Article

www.acsnano.org

Design of Amorphous Manganese

Oxide@Multiwalled Carbon Nanotube Fiber for
Robust Solid-State Supercapacitor
Peipei Shi,† Li Li,† Li Hua,† Qianqian Qian,† Pengfei Wang,‡ Jinyuan Zhou,§ Gengzhi Sun,*,†
and Wei Huang*,†,∥
†
Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation
Center for Advanced Materials (SICAM), Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, China
‡
CAS Key Laboratory of Mechanical Behavior and Design of Materials, Department of Modern Mechanics, University of Science and
Technology of China, Hefei 230026, China
§
School of Physical Science and Technology, Lanzhou University, 222 South Tianshui Road, Lanzhou 730000, China
∥
Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National
Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan
Road, Nanjing 210023, China
*
S Supporting Information

ABSTRACT: Solid-state fiber-based supercapacitors have

been considered promising energy storage devices for
wearable electronics due to their lightweight and ame-
nability to be woven into textiles. Efforts have been made to
fabricate a high performance fiber electrode by depositing
pseudocapacitive materials on the outer surface of carbona-
ceous fiber, for example, crystalline manganese oxide/
multiwalled carbon nanotubes (MnO2/MWCNTs). How-
ever, a key challenge remaining is to achieve high specific
capacitance and energy density without compromising the
high rate capability and cycling stability. In addition,
amorphous MnO2 is actually preferred due to its disordered
structure and has been proven to exhibit superior electro-
chemical performance over the crystalline one. Herein, by incorporating amorphous MnO2 onto a well-aligned MWCNT
sheet followed by twisting, we design an amorphous MnO2@MWCNT fiber, in which amorphous MnO2 nanoparticles are
distributed in MWCNT fiber uniformly. The proposed structure gives the amorphous MnO2@MWCNT fiber good
mechanical reliability, high electrical conductivity, and fast ion-diffusion. Solid-state supercapacitor based on amorphous
MnO2@MWCNT fibers exhibits improved energy density, superior rate capability, exceptional cycling stability, and
excellent flexibility. This study provides a strategy to design a high performance fiber electrode with microstructure control
for wearable energy storage devices.
KEYWORDS: amorphous manganese oxide, carbon nanotube, fiber, supercapacitor, energy storage

and weaving process.2 Although the solid-state supercapacitors

T he rapid development of portable and wearable

electronics urgently calls for matchable energy storage
devices as power supply.1−4 Because of their high
power density, long cycling lifetime, lightweight, and excellent
weavability, solid-state fiber-based supercapacitors have at-
based on MWCNT fibers were demonstrated,8−11 the highly
compact structure of MWCNT fibers degraded their double
layer capacitance significantly.8 Therefore, the as-made
MWCNT fiber-based supercapacitors still suffer from low
tracted significant attention in recent years.5−7 A number of
fibriform materials have been utilized in supercapacitors, among specific capacitance and low energy density, seriously hindering
which the multiwalled carbon nanotube (MWCNT) fiber their practical applications.
fabricated from a vertically aligned MWCNT array is
particularly intriguing because of its high surface area, good Received: September 20, 2016
mechanical strength, excellent electrical conductivity, remark- Accepted: December 27, 2016
able flexibility, and compatibility with traditional fiber spinning Published: December 27, 2016

© 2016 American Chemical Society 444 DOI: 10.1021/acsnano.6b06357

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Incorporation of pseudocapacitive materials onto MWCNT

fiber is a promising strategy to improve the capacitance of fiber-
based supercapacitor. Although great efforts have been devoted
to hybridizing MWCNT fiber with other materials, such as
manganese oxide (MnO2),12−14 nickel oxide (NiO),15 polyani-
line (PANI),16−18 reduced graphene oxide (rGO),19,20 poly-
(3,4-ethylenedioxythiophene) (PEDOT),21 or molybdenum
disulfide (MoS2),22 through electrochemical deposition12−19
or physical blending,20−22 insufficient attention has been paid
to the microstructural design of a fiber electrode, which has a
good chance to realize the synergistic effect between
pseudocapacitive materials and conductive filaments. For
instance, among all the aforementioned pseudocapacitive
materials, MnO2 has been considered to be the most
competitive material for supercapacitors owing to its high Figure 1. Schematic illustration of the fabrication of amorphous
theoretical specific capacitance, environmental benignity, MnO2@MWCNT fiber.
natural abundance, and low cost.23−26 Particularly, amorphous
MnO2 is preferred over the crystalline one27−30 because of its solution (at 80 °C) for 20−420 s in order to deposit
highly disordered structure, leading to rapid ion-diffusion, amorphous MnO2 nanoparticles on the MWCNT surface.
superior structural stability and fast electrode kinetics during According to a previous study,28 amorphous MnO2 nano-
electrochemical charge−discharge cycles. Recently, the hybrid- particles can spontaneously deposit on the surface of
ization of MnO2 nanocrystals and MWCNT fiber was achieved MWCNTs through the following redox reactions:
by electrochemical deposition.12−14 However, because of the
hydrophobic nature of MWCNTs, the electrochemical 4MnO4 − + 3C + H 2O → 4MnO2 + CO32 − + 2HCO3−
deposition of MnO2 nanocrystals primarily occurred at the (1)
outer surface of the MWCNT fiber, and the poor electrical − +
conductivity of MnO2 nanocrystals was not effectively 4MnO4 + 4H → 4MnO2 + 3O2 + 2H 2O (2)
improved.13 Therefore, the high pseudocapacitance of MnO2 34
The well-aligned characteristics and the interconnection
cannot be efficiently utilized, resulting in low specific between individual MWCNTs35 provide MWCNT sheet high
capacitance and inferior high rate capability as well as poor surface area,36 guaranteeing the exposure of MWCNTs to
cycling stability.13,14,31 Moreover, the as-made hybrids were MnO4− ions, and thus giving uniform coating of amorphous
sensitive to mechanical deformation such as folding and MnO2 nanoparticles on MWCNTs. Once the amorphous
twisting as a result of the fragile character of metal oxide- MnO2-MWCNT hybrid sheet was washed thoroughly with
based nanostructures,13,32 resulting in poor mechanical stability. ethanol/water (volume ratio of 1:1), it was peeled off from the
To overcome the aforementioned drawbacks, through glass slide and twisted into amorphous MnO2@MWCNT fiber
rational structural design, we created amorphous MnO2@ using an electric motor at rotating speed of 200 rpm for 2 min.
MWCNT fiber, in which amorphous MnO2 nanoparticles were The well-orientated MWCNTs (Figure S1) offered the
incorporated into MWCNT fiber uniformly. The incorporated interconnected MWCNT scaffold with good electrical con-
amorphous MnO2 nanoparticles, the well-aligned characteristic ductivity and mechanical strength. Figure 2a shows a typical
of interconnected MWCNT scaffold and the proposed scanning electron microscopy (SEM) image of the MnO2-
microstructure enable the resultant amorphous MnO2@ MWCNT hybrid sheet with an immersion time of 60 s. The
MWCNT fiber good mechanical robustness, highly electrical incorporation and uniform dispersion of MnO2 nanoparticles
conductivity and fast ion-diffusion. Solid-state supercapacitor on MWCNTs were confirmed by the energy disperse
based on such hybrid fibers exhibits high specific capacitance of spectroscopy (EDS) mapping. Dark-field transmission electron
8.5 F cm−3 (corresponding to specific length capacitance of microscopy (TEM) images of a MWCNT sheet (Figure S2a)
22.6 μF cm−1 and gravimetric capacitance of 8.0 F g−1) at a and MnO2-MWCNT hybrid sheet (Figure S2b) indicate that
current density of 1 A cm−3 (nearly 13 times higher than that of small MnO2 nanoparticles were decorated on the MWCNTs.
MWCNT fiber-based device, 0.66 F cm−3), high energy density The selected area electron diffraction (SEAD) pattern of the
of 1.5 mWh cm−3, and exceptional cycling stability with MnO2−MWCNT hybrid sheet only shows the disperse rings of
capacity retention of over 90% after 15 000 cycles. graphite (Figure S3), indicating the amorphous characteristic of
Furthermore, the amorphous MnO2@MWCNT fiber-based the generated MnO 2 nanoparticles which is an ideal
supercapacitor displays excellent flexibility and mechanical pseudocapacitive material for a supercapacitor.28 The high
reliability, guaranteeing the supercapacitor can work properly resolution TEM (HRTEM) image shown in Figure S4 gives
under folding−unfolding states. further evidence of the amorphous structure of MnO2
nanoparticles. The oxidation state of amorphous MnO2
RESULTS AND DISCUSSION nanoparticles on MWCNTs was determined using X-ray
Typically, the well-aligned MWCNT sheet was continuously photoelectron spectroscopy (XPS) analysis (Figure 2b,c). The
drawn out from the MWCNT array, which was obtained by binding energy separation between Mn 3s doublet peaks is 4.95
chemical vapor deposition (CVD).33 As schematically shown in eV (Figure 2b), which suggests an intermediate oxidation state
Figure 1, three layers of MWCNT sheets with the width of ∼2 between Mn4+ and Mn3+.28,37,38 On the basis of the analysis of
mm and a length of ∼7.5 cm were stacked on a glass slide. the O 1s orbital spectrum (Figure 2c), the intensity ratios of
Subsequently, the stacked MWCNT sheets were immersed into three overlapping peaks, Mn−O−Mn, Mn−O−H, and H−O−
a preheated 0.1 g mL−1 KMnO4/0.1 M H2SO4 aqueous H, were determined to be 0.23, 0.06, and 1, respectively.
445 DOI: 10.1021/acsnano.6b06357
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Figure 2. (a) EDS mapping of amorphous MnO2-MWCNT hybrid sheet. (b,c) XPS spectra of MnO2 on a hybrid sheet for the determination of
oxidation state. Si served as substrate for EDS and XPS characterizations.

According to a previous study,37 the oxidation state can be reliability of the amorphous MnO2@MWCNT fiber. As shown
mathematically calculated to be 3.74 using the following in Figure 4a,b, the conductivity and strength of amorphous
equation: MnO2@MWCNT fibers degraded gradually as a function of
(4SMn ‐ O ‐ Mn − SMn ‐ OH) immersion time because of the etching of MWCNT walls,
ox state = which was observed by the HRTEM shown in Figure S6. The
SMn ‐ O ‐ Mn (3) supercapacitive performances of amorphous MnO2@MWCNT
where S is the peak intensity. This result is in good accordance fibers were electrochemically tested in a three-electrode
with the XPS analysis of the Mn 3s spectrum. configuration. Figure 4c shows the galvanostatic charge−
The morphology of amorphous MnO2@MWCNT fibers was discharge curves of amorphous MnO2@MWCNT fiber electro-
characterized using SEM (Figure 3). The diameter of fibers des at 1 A cm−3 in 6 M LiCl aqueous solution as a function of
increased slightly with increasing immersion time because of immersion time. The symmetric triangular-shape and small IR
the deposition of amorphous MnO2 nanoparticles. For drop indicate pseudocapacitive behavior and small interior
MWCNT fiber (Figure 3a,b), the well-aligned and clean resistance of the amorphous MnO2@MWCNT fiber electrode
MWCNTs guarantee high electron transport pathways, but its with high Coulombic efficiency.22,39 The volumetric capaci-
low capacitance is unavoidable because of the highly compact tance (CV) increases with immersion time due to the increased
structure of the MWCNT fiber and hydrophobic nature of mass loading of amorphous MnO2 nanoparticles. It was found
MWCNT walls.8 Deposition of amorphous MnO2 onto the that the capacitance of the amorphous MnO2@MWCNT fiber
MWCNT surface can be observed in Figure 3c−f. The surface
increased rapidly within the immersion time of 60 s, but leveled
roughness of amorphous MnO2@MWCNT fiber became more
off with prolonged immersion time, which can be attributable
obvious at an immersion time of 420 s (Figure 3f) than at an
immersion time of 60 s (Figure 3d). It was also more obvious to the thick MnO2 deposition resulting in lower electrical
than the surface roughness of the MWCNT fiber (Figure 3b), conductivity and longer ion diffusion pathway. Therefore,
which can be attributed to the increase of both particle size and taking both the physical properties of mechanical strength and
particle numbers evidenced by the TEM images shown in electrical conductivity, and the specific capacitance of the
Figure S5. hybrid fiber into account, we selected the amorphous MnO2@
The electrical conductivity and mechanical strength crucially MWCNT fibers with an immersion time of 60 s for the
determine the electrochemical performance, weavability, and following study.
446 DOI: 10.1021/acsnano.6b06357
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The cyclic voltammetry (CV) curves of the amorphous

MnO2@MWCNT fiber (immersion time of 60 s) electrode
were investigated at scan rates from 0.02 to 1 V s−1 (Figure 5a).
The rate capability of the amorphous MnO2@MWCNT
electrode is remarkable, and the CV curves maintained a
rectangular shape even at the scan rate of 1 V s−1, with only
∼28% loss of capacitance compared to that measured at the
scan rate of 0.02 V s−1 (Figure 5b). This performance is
superior to the performances of MnO2/CNT fiber electrodes
fabricated using electrochemical deposition,13,14,40 where
rectangular shape of the CV was found to distort considerably
at the scan rate of 1 V s−1. The galvanostatic charge−discharge
curves of the amorphous MnO2@MWCNT fiber electrode
were tested at the current density ranging from 0.2 to 20 A
cm−3 (Figure 5c,d). The CV of the amorphous MnO2@
MWCNT fiber electrode decreased to 44.1 F cm−3 at the high
current density of 20 A cm−3 with 69% retention.
The symmetric solid state supercapacitors were fabricated
using the amorphous MnO2@MWCNT fibers (immersion time
of 60 s) in a two-electrode configuration (Figure S7). Figure 6a
shows the CV curves of MWCNT fiber-based device and the
amorphous MnO2@MWCNT (immersion time of 60 s) fiber-
based device at the scan rate of 0.1 V s−1. The CV curve of the
MWCNT fiber-based device was tested as reference, which has
a rectangular shape with a typical electric double-layer
Figure 3. SEM images of (a,b) MWCNT fiber, and amorphous capacitance behavior. The amorphous MnO2@MWCNT
MnO2@MWCNT fibers with immersion time of (c,d) 60 s and (e,f) fiber-based device also exhibits a rectangular-shaped CV curve
420 s. with a much higher current density, attributable to the
pseudocapacitive contribution from amorphous MnO2. Amor-
phous MnO2 nanoparticles and α-MnO2 nanotubes were also

Figure 4. Electrical conductivity (a) and mechanical strength (b) of amorphous MnO2@MWCNT fiber as a function of immersion time. (c)
Galvanic charge−discharge curves of amorphous MnO2@MWCNT fiber electrode test in a three-electrode configuration as a function of
immersion time. (d) The CV of amorphous MnO2@MWCNT fiber electrode as a function of immersion time.

447 DOI: 10.1021/acsnano.6b06357

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Figure 5. (a) The CV curves of amorphous MnO2@MWCNT fiber electrode. (b) Capacitance retention of amorphous MnO2@MWCNT fiber
electrode calculated from the CV curves shown in panel a. (c) Galvanic charge−discharge curves of amorphous MnO2@MWCNT fiber
electrode as a function of charge−discharge current density. (d) The CV of amorphous MnO2@MWCNT fiber electrode as a function of
charge−discharge current density.

synthesized (Figure S8a−d) and incorporated into MWCNT fabricated by electrochemical deposition.13 The volumetric
fibers using the method reported in our previous study.22 energy density and power density can be calculated by EV =
Supercapacitors based on MWCNT fibers, amorphous MnO2@ 1
/2CVV2 and PV = EV/tdischarge, where CV, V, and tdischarge are the
MWCNT fibers, amorphous MnO2/MWCNT fibers, and α- volumetric capacitance, cell voltage, and discharge time,
MnO2/MWCNT fibers were then compared. Electrochemical respectively. As observed at a given PV, the EV of our
impedance spectra (EIS) show similar equivalent series supercapacitor based on amorphous MnO2@MWCNT fibers
resistances at high frequency rage (Figure S8e). At low is significantly enhanced without compromising PV over that of
frequency range, the EIS slope for amorphous MnO2@ the MWCNT fiber-based device (Figure 6d). The EV varies
MWCNT fiber-based supercapacitor is slightly compromised from 1.5 to 0.96 mWh cm−3 and the PV falls in the range of
due to the involvement of redox reaction at Mn sites in MnO2 0.05−2.5 W cm−3, which is superior to the PV of devices based
when compared to MWCNT fiber-based supercapacitor, but on ZnO@MnO2/carbon fibers42 and MnO2/carbon fibers.32 In
much higher than that of amorphous MnO2/MWCNT fiber- comparison, the performance of our device is comparable to
and α-MnO2/MWCNT fiber-based devices, suggesting a fast that of the asymmetric device made of MoS2-rGO/MWCNT
ion diffusion rate.41 In addition, the amorphous MnO2@ fibers (0.97 mWh cm−3 at 2.3 W cm−3),22 symmetric devices
MWCNT fiber-based supercapacitor exhibits the highest made of rGO/MWCNT fibers (0.16 mWh cm−3 at 0.14 W
capacitance at a current density of 1 A cm−3 (Figure S8f), cm−3),22 MnO2/MWCNT fibers (0.75 mWh cm−3 at 3 W
giving further evidence to the advantages of our fiber electrode. cm−3),13 and PEDOT/MWCNT fibers (0.9 mWh cm−3 at 3.5
Figure 6b displays the galvanostatic charge−discharge curves of W cm−3).43
the amorphous MnO2@MWCNT fiber-based supercapacitor at In addition, we can connect several devices together in order
charge−discharge current density ranging from 0.1 to 5 A cm−3 to multiply the capacity or cell voltage which is critically
(Figure 6b). The CV of the amorphous MnO2@MWCNT fiber- important for practical applications.41 As shown in Figure 7a,b,
based device was determined to be 10.9 F cm−3 (corresponding the charge/discharge voltage window was doubled when two
to specific length capacitance of 28.9 μF cm−1 and gravimetric individual devices were connected in series, while both the
capacitance of 10.3 F g−1) at the current density of 0.1 A cm−3. output current and discharge time increased by a factor of 2
With the increase of charge−discharge current density, the CV when two devices were connected in parallel, indicating small
decreased to 6.9 F cm−3 (corresponding to specific length device-to-device variation and the feasibility to scale up the
capacitance of 18.3 μF cm−1 and gravimetric capacitance of 6.5 output by combining several fiber-based devices. Well-aligned
F g−1) with a retention of 63.3% at the current density of 5 A MWCNTs not only provide highly conductive pathways, but
cm−3 (Figure 6c), superior to the MnO2/MWCNT fibers also give highly reliable mechanical support to the hybridized
448 DOI: 10.1021/acsnano.6b06357
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Figure 6. (a) The CV curves of solid-state supercapacitors made of MWCNT fibers and amorphous MnO2@MWCNT fibers. (b) Galvanic
charge−discharge curves of amorphous MnO2@MWCNT fiber-based supercapacitor. (c) The CV of amorphous MnO2@MWCNT fiber-based
supercapacitor as a function of charge−discharge current density. (d) Plot of volumetric energy density (EV) versus volumetric power density
(PV) for our fiber-based supercapacitor (MnO2@MWCNT) and other reported MWCNT fiber-based supercapacitors.

components. As shown in Figure 7c, the CV curves of an pathways and highly reliable mechanical support. Therefore,
amorphous MnO2@MWCNT fiber-based supercapacitor did the aforementioned microstructure and facile fabrication
not alter while the device was highly curved (180° folded). In process of the amorphous MnO2@MWCNT fibers, together
addition, the CV of amorphous MnO2@MWCNT fiber-based with the high performance of our fiber-based supercapacitors
device showed a very small reduction in capacitance (<10% make it promising to scale-up for wearable electronics
decay) even after 15 000 charge−discharge cycles (Figure 7d) applications.
and had almost 100% retention after 5000 bending−unbending
cycles (Figure S9), indicating the excellent cycling stability and EXPERIMENTAL SECTION
reliability of the device.
Lithium chloride (LiCl, > 99%) and poly(vinyl alcohol) (PVA, MW
85 000 to 124 000) were obtained from Adamas-Beta and Sigma-
CONCLUSIONS Aldrich, respectively. Sulfuric acid (H2SO4, 95.0−98.0%), hydrochloric
In this study, robust amorphous MnO2@MWCNT fibers have acid (HCl, 36.0−38.0%), potassium permanganate (KMnO4, ≥99.5%),
been successfully fabricated. The nanosized amorphous MnO2 potassium chloride (KCl, ≥99.5%) and ethanol (≥99.7%) were
particles decorated on MWCNTs were distributed uniformly in purchased from Shanghai Ling Feng Chemical Reagent Co., Ltd. All
the fiber. The as-made amorphous MnO2@MWCNT fibers chemicals were used as received.
showed improved specific capacitance and excellent rate The spinnable multiwalled carbon nanotube (MWCNT) array was
grown by chemical vapor deposition (CVD) method in a quartz tube
capability. Based on amorphous MnO2@MWCNT fibers furnace according to our previous study.33,44−48 The growth was
(immersion time of 60 s), the solid-state supercapacitor carried out at 750 °C for 10 min using a Fe (99.5%) thin film (1 nm)
exhibited high specific capacitance and energy density, excellent deposited on SiO2/Si substrate as catalyst, C2H4 (99.95%) and Ar
cycling stability, and mechanical reliability, which can be (99.99%) as carbon source and carrier gas, respectively. The well-
attributed to the following: (1) The small particle size of aligned MWCNT sheet was continuously drawn out from the
amorphous MnO2 enables an enlarged electrolytic surface area MWCNT array. Three layers of MWCNT sheets with the width of
with more active sites for cations during faradaic reaction, ∼2 mm and length of ∼7.5 cm were stacked on a well-cleaned glass
shortened electron- and ion-diffusion length, thus facilitating slide. Subsequently, the stacked MWCNT sheets were immersed into
full utilization of MnO2 even at a high scan rate. (2) The a KMnO4 (0.1 g mL−1)/H2SO4 (0.1 M) aqueous solution, which was
heated at 80 °C, in order to deposit amorphous MnO2 nanoparticles
amorphous MnO2 nanoparticles uniformly distributed in the on MWCNT surface forming amorphous MnO2-MWCNT hybrid
fiber prevent the stacking of MWCNTs, further advancing the sheet. The loading amount of amorphous MnO2 nanoparticles was
ion transportation. (3) Because of the intimate contact between controlled by immersion time ranging from 20 to 420 s. Once the
amorphous MnO2 and MWCNTs, the scaffold of a well-aligned amorphous MnO2-MWCNT hybrid sheet was washed thoroughly by
MWCNT network provides highly electrical conductive ethanol/water (volume ratio of 1:1), it was peeled off from glass slide

449 DOI: 10.1021/acsnano.6b06357

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Figure 7. (a) The CV curves of a single and two amorphous MnO2@MWCNT fiber-based supercapacitors connected in series or in parallel.
(b) Galvanic charge−discharge curves of a single and two amorphous MnO2@MWCNT fiber-based supercapacitors connected in series or in
parallel. (c) The CV curves of amorphous MnO2@MWCNT fiber-based supercapacitor at original or folded states. (d) Cycling and bending
stability of CV at current density of 1 A cm−3.

and twisted into a hybrid fiber using an electric motor at 200 rpm for 2 The mass of MWCNT fiber and amorphous MnO2@MWCNT
min before being dried. fiber was determined by an ultra-accurate microbalance (METTLER
Amorphous MnO2 nanoparticles and α-MnO2 nanotubes were also TOLEDO, M × 5) with a readability of 1 μg. The scanning electron
synthesized and incorporated into MWCNT fibers for comparison. In microscopy (SEM) and energy disperse spectroscopy (EDS) were
brief, amorphous MnO2 nanoparticles were synthesized by adding performed on a field-emission scanning electron microscope (JEOL,
ethanol dropwise into 1.5 mM KMnO4 aqueous solution (15 mL) JSM-6700F, Japan). The electrical properties and the mechanical
until the purple color disappeared.49 For the synthesis of α-MnO2 strength of the amorphous MnO2@MWCNT fibers were charac-
nanotube, 0.5 mL of concentrated HCl was mixed with 1.5 mM terized using Kaithley 2400 and a universal testing instrument (HY-
KMnO4 (15 mL), then sealed into a Teflon-lined stainless steel 0350). Transmission electron spectroscopy (TEM) images were taken
autoclave. The autoclave was heated to 140 °C for 12 h.50 The with JEOL-2100F at an acceleration voltage of 200 kV. X-ray
precipitated amorphous MnO2 and α-MnO2 were collected and photoelectron spectroscopy (XPS) measurements were carried out
washed thoroughly using deionized water. Amorphous MnO2/ with Al Kα radiation. The spectra were corrected by referencing the
MWCNT fiber and α-MnO2/MWCNT fiber were fabricated binding energy to the C 1s peak at 284.6 eV. X-ray diffraction (XRD)
according to our previous study.22 Briefly, three layers of MWCNT was taken with Rigaku D/Max Ultima II powder X-ray diffractometer.
sheets were stacked on a polytetrafluoroethylene (PTFE) substrate. The electrochemical characterizations were obtained by a CHI 660E
Amorphous MnO2 nanoparticles and α-MnO2 nanotubes dispersed in electrochemical workstation. Electrochemical impedance spectra (EIS)
ethanol (0.2 mg mL−1) were drop-casted on MWCNT sheets, were conducted by applying a sinusoidal voltage of 5 mV in a
respectively, then dried at room temperature. The resulting hybrid frequency range from 0.01 to 100 kHz.
sheets were peeled off from the PTFE substrate, and twisted into fibers The specific volumetric capacitances (CV) of the fiber-electrodes
by an electric rotator at 200 rpm for 2 min. and fiber-based supercapacitors were calculated from charge−
The single fiber electrode was characterized using a three-electrode discharge curves according to the following equation:
configuration. LiCl aqueous solution (6 M) was used as electrolyte, C V = [i/(dV /dt )]/Vfiber (4)
and Pt plate and Ag/AgCl (saturated KCl) were used as counter and
reference electrode, respectively. The capacitive performance of solid- where i is the discharge current and dV/dt is the slope of discharge
state fiber-based supercapacitor was measured in a two-electrode curve. In three-electrode system, Vfiber is the volume of fiber immersed
configuration. The device was fabricated by placing two amorphous in LiCl electrolyte. In the case of a fiber-based supercapacitor tested in
MnO2@MWCNT fibers close (∼0.5 mm gap) and in parallel on a two-electrode configuration, Vfiber refers to the total volume of two
polyethylene terephthalate (PET) substrate, and then coating a thin fibers exposed to the PVA−LiCl gel electrolyte.
layer of PVA−LiCl (6 M) gel electrolyte. The PVA−LiCl gel The specific gravimetric capacitances (Cg) of the fiber-based
electrolyte was prepared by mixing 10 mL of LiCl (6 M) with 1 g of supercapacitors were calculated from charge−discharge curves
PVA powder which was heated at 90 °C with vigorous stirring until a according to the following equation:
homogeneous gel-like suspension was obtained. Ag paste was used as
Cg = [i/(dV /dt )]/g fiber
electrical leads at the ends of two fibers for electrochemical tests. (5)

450 DOI: 10.1021/acsnano.6b06357

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AUTHOR INFORMATION Carbon Nanotube Fibers for Electrochemical Applications: Effect of
Corresponding Authors Enhanced Interfaces by an Acid Treatment. Nanoscale 2012, 4, 7464−
*E-mail: [email protected]. 7468.
*E-mail: [email protected]. (17) Wang, K.; Meng, Q. H.; Zhang, Y. J.; Wei, Z. X.; Miao, M. H.
High-Performance Two-Ply Yarn Supercapacitors Based on Carbon
ORCID
Nanotubes and Polyaniline Nanowire Arrays. Adv. Mater. 2013, 25,
Gengzhi Sun: 0000-0002-8000-8912 1494−1498.
Wei Huang: 0000-0001-7004-6408 (18) Cai, Z. B.; Li, L.; Ren, J.; Qiu, L. B.; Lin, H. J.; Peng, H. S.
Notes Flexible, Weavable and Efficient Microsupercapacitor Wires Based on
The authors declare no competing financial interest. Polyaniline Composite Fibers Incorporated with Aligned Carbon
Nanotubes. J. Mater. Chem. A 2013, 1, 258−261.
ACKNOWLEDGMENTS (19) Wang, B. J.; Fang, X.; Sun, H.; He, S. S.; Ren, J.; Zhang, Y.;
Peng, H. S. Fabricating Continuous Supercapacitor Fibers with High
This work was supported by NanjingTech Start-Up Grant Performances by Integrating All Building Materials and Steps into One
(3983500150), Jiangsu Specially-Appointed Professor program Process. Adv. Mater. 2015, 27, 7854−7860.
(Grant No. 54935012) and the National Natural Science (20) Sun, G. Z.; Zhang, X.; Lin, R. Z.; Chen, B.; Zheng, L. X.; Huang,
Foundation of China (11674140). X.; Huang, L.; Huang, W.; Zhang, H.; Chen, P. Weavable, High-
Performance, Solid-State Supercapacitors Based on Hybrid Fibers
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452 DOI: 10.1021/acsnano.6b06357

ACS Nano 2017, 11, 444−452