Electrochimica Acta 395 (2021) 139141

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

High performance stretchable fibrous supercapacitors and flexible

strain sensors based on CNTs/MXene-TPU hybrid fibers
Guiqing Wu a, Zhipeng Yang a, Zhenyi Zhang a, Bingyan Ji a, Chengyi Hou a, Yaogang Li a,b,
Wei Jia c, Qinghong Zhang a, Hongzhi Wang a,∗
a
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University,
Experimentation, Shanghai 201620, People’s Republic of China
b
Engineering Research Center of Advanced Glasses Manufacturing Technology, MOE, College of Materials Science and Engineering, Donghua University,
Shanghai 201620, People’s Republic of China
c
State Key Laboratory for Space Power Sources Technology, Shanghai 201109, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: In order to improve the practicability of fibrous supercapacitors, stretchability is a significant character-
Received 15 March 2021 istic for the devices, which puts forward high requirements for electrode materials. In this work, highly
Revised 17 August 2021
stretchable and conductive CNTs/MXene-TPU hybrid fiber electrodes with porous structure were prepared
Accepted 21 August 2021
by wet spinning technique. The mechanical and electrical properties of the fiber electrodes remained sta-
Available online 30 August 2021
ble during the tensile process when the amount of CNTs/MXene is 10 wt%. Meanwhile, the electrodes
Keywords: also showed a high volumetric specific capacitance of 3.9 F cm−3 even at the scan rate of 1 V s−1 . The
Stretchable all-solid-state fibrous supercapacitors based on CNTs/MXene-TPU fiber electrodes also exhibited superior
Hybrid fibers electrochemical performance and can be stretched by more than 50% strain. The specific capacitance of
Fibrous supecapacitors the devices changed with the tensile strain and reached 3.1 F cm−3 while the stain was 50%. Based on
Strain sensors these characteristics, the fibrous supercapacitors were further applied to flexible strain sensors, which
Flexible electronics
can convert action signals to electrochemical signals rapidly. The stretchable fibrous supercapacitor can
be used not only for energy storage, but also as a strain sensor to monitor human movements, making it
very promising for the next generation smart textiles.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction certain requirements for the electrical conductivity. The common

With the rapid development of intelligent wearable electronics,
higher requirements are put forward for flexible energy storage de-
vices. As an important part of flexible energy storage devices, flexi-
ble supercapacitors have a series of advantages, such as fast charge
and discharge rate, high power density, long cycle life and so on
[1–5]. In addition, used as flexible power sources, flexible super-
capacitors can guarantee the continuous and stable energy output
under the condition of mechanical deformation, so it can be em-
bedded in the deformable objects with arbitrary shapes, which is
impossible for the traditional power source [6–8].
Fibrous supercapacitors have attracted a lot of interests since
they were first proposed in [9–10]. Compared with three and two
dimensional flexible supercapacitors, the fibrous supercapacitors
have better flexibility and can be easily integrated into fabrics [11–
14]. As the electrode material of fibrous supercapacitor, there are
∗
Corresponding author.
E-mail addresses: yaogao_li@dhu.edu.cn (Y. Li), wanghz@dhu.edu.cn (H. Wang).
fibrous electrodes mainly include metal wires [15], carbon fibers
[16], graphene fibers [17,18], carbon nanotube fibers [19,20]. Such
as, Kou et al. prepared polyelectrolyte-wrapped graphene fibers
through a continuously coaxial wet-spinning strategy [17]. The
graphene fiber supercapacitor based on the core-sheath fibers can
be woven and is suitable for wearable and safe electronics. How-
ever, the electrochemical performance of the device with a single
component of pure conductive fibers as the electrodes often cannot
meet the practical requirements, while some researchers tried to
improve it by preparing multi-component hybrid fiber electrodes
[21–22]. Conducting polymers [23,24], metal oxides [25,26], noble
metals [27,28] and other active materials [29,30] are often intro-
duced to increase electrode surface area, conductivity and voltage
window. Sun et al. prepared CNT/rGO composite fibers by adding
0.025 wt% graphene oxide (GO) in the process of CNT dry spinning
and by reduction [31]. The specific capacitance of the composite
fiber is much higher than that of pure CNT fiber.
While it is important to improve the performance of fibrous
supercapacitors, these fibrous devices are prone to breakage dur-
ing practical use and their low ductility limits their integration

https://doi.org/10.1016/j.electacta.2021.139141
0013-4686/© 2021 Elsevier Ltd. All rights reserved.
G. Wu, Z. Yang, Z. Zhang et al.
and applications in smart fabrics and apparel. Therefore, stretch-
ability is very important for fibrous supercapacitors, which needs
to be realized by elastic fiber electrodes [32–34]. Pan et al. pre-
pared an elastic fibrous electrode for electrochemical energy stor-
age based on an elastic polymer fiber wrapped with aligned CNT
sheets [32]. In order to further promote the conductivity and ca-
pacitance, a thin layer of PEDOT: PSS was then coated on the CNT
layer. However, the coating method has high requirements for the
preparation process and the device may fail to work in practical
operation due to the poor interface bonding force and mechani-
cal property mismatch between coating layers and fiber substrate.
Hence, direct doping of conductive materials and active materials
into elastic fibers by spinning technology has attracted more and
more attention [35,36]. Recently, Seyedin et al. prepared MXene/PU
composite fiber with high conductivity and high strechability by
wet spinning technology and further constructed wearable sensing
fabric based on this composite fiber [35]. This spinning approach,
which integrates the functional fillers in elastomeric polymer, has
the advantages of scalable production, high efficiency and low cost.
However, for the electrodes in fibrous supercapacitors, the intro-
duction of fillers may lead to the fibers with low strechability or
low conductivity and the difficulties of intercalation and deinterca-
lation of ions.
To solve these problems, CNTs/MXene thermoplastic
polyurethane (CNTs/MXene-TPU) hybrid fibers were fabricated
via wet spinning method, in which TPU molecular chains are main
skeleton, while CNTs and MXene constitute conductive networks.
As an electroactive material with high conductivity, MXene can not
only contribute capacitance, but also prevent restacking of CNTs.
What’s more, due to the differences in the mass transfer rates
between multi components during solidification, the CNTs/MXene-
TPU hybrid fibers formed porous structure. The all-solid-state
fibrous supercapacitors based on the CNTs/MXene-TPU hybrid fiber
electrodes show superior electrochemical performance and good
strechability. Furthermore, a flexible strain sensor was constructed
based on the fibrous supercapacitor, of which the sensitivity is
4 times higher than resistive sensor based on CNTs/MXene-TPU
hybrid fibers.
2. Experimental section
2.1. Chemicals
All raw materials and reagents were obtained from commercial
sources and have not been further purified. Single-walled carbon
nanotubes (CNTs, 95%) were purchased from Nanjing XFNANO ma-
terials technology Co., Ltd. Ti3 C2 Al MAX phase (200 mesh, 98%)
was purchased from 11 (Jilin) technology Co., Ltd. Polyvinyl alco-
hol (PVA, Mw 890 0 0–980 0 0) was purchased from Aldrich Chem-
ical Co., Inc. Thermoplastic polyurethane (TPU, Elatollan 1185A)
was purchased from BASF Co., Ltd. N,N-dimethylformamide (DMF),
lithium fluoride (LiF), hydrochloric acid (HCl, 36–38%) and sul-
furic acid (H2 SO4 , 98%) were received from Sinopharm Chemi-
cal Reagent Co., Ltd. Deionized water (H2 O), with a resistivity of
18.0 MΩ cm, was obtained from a Millipore deionized water sys-
tem.
2.2. Synthesis of CNTs/MXene-TPU spinning dispersion
The Ti3 C2 MXene was prepared by a previously reported
method of selectively etching the metal atoms in Ti3 AlC2 MAX
phase with LiF and HCl solution [34]. 1.6 g of LiF was dispersed in
20 mL of 9 M HCl solution and stirred for 5 min to obtain the clar-
ified dispersion. Then 1 g of Ti3 C2 Al MAX was added slowly and
stirred at 35 °C for 24 h. The obtained acid dispersion was cen-
trifuged (Eppendorf 5810R) for 2 min at 3500 rpm. The centrifu-
2
Electrochimica Acta 395 (2021) 139141
gation process was repeated 3 to 5 times until the precipitation
approached neutral. Afterwards, the obtained precipitate was fur-
ther centrifuged for another 30 min at 3500 rpm to remove multi-
layer MXene and MAX that haven’t been etched. After centrifuging
the resulting suspension for 1 h at 80 0 0 rpm, the product was ob-
tained by vacuum freeze-drying method.
MXene powder was dispersed into DMF and ultrasonicated
in water bath for 30 min. Then CNTs were added. The mass
ratio of MXene to CNTs was 1:4. The mixture was stirred for
30 min and then dispersed by probe for 2 h to obtain stable
dispersion of CNTs/MXene. Then a certain mass of thermoplastic
polyurethane (TPU) was added and stirred at 70 °C to get carbon
nanotubes/MXene-polyurethane spinning solution, in which CNTs/
MXene accounted for 5, 10, 15, 20% of the system.
2.3. Preparation of CNTs/MXene-TPU hybrid fibers
The CNTs/MXene-TPU spinning dispersion was inhaled into a
syringe and injected into the coagulation bath which consisted of
deionized water. When the spinning dispersion is injected into the
coagulation bath at a speed of 2–5 mL h−1 , the DMF solvent in the
spinning dispersion rapidly diffused from the CNTs, MXene sheets
and TPU molecules to deionized water in coagulation bath. Af-
ter coagulation, the CNTs/MXene-TPU hybrid fibers were prepared
continuously and dried in air. The same method was used to pre-
pare TPU fibers.
2.4. Fabrication of all-solid-state fibrous supercapacitors
PVA/H2 SO4 gel electrolyte was prepared by a previously re-
ported method [6]. Before assembling the fibrous supercapacitor,
the CNTs/MXene-TPU hybrid fiber electrodes were immersed into
1 M H2 SO4 solution overnight, so that the ions in the electrolyte
could fully infiltrate into the electrodes. Then one end of the wet
hybrid fiber was immersed in the PVA/H2 SO4 electrolyte for 5 min
and taken out and dried for 30 min. After repeating the processes
for 3 times, the hybrid fiber electrodes coated with electrolyte
were obtained. An all-solid-state fibrous supercapacitor was as-
sembled by winding two hybrid fiber electrodes coated with gel
electrolyte.
2.5. Characterization
The morphologies of MXene sheets, CNT/MXene fibers and fi-
brous supercapacitors and the dispersion were studied by a high-
resolution field-emission scanning electron microscopy (FESEM,
JSM-6700F) and a transmission electron microscope (TEM, FEI Ta-
los F200). Phase analysis of MXene were performed by RigaKu
D/Max-2550PC X-ray diffractometer (XRD, tube pressure: 40 kV,
current: 30 mA, CuK, = 1.54,056 Å). An electronic universal test-
ing machine (Model 5969, Instron) was used for studying mechan-
ical properties of the hybrid fibers, which was also used in con-
junction with a source meter unit (Keithley 2400) to measure the
change of resistance values under different strains. Electrochemi-
cal characterization, including cyclic voltammetry (CV), galvanos-
tatic charge-discharge (GCD) and electrochemical impedance spec-
troscopy (EIS), were performed by a Bio-Logic VSP-300 worksta-
tion system. The EIS measurements were performed at open cir-
cuit potential with a single sine signal over a frequency range from
100 kHz to 100 mHz at an amplitude of 10 mV. Digital photos were
taken by a digital single lens reflex (DLSR) camera (Nikon, D70 0 0).
2.6. Electrochemical calculations
The CV curves were used to calculate the specific capacitances
of single fiber electrode and device using the following equation:
G. Wu, Z. Yang, Z. Zhang et al. Electrochimica Acta 395 (2021) 139141

Fig. 1. (a) Schematic illustration of preparation of CNTs/MXene-TPU hybrid fibers and supercapacitors. (b) Digital photo and (c) SEM image of CNTs/MXene-TPU hybrid fibers.
(d) SEM image of all-solid-state fibrous supercapacitor based on CNTs/MXene-TPU hybrid fiber electrodes.

 catalysis, electromagnetism shield, absorption, photothermal con-

I
version and so on [37–42]. The Ti3 C2 MXene was prepared by se-
CM = (V )dv/2vVU (1)
lectively etching the metal atoms in Ti3 AlC2 MAX phase with LiF
and HCl solution. After centrifugation and mechanical exfoliation,
where ∫I(V) is equal to the integrated area under the CV curves; V
Ti3 C2 MXene sheets were obtained, as shown in Fig. 2a and b. The
is the electrode/device volume (V); ν is the scan rate; and U is
TEM and SEM images of Ti3 C2 MXene indicate that Ti3 C2 MXene
the test potential or voltage window.
was effectively exfoliated into monolayer or fewer layers. In the
The energy density and power density of fibrous supercapaci-
XRD spectra (Fig. 2d), the diffraction peaks are equally spaced, cor-
tors were obtained from the following equations:
 responding to the (0 02), (0 04), (0 06), (0 08), (0 010) and (0012) lat-
E=I Udt (2) tice planes of Ti3 C2 MXene [43]. The prepared MXene sheets and
CNTs were dispersed uniformly in DMF through sufficient stirring
and ultrasound, as shown in Fig. 2c. In this work, on one hand,
P = E/t (3) the highly conductive MXene sheets can improve the conductiv-
ity and electrochemical performance of the CNTs/MXene-TPU hy-
where t is the discharge time and I is the constant current density.
brid fiber electrodes; on the other hand, MXene sheets can pre-
vent the entanglement of CNTs. As shown in Figs. 2f and S1, Ti, C
3. Result and discussion
and O are distributed evenly on the inner network and surface of
the hybrid fiber, which suggests that the uniformly dispersed state
Fig. 1a is the schematic illustration of the preparation of
of the precursor in the spinning fluid was well preserved in the
CNTs/MXene-TPU hybrid fibers and their all-solid-state fibrous su-
CNTS/MXene-TPU hybrid fibers.
percapacitors. The precursor spinning solution, which consisted of
As the conductive fillers, the content of MXene and CNTs has
CNTs, MXene and TPU, were injected into deionized water through
great impact on the electrochemical and mechanical properties of
a syringe. Due to the rapid diffusion of DMF and deionized water
CNTs/MXene-TPU hybrid fibers. From Fig. 3a, the tensile strength
in the coagulation bath, the CNTs/MXene-TPU hybrid fibers were
of pure TPU fiber is 28 MPa, while the elongation at break is
gradually formed and winded with coils after drying, as shown in
over 300 %. With the increase of conductive fillers, the tensile
Fig. 1b. According to SEM images (Figs. 1c, 2c), the radius of the
strength and max elongation gradually decreased. When the con-
dried hybrid fibers is about 50 μm and the surface is wrinkled. Ob-
tent of CNTs and MXene reached up to 20 wt%, the strength and
served from the high magnification SEM image (Fig. S1a), there are
strain at break was only 12 MPa and about 100%, respectively. The
many pores inside the fiber. MXene and CNTs were used as con-
main reason is that the addition of conductive additives in the hy-
ductive fillers to form the internal conductive network of the fibers
brid fibers interfered with the tight connection between the orig-
and connected TPU molecules. In the process of fiber forming, the
inal TPU particles. Although the excess CNTs and MXene had neg-
deformation degree of CNTs/MXene network is less than that of
ative influence on fibers mechanical properties, the electrical con-
TPU molecular chains, which lead to the formation of the several
ductivity of the hybrid fibers significantly improved. What’s more,
hundred nanometers pores. This kind of porous in the fiber struc-
Fig. 3b revealed an increase in R/R0 with stretching (R0 : initial
ture and the folds on the surface favor the infiltration of electrolyte
resistance), which is indicative of strain sensing behavior. When
and improve the carrier migration rate. Then, two segments of the
the tensile strain remains constant of 50%, the resistance varia-
fiber were coated with PVA/H2 SO4 gel electrolyte and wound to
tion increases with the increase of conductive fillers. As shown
prepare the all-solid-state fibrous supercapacitor with the hybrid
in Fig. 3c, with the increase of the filling amount, the mechanical
fiber as the electrode. Its structure is shown in Fig. 1d. The gel
properties of the fiber decrease, but the sensitivity of the resistance
electrolyte acts as a membrane, preventing short circuits between
increases.
the electrodes and allowing ions to pass through.
For stretchable fibrous supercapacitors, it is necessary for the
As a promising member of the two-dimensional nanosheets
fibrous electrode to maintain the stability of mechanical properties
family, MXene have been applied to the fields of FET, energy con-
and electrical conductivity in the tensile state, so the hybrid fibers
version and storage, membrane separation, cell imaging, sensors,

3
G. Wu, Z. Yang, Z. Zhang et al. Electrochimica Acta 395 (2021) 139141

Fig. 2. (a) TEM image and (b) SEM image of MXene sheets. (c) TEM image of CNTs/MXene-TPU gel. (d) XRD spectra of MXene. (e) SEM image of CNTs/MXene-TPU hybrid
fiber. (f) Ti element SEM mapping of CNTs/MXene-TPU hybrid fiber.

Fig 3. (a) Stress-strain curves of pure TPU fibers and various CNTs/MXene-TPU hybrid fibers. (b) Strain sensing behavior of various CNTs/MXene-TPU fibers under uniaxial
tensile stretching. (c) Strain at break and R/R0 of various CNTs/MXene-TPU hybrid fibers. (d) Stress-strain curves with different strains of 10, 20, 30, 40, 50% for 5 cycles.
(e) Tensile stress and (f) R/R0 of CNTs/MXene-TPU hybrid fibers under cyclic stretching-releasing for 50% strain.

with the addition amount of 10 wt% were chose as the research
object later. To investigate mechanical stability, the hybrid fibers
were recycled for 5 times under different strain conditions of 10%,
20%, 30%, 40, and 50% respectively. Except for the first stretch, the
remaining stretch cycle curves were basically identical. And at a
tensile strain of 50% for 50 cycles, the maximum tensile strength
barely dropped, which show that the hybrid fiber has good ten-
sile properties. Moreover, observed from Fig. 3f, when the strain is
50%, the resistance change is almost less than 0.1, which indicates
the electrical conductivity of the CNTs/MXene-TPU hybrid fibers is
relatively stable when stretched.
The electrochemical properties of the CNTs/MXene-TPU hybrid
fibers were further investigated using a three-electrode system, in
which the hybrid fiber was used as the working electrode, the
counter electrode was platinum wire and Ag/AgCl was used as the
reference electrode. The cyclic voltammeter curves in Fig. 4a show
that the CNTs/MXene-TPU hybrid fibers can work stably under the
potential window of 0-0.6 V at the scan rate of 50 mV/s. When
the potential window extended to 0-0.7 V, there is an obvious po-
larization phenomenon in the CV curve. At the same time, there
is an obvious redox peak at 0.2–0.4 V, which is mainly due to
the redox reactions between MXene and electrolyte [44]. However,
the redox peaks in the CV curves disappeared gradually when the
scan rate gradually increased from 10 mV s−1 to 1 V s−1 . When
the scan rate increased, redox processes controlled by diffusion of
charge compensating ions tend to disappear since the current of
this process does not increase in the same proportion with the
scan rate [45]. The main stored charge is attributed to the sur-
face capacitive charge storage. Observed from Fig. 4b, when the
scan rate even reached up to 1 V s−1 , the CV curve still remained
quasi rectangular shape. The rapid response between potential and
current mainly resulted from the porous structure of CNTs/MXene-
TPU hybrid fibers. When the electrode was charged and discharged,
the ions can be quickly embedded and released. The galvanostatic
charge-discharge curves can also illustrate this point. When the hy-
brid fibers were charged and discharged rapidly at high current
density, the curve can still maintain a nearly symmetrical triangu-
lar shape, showing rapid charge-discharge characteristics. Accord-
ing to Fig. 4d, it can be seen that the volumetric capacitance of
the hybrid fiber electrode is 8.8 F cm−3 at the scan rate of 50 mV

4
G. Wu, Z. Yang, Z. Zhang et al. Electrochimica Acta 395 (2021) 139141

Fig. 4. (a) Cyclic voltammetry (CV) curves of CNTs/MXene-TPU hybrid fibers for various potential windows at a scan rate of 50 mV s−1 . (b) CVs of the CNTs/MXene-TPU
hybrid fibers at different scan rates. (c) GCD curves of CNTs/MXene-TPU hybrid fibers at different current densities. (d) Volume specific capacitances of CNTs/MXene-TPU
hybrid fiber electrodes at different scan rates.

Fig. 5. (a) CV curves of fibrous supecapacitors based on CNTs/MXene-TPU hybrid fibers for various voltage windows at a scan rate of 50 mV s−1 . (b) CVs of fibrous supeca-
pacitors based on CNTs/MXene-TPU hybrid fibers at different scan rates. (c) GCD curves of fibrous supecapacitors based on CNTs/MXene-TPU hybrid fibers at different current
densities. (d) Electrochemical impedance spectroscopy data. (e) Capacitance change versus tensile strain. Inset: digital images of stretched fibrous supercapacitors.

s−1 , while it is still up to 3.9 F cm−3 at the scan rate of 1 V s−1 .
The hybrid fiber electrode shows excellent rate capability.
Fibrous all-solid-state supercapacitors were constructed using
CNTs/MXene-TPU hybrid fibers as electrodes and coated with
PVA/H2 SO4 gel electrolyte. The electrochemical performance of su-
percapacitors was firstly characterized by cyclic voltammetry and
galvanostatic charge-discharge tests. As shown in Fig. 5a, the sta-
ble operating voltage window of the fibrous supercapacitors is 0-
0.8 V, while the CV curve began to deform when the voltage win-
dow extended to 0-1 V. Fig. 5b shows that CV curves always main-
tain quasi-rectangular shapes as the scan rate increased. Even at
the high scan rate of 5 V/s, there is still no obvious deformation.
The superior rate ability is attributed to good electrical conductiv-
ity of CNTs/MXene-TPU hybrid fiber electrodes and porous struc-
ture, which can realize rapid adsorption and desorption of ions.
The volumetric specific capacitance can reach up to 7.3 F cm−3
at the scan rate of 10 mV s−1 , which is higher than some other
stretchable fibrous supercapacitors [33,46] and even comparable
to graphene-based devices [47]. Moreover, galvanostatic charge-
discharge curves show good triangular symmetry at different cur-
rent densities, which not only indicating superior coulomb effi-
ciency, but also proving the excellent rate ability of the fibrous su-
percapacitors. Electrochemical impedance spectroscopy (EIS) tests
were also carried out to characterize the behavior of electrolyte ion
transport and interfacial charge storage. The equivalent series resis-
tance (ESR) was estimated to 107  from the high-frequency range

5
G. Wu, Z. Yang, Z. Zhang et al.
Fig. 6. Fractional capacitance changes corresponding to actions.
of the Nyquist plot, which shows a sloping line at low-frequency
region. Meanwhile, from the EIS curve, the low charge transfer re-
sistance indicates the rapid movements of ions in the electrolyte.
What’s more, the energy density of the fibrous supercapacitors can
reach 1.16 mWh cm−3 while the power density is 0.16 W cm−3 ,
which is comparable to the commercial supercapacitors (Fig. S2)
[48].
Owing to the stretchable CNTs/MXene-TPU hybrid fiber elec-
trodes, the all-solid-state fibrous supercapacitors can also be
stretched more than 50% strain, as shown in Fig. 5d. At the scan
rate of 1 V s−1 , the initial volumetric capacitance of the device is
1.58 F cm−3 . With the elongation of the device, the specific capac-
itance shows a trend of obvious increase. Although the resistance
of the hybrid fiber will increase in the tensile state, the range of
the changed resistance is less than 0.1 according to the above re-
sults (Fig. 3d). Therefore, when the device was stretched, the dis-
tance between the two fiber electrodes was smaller, which lead to
the quick adsorption and desorption of more ions and the increase
of the specific capacitance. According to Fig 5d and Fig. S3, when
the tensile strain was 50%, the specific capacitance of the device
can reach up to 3.1 F cm−3 . Compared to the CNTs/MXene-TPU hy-
brid fiber electrodes, the range of the capacitance change increased
nearly 4 times at 50% strain.
Hence, the all-solid-state fibrous supercapacitors were further
used as flexible strain sensor to monitor human movement, as
shown in Fig. 6. The strain sensors were placed on knuckles, wrists
and knees, which can translate action signals to electrical signals
by the change of capacitance. According to the curve in Figs. 6 and
S4, when the fingers bent at an angle of 30 °, the value of C/C
is about 27% and became to 45% when the angle extended to 90 °.
Similarly, C/C was 37% and 46%, respectively, when the angle is
20 °and 45 ° for wrists; For knees, the values are 49 and 55%. The
strain sensor in this work has high sensitivity, fast response, good
flexibility and can be applied to the fields of wearable fabric, sports
health monitoring, human-computer interaction and so on.
4. Conclusion
A kind of stretchable conductive CNTs/MXene-TPU hybrid fibers
were prepared through a common, low cost and high-throughput
wet-spinning method, in which CNTs and MXene were used as
conductive fillers and TPU was used as polymer framework. When
the tensile strain is 50%, the mechanical and electrical properties
of the hybrid fibers remain relatively stable. At the same time, due
to the porous structure in the fiber, CNTs/MXene-TPU hybrid fibers
show superior electrochemical performance and the volumetric
specific capacitance can reach up to 8.8 F cm−3 . Therefore, the all-
solid-state fibrous supercapacitor based on the CNTs/MXene-TPU
hybrid fibers can be stretched and shows an energy density of
1.16 mWh cm−3 . Furthermore, based on the variation of the capac-
itance of the device at different strains, the fibrous supercapacitors
6
Electrochimica Acta 395 (2021) 139141
can also be applied to strain sensors with high sensitivity, fast re-
sponse, and good flexibility.
Declaration of Competing Interest
There are no interest conflicts to declare.
Credit authorship contribution statement
Guiqing Wu: Conceptualization, Methodology, Data curation,
Formal analysis, Writing – original draft. Zhipeng Yang: Data cu-
ration, Formal analysis. Zhenyi Zhang: Data curation. Bingyan Ji:
Formal analysis. Chengyi Hou: Conceptualization, Formal analysis.
Yaogang Li: Supervision, Writing – review & editing. Wei Jia: Data
curation. Qinghong Zhang: Formal analysis. Hongzhi Wang: Con-
ceptualization, Supervision, Project administration, Writing – re-
view & editing.
Acknowledgments
We gratefully acknowledge the financial support of the Natural
Science Foundation of China (Grant No. 51873033), Science and
Technology Commission of Shanghai Municipality (19JC1410600),
and the Fundamental Research Funds for the Central Universities
(2232020A-01). The project was also funded by State Key labora-
tory for Space Power-sources Technology (No. YF07050117F0768).
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.electacta.2021.139141.
References
[1] V.V. Chandu, M. Gopi, R. Vinodh, S. Sambasivam, I.M. Obaidat, H.J. Kim, Recent
progress of advanced energy storage materials for flexible and wearable super-
capacitor: From design and development to applications, J. Energy Storage 27
(2020) 101035.
[2] W. Raza, F. Ali, N Raza, Y. Luo, K.H. Kim, J. Yang, S. Kumar, A. Mehmood,
E.E. Kwon, Recent advancements in supercapacitor technology, Nano Energy
52 (2018) 441–473.
[3] W. Wang, A. Yu, J. Zhai, Z.L. Wang, Recent progress of functional fiber and
textile triboelectric nanogenerators: towards electricity power generation and
intelligent sensing, Adv. Fiber Mater. (2021), doi:10.1007/s42765- 021- 0 0 077-9.
[4] R. Kunwar, M. Harilal, S.G. Krishnan, B. Pal, I.I. Misnon, C.R. Mariappan,
F.I. Ezema, H.I. Elim, C. Yang, R. Jose, Pseudocapacitive charge storage in thin
nanobelts, Adv. Fiber Mater. 1 (2019) 205–213.
[5] S. Najib, E. Erdem, Current progress achieved in novel materials for superca-
pacitor electrodes: mini review, Nanoscale Adv. 1 (2019) 2817–2827.
[6] Y. Shao, M.F. El-Kady, L. Wang, Q. Zhang, Y. Li, H. Wang, M.F. Mousavi,
R.B. Kaner, Graphene-based materials for flexible supercapacitors, Chem. Soc.
Rev. 44 (2015) 3639–3665.
[7] Q. Shi, J. Sun, C. Hou, Y. Li, Q. Zhang, H. Wang, Advanced functional fiber and
smart textile, Adv. Fiber Mater. 1 (2019) 3–31.
[8] Y. Han, Y. Ge, Y. Chao, C. Wang, G.G. Wallace, Recent progress in 2D materials
for flexible supercapacitors, J. Energy Chem. 27 (2018) 57–72.
[9] J. Bae, Y.J. Park, M. Lee, S.N. Cha, Y.J. Choi, C.S. Lee, J.M. Kim, Z.L. Wang,
Single-fiber-based hybridization of energy converters and storage units using
graphene as electrodes, Adv. Mater. 23 (2011) 3446–3449.
[10] J. Bae, M.K. Song, Y.J. Park, J.M. Kim, M. Liu, Z.L. Wang, Fiber supercapacitors
made of nanowire-fiber hybrid structures for wearable/flexible energy storage,
Angew. Chem. Int. Ed. 50 (2011) 1683–1687.
[11] Y Guo, X Hong, Y Wang, Q. Li, J. Meng, R. Dai, X. Liu, L. He, L. Mai, Multicom-
ponent hierarchical Cu-doped NiCo-LDH/CuO double arrays for ultralong-life
hybrid fiber supercapacitor, Adv. Funct. Mater. 29 (2019) 1809004.
[12] L. Gao, J. Song, J.U. Surjadi, K. Cao, Y. Han, D. Sun, X. Tao, Y. Lu,
Graphene-bridged multifunctional flexible fiber supercapacitor with high en-
ergy density, ACS Appl. Mater. Interfaces 10 (2018) 28597–28607.
[13] Q. Liu, L. Zang, C. Yang, C. Wei, J. Qiu, C. Liu, X. Xu, A flexible and knittable
fiber supercapacitor for wearable energy storage with high energy density and
mechanical robustness, J. Electrochem. Soc. 165 (2018) A1515.
[14] J. Yu, W. Lu, J.P. Smith, K.S. Booksh, L. Meng, Y. Huang, Q. Li, J. Byun, Y. Oh,
Y. Yan, T. Chou, A high performance stretchable asymmetric fiber-shaped su-
percapacitor with a core-sheath helical structure, Adv. Energy Mater. 7 (2017)
1600976.
G. Wu, Z. Yang, Z. Zhang et al.
[15] T. Chen, L. Qiu, Z. Yang, Z. Cai, J. Ren, H. Li, X. Sun, Peng H, An integrated
“energy wire” for both photoelectric conversion and energy storage, Angew.
Chem Int. Ed. 51 (2012) 11977–11980.
[16] J. Noh, C. Yoon, Y.K. Kim, J. Jiang, High performance asymmetric supercapaci-
tor twisted from carbon fiber/MnO2 and carbon fiber/MoO3 , Carbon 116 (2017)
470–478.
[17] L. Kou, T. Huang, B. Zheng, Y. Han, X. Zhao, K. Gopalsamy, H. Sun, C. Gao, Coax-
ial wet-spun yarn supercapacitors for high-energy density and safe wearable
electronics, Nat. Commun. 5 (2014) 1–10.
[18] Q. Yang, Z. Xu, C. Gao, Graphene fiber based supercapacitors: Strategies and
perspective toward high performances, J. Energy Chem. 27 (2018) 6–11.
[19] Z. Lu, R. Raad, F. Safaei, J. Xi, Z. Liu, J. Foroughi, Carbon nanotube based fiber
supercapacitor as wearable energy storage, Front. Mater. 6 (2019) 138.
[20] Y. Zhou, C. Wan, W. Lu, L. Dai, Recent advances in fiber-shaped supercapacitors
and lithium-ion batteries, Adv. Mater. 32 (2020) 1902779.
[21] C. Wang, S. Zhai, Z. Yuan, J. Chen, X. Zhang, Q. Huang, Y. Wang, X. Liao,
L. Wei, Y. Chen, A core-sheath holey graphene/graphite composite fiber in-
tercalated with MoS2 nanosheets for high-performance fiber supercapacitors,
Electrochim. Acta 305 (2019) 493–501.
[22] X. Lu, C. Shen, Z. Zhang, E. Barrios, L. Zhai, Core–shell composite fibers for
high-performance flexible supercapacitor electrodes, ACS Appl. Mater. Inter-
faces 10 (2018) 4041–4049.
[23] Q. Meng, K. Cai, Y. Chen, L. Chen, Research progress on conducting polymer
based supercapacitor electrode materials, Nano Energy 36 (2017) 268–285.
[24] D.D. Potphode, S.P. Mishra, P. Sivaraman, M. Patri, Asymmetric supercapacitor
devices based on dendritic conducting polymer and activated carbon, Elec-
trochim. Acta 230 (2017) 29–38.
[25] W. Ma, S Chen, S Yang, W. Chen, M. Zhu, Flexible all-solid-state asymmetric su-
percapacitor based on transition metal oxide nanorods/reduced graphene ox-
ide hybrid fibers with high energy density, Carbon 113 (2017) 151–158.
[26] X. Zhang, J. Luo, P. Tang, X. Ye, X. Peng, H. Tang, S. Sun, J. Fransaer, A universal
strategy for metal oxide anchored and binder-free carbon matrix electrode: a
supercapacitor case with superior rate performance and high mass loading,
Nano Energy 31 (2017) 311–321.
[27] Y. Yan, T. Wang, X. Li, H. Pang, H. Xue, Noble metal-based materials in high-
-performance supercapacitors, Inorg. Chem. Front. 4 (2017) 33–51.
[28] H. Tong, Q. Meng, J. Liu, T. Li, D. Gong, J. Xiao, L. Shen, T. Zhang, D. Bing,
X. Zhang, Cross-linked NiCo2 O4 nanosheets with low crystallinity and rich
oxygen vacancies for asymmetric supercapacitors, J. Alloy. Compd. 822 (2020)
153689.
[29] Q. Jiang, N. Kurra, M. Alhabeb, Y. Gogotsi, H.N. Alshareef, All pseudocapac-
itive MXene-RuO2 asymmetric supercapacitors, Adv. Energy Mater. 8 (2018)
1703043.
[30] Y. Zhou, K. Maleski, B. Anasori, J.O. Thostenson, Y. Pang, Y. Feng, K. Zeng,
C.B. Parker, S. Zauscher, Y. Gogotsi, J.T. Glass, C. Cao, Ti3 C2 Tx MXene-reduced
graphene oxide composite electrodes for stretchable supercapacitors, ACS Nano
14 (2020) 3576–3586.
[31] H. Sun, X. You, J. Deng, X. Chen, Z. Yang, J. Ren, H. Peng, Novel graphene/carbon
nanotube composite fibers for efficient wire-shaped miniature energy devices,
Adv. Mater. 26 (2014) 2868–2873.
[32] Z. Pan, J. Yang, L. Li, X. Gao, L. Kang, Y. Zhang, Q. Zhang, Z. Kou, T. Zhang,
L. Wei, Y. Yao, J. Wang, All-in-one stretchable coaxial-fiber strain sensor inte-
grated with high-performing supercapacitor, Energy Storage Mater. 25 (2020)
124–130.
Electrochimica Acta 395 (2021) 139141
[33] C. Choi, J.M. Lee, S.H. Kim, S.J. Kim, Twistable and stretchable sandwich struc-
tured fiber for wearable sensors and supercapacitors, Nano Lett. 16 (2016)
7677–7684.
[34] T. An, W. Cheng, Recent progress in stretchable supercapacitors, J. Mater. Chem.
A 6 (2018) 15478–15494.
[35] S. Seyedin, S. Uzun, A. Levitt, B. Anasori, G. Dion, Y. Gogotsi, J.M. Razal,
MXene composite and coaxial fibers with high stretchability and conduc-
tivity for wearable strain sensing textiles, Adv. Funct. Mater. 30 (2020)
1910504.
[36] G. Wu, X. Yang, J. Li, S. Nan, C. Hou, Y. Li, H. Wang, Highly stretchable and con-
ductive hybrid fibers for high-performance fibrous electrodes and all-solid-s-
tate supercapacitors, Chin. J. Polym. Sci. 38 (2020) 531–539.
[37] J. Zhang, S. Uzun, S. Seyedin, P.A. Lynch, B. Akuzum, Z. Wang, S. Qin, M. Al-
habeb, C.E. Shuck, W.W. Lei, E.C. Kumbur, W. Yang, X. Wang, G. Dion, J.M. Razal,
Y. Gogotsi, Additive-free MXene liquid crystals and fibers, ACS Cent. Sci. 6
(2020) 254–265.
[38] L. Yin, G. Xu, P. Nie, H. Dou, X. Zhang, MXene debris modified eggshell mem-
brane as separator for high-performance lithium-sulfur batteries, Chem. Eng. J.
352 (2018) 695–703.
[39] X. Li, X. Yin, C. Song, M. Han, H. Xu, W. Duan, L. Cheng, L. Zhang, Self-assem-
bly core–shell graphene-bridged hollow MXenes spheres 3D foam with ul-
trahigh specific EM absorption performance, Adv. Funct. Mater. 28 (2018)
1803938.
[40] T. Yun, H. Kim, A. Iqbal, Y.S. Cho, G.S. Lee, M. Kim, S.J. Kim, D. Kim, Y. Gogotsi,
S.O. Kim, C.M. Koo, Electromagnetic shielding of monolayer MXene assemblies,
Adv. Mater. 32 (2020) 1906769.
[41] X. Liang, X. Ren, Q. Yang, L. Gao, M. Gao, Y. Yang, H. Zhu, G. Li, T. Ma,
A. Liu, A two-dimensional MXene-supported metal–organic framework for
highly selective ambient electrocatalytic nitrogen reduction, Nanoscale 13
(2021) 2843–2848.
[42] A. Levitt, J. Zhang, G. Dion, Y. Gogotsi, J.M. Razal, MXene-based fibers, yarns,
and fabrics for wearable energy storage devices, Adv. Funct. Mater. 30 (2020)
20 0 0739.
[43] W. Eom, H. Shin, R.B. Ambade, S.H. Lee, K.H. Lee, D.J. Kang, T.H. Han, Large-s-
cale wet-spinning of highly electroconductive MXene fibers, Nat. Commun. 11
(2020) 1–7.
[44] J. Li, H. Wang, X. Xiao, Intercalation in two-dimensional transition metal car-
bides and nitrides (MXenes) toward electrochemical capacitor and beyond, En-
ergy Environ. Mater. 3 (2020) 306–322.
[45] L. Yu, G.Z. Chen, Supercapatteries as high-performance electrochemical energy
storage devices, Electrochem. Energy R 3 (2020) 271–285.
[46] Z. Pan, J. Yang, L. Li, X. Gao, L. Kang, Y. Zhang, Q. Zhang, Z. Kou, T. Zhang,
L. Wei, Y. Yao, J. Wang, All-in-one stretchable coaxial-fiber strain sensor inte-
grated with high-performing supercapacitor, Energy Storage Mater. 25 (2020)
124–130.
[47] G. Wu, X Yang, C Hou, Y. Li, Q. Zhang, H. Wang, High volumetric en-
ergy density asymmetric fibrous supercapacitors with coaxial structure
based on graphene/MnO2 hybrid fibers, ChemElectroChem 7 (2020) 4641–
4648.
[48] M.F. El-Kady, V. Strong, S. Dubin, R.B. Kaner, Laser scribing of high-perfor-
mance and flexible graphene-based electrochemical capacitors, Science 335
(2012) 1326–1330.