J Mater Sci (2022) 57:3497–3512

Energy
E N E R G Y Mmaterials
ATERIALS

Fabrication of uniform MnO2 layer-modified activated

carbon cloth for high-performance flexible quasi-solid-
state asymmetric supercapacitor
Pengcheng Du1,* , Yuman Dong1, Yiwei Dong1, Xue Wang2, and Haijuan Zhang3

1
State Key Laboratory of Applied Organic Chemistry and Institute of Polymer Science and Engineering, College of Chemistry and
Chemical Engineering, Lanzhou University, Lanzhou 730000, People’s Republic of China
2
College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People’s Republic of China
3
State Key Laboratory of Grassland Agro-Ecosystems, Institute of Innovation Ecology, Lanzhou University, Lanzhou 730000,
People’s Republic of China

Received: 19 June 2021 ABSTRACT

Accepted: 6 November 2021 Aqueous supercapacitors (SCs) attracted widespread attention owing to the
Published online: advantages of high power density, low-cost, safety and environmental friend-
3 January 2022 liness. However, the improvement of energy density is restricted by low cell
voltage. Herein, a uniform MnO2 layer-modified activated carbon cloth (ACC-
Ó The Author(s), under MnO2) is constructed by controlling the deposited time of MnO2 via a self-
exclusive licence to Springer limiting electroless deposition process. The targeted flexible electrode exhibits
Science+Business Media, LLC, optimal areal capacitance of 423.7 mF/cm2 at 0.5 mA/cm2 and also shows
part of Springer Nature 2021 excellent cycle stability * 81% of its original value after 10 000 cycles scanned at
100 mV/s. Moreover, the flexible quasi-solid-state asymmetric SCs (FQSASCs)
are assembled based on ACC-MnO2 as a flexible positive electrode, ACC as a
flexible negative electrode, and PVA-LiCl as a gel electrolyte. The FQSASCs
possess an extended voltage up to 2.0 V, show extremely excellent cycle stability
(maintaining over 100% capacitance retention value after 5000 cycles at 10 mA/
cm2), deliver excellent energy density (0.78 mWh/cm3) and power density
(71.86 mW/cm3), and also exhibit superior mechanical properties (keeping over
100% of its initial capacitance after bending at 180° for 500 cycles). FQSASCs
reveal potential applications as a candidate in flexible electronic devices.

Handling Editor: Joshua Tong.

Address correspondence to E-mail: [email protected]

https://doi.org/10.1007/s10853-021-06728-x
3498 J Mater Sci (2022) 57:3497–3512

Introduction of 331 mF/cm2 [25]. MnO2-modified carbon fiber

paper (CFP) composite electrodes with various mor-
phologies were constructed through the electro-
Supercapacitors (SCs), also called electrochemical chemical deposition method, and MnO2 nanorod/
capacitors, are recognized as one of new generation CFP achieved a high areal capacitance of 0.54 F/cm2
clean energy-storage devices, which reduce the huge [24]. MnO2/FeOOH core–shell flexible electrode was
gap between conventional capacitors and chemical fabricated based on hydrothermal method and
batteries in power density and energy density, and exhibited maximum capacitance of 0.252 F/cm2 at a
possess numerous advanced properties, such as fast current density of 1 mA/cm2 [28]. Flexible electrodes
charge–discharge rate, high power density and long- with distinctive nanostructures MnO2 have imple-
term cycle life. Nowadays, SCs have been extensively mented significantly improved electrochemical
used as the supplement to batteries, backup power properties of flexible SCs. Thus, the MnO2-based
sources and stand-by power systems [1–6]. flexible electrode exhibits wide prospects in flexible
In recent years, with the rapid development of the SCs.
electronic manufacturing industry, portable and However, low operation voltage in aqueous SCs
wearable electronics have attracted more and more limits the further increase in energy density and
attention and exhibit increasing application prospects power density. The energy density (E) is measured
in lots of emerging fields including flexible sensors, according to the equation E = 1/2CcellDV2, where
electronic display and medical electronics. As an Ccell is specific capacitance of the device and DV is the
indispensable part of portable and wearable elec- operational potential window. Obviously, the energy
tronics, flexible energy storage devices have become density can be increased by maximizing the specific
more and more important to achieve real flexibility capacitance and operation potential window [29–33].
[7–10]. Among these flexible energy storage devices, So how to broaden the operation voltage becomes an
flexible solid-state SCs show incomparable advan- effective strategy to enhance the properties of flexible
tages as flexible energy supply devices in SCs. The asymmetric SCs (ASCs) can widen the
portable and wearable systems, such as high energy operation voltage in aqueous electrolyte, which can
density, light-weight, flexibility, safety and long cycle extend the operation voltages in the range of
life [11–15]. Concretely for high specific capacitance, 1.5–2.4 V to increase the energy density of the ASCs.
various types of electrode materials with a high the- For example, Lu et al. developed flexible quasi-solid-
oretical specific capacitance were explored to apply state asymmetric SCs (FQSASCs) based on
in SCs, such as transition metal oxides/hydroxide H-TiO2@MnO2//H-TiO2@C core–shell nanowires
(MnO2, NiO, Co3O4, Ni(OH)2 and Ni-Co layered with 1.8 V operation voltage and delivered the max-
double hydroxide (LDH)), conductive polymers imum volumetric energy of 0.30 mWh/cm3 [31]. A
(polypyrrole (PPy) and polyaniline (PANI)), metal– hierarchical PPy-coated MnO2 nanowires structure
organic frameworks (MOFs) [16–22], and so on. on CF (PPy@MnO2@CF) fabricated through
However, intrinsic electrode materials mainly in hydrothermal electrode position method and chemi-
powder states are not beneficial for flexible electronic cal vapor deposition was used as a flexible positive
devices. So numerous efforts have been devoted to electrode to assemble FQSASCs, which possessed the
developing high-performance flexible electrodes operation voltage up to 2.0 V and delivered a maxi-
modified with high theoretical capacitance electrode mal energy density of 1.93 mWh/cm3 [26]. However,
materials for flexible SCs. Among these electrode elaborate and complex fabrication procedures of
materials, the MnO2 electrode material, with high flexible electrodes can reduce industrial application
theoretical specific capacitance, abundant source, low value. Thus, there are still huge challenges in
price, simple and varied preparation methods, has designing and optimizing FQSASCs to improve both
attracted wide attention in flexible electrodes [23–26]. the superior fabrication efficiency and excellent
Thus, numerous works were focused on constructing electrochemical performance.
flexible electrodes based on MnO2 materials [27]. For Herein, CC was chosen as a flexible substrate and
example, MnO2-modified microwave-treated carbon firstly activated by oxidation treatment, and then
cloths (MnO2/m-CCs) were used as a flexible elec- uniform MnO2 layers were easily deposited on the
trode and exhibited a maximum specific capacitance surface of ACC by controlling the reaction time in
J Mater Sci (2022) 57:3497–3512 3499

diluted KMnO4 solution. The depositing process of Preparation of MnO2-modified ACC (ACC-
MnO2 was monitored by SEM, XPS, Raman spectra MnO2)
and electrochemical measurement. As a result, the
uniform MnO2-modified ACC electrode (ACC- MnO2 can deposit on the surface of ACC via a self-
MnO2) exhibits an optimal areal capacitance of limiting electroless deposition process. The precursor
423.7 mF/cm2 at 0.5 mA/cm2 and also reveals solution was mixed with an equal volume of 0.1 M
excellent cycle stability. Moreover, the FQSASCs are KMnO4 and 1 M Na2SO4 solution. Then one piece of
assembled based on ACC-MnO2 and ACC, which ACC was immersed in the solution for a set time to
possess an extended voltage up to 2.0 V, deliver deposit MnO2 on the surface of ACC. Then, the target
excellent energy density (0.78 mWh/cm3) and largest products were washed with DI-water several times
power density (71.86 mW/cm3), and also exhibit and then dried in an oven.
superior mechanical properties (keeping about 100%
of its initial capacitance after bending at 180° for 500 Assembly of flexible quasi-solid-state
cycles). asymmetric supercapacitors (FQSASCs)
based on ACC-MnO2 and ACC

Experimental section Electrodes of ACC-MnO2 (about 1 cm wide) and

ACC (about 1.1 cm wide) were separately coated
Materials and reagents with PVA-LiCl gel. After excess water was evapo-
rated in a 50 °C oven, two different electrodes pre-
Carbon cloth (CCP20, Fuel Cell Earth) was used as coated gel electrolyte were pressed together with
substrate. H2O2 solution (25% * 27%), hydrazine 1 cm in length using NKK cellulose coated with PVA-
hydrate (80%), concentrated sulfuric acid (H2SO4), LiCl gel as a separator (Scheme 1).
concentrated nitric acid (HNO3), potassium perman-
ganate (KMnO4) and sodium sulfate (Na2SO4) were Characterization
used without further purification.
Scanning electron microscopy (SEM S-4800 micro-
Preparation of activated carbon cloth (ACC) scope (Hitachi, Japan)) was used to investigate the
morphology of CC, ACC and ACC-MnO2. EDX was
CC was firstly cut into an area of 2 9 4 cm2 and used to characterize the element mapping of ACC-
several pieces of CC were fully immersed in 30 mL of MnO2. Raman spectra were recorded on a Thermo
a mixture of concentrated H2SO4/HNO3 (2:1) solu- Scientific DXR Raman Microscope. The X-ray photo-
tion, and the reaction was performed at 35 °C for 2 h electron spectroscopy (XPS) spectra were obtained
after 3 g of KMnO4 was added. Then, 100 mL DI- using a VersaProbe II Scanning XPS Microprobe from
water was poured into the solution and stirred for Physical Electronics (PHI). Static contact angle anal-
another 2 h. H2O2 solution was then added until no ysis was investigated utilizing a XG-CAMA1 contact
gas bubbles evolved. The oxidized CC was washed angle meter. X-ray diffraction (XRD) patterns were
with DI-water and dried in an oven. Afterward, performed by a Shimadzu XRD-6000 X-ray diffrac-
oxidized CC was reduced using hydrazine solution tometer (Shimadzu Corp., Kyoto, Japan) from 10° to
(1 mL) in stainless steel autoclave performed at 80°. Thermogravimetric analysis (TGA) was carried
100 °C for 24 h. out using TA Instrument 2050 thermogravimetric
analyzer (TA Instruments, New Castle, DE) from 25
to 600 °C with a heating rate of 10 °C/min at O2
atmosphere. The specific surface area (BET) was
characterized by BET test (Micromeritics, ASAP2020,
Atlanta, USA).
3500 J Mater Sci (2022) 57:3497–3512

Scheme 1 Schematic diagram

of the fabrication process of
FQSASCs.

Electrochemical measurement Furthermore, the MnO2-modified ACC is fabricated

via a self-limiting electroless deposition process as
The measurements of cyclic voltammetry (CV) curves shown in Fig. 1c–f. The modified reaction between
and galvanostatic charge–discharge (GCD) curves of ACC and KMnO4 possess by following reaction
all-prepared flexible electrodes were carried out by processes: 4MnO4- ? 3C ? H2O = 4MnO2 ? CO32--
CHI 660E potentiostat electrochemical workstation ? 2HCO3- [27]. When ACC is immersed in KMnO4
using a three-electrode system with 5 M LiCl as the solution, the surface of ACC shows a dramatic
electrolyte, in which platinum foil acted as a counter change after being modified by MnO2 (Fig. 1c–f). In
electrode, and a saturated calomel electrode (SCE) the reaction process, the MnO2 layer can uniformly
was used as a reference electrode. Electrochemical grow on the surface of ACC (Fig. 1c–e), when the
impedance spectroscopy (EIS) was evaluated in the reaction time is less than 2 h. However, when the
frequency range of 105–0.01 Hz. reaction time is raised to 2.5 h, the MnO2 layer can
crack off due to too much MnO2 loaded and causing
more particles to accumulate on the surface as shown
Results and discussion in Fig. 1f. Furthermore, the X-ray diffraction (XRD)
was performed to investigate the structure of ACC-
Carbon cloth (CC), a highly conductive textile, is MnO2, ACC and CC. As shown in Fig. S1, two
always used as an electrode substrate with excellent diffraction peaks located at about 25° and 43.3° are
mechanical flexibility and strength. However, the assigned to (002) and (101) planes of graphite.
specific capacitance of CC (1–2 F/g) is too low to However, there are no obvious peaks of MnO2 in
directly use as an electrode in supercapacitors (SCs) XRD pattern of ACC-MnO2-2 h (Fig. S1) due to the
because of the smooth hydrophobic surface (Fig. 1a). low content of MnO2. The content of MnO2 on the
Hummers’ method was successfully used to activate surface of ACC is calculated to be about 33.5 wt.%
the CC and improve the surface area through con- measured by TGA (Fig. S2) and the mass of MnO2 is
trolled exfoliation of the carbon fibers in order to about 0.3 mg/cm2 weighed by an analytical balance
achieve high capacitance [34, 35]. SEM and contact [36].
angle tests were used to investigate the surface The energy-dispersive X-ray spectrometry (EDS)
change between the CC and activated CC (ACC) as mapping was used to further confirm the deposit
shown in Fig. 1a and b, respectively. The ACC exhi- uniformity of MnO2 (Fig. 2a–d). It is noted that the
bits a rough surface and a hydrophilic surface elements of C, Mn and O of ACC-MnO2-2 h dis-
(Fig. 1b). By contrast, the original CC shows strong tribute evenly obtained from the EDS mapping
hydrophobic and the contact angle can reach about (Fig. 2b–d), obvious uniform distribution of Mn and
136.9° (Fig. 1a). The activated process of CC with O elements reveals that the MnO2 evenly coats on the
Hummers’ method results in the wettability of the surface of the ACC.
ACC and the contact angle goes down to about 0°.
J Mater Sci (2022) 57:3497–3512 3501

Figure 1 SEM images of

a untreated CC inserted with
an optical image showing the
water droplets, b ACC
inserted with an optical image
showing the water droplets,
c ACC-MnO2-1 h, d ACC-
MnO2-1.5 h, e ACC-MnO2-
2 h and f ACC-MnO2-2.5 h.

The X-ray photoelectron spectroscopy (XPS) was respectively. Figure 3d shows that the high-resolu-
used to test the electronic state of CC, ACC and ACC- tion Mn 2p spectrum is fitted to two peaks at 642.5 eV
MnO2-2 h, and the chemical composition of ACC- and 654.6 eV assigned to Mn 2p3/2 and Mn 2p1/2
MnO2-2 h. The survey spectra are shown in Fig. 3. energy levels of Mn element, which are correspond-
The ACC exhibits C, N and O elements (Fig. 3a). ing to Mn4? two oxidation states (Fig. 3e) [27, 37]. In
Furthermore, the high-resolution C 1s peak of ACC is addition, an identifiable narrow peak at the top of the
fitted into four peaks of C–C (28.7 eV), C–N Mn 2p3/2 peak also demonstrates the MnO2 state [38].
(281.6 eV), C–O (282.5 eV) and C = O (283.4 eV) This evidence confirms the successful preparation of
groups, respectively (Fig. 3b). The high-resolution N the MnO2-modified flexible electrode material.
1s spectrum consists of three peaks at 395.2 eV (– Furthermore, the specific surface area and pore size
N =), 396.1 eV (–NH–) and 397.2 eV (–N?–), respec- of CC, ACC and ACC-MnO2-2 h were performed by
tively (Fig. 3c). Furthermore, the presence of four BET measurement, and the results are presented in
elements (Mn, C, O and Na) proves that absence of Fig. S3 and Table S1. The specific surface area of ACC
other impurities is presented on the surface of ACC- is 0.24 m2/g, which is higher than the CC due to the
MnO2-2 h. The C element signal is attributed to ACC, surface activation. After the MnO2 is deposited on the
and Na signals come from Na2SO4 precursor, surface of ACC, the specific surface area of ACC-
3502 J Mater Sci (2022) 57:3497–3512

Figure 2 SEM images of

ACC-MnO2 a elemental
mapping of C b, Mn c and O
d, respectively.

MnO2-2 h increases to 0.38 m2/g. The pore size of and b illustrates the CV curves and GCD curves of
ACC-MnO2-2 h is 18.57 nm obtained from the pore the as-prepared electrodes (ACC, ACC-MnO2-1 h,
size distribution curve through the BJH method ACC-MnO2-1.5 h, ACC-MnO2-2 h and ACC-MnO2-
(Table S1). The introduction of nanoscale MnO2 can 2.5 h, respectively). The electrode of ACC-MnO2-2 h
improve the specific surface area and enhance the exhibits the largest integral area (Fig. 5a) and longest
capacitive property. In addition, Raman spectrums discharge time on one cycle test (Fig. 5b) indicating
were used to estimate the graphitization and lattice the optimal electrochemical performance and perfect
structure of the CC, oxidized CC and ACC, respec- reaction time of ACC-MnO2-2 h. Otherwise, CV
tively. The G band associated with the i2g mode of curves of all ACC-MnO2 electrodes show a larger
graphite is centered at * 1598 cm-1, and the D band area than the ACC, which means that the introduc-
corresponding to the defect-induced mode is pre- tion of MnO2 can improve the capacitance perfor-
sented * 1356 cm-1 [20, 39, 40] as shown in Fig. 4. mance of the flexible electrode. Figure 5c presents CV
Oxidized CC shows a broader characteristic D-band curves of ACC-MnO2-2 h scanned from 5 to 100 mV/
than that of the CC, indicating an increased surface s, and the rectangular CV curves reveal the fast,
disorder induced by the chemical oxidation treat- reversible successive surface redox reactions of the
ment. The peak intensity ratios (ID/IG) based on CC, deposited MnO2 on ACC. Figure 5d shows the GCD
oxidized CC and ACC are calculated to about 0.84, curves of ACC-MnO2-2 h from 0.5 to 20 mA/cm2,
1.91, and 1.78, respectively. The increasing of ID/IG and the areal capacitances (Ca) are obtained from the
indicates a higher degree of disorder of the oxidized GCD data (Fig. 5d and Fig. S4) according to Eq. 1
CC. (S1). As a result, the ACC-MnO2-2 h exhibits excel-
The electrochemical performance of all prepared lent electrochemical performance and the Ca reaches
electrodes was performed to evaluate the perfor- 423.7 mF/cm2 at 0.5 mA/cm2 and 139 mF/cm2 at
mance through cyclic voltammetry (CV) and gal- 20 mA/cm2. In addition, the ACC-MnO2-2.5 h only
vanostatic charge–discharge (GCD) tests using shows 390 mF/cm2 at 0.5 mA/cm2 because of the
3-electrode system (Fig. 5a–d and Fig. S4). Figure 5a broken surfaces and more aggregate particles.
J Mater Sci (2022) 57:3497–3512 3503

Figure 3 a XPS spectra of CC (a) (b)

CC
and ACC. b C 1s spectrum of C ACC C=C
ACC. c N 1s spectrum of
ACC. d XPS spectra of ACC-

Intensity (a.u.)
Intensity (a.u.)
MnO2. e Mn 2p spectrum of
ACC-MnO2. O
N
C-N

C-O
C=O

0 200 400 600 800 290 288 286 284 282 280 278 276
Binding Energy (eV) Binding energy (eV)

(c) (d)

Mn 2p2/2

Intensity (a.u.)
Intensity (a.u.)

O 1s Mn 2p1/2

-NH- Mn 2s
-N=
-N+-

C 1s
Mn 3p Na Auger
Mn 3s

404 402 400 398 396 394 392 390 0 100 200 300 400 500 600 700 800
Binding energy (eV) Binding Energy (eV)

(e)
Mn 2p
Mn 2p3/2 (642.85 eV)
Intensity (a.u.)

Mn 2p1/2 (654.34 eV)

635 640 645 650 655 660 665

Binding energy (eV)

Moreover, electrochemical impedance spectroscopy thicker uniform MnO2 layer which owns greater
(EIS) is an important parameter to evaluate the elec- resistance to ion/electron transport. Cycle stability is
trochemical behavior and the result is presented in one of the very important evaluation parameters, and
Fig. 5f. Compared with other flexible electrodes, the it is noted that the ACC-MnO2-2 h electrode main-
ACC-MnO2-2 h exhibits small equivalent series tains 85.4% of its initial capacitance at a scan rate of
resistance (ESR) indicating high conductivity. Addi- 100 mV/s after 5000 cycles. When the cycle number
tionally, the lower slope of the ACC-MnO2-2 h in the is extended to 10 000 cycles, the value of capacitance
low-frequency region (Fig. 5f) is caused by the retention also keeps 80.6% (Fig. 6a). The cycle
3504 J Mater Sci (2022) 57:3497–3512

2000 stability of ACC-MnO2-2 h electrode is further mea-

CC
Oxization CC sured at a current density of 8 mA/cm2, and the
1500
ACC capacitance maintains about 86.2% after 10 000 cycles
ACC-MnO2
Intensity (a.u)

(Fig. 6b). The results demonstrate good long-term

stability by repetitive CV tests at 100 mV/s and GCD
1000 tests at a current density of 8 mA/cm2 during 10 000
cycles. Additionally, SEM characterizations were
500 performed on ACC-MnO2-2 h after 5000 and 10 000
cycles, respectively (Fig. 6b and c). Compared with
the original sample, no obvious structural changes of
0
500 1000 1500 2000 2500 3000 ACC-MnO2-2 h occurred during the recycle stability
Wavenumber (cm )
-1 tests, indicating the superior stability of ACC-MnO2-
2 h [41].
Figure 4 Raman spectra of the CC, oxidation CC, ACC and
ACC-MnO2.

Figure 5 a CV curves of (a) (b) 1.0

ACC
MnO2-modified ACC under

Potential (V vs. SCE)

ACC-MnO2-1h
0.004
Current density (A/cm2)

different reaction time (1 h, 0.8 ACC-MnO2-1.5h

ACC-MnO2-2h
1.5 h, 2 h and 2.5 h). b GCD ACC-MnO2-2.5h
curves of MnO2-modified 0.000 0.6

ACC under different reaction

0.4
times (1 h, 1.5 h, 2 h and ACC
-0.004 ACC-MnO2-1h
2.5 h). c CV curves of ACC- ACC-MnO2-1.5h 0.2
ACC-MnO2-2h
MnO2-2 h with a scan rate
ACC-MnO2-2.5h
from 5 to 100 mV/s. d GCD -0.008 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0 200 400 600 800
curves of ACC-MnO2-2 h at a Potential (V vs. SCE) Time (s)
current density from 0.5 to
20 mA/cm2. e The areal (c) 0.02 (d) 1.2 2
0.5 mA/cm
capacitance of MnO2-modified 1 mA/cm
2
Potential (V vs. SCE)

1.0
ACC under different reaction 2
Current density (A)

2 mA/cm
0.01 5 mA/cm
2

times. f Nyquist plots of MnO2 0.8 8 mA/cm

2

2
modified ACC under different 10 mA/cm
2
0.00 0.6 15 mA/cm
reaction times. 20 mA/cm
2

5 mV/s 0.4
10 mV/s
-0.01 20 mV/s
50 mV/s 0.2
80 mV/s
100 mV/s
-0.02 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0 500 1000 1500 2000 2500

Potential (V vs. SCE) Time (s)

(e) 600 (f) 50
Specific Capacitance (mF/cm2)

ACC-MnO2-1h
ACC-MnO2-1.5h
500 40
ACC-MnO2-2h
ACC-MnO2-2.5h
400
30
-Z"/ohm

300
20
200
ACC-MnO2-1h
100 10 ACC-MnO2-1.5h
ACC-MnO2-2h
ACC-MnO2-2.5h
0 0
0 4 8 12 16 20 0 10 20 30 40 50
Current density (mA/cm2) Z'/ohm
J Mater Sci (2022) 57:3497–3512 3505

a 120 b
Capacitance Retention (%)
100

Capacitance retention (%)

100
80
80
60
60
40
40
20 20

0 0
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000
Cycle number Cycle numbers

Figure 6 a Cycle stability of ACC-MnO2-2 h at a scan rate of MnO2-2 h after 5000 cycles scanned at 100 mV/s d ACC-MnO2-
100 mV/s. b Cycle stability of ACC-MnO2-2 h at a current 2 h after 10 000 cycles scanned at 100 mV/s e.
density of 8 mA/cm2. SEM images of ACC-MnO2-2 h c ACC-

Figure 7a and Scheme 1 show the schematic dia- ASC with a ratio of 1:1.1 can be expanded to 2.0 V
gram of flexible quasi-solid-state asymmetric super- with no obvious polarization. However, there is an
capacitors (FQSASCs), which are assembled based on obvious polarization phenomenon when the voltage
the flexible positive electrode (ACC-MnO2-2 h), the increases to 2.1 V or 2.2 V (Fig. S6b). Furthermore, the
flexible negative electrode (ACC) and a gel electrolyte electrochemical performance of FQSASCs was eval-
(PVA-LiCl). The cyclic voltammetry (CV), galvanos- uated by CV and GCD tests. Figure 7c shows the CV
tatic charge–discharge (GCD) and cycle stability curves of FQSASCs with a potential range from 1.0 to
scanned at 100 mV/s for 10 000 cycles are used to 2.0 V scanned at 100 mV/s, and the results prove that
measure the electrochemical performance of ACC the potential of FQSASCs can reach as high as 2.0 V.
based on a 3-electrode system. The result is presented In addition, the GCD curves are performed from 1.0
in Fig. S4i-k, and ACC exhibits excellent cycle sta- to 2.0 V at a current density of 1 mA/cm2 shown in
bility with about 91.73% capacitance retention after Fig. 7d, which prove that the FQSASCs can also reach
10 000 cycles. Figure 7b presents the CV curves of a potential of 2.0 V. The detailed CV curves of
ACC-MnO2-2 h and ACC at a scan rate of 20 mV/s, FQSASCs were tested from 0 to 2.0 V at a scan rate
and the total voltage range is up to 2.0 V. In addition, from 5 to 500 mV/s (Fig. 7e). All of the CV curves
the ASCs based on the different ratios of positive display an approximately rectangular shape indicat-
electrode and negative electrode were measured and ing that the FQSASCs own a large operation window
the result is presented in Fig. S6a. Compared with as high as 2.0 V. Furthermore, the GCD curves
other ratios, the ASC based on the ratio of 1:1.1 (Fig. 7f) were performed from 0 to 2.0 V at a current
exhibits maximum integral area, meaning the optimal density from 0.5 to 20 mA/cm2. The energy density
electrochemical performance. The voltage ranges of and power density were calculated based on the GCD
3506 J Mater Sci (2022) 57:3497–3512

(a) (b) 0.010

2V

Current density (A)

0.005

0.000

-0.005
ACC
ACC-MnO2-2h
-0.010
-1.0 -0.5 0.0 0.5 1.0
Potential (V vs. SCE)

(c) (d) 2.5

0.006 0-1 V
0-1.2 V
0.004 2.0 0-1.4 V
Current density (A)

0-1.6 V
0-1.8 V

Voltage (V)
0.002
1.5 0-2.0 V

0.000

0-1 V
1.0
-0.002
0-1.2 V
0-1.4 V
-0.004 0-1.6 V 0.5
0-1.8 V
-0.006 0-2.0 V
0.0
0.0 0.5 1.0 1.5 2.0 0 100 200 300 400
Voltage (V) Time (s)

(e) (f)
0.020 2.5 2
0.5 mA/cm
2
0.015 0.75 mA/cm
2
2.0 1 mA/cm
Current density (A)

0.010 2 mA/cm
2

2
Voltage (V)

0.005 5 mA/cm
1.5 8 mA/cm
2

2
0.000 10 mA/cm

-0.005 1.0

-0.010 5 mV/s 80 mV/s

10 mV/s 100 mV/s 0.5
-0.015 20 mV/s 200 mV/s
50 mV/s 500mV/s
-0.020 0.0
0.0 0.5 1.0 1.5 2.0 0 400 800 1200
Voltage (V) Time (s)

(g) (h) 103

50
Power density (mW/cm3)

FQSASCs-ACC-MnO2//ACC
40 102

2
30 101 Ref. 43
-Z"/ohm

Ref. 23
FSSCs-ACC//ACC Ref. 44
-Z"/ohm

Ref. 42
20 1 100
Ref. 20
10 10-1
0
6 8 10
Z'/ohm
0 10-2
0 20 40 60 80 100 10-3 10-2 10-1 100 101
3
Z'/ohm Energy density (mWh/cm )
 J Mater Sci (2022) 57:3497–3512 3507

b Figure 7 a Schematic illustration of the FQSASCs based on 0.011 mWh/cm3 with a power density of 19 mW/
ACC-MnO2-2 h as the positive electrode and ACC as the negative cm3) [43], FSSCs based on rGO-bridged multifunc-
electrode. b CV curves of ACC-MnO2-2 h with a potential range tional flexible fiber (0.61 mWh/cm3, 4.17 mW/cm3)
from 0 to 1.0 V and ACC with a potential range from -1.0 to 0 V [44].
at a scan rate of 20 mV/s. c CV curves of the FQSASCs with a
The result of electrochemical impedance spec-
voltage range from 1 to 2.0 V with the scan rate at 100 mV/s.
troscopy (EIS) (Fig. 7g) shows that the FQSASCs
d GCD curves of the FQSASCs with a voltage range from 1 to
2.0 V at a current density of 1 mA/cm2. e CV curves of the possess a small electrical conductivity. For instance,
FQSASCs with the scan rate from 5 mV/s to 500 mV/s. f GCD the equivalent series resistance (Rs), observed from
curves of the FQSASCs with the current density from 0.5 mA/cm2 the EIS, is 6.5 X. In addition, the small value of charge
to 10 mA/cm2. g Nyquist plots of FQSASCs, h Ragone plots transfer resistance (RCT) reveals that the FQSASCs
(power density vs energy density) of FQSASCs. have a relatively high-speed charge transfer ability.
Cycle stability of FQSASCs was characterized by 5000
times repetitive GCD testes under 10 mA/cm2, and
data according to Equations S2 and S3, and the Fig. 8a presents the results of cycle stability. As a
Region plot of FQSASCs was presented in Fig. 7h. As result, the capacitance retention can maintain about
a result, the FQSASCs can reach a high energy den- 109.4% of its initial capacitance after 5000 GCD
sity value at 0.78 mWh/cm3 when the power density cycles. The first ten cycles and last ten cycles are
is 6.16 mW/cm3, and the perfect power density can presented in Fig. 8b, which revealed that the shapes
rise to 71.86 mW/cm3 at the power density of 0.050 of GCD cycle also kept its original shape, demon-
mWh/cm3. The FQSASCs exhibit more excellent strating the excellent long-term cycle stability of
properties than the FSSCs based on ACC (0.10 mWh/ FQSASCs.
cm3 when the power density is 3.06 mW/cm3) Mechanical properties appear to be crucial in flex-
(Fig. 7h). This energy density and power density are ible energy storage devices. As for FQSASCs based
comparable or relatively higher than some recent on ACC-MnO2-2 h//ACC, the mechanical properties
flexible SCs (Fig. 7h), such as FSSCs based on fCC- were measured through testing the CV curves and
PANI array-rGO (energy density of 0.22 mWh/cm3 GCD curves under bending different angles (Fig. 9b–
at a power density of 0.50 mW/cm3) [20], FSSCs e) and the mechanical durability was investigated by
based on ZnO@MnO2//rGO (energy density of CV curves through bending different times (Fig. 9f
0.234 mWh/cm3 and volumetric power density of and g). Figure 9a presents the photographs of
3.2 mW/cm3) [42], FSSCs based on aligned CNT FQSASCs under different bending angles. As shown
arrays (energy density of 0.1 mWh/cm3 with a in Fig. 9b, the CV curves of FQSASCs were per-
power density of 14 mW/cm3 [23], FSSCs based on formed in a bending state from 08 to 1808. These CV
TiO2@C core–shell nanowires (energy density of curves are almost overlapped even the FQSASCs

Figure 8 a Cycle stability of (a) (b) 2.5

FQSASCs at a current density 120 First ten cycles
Capacitance retention (%)

Last ten cycles

of 10 mA/cm2. b GCD curves 2.0
100
of the first ten cycles and last
Voltage (V)

ten cycles. 80 1.5

60
1.0
40
0.5
20

0 0.0
0 1000 2000 3000 4000 5000 0 100 200124900 125000 125100
Cycle numbers Time (s)
3508 J Mater Sci (2022) 57:3497–3512

(a)
(b) 0.010

Current density (A)

0.005
0°
45°
0.000 90°
135°
180°
135°
-0.005
90°
45°
0°
-0.010
0.0 0.5 1.0 1.5 2.0 2.5
Voltage (V)

(c)
140 (d) 2.0
0°
Capacitance retention (%)

120 45°
90°
100
1.5 135°

Voltage (V)
180°
80 135°
90°
1.0
45°
60
0°

40
0.5
20

0 0.0
0° 45° 90° 135° 180° 135° 90° 45° 0° 0 100 200 300 400 500
Bent angel Time (s)

(e) (f)
140 0.010
Capacitance retention (%)

120 0
Current density (A)

20
0.005 50
100
75
80 100
150
0.000
200
60
250
300
40 350
-0.005
400
20 450
500
0 -0.010
0° 45° 90° 135° 180° 135° 90° 45° 0° 0.0 0.5 1.0 1.5 2.0 2.5
Bent angel Voltage (V)

(g)
140
Capacitance retention (%)

120

100

80

60

40

20

0
0 100 200 300 400 500
Bent times
 J Mater Sci (2022) 57:3497–3512 3509

b Figure 9 a Photographs of FQSASCs under different bending used in potential applications as high-performance
angles. b CV curves of FQSASCs after bending different angles. flexible energy-storage devices.
c Capacitance retention of FQSASCs after bending different
angles. d GCD curves of FQSASCs after bending different angles.
e Capacitance retention of FQSASCs after bending different
Conclusion
angles. f CV curves of FQSASCs while bent under 1808 after
different bending cycles. g Capacitance retention of FQSASCs
In summary, flexible quasi-solid-state asymmetric
after different bending cycles.
supercapacitors (FQSASCs) are fabricated based on
MnO2-modified activated carbon cloth (ACC-MnO2)
and ACC. Compared with CC, activation of CC by
after bending at 1808, and the capacitance can main- Hummers’ method can increase the wettability. After
tain over 93.7% during the bending process (Fig. 9c). that, the ACC is modified by MnO2, the introduction
In addition, the GCD curves also exhibit even over- of MnO2 layer can dramatically enhance the capaci-
lapped after bending at 1808 (Fig. 9d), and the tance of ACC, and the value of Ca reaches 423.4 mF/
capacitance retention can keep about 98.3% during cm2 when the current is 0.5 mA/cm2. Furthermore,
the bending process (Fig. 9e). Furthermore, mechan- the FQSASCs assembled based on ACC-MnO2-2 h//
ical durability was evaluated by CV testes scanned at ACC exhibit a high operation voltage at 2.0 V even
100 mV/s through repeatedly bending the FQSASCs though the current density is low. In addition, the
from 08 to 1808. It is very clear that the CV curves FQSASCs can possess a high energy density at
show approximately overlapped state even though 0.78 mWh/cm3 when the power density is 6.16 mW/
the bend times extended to 500 times (Fig. 9f), and cm3, and the perfect power density can rise to
the value of capacitance retention exhibits over 100% 71.86 mW/cm3 at the power density of 0.050 mWh/
even though the FQSASCs are bent for 500 times cm3. Moreover, the FQSASCs also exhibit extreme
(Fig. 9g), demonstrating that the as-prepared cycle stability (maintain about 109.4% of its initial
FQSASCs possess excellent mechanical properties, capacitance after 5000 GCD cycles) and excellent
flexibility and mechanical durability. mechanical durability (keeping over 100% capaci-
To explore the application, the FQSASCs device tance retention even after bending for 500 times). All
was used to light up a red LED (Fig. 10a, b). Obvi- the excellent electrochemical properties, flexible and
ously, one single FQSASCs device can drive a red mechanical durability reveal that the uniform MnO2
LED (Fig. 10a) indicating that FQSASCs reveal high layer-modified CC can act as a great promising flex-
voltage. Furthermore, two FQSASCs in series can ible electrode for flexible SCs, and the FQSASCs
light up a red LED brighter than a single device based on ACC-MnO2-2 h//ACC have potential
(Fig. 10b). Therefore, the FQSASCs are expected to be applications as flexible energy-storage devices.

Figure 10 Pictures of lighting

a red LED with a single
FQSASCs a and two tandem
FQSASCs b.
3510 J Mater Sci (2022) 57:3497–3512

Acknowledgements Storage Mater 9:150. https://doi.org/10.1016/j.ensm.2017.0

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