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Nano Research

DOI 10.1007/s12274-014-0649-y

Highly stretchable, electrically conductive textiles


fabricated from silver nanowires and cupro fabrics
using a simple dipping–drying method
Hui-Wang Cui1 (), Katsuaki Suganuma1, and Hiroshi Uchida2

1
Institute of Scientific and Industrial Research, Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan
2
Institute for Polymers and Chemicals Business Development Center, Showa Denko K. K., 5-1 Yawata Kaigan Dori, Ichihara, Chiba
290-0067, Japan

Received: 7 October 2014 ABSTRACT


Revised: 11 November 2014 In this study, we combined silver nanowires with cupro fabrics using a dipping–
Accepted: 19 November 2014 drying method to prepare electrically conductive fabrics. The silver nanowires
were first adhered to and then absorbed by microfibers to form electrically
© Tsinghua University Press conductive fibers. They also filled the gaps and spaces between the microfibers,
and Springer-Verlag Berlin and were stacked or piled together to form networks with high electrical
Heidelberg 2014 conductivity. The electrically conductive fabric had low resistance and good
stretchability, e.g., 0.0047–0.0091 Ω in the strain range of 0–190%. They also
KEYWORDS exhibited stable electrical conductivity, as well as excellent flexibility, which
fabrics/textiles, remained even when the fabric was stretched, shrunk, or bent. The results show
metals, that the electrically conductive fabric can be used as a smart textile, especially in
smart materials, fields associated with weaving, clothing, food products, lifestyle products,
electrical properties medicine, biology, electronics, aviation, and military equipment and accessories.

1 Introduction of functional smart textiles, e.g., thermostatic textiles,


physiological-state telemetry textiles, solar textiles,
Smart textiles, a class of fabric integrated by shape-memory textiles, waterproof and moisture-
multidisciplinary knowledge on textiles, electronics, permeable textiles, color-changing textiles, and E-smart
chemistry, physics, mechanics, biology, medicine, etc., textiles, have been developed. Among them, E-smart
are based on the concept of biomimicry to simulate textiles are a class of novel textiles based on electronics
life systems. They serve dual functions of effectively and the integration of high-tech solutions such as
perceiving and responding to various changes and sensing, telecommunications, and artificial intelligence
stimuli from the environment, such as mechanical into fabrics. While E-smart textile applications have
forces, heat, light, temperature, electromagnetic forces, made limited commercial impact so far, with relatively
chemicals, and biological odors. Until now, a variety small volumes of commercial products launched

Address correspondence to cuihuiwang@hotmail.com


2 Nano Res.

primarily in the high-performance apparel sector, the 2 Experimental


overall market is predicted to grow significantly. As
cutting-edge technologies such as microelectronics, 2.1 Samples
nanotechnology, and biotechnology become deeply
First, AgNWs were synthesized on a large scale
integrated, E-smart textiles are one of the most dynamic
according to previously reported procedures of the
and fast growing sectors with many opportunities for
polyol process [26, 27]. They were 60–100 μm in length,
innovation [1–2].
and their diameter was ~60 nm. The AgNWs were
The preparation of electrically conductive fabrics
dispersed in ethanol to form a 0.5% suspension
(also called electrically conductive fibers) is the key to
(Fig. 1(a)). The textile selected for the study, measuring
producing E-smart textiles. The methods of coating [3],
100 mm × 100 mm × 250 μm, was a cellulosic product,
deposition [4], spinning [5], printing [6], synthesis [7],
a cupro fabric named BEMCOTTM M-3 (Asahi Kasei
dipping [8], and solution growing [9] have been
Fibers Corporation, Tokyo, Japan). The fabrication
widely used to fabricate electrically conductive fabrics
process of the electrically conductive fabric is illustrated
from conductive polymers such as polypyrrole [10],
in Fig. 1(a). Samples of the pure fabric were dipped
polyaniline [11], a mixture of poly(3,4-ethylenedioxy- into the AgNW suspension for about 2 h and then
thiophene) and poly(4-styrenesulfonate) [12]), metal
particles (e.g., Ag [13], Cu [14], Ni [15], Al [16], Zn [17]),
and carbon fillers (e.g., graphite nanoplatelets [18] and
carbon nanotubes [19]). In particular, Ag particles are
often used for Ag-based smart textiles. For example,
Xue et al. produced Ag nanoparticles on cotton fibers
by reducing the [Ag(NH3)2]+ complex with glucose,
and the Ag nanoparticles formed a dense coating
around the fibers, rendering the intrinsically insulating
cotton fabric conductive [20]. Paul et al. fabricated
electrodes from electrically conductive fabrics. They
first printed a polyurethane paste on a woven textile
to create a smooth interface with high surface energy
and then printed a Ag paste on top of this interface
layer to provide a conductive track, which was then
encapsulated with another layer of polyurethane paste
to protect the Ag-track from abrasion and creasing
[21, 22]. Apparently, the use of silver nanowires
(AgNWs), which have a large aspect ratio and higher
flexibility than Ag particles [23–25], to fabricate smart Figure 1 (a) Fabrication process of electrically conductive textiles;
textiles has seldom been reported. Therefore, in this the inset shows scanning electron microscope (SEM) images of
the grid-like structures of the pure fabric and the electrically
study, we combined AgNWs with cupro fabrics using
conductive fabric. (b) Sample (50 mm × 10 mm × 250 μm) of the
a dipping–drying method to prepare electrically con- electrically conductive fabric. (c) SEM images of the electrically
ductive fabrics (Fig. 1(a)). The AgNWs were adhered conductive fibers and the electrically conductive networks formed
to and absorbed on microfibers to form electrically between them; the inset shows high-magnification images of the
conductive fibers. They were also filled into the gaps electrically conductive fibers and electrically conductive networks.
(d) Stretch, break, and stress areas, as well as the directions of
and spaces between microfibers and stacked or piled
force on the electrically conductive fabric at 210% strain; the SEM
together to form the electrically conductive networks. images in the inset show the disorderly bundle structures, the
As a result, high electrical conductivity was imparted electrically conductive fibers, and the torn electrically conductive
to the electrically conductive fabrics. networks.

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Nano Res. 3

dried at room temperature to completely volatilize the at diffraction angles (2θ) of 37.98°, 43.94°, 64.07°,
ethanol, to obtain samples of the electrically conductive 77.61°, and 81.58° in the WAXRD patterns, which
fabric. correspond to the characteristic diffraction peaks of
(111), (200), (220), (311), and (222), respectively, for
2.2 Characterization AgNWs (Fig. 2(a)). The char yield of the pure fabric
Wide-angle X-ray diffraction (WAXRD) data were was 7% at temperatures up to 900 °C, while that of the
collected on an area detector with a curved imaging electrically conductive fabric was 40%, which shows
plate (RINT RAPID, Rigaku Corporation, Tokyo, Japan) that the electrically conductive fabric samples contained
using Mo Kα radiation (λ = 1.54 Å) at 40 kV and 30 mA ~ 30% AgNWs (Fig. 2(b)). The electrically conductive
for 10 min. The thermal degradation of the samples fabric samples had more apparent grid-like structures
was measured using a thermogravimetric analyzer than the pure fabric samples. It appeared that the
(TGA; 2000SE/H/24/1, NETZSCH, Selb, Germany) that AgNWs played a role in densely bonding the hundreds
was operated under a pure N2 atmosphere. The sample of microfibers to form the solid grid frameworks
(~10 mg) was placed in a Pt cell and heated at a rate (Fig. 1(a) and the SEM image in the inset). AgNWs
of 10 °C·min–1 from 30 to 900 °C under N2 flowing at were absorbed and adhered on the microfibers by
a rate of 60 mL·min–1. Scanning electron microscopic physical effects to form the electrically conductive
(SEM) images of the samples were recorded using a fibers (Fig. 1(c) and the SEM image in the inset). In
field-emission scanning electron microscope (FE-SEM; addition, the AgNWs also filled the gaps and spaces
SU8020, Hitachi, Tokyo, Japan) operating at an between these microfibers and were stacked or piled
accelerating voltage of 5 kV and an accelerating current together to form the electrically conductive networks
of 2 μA. Figure S1 in the Electronic Supplementary (Fig. 1(c) and the inset SEM image). These electrically
Material (ESM) shows the experimental setup to mea- conductive fibers and networks accounted for the
sure the electrical resistance during tensile stretching. high electrical conductivity of the resulting electrically
The samples (50 mm × 10 mm × 250 μm) (Figs. 1(b) conductive fabric.
and S1 in the ESM) were uniaxially stretched to 210% The electrical resistance was closely related to the
strain at a rate of 1 mm·min–1 using an compact table- electrically conductive channels: More electrically
top universal tester (EZ test, Shimadzu, Kyoto, Japan). conductive channels mean lower electrical resistance
The distance between the two chucks on the tester [28, 29]. In the electrically conductive fabric, the
was 30 mm at the beginning. The electrical resistance electrically conductive channels consisted of electrically
of the samples during tensile stretching was measured conductive fibers and networks. The AgNW-covered
by the four-point probe method, using a multimeter
(34410A, Agilent Technologies, Santa Clara, California,
USA) and a Kelvin probe (11059A, Agilent Technologies).

3 Results and discussion


As shown in Fig. 1(a), the white pure textile, before it
was dipped into the AgNWs suspension, had loose
grid-like structures, and the grid frameworks consisted
of hundreds of microfibers, which were physically
knitted together (SEM image in the inset of Fig. 1(a)).
After the samples were dipped into the AgNWs
suspension, they became electrically conductive and
the color turned silver gray. Compared to the pure Figure 2 (a) WAXRD patterns and (b) TGA traces of the pure
fabric, the electrically conductive fabric exhibited peaks fabric and electrically conductive fabric.

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4 Nano Res.

electrically conductive fibers and stacked-AgNW and only the loaded force caused the rupture of the
electrically conductive networks increased the number grid-like structures in these areas.
of electrically conductive channels to generate low Figure 4(b) shows that the electrically conductive
electrical resistance of the electrically conductive textile. fabric samples did not have any ruptures at strains
Figure 3 shows the electrical resistance of the of 0%, 50%, 100%, and 150%, and the clear, grid-like
electrically conductive fabric as a function of the structures remained. The grid size also became larger
stretching strain. At 0% strain, i.e., when the fabric was with increasing strain. While the grid-like structures
unstretched, the electrical resistance was 0.0047 Ω; it appeared fuzzy and showed slight ruptures at strains
increased very slowly with increasing strain, reaching of 200% and 210%, only a few grids were found, as
0.0067 Ω at 180% strain and 0.0091 Ω at 190% strain. confirmed by further SEM analysis. The grids were
The change in electrical resistance was so small that it the largest at 100% strain (Fig. 5(c)), followed by
can almost be considered a constant value in the strain those at 50% strain (Fig. 5(b)) and 0% strain (Fig. 5(a)),
range of 0–190%. The electrical resistance increased caused by the stretching; the grid frameworks were
to 0.0274 Ω at 200% strain and then sharply to the still dense and solid at strains of 0 and 50% (Figs. 5(a)
highest value of 112.1649 Ω at 210% strain in all the and 5(b)), but loose at 100% strain (Fig. 5(c)). Only
tests of this study. several grids were observed at 150% strain (Fig. 5(d)),
The electrically conductive fabric showed low and no grids were observed at strains of 200% and
electrical resistance, which was closely related to 210% (Figs. 5(e) and 5(f)), when their frameworks were
changes in the grid-like structures during stretching. completely destroyed and the fibers were gathered
After the uniaxial force was applied, the electrically into irregular bundles.
In the stress areas, because the sample was sand-
conductive fabric samples were stretched gradually
wiched between the two chucks of the universal tester
at a rate of 1 mm·min–1. They displayed two different
(Fig. S1 in the ESM), the chucks had significant effect
stretching states, called stretch areas and stress areas,
on the stretching state and produced stress to accelerate
in the strain range of 0–190%, and three different
the rupture of the samples. Figure 4(c) shows that the
stretching states, called stretch areas, break areas, and
electrically conductive fabric samples did not display
stress areas, in the strain range of 200–210% (Figs. 1(d)
any ruptures at strains of 0% and 50% and the grids
and 4). As each fabric sample was stretched, the loaded
grew bigger. They displayed slight ruptures at 100%
uniaxial force acted on the microfibers; the force was
strain, and significant ruptures occurred at strains
parallel in the stretch areas, as shown in Fig. 1(d),
of 150%, 200%, and 210%; their grid-like structures
were destroyed completely and turned into bundles
of microfibers. When observed under the SEM, the
electrically conductive fabric showed small grids at
0% strain, while the large grids appearing at 50% strain
had looser grid frameworks than those at 0% strain;
the grid-like structures remained clearly visible at these
strain levels (Figs. 5(g) and 5(h)). Only several grids
were observed in the electrically conductive fabric
samples at 100% strain, and none was found at strains
of 150%, 200%, and 210%; the grid frameworks were
completely destroyed and changed into bundles of
disordered microfibers at these strain levels (Figs. 5(i),
5(j), 5(k), and 5(l)). Obviously, the changes in the grid-
Figure 3 Electrical resistance of the electrically conductive
fabric vs strain; the insets show digital images of LED integrated like structures in the stretch areas were somewhat
circuits with electrically conductive fabrics at (a) 0% strain, (b) different from those in stress areas, but all grids
150% strain, and (c), (d) as electronic skins. became larger with increasing strain and all solid and

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Nano Res. 5

Figure 4 Microstructures of (a) stretched samples, (b) stretch areas, and (c) stress areas of electrically conductive fabric samples at
strains of 0%, 50%, 100%, 150%, 200%, and 210%. (d) Microstructures of break areas of electrically conductive fabric samples at
strains of 200% and 210%.

dense grid frameworks changed into loose networks conduction of electricity. The adhering states or
until they eventually ruptured and were completely arrangements of AgNWs on the microfibers can be
destroyed, resulting in disordered bundles of micro- seen in the high-magnification images in Figs. 6(a3)–
fibers (Figs. 4 and 5). 6(f3), which show them stacked or piled densely
As mentioned above and shown in Figs. 4 and 5, together. It can also be seen that the stretching did
even though the stretch and stress areas of the not affect the irregular and disordered arrangements
electrically conductive fabric changed with increasing of the AgNW stacks at strains between 0% and 210%.
strain and their frameworks ruptured eventually, the As shown in Fig. 1(c), the electrically conductive
AgNWs continued to adhere to the microfibers so channels consisted of the electrically conductive fibers
that they remained electrically conductive. Figure 6 with adhering AgNWs and the electrically conductive
shows the microstructures of these electrically networks of AgNWs in the gaps and spaces between
conductive fibers. The stretching did not affect the microfibers.
rod-like appearance of the electrically conductive During or after the stretching, the microstructures
fibers at strains of 0% (Figs. 6(a1) and 6(a2)), 50% of the electrically conductive fibers were not changed,
(Figs. 6(b1) and 6(b2)), 100% (Figs. 6(c1) and 6(c2)), and the resulting electrically conductive channels
150% (Figs. 6(d1) and 6(d2)), 200% (Figs. 6(e1) and were not destroyed, as shown in Fig. 6. However, the
6(e2)), and 210% (Figs. 6(f1) and 6(f2)). The AgNWs electrically conductive networks were destroyed to a
covered and packed the microfibers densely, forming certain extent by the stretching. Figure 7(a) shows
the electrically conductive channels for effective that the AgNWs were not stretched at 0% strain and

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6 Nano Res.

Figure 5 SEM images of stretch areas of electrically conductive fabric samples at strains of (a) 0%, (b) 50%, (c) 100%, (d) 150%, (e)
200%, and (f) 210% SEM images of stress areas of electrically conductive fabric samples at strains of (g) 0%, (h) 50%, (i) 100%, (j)
150%, (k) 200%, and (l) 210%.

large, dense, and solid electrically conductive networks contacts between electrically conductive networks
developed among the microfibers. These AgNWs and electrically conductive fibers, thus imparting low
were stacked, piled, and arranged disorderly, as shown electrical resistance to the electrically conductive fabric.
in the SEM image in the inset Fig. 7(a). When a uniaxial Therefore, as shown in Fig. 3, the electrical resistance
force was applied, the electrically conductive fabric of the electrically conductive fabric samples increased
samples were stretched and the electrically conductive from 0.0047 to 0.0091 Ω as the strain was increased
networks gradually cracked. As the strain was from 0% to 190% strain; the increase was rather small,
increased from 0% to 210%, the electrically conductive however.
networks were destroyed, changing from large, con- Besides the stretch and stress areas, the electrically
tinuous structures to the size of a small flake (Figs. 7(b), conductive fabric also had break areas caused by the
7(c), 7(d), 7(e), and 7(f)). Because the electrically con- broken microfibers at 200% and 210% strain. Similar
ductive networks were separate from the microfibers to the stretch areas, only the loaded uniaxial force
with adhering AgNWs, they did not combine with acted on the microfibers, and the force was parallel to
the electrically conductive fibers as closely as those the break areas (Fig. 1(d)). As shown in Fig. 4(d), only
under 0% strain. Nevertheless, the electrically con- limited electrically conductive fibers existed in the
ductive networks still had enough conductive channels break areas, and they were all torn and almost dis-
resulting from the contacts between the flakes, as connected. SEM images confirmed that there were
well as the conductive channels resulting from the only a few scattered electrically conductive fibers

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Nano Res. 7

Figure 6 SEM images of electrically conductive fibers at strains of (a1), (a2), (a3) 0%, (b1), (b2), (b3) 50%, (c1), (c2), (c3) 100%, (d1),
(d2), (d3) 150%, (e1), (e2), (e3) 200%, and (f1), (f2), (f3) 210%, shown at magnifications of ×400 k, ×2.00 k, and ×10.0 k (from left to right).

(Figs. 8(a1) and 8(b1)), which is vastly different from conductive fibers were disconnected, the resulting
those in the stretch and stress areas shown in Fig. 5. electrically conductive channels were reduced, and the
In addition, the electrically conductive networks were electrical resistance increased significantly to 0.0274 Ω
almost completely destroyed, with only a few small at 200% strain and 112.1649 Ω at 210% strain, which
flakes remaining, so that the resulting electrically are much higher than the values in the strain range
conductive channels were nearly broken (Figs. 8(a2) of 0%–190% (Fig. 3).
and 8(b2)). Although most electrically conductive As mentioned earlier, the AgNWs were absorbed
fibers were broken or disconnected in the break areas, and adhered to the microfibers by physical effects
the remaining ones still exhibited high electrical to form electrically conductive fibers (Fig. 1(c) and
conductivity. The microstructures also were not its inset), and additional AgNWs filling the gaps and
completely destroyed, with AgNWs still adhering to spaces between these microfibers were stacked together
the microfibers, as well as being stacked and arranged to formed the electrically conductive networks (Fig. 1(c)
disorderly at strains of 200% and 210% (Figs. 8(a3)– and its inset). The absorbance and adherence were
(a5) and 8(b3)–(b5)), similar to the microfibers shown reflected by the durability of the electrical resistance
in Fig. 6. Because the electrically conductive networks of the electrically conductive fabric against washing
were almost completely broken and most electrically in water. As shown in Fig. 9, when the electrically

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8 Nano Res.

Figure 7 SEM images of electrically conductive networks at strains of (a) 0%, (b) 50%, (c) 100%, (d) 150%, (e) 200%, and (f) 210%;
the inset in (a) shows a magnified image of a section of the electrically conductive network.

Figure 8 SEM images of (a1) break areas of electrically conductive textiles at 200% strain, (a2) the torn electrically conductive
networks, and the electrically conductive fibers at (a3) ×400 k, (a4) ×2.00 k, and (a5) ×10.0 k magnification. SEM images of (b1) break
areas of electrically conductive textiles at 210% strain, (b2) the torn electrically conductive networks, and the electrically conductive
fibers at (b3) ×400 k, (b4) ×2.00 k, and (b5) ×10.0 k magnification.

conductive fabric samples (100 mm × 10 mm × 250 μm) ductive fabric displayed high durability, and the
were dipped into 25 °C water that was agitated by a AgNWs were well absorbed and adhered to the
magnetic stirrer (SAS-700, SANYO, Tokyo, Japan) at microfibers so that they could not be easily removed
500 rpm, the electrical resistance stayed stable in the or scratched. The stable and high electrical conductivity
range of 0.0035–0.0048 Ω, which is close to the value of this electrically conductive fabric was also indicated
of 0.0047 Ω for the un-stretched fabric in Fig. 3. by the digital images of an LED integrated circuit
Therefore, it can be seen that the electrically con- consisting of the un-stretched and stretched electrically

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Nano Res. 9

exhibited super-low electrical resistance of 0.0047 Ω


before it was stretched, while the electrically conductive
textiles fabricated from graphite nanoplatelets, carbon
nanotubes, and Ag particles had electrical conductivity
of 0.22 S·cm–1 [18], electrical resistance of 200–400 Ω
[19] and 10–20 Ω [19], and sheet resistance of 3 Ω·sq–1
[30], respectively. (4) The electrically conductive fabric
prepared in this study showed electrical resistance of
0.0047 Ω at 0% strain, 0.0067 Ω at 180% strain, 0.0091 Ω
at 190% strain, and 0.0274 Ω at 200% strain, indicating
that the electrical resistance could be considered con-
stant in the strain range of 0%–190%, which is similar
or even superior to the stable specific capacity at
Figure 9 Durability of the electrical resistance of electrically
62 F·g–1 of a stretchable conductor with porous textile
conductive textiles in 25 °C water that was stirred at @500 rpm;
the inset shows the electrically conductive fabric in stirring water. conductors as electrodes and current collectors before
and after stretching to 120% strain [30]. (5) This
conductive fabric at 0% strain (Fig. 3(a)) and 150% study’s electrically conductive fabric showed highly
strain (Fig. 3(b)), respectively. Moreover, pieces of the durable electrical resistance that was stable in the
electrically conductive fabric were further adhered range of 0.0035–0.0048 Ω when the fabric was dipped
onto fingers, like electronic skins, where they remained into the 25 °C water that was stirred at 500 rpm, which
through stretching, shrinking, or bending of the joints. is close to the value of 0.0047 Ω for the unstretched
They also showed stable and high electrical conduc- electrically conductive fabric. The electrical resistance
tivity, as shown in Figs. 3(c) and 3(d). is also similar or even superior to the unchanged
Compared to previously reported methods for sheet resistance of 3 Ω·sq–1 for single-walled carbon
fabricating electrically conductive textiles, the method nanotubes and cotton fibers before and after washing
reported in this study displayed several advantages. in water [30]. (6) The cupro fabric used in this study
(1) The dipping–drying method was much simpler came from natural cellulose, rather than chemical
than the methods of coating [3], deposition [4], fibers from conductive polymers [10–12], which could
spinning [5], printing [6], synthesis [7], and solution impart good biological properties and biocompatibility
growing [9], as well as the reported methods for pre- to the electrically conductive fabric. (7) Since the
paring Ag-based smart textiles [20–22], even though AgNWs were industrially fabricated on a large scale
it was similar to that of the “dying” textiles from and the cupro fabric was derived from natural
single-walled carbon nanotubes and cotton fibers [30]. cellulose, the electrically conductive fabric produced
(2) The AgNWs used in this study were industrially in this study definitely had a lower cost than those
fabricated on a large scale using the polyol process, prepared from conductive polymers [10–12], graphite
which had higher output than the fabrication process nanoplatelets [18], and carbon nanotubes [19, 30].
of graphite nanoplatelets [18] and carbon nanotubes Moreover, to further reduce the cost, the preparation
[19, 30]. The diameter was about 60 nm and the method could be modified to yield a high coverage
length was more than the 60-μm long AgNWs used ratio on the microfibers using as few AgNWs as
in this study, while the aspect ratio was more than possible. For example, the concentration of the AgNW
1,000, much larger than those of graphite nanoplatelets, suspension could be adjusted, the dipping time of the
carbon nanotubes, and silver particles used by Nilsson fabric in the AgNW suspension could be changed, and
et al. [18], Khumpuang et al. [19], Xue et al. [20], Paul the Ag ions could be allowed to grow into nanowires
et al. [21, 22], and Hu et al. [30], which ensured the along the seeds of the microfibers. These modifications
high electrical conductivity of the fabric prepared in will be carried out in the future to obtain better results
this study. (3) This study’s electrically conductive fabric for the electrically conductive fabric. In short, the

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10 Nano Res.

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