electrolyte. The actived carbon is prepared with a facile calcination-activation process, and it exhibits high
specific surface area (2619 m2 g−1). Though without extra heteroatom doping, ACC demonstrates a superb specific capacitance
in acidic, alkaline and neutral electrolytes. The assembled AZHS exhibits a high energy density of 94 W h kg−1 at 68 W kg−1 in a
potential window of 0.2−1.8 V, and an excellent cycle stability with only 1.8% capacitance decay is obtained after 10 000 cycles
at 5 A g−1. These results suggest that a low cost supercapacitor with high energy density can be achieved by a hybrid system
design using electrodes with high capacitance.
KEYWORDS: corncob-derived carbon, hierarchical porous structure, energy density, zinc, aqueous hybrid supercapacitors

1. INTRODUCTION Two principle strategies can be used to increase the energy

The intermittent feature of the renewable energy promotes the density of supercapacitors: widening the operation voltage
development of new energy storage devices with safety, low- window and increasing the capacitance of the electrodes. To
cost, and high performance.1−3 At present, fuel cells, chemical widen the operation voltage, an organic electrolyte with wider
batteries, and supercapacitors have been extensively applied to electrochemical window is often used because the electro-
various fields, such as portable electronic devices and electric chemical window of an organic electrolyte is larger than that of
vehicles.4 Compared with fuel cells and batteries, super- aqueous solutions,18,19 but it is accompanied by a safety issue
capacitors possess the advantages of high power density, and because the organic electrolyte is flammable. When a safe
long cycle life.5−10 Despite great progress having been made in aqueous electrolyte is used, the operation voltage of the
the last decades,11 widespread application of supercapacitors is supercapacitor is limited by the electrochemical decomposition
hindered because of their relatively low energy density of water, that is, the evolution reactions of H2 and O2. The
compared with batteries.12−16 Thus, it is imperative to develop operation voltage window of supercapacitors can be maximized
supercapacitors with higher energy density without sacrificing
the power density and cycling stability.17 The exploration of Received: May 17, 2019
the capacitor systems and optimization of the electrode Accepted: July 23, 2019
materials are essential. Published: July 23, 2019

© 2019 American Chemical Society 5835 DOI: 10.1021/acsaem.9b00981

ACS Appl. Energy Mater. 2019, 2, 5835−5842
ACS Applied Energy Materials Article

by optimizing the surface charge of the electrodes20,21 and product was denoted as CC. The other part was mixed with KOH
tuning the intrinsic properties of the electrode materials.22−24 with the mass ratio of 1:5 in 10 mL of UP water and then dried at 80
Besides modifying the electrodes, optimizing the system of a °C overnight. Finally, the mixture was annealed in a tubular furnace at
supercapacitor would be an effective strategy. Recently, we 800 °C for 2 h in Ar atmosphere at a heating rate of 5 °C min−1. The
resulting product was washed with 1 M HCl and ultrapure water until
have designed a hybrid aqueous supercapacitor with an the pH of the filtrate becomes 7 and then dried at 80 °C for 12 h the
alkaline−acidic electrolyte at negative and positive electrodes. obtained product was denoted as ACC.
The unique design enables the aqueous symmetric super- Materials Characterizations. The morphology of the samples
capacitor operated at a high voltage of 2 V.25 To increase the was characterized by field emission scanning electron microscopy
capacitance of the electrodes, pseudocapacitive materials have (FE-SEM) JSM-7800F and high-resolution transmission electron
been extensively studied, including metal oxides,26−28 metal microscopy (HR-TEM) JEM-2100F. The X-ray diffraction (XRD)
sulfides,29−31 and conductive polymers.32 However, the price patterns were examined using Cu−Kα radiation with a scan rate of
of those materials are higher than that of carbon, which hinders 10° min−1. For studying the graphitization of materials, Raman
spectra was analyzed using WITEC Alpha300M+ at a laser
their large-scale application. Currently, the common carbon wavelength of 488 nm. The porous structure was analyzed from the
materials used for supercapacitors include carbon fibers,33,34 N2 adsorption/desorption isotherms at 77 K using a Quantachrome
carbon nanotubes,35 graphene,36,37 carbon aerogels,38 and instrument. X-ray photoelectron spectroscopy was carried out on
activated carbon.10,15 Among the aforementioned carbon AXIS UltraDLD using Al-Kα radiation.
materials, activated carbon with rich source, low price, large- Electrochemical Measurements. The electrochemical perform-
scale industrial production, and high specific surface area, has ance of the as-obtained carbon materials was determined in a three-
been widely used in supercapacitors. However, most of the electrode cell with the aqueous solutions at room temperature. The
commercial activated carbons possess low energy density (5−8 working electrodes were prepared by mixing the obtained carbon
W h kg−1), resulting from their low specific capacitances (<200 materials, acetylene black, and polytetrafluoroethylene (PTFE) binder
with a mass ratio of 8:1:1; the mixture was pressed on nickel foam,
F g−1).39,40 Developing a hierarchical porous structure with titanium foil, and stainless-steel mesh, respectively, and then dried at
micro-, meso-, and macropores is a prevalent way to obtain a 80 °C overnight. The weight loading of the working electrode was
large specific capacitance (micropores and mesopores) and a about 6 mg cm−2. For the three-electrode system, 6 M KOH, 1 M
high rate capability (mesopores and macropores).41−43 H2SO4, and 1 M Na2SO4 were employed as the electrolytes,
In this contribution, waste corncob, a large yielded respectively. In 6 M KOH, Pt was used as the counter electrode
byproduct from the corn planting with porous framework in and Hg/HgO electrode as the reference. The carbon rod and
nature, was used as precursor to prepare the electrode material stainless-steel mesh served as the counter electrode respectively in 1
of supercapacitor with high surface area. By carefully tuning the M H2SO4 and 1 M Na2SO4, and saturated calomel electrode (SCE)
was used as the reference electrode in both electrolytes. The cyclic
parameters in a calcination−activation process, the activated
voltammetry and galvanostatic performance of ACC-based sym-
corncob carbon (denoted as ACC) with high specific surface metrical aqueous supercapacitors with a symmetric two-electrode
area of 2619 m2 g−1 was obtained, much higher than that of system were tested at 0−1.8 V in 1 M Na2SO4 and 0−1 V in both 6 M
other carbon materials derived from corncob in literature.44 KOH and 1 M H2SO4. The electrochemical behaviors of the ACC
Though without extra heteroatom doping, a strategy were further tested by a coin cell, using ACC and Zn foil as the
commonly used to improve the electrochemical performance positive and negative electrodes, glass fiber as the membrane, and 2 M
of carbon materials,45−48 the obtained ACC exhibits high ZnSO4 aqueous solution as the electrolyte. The cyclic voltammetry
specific capacitances of 311, 357, and 155 F g−1 at 1 A g−1 in (CV) at different scanning rates, galvanostatic charge/discharge
alkaline, acidic, and neutral electrolytes, respectively. Fur- (GCD) at various current densities, and electrochemical impedance
spectroscopy (EIS) were carried out using a CHI660C electro-
thermore, by taking advantages of Zn metal, that is., high chemical workstation (Shanghai Chenhua). The cycling life measure-
stability in water, high theoretical capacity of 823 mAh g−1 ment was performed using a LAND-CT2001A (Wuhan Jinnuo
(Zn/Zn2+), and a redox voltage of −0.762 V versus standard Electronics Ltd.).
hydrogen electrode (lower than that of other negative Calculations. The value of specific capacitance CS (F g−1) can be
electrodes used in aqueous electrolyte)49−51 and using ACC calculated from the GCD discharge curves according to the formula
and zinc metal as positive and negative electrodes, respectively, below
a low-cost hybrid aqueous supercapacitor with high energy I × Δt
density can be realized. The ACC in the assembled aqueous CS =
m × ΔV (1)
Zn-based hybrid supercapacitor (AZHS) exhibits a high energy
density of 94 W h kg−1 at 68 W kg−1 in the voltage range of where I (A) is the constant discharge current, Δt is the discharge time,
0.2−1.8 V at 0.1 A g−1, calculated based on the mass of both m is the weight of active material (the total mass of active materials on
two electrodes in symmetric supercapacitors), and ΔV is the potential
electrode materials. The AZHS also exhibits an exceptional
change in discharge process (removing the IR drop).
cycling stability with 98.2% capacitance retention after 10 000 The energy density E (W h kg−1) was obtained by the following
cycles at a current density of 5 A g−1. The electrochemical equation
performance of AZHS is superior to those of the Zn ion hybrid
supercapacitors recently reported.50,52 CS × V 2
E=
2 × 3.6 (2)
2. EXPERIMENTAL SECTION where V is the difference between the initial and the final discharge
Preparation of CC and ACC. In brief, corncob was washed with voltage and the constant 3.6 is the unit of E converted from J g−1 to W
acetone and ultrapure water (UP water) several times and then dried h kg−1.
at 80 °C for 12 h. Later, the corncob was calcined in a tubular furnace The power density P (W kg−1) was calculated by the equation
at 450 °C for 1 h and then up to 800 °C for 2 h under an Ar E × 3600
atmosphere with a heating rate of 5 °C min−1. Then, the resulting P=
(3)
Δt
sample was divided into two equal parts. One part was further
calcined in a tubular furnace at 800 °C under Ar, and the obtained where the number 3600 is the conversion between hours and seconds.

5836 DOI: 10.1021/acsaem.9b00981

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Figure 1. FE-SEM image (A) and TEM image (inset is HR-TEM image) (B) of ACC sample. XRD patterns (C), Raman spectra (D), N2
adsorption−desorption isotherms (E), and pore size distribution measured by the DFT method (F) of CC and ACC samples.

The energy and power density EAZHS (W h kg−1) of AZHS was Two peaks can be observed at around 24° and 44° from the
obtained based on the mass of both positive and negative electrodes. XRD patterns of ACC and CC (Figure 1C), which correspond
The mass of negative electrode was calculated based on the to the (002) and (100) planes of graphitized carbon. Both of
theoretical capacity of zinc.
the peaks are broad for samples CC and ACC, which is
ascribed to the amorphous and the disordered feature of the
3. RESULTS AND DISCUSSION as-prepared materials.54 The Raman spectra of both samples
The FE-SEM investigation shows that ACC (Figure 1A) (Figure 1D) display two peaks at around 1355 and 1595 cm−1,
possesses an interconnected macro-pores structure resulting corresponding to the D and G bands of carbon.55,56 The
from the oxidation of the carbon by KOH.53 In contrast, no degree of graphitization can be expressed by the intensity ratio
obvious pores are found for CC sample (Figure S1). These of the D and G bands (ID/IG), and the result of ACC (0.99) is
interconnected macropores are helpful for the diffusion of an slightly higher than that of CC (0.98), indicating more defects
electrolyte ion into the inner micropores. The hierarchical and disordered graphite structure are generated after KOH
porous structure of the ACC sample can be further confirmed activation. C, O, and a negligible amount of N elements are
by the TEM image (Figure 1B). The distorted lattice fringe of detected from X-ray photoelectron spectroscopy for both ACC
the ACC material can be observed from the HR-TEM image, and CC, and the atomic ratio of C and O are almost same
illustrating the partial graphitization feature of the sample. (Table S1).
5837 DOI: 10.1021/acsaem.9b00981
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Figure 2. Electrochemical performance in 6 M KOH aqueous solution: CV curves of CC and ACC electrodes at 10 mV s−1 (A), GCD plots of CC
and ACC electrodes at 1 A g−1 (B), specific capacitance of CC and ACC electrodes at different current densities (C), CV curves of ACC electrode
at different scan rates (D), GCD plots of ACC electrode at various current densities (E), and cycling performance of the ACC electrode at 5 A g−1
over 40 000 cycles (F).

Figure 3. Electrochemical performance of the ACC electrode in acidic and neutral electrolytes in a three-electrode system: CV curves at different
scan rates in 1 M H2SO4 (A), GCD plots at various current densities in 1 M H2SO4 (B), specific capacitance at different current densities in 1 M
H2SO4 (C), cycling performance in 1 M H2SO4 at 5 A g−1 over 20000 cycles (D), CV curves at different scan rates in 1 M Na2SO4 (E), GCD plots
at various current densities in 1 M Na2SO4 (F), and specific capacitance at different current densities in 1 M Na2SO4 (G).

To further analyze the porous structure of the carbon determined from the density functional theory (DFT) method,
samples, the N2 adsorption−desorption measurements at 77 K as shown in Figure 1F, whereas for CC the pore sizes are
were carried out as displayed in Figure 1E, and both the carbon mainly distributed at 0.5 nm. This result is consistent with the
materials show a type I sorption isotherm,57 indicating the SEM analyses. With the activation of KOH, the specific surface
existence of both micropores and mesopores. For ACC, the area of the sample increases obviously, rising from 600 to 2619
pores with sizes of 0.5, 0.8, 1.1, and 2.2−3.3 nm can be m2 g−1. The porous textural properties of both carbon
5838 DOI: 10.1021/acsaem.9b00981
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ACS Applied Energy Materials Article

Figure 4. Electrochemical performance of the AZHS: CV curves at different scan rates (A), GCD plots at various current densities (B), specific
capacitance at various current densities (C), Ragone plots of AZHS, symmetric supercapacitors assembled based on ACC in different electrolyte
and other supercapacitors reported in literatures (D), and cycling performance of AZHS at 1 and 5 A g−1 (E,F). Note that the value of energy
density and power density in refs 50 and 52 are calculated without removing the IR drop, and the value plotted in Figure 4D would be larger than
the fact.

materials are listed in Table S2. These results indicate that transportation channels and better contact of electrolyte with
ACC presents a more hierarchical porous structure than CC. the electrode surface.
The high specific surface area of ACC results from the In a three-electrode device with 1 M H2SO4 as the
precarbonization and activation processes; for details, please electrolyte, an EDL behavior of the ACC electrode can be
see discussion in Figure S1. observed in a potential window of 0−1 V (Figure 3A). It
Aqueous solutions, such as KOH, H2SO4, and Na2SO4, are delivers a high discharge capacitance of 374, 357, and 223F g−1
generally used as the electrolyte for aqueous supercapacitors. at 0.5, 1, and 3 A g−1 (Figure 3B,C). The fast charge/discharge
The electrochemical performances of both carbon samples behavior can be further evidenced by the impedance
were first investigated in 6 M KOH aqueous electrolyte in a spectroscopy (Figure S2). The rate capability of ACC in 1
three-electrode system (Figure 2). The cyclic voltammetry M H2SO4 electrolyte is inferior to that in 6 M KOH
(CV) curves of both carbon samples at 10 mV s−1 and other electrolyte; it is ascribed to the smaller internal and charge
scan rates (Figure 2A,D) show that both CC and ACC present transfer resistances of 6 M KOH electrolyte than those of 1 M
a quasi-rectangular shape, indicating the formation of an H2SO4 electrolyte, which can be seen from our EIS
electrochemical double-layer (EDL) during cycling. It is clear investigation (Figure S2). The electrochemical performance
that the electrochemical activity of ACC is much larger of ACC outperforms the majority of the reported carbon
compared with that of CC, revealing a better capacitive materials (Table S4). Moreover, it exhibits an excellent cycle
performance of ACC, which is attributed to the high specific life with 100% of retention after 20 000 cycles at 5 A g−1
surface area and interconnecting hivelike structure. In the (Figure 3D).
galvanostatic measurement at current densities of 0.5−60 A g−1 The electrochemical performance of the ACC electrode in 1
in the voltage range from −1 to 0 V versus Hg/HgO (Figure M Na2SO4 aqueous solution was investigated in two different
2B,E), both ACC and CC exhibit typical EDL behavior and voltage windows, 0−0.8 and −1−0 V, because in the two
high electrochemical reversibility with no obvious potential voltage regimes the absorption behavior and the side reactions
drop (IR drop), which is consistent with the CV results. In are different. In 0−0.8 V, it is the SO42− absorption/desorption
addition, ACC delivers higher storage capacitance than that of at/from the surface of ACC during the energy storage process,
the CC sample, the corresponding capacitances of ACC are and the oxygen evolution reaction (OER) determines the
318, 311, and 231 F g−1 at 0.5, 1, and 60 A g−1 (73% upper limit voltage; whereas in the voltage regime of −1−0 V,
retention), respectively, whereas for CC, the specific the cations accumulate at the surface of ACC upon charge
capacitance at 0.5, 1, and 60 A g−1 are 122, 115, and 96 F when lowering the voltage, and the operation voltage should be
g−1 (Figure 2C). The electrochemical impedance spectrum above that of hydrogen evolution reaction (HER). In both
(EIS) of ACC sample (Figure S2) demonstrates a high ionic voltage regimes, the ACC electrode exhibits rectangle-liked CV
conductivity and fast storage kinetics of ACC. Moreover, ACC curves, which is typical for the EDL behavior (Figure 3E). In
exhibits an excellent cycling stability with no loss after 40 000 the voltage of 0−0.8 V, the ACC electrode delivers a
cycles at a current density of 5 A g−1 (Figure 2F). The capacitance of 103 F g−1 at 0.5 A g−1; when the current
excellent capacitance and rate performance of ACC are density increases to 1, 2, 3, 5, 8, and 10 A g−1, the capacitance
superior to most previously reported biomass-derived carbons can still be kept as 90, 80, 73, 64, 55, and 49 F g−1, respectively.
for a supercapacitor (for details see Table S3). The excellent In the voltage range of −1.0−0 V, the specific capacitances of
capacitance is ascribed to the hierarchical porous structure and the ACC electrode are 188, 155, and 140 F g−1 at current
high surface area of ACC, facilitating convenient ion densities of 0.5, 1, and 3 A g−1, respectively (Figure 3F,G). The
5839 DOI: 10.1021/acsaem.9b00981
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ACS Applied Energy Materials Article

internal resistance and charge transfer resistance RCT are 0.89 only 1.8% capacitance loss at 5 A g−1 after 10 000 cycles is
and ∼2.6 Ω from the EIS measurement at the open circuit achieved (Figure 4F).
voltage (Figure S2). It is noted that the capacitance of the To further understand the electrochemical process of the
ACC electrode in the neutral electrolyte (1 M Na2SO4) is AZHS, the structure evolution of both negative and positive
smaller than that in alkaline (6 M KOH) and acidic (1 M electrodes was analyzed. The surface of the zinc metal becomes
H2SO4) electrolytes, which is ascribed to the low conductivity rougher after Zn deposition and dissolution during the first
of the neutral electrolyte rather than that of alkaline and acidic cycle (Figure S6). Flake-structured precipitants are observed
electrolytes.7,25,58 It is further confirmed by EIS measurement, on the surface of the zinc metal during cycling, which can be
as shown in Figure S2, that the internal resistance of ACC identified as Zn4SO4(OH)6·nH2O, from the investigation of
electrodes in neutral electrolyte is larger (0.89 Ω) than that of energy dispersive X-ray spectroscopy (EDS) mapping and
in alkaline and acidic electrolytes (0.39 and 0.52 Ω). XRD (Figure S6). The morphology of Zn is stable even after
Symmetric aqueous supercapacitors in different electrolytes 6000 cycles, which is in line with excellent cycle stability of
were also assembled by using the ACC electrode as both AZHS (Figure S6F). The morphology of the positive electrode
positive and negative electrodes. In the neutral electrolyte, the does not change much during cycling. Similar as the negative
supercapacitor can be operated in the voltage of 0−1.8 V. It electrode, flakelike Zn4SO4(OH)6·nH2O can be observed at
exhibits a high energy density of 13.5 Wh kg−1 at a power the surface of the ACC electrode (Figure S7 and Figure S8),
density of 214.6 W kg−1 and is calculated based on the total yet the amount of Zn4SO4(OH)6·nH2O is less than that on the
mass of active materials on two electrodes. This value is zinc metal. The formation of Zn4SO4(OH)6·nH2O was
superior to those from the previous reports, for instance, an reported previously in the aqueous systems with Zn as the
energy density of 11.7 Wh kg−1 is obtained for graphene/ negative electrode and ZnSO4 as the electrolyte, that is, Zn//
CNTs//graphene/CNTs symmetric supercapacitor,59 and for MnO2,61−63 Zn//V3O7·H2O batteries,64 and Zn//active
a N-doped CNTs//N-doped CNTs symmetric supercapaci- carbon.50 The formation of Zn4SO4(OH)6·nH2O might be
tor60 the energy density is 8.7 Wh kg−1 at a power density of ascribed to the following chemical reaction
195 W kg−1 (Figure 4D). The energy density of the
supercapacitor with ACC as both negative and positive 4Zn 2 + + 6OH− + SO4 2 − + nH 2O
electrodes in the neutral electrolyte is higher than that in ↔ Zn4SO4 (OH)6 nH 2O↓ (4)
alkaline and acidic electrolytes (Figure S3−S5), which is
ascribed to the narrower operation voltage ranges of acidic and Different from the other reports, we did not observe a
basic electrolytes than that of the neutral electrolyte (Figure regular trend of formation and dissolution of Zn4SO4(OH)6·
4D and Figures S3−S5). The aforementioned results nH2O during the first cycle at the positive electrode (Figure
demonstrate that with a simple but well-controlled calcina- S7). The reason is not clear yet. A possible reaction of the
tion-activation process and low cost corncob as precursor the hydroxysulfate dissolution is64
carbon materials with high specific surface area and excellent
electrochemical performance for supercapacitor can be Zn4SO4 (OH)6 ·nH 2O ↔ Zn 2 + + 3ZnO + SO4 2 − + nH 2O (5)
obtained.
Taking advantages of the wider electrochemical window of The balance between formation and dissolution of
the neutral electrolyte, a hybrid aqueous supercapacitor with a Zn4SO4(OH)6·nH2O would be the key to understand this
mild electrolyte is assembled, using ACC as the positive process. Nevertheless, the formation of Zn4SO4(OH)6·nH2O is
electrode, 2 M ZnSO4 solution as the electrolyte, and zinc not significant during the cycling of the AZHS; the pH value
metal as the negative electrode, to achieve a higher energy increases from 4.5 to 5.5 during the first charge and remains
density without sacrificing the cycle performance and power almost the same afterward. The Coulombic efficiency is
density. With a mild electrolyte, the AZHS can be operated up 99.94% for the first cycle and increases to 100% over 13 cycles
to 1.8 V (Figure 4A). During the charging process, the anions (Figure 4E).
(SO42−) are absorbed on the surface of the ACC positive
electrode, along with the reduction of Zn2+ ions and 4. CONCLUSION
precipitation of the zinc. Upon discharge, the Zn metal is To summarize, we have successfully prepared a corncob-based
oxidized and the Zn2+ ions are absorbed on the surface of the porous carbon (ACC) with a large specific surface area and
ACC, accompanied by the diffusion of the SO42− ions back hierarchical porous structure via a simple calcination-activation
into the electrolyte. The shape of the CV curves of ACC at a approach. Although without extra heteroatom doping, ACC
voltage range of 0.2−1.8 V do not change much even at high electrode shows excellent electrochemical performance, a high
scan rate of 200 mV s−1 (Figure 4A), confirming the fast specific capacitance of 311, 357, and 155 F g−1 at 1 A g−1 in 6
kinetics of AZHS during charge/discharge processes and the M KOH, 1 M H2SO4, and 1 M Na2SO4, respectively. In
ability of fast energy storage. The galvanostatic charge− addition, a safe, eco-friendly and low-cost hybrid super-
discharge profiles present a linear-like shape, showing a capacitor (AZHS) has been designed with ACC and zinc
supercapacitor behavior (Figure 4B). The AZHS exhibits a metal as positive and negative electrodes. The AZHS possesses
high energy density of 94 Wh kg−1 (68 W kg−1 on the basis of remarkable electrochemical performances, including a high
the two electrodes) (Figure 4B,C), outperforming the reported energy density of 94 W h kg−1 at 68 W kg−1 and a long-term
Zn based hybrid supercapacitors Zn//2 M ZnSO 4 // cyclic stability up to 98.2% capacitance retention at 5 A g−1
commercial AC50 and Zn//1 M Zn(CF3SO3)2//AC52 (Figure over 10 000 cycles, which is superior to the symmetric
4D). Furthermore, ZAHS exhibits excellent cycling stability, supercapacitors and outperforms other Zn-based hybrid
94% capacitance retention, and 100% Coulombic efficiency supercapacitors reported. This study would shed light on the
can be retained over 1000 cycles at a current density of 1 A g−1 material and system design of low-cost supercapacitors with
(Figure 4E). Impressively, an ultralong cycling stability with high energy density.
5840 DOI: 10.1021/acsaem.9b00981
ACS Appl. Energy Mater. 2019, 2, 5835−5842
ACS Applied Energy Materials Article

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