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org Research Article

High-Strength Superstretchable Helical Bacterial Cellulose Fibers

with a “Self-Fiber-Reinforced Structure”
Qianqian Liang, Dong Zhang, Peng Ji,* Nan Sheng, Minghao Zhang, Zhuotong Wu, Shiyan Chen,*
and Huaping Wang
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ABSTRACT: As a hydrogel membrane grown on the gas−liquid

interface by bacterial culture that can be industrialized, bacterial
cellulose (BC) cannot give full play to the advantages of its natural
Downloaded via DEAKIN UNIV on March 1, 2023 at 05:21:14 (UTC).

nanofibers. Conversion to the properties of nanofibers from high-

performance to macrofibers represents a difficult material
engineering challenge. Herein, we construct high-strength BC
macrofibers with a “self-fiber-reinforced structure” using a dry-wet
spinning method by adjusting the BC dissolution and concentration. The macrofiber with a tensile strength of 649 MPa and a strain
of 17.2% can be obtained, which is one of the strongest and toughest cellulose fibers. In addition, the macrofiber can be fabricated to
a superstretchable helical fiber without adding other elastomers or auxiliary materials. When the helical diameter is 1.6 mm, the
ultimate stretch reaches 1240%. Meanwhile, cyclic tests show that the mechanical properties and morphology of the fiber remained
stable after 100 times of 100% cyclic stretching. It is exciting that the helical fiber also owns outstanding knittability, washability,
scalability, and dyeability. Furthermore, superstretchable functional helical BC fibers can be fabricated by embedding functional
materials (carbon materials, conductive polymers, etc.) on BC or in the spinning dope, which can be made to wearable devices such
as fiber solid-state supercapacitors. This work provides a scalable way for high-strength superstretchable and multifunctional fibers
applied in wearable devices.
KEYWORDS: bacterial cellulose, dry-wet spinning, macrofiber, self-fiber-reinforced, helical fiber, scalable

1. INTRODUCTION which to the disadvantage of industrial continuous produc-

The exhaustion of nonrenewable resources such as petroleum tion.3,4 Dissolution spinning, as a simple process and
makes the development of renewable resources imminent. continuous production method, has been widely used in
various fiber fabrications. At present, the main solvents used to
Cellulose is an inexhaustible resource on earth and has great
dissolve cellulose are NaOH/urea solution,6 N-methylmorpho-
potential to replace petroleum-based products.1 Bacterial
line-N-oxide monohydrates,7 ionic liquids (ILs),8,9 and N,N-
cellulose (BC) is a kind of cellulose grown on the gas−liquid
dimethylacetamide (DMAc)/lithium chloride (LiCl).10 By
interface by bacterial culture in the form of fibrillar ribbons of
virtue of the dissolution process, using DMAc/LiCl as the
pure cellulose (no hemicellulose and lignin) with high
solvent is simple and does not require energy supply of
crystallinity (70−89%).2 The highly crystalline structure of
temperature and pressure, so it is widely used in laboratory
such thin elementary fibrils confers the fibers extraordinary
research.11
mechanical properties (a Young modulus of 114 GPa).3 Now,
Spinning high-strength BC macrofibers by adjusting the
it can be produced on an industrial scale at a very low price.
spinning process and the presentation form of BC are the basic
Many food companies in China can produce several tons of BC
requirements for expanding the application.12 The BC
per day.4 As a kind of hydrogel, BC cannot give full play to its
macrofiber can be prepared by wet spinning or combining
unique mechanical properties. How to transfer the properties
wet twisting and wet spinning, and its tensile strength can
of nanofibers from high-performance to macrofibers represents
reach 357.5 and 535.4 MPa, respectively, but the process is
a difficult material engineering challenge. In recent reports, BC extremely complicated.2,5 Also, in the actual application of the
macrofibers are mainly prepared through wet spinning of
TEMPO oxidative nanofibers and twisting processes. For the
wet spinning of TEMPO oxidized nanofibers, the entire Received: October 26, 2020
oxidation process is complicated and time-consuming, and the Accepted: December 16, 2020
mechanical properties of the prepared macrofibers are Published: December 30, 2020
inobtrusive.2,5 A tensile strength of 826 MPa can be obtained
by cutting the BC film into long strips and then stretching and
twisting. However, the preparation process is discontinuous,

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Figure 1. Schematic illustration of the preparation process of the superstretchable BC helical fibers.
macrofiber, stretchability is also a necessary condition for
expanding its application. The stretchability of the fiber not
only is conducive to the improvement of responsiveness but
also can be perfectly integrated with clothing as a wearable
device,13,14 such as supercapacitors and sensors. Three main
types of stretchable structures have been proposed: island
bridges, 15,16 twisted structures,17−19 and helical struc-
tures.12,14,20,21 However, they are all added elastic materials
or loaded on the elastic matrix, which not only increases the
complexity of preparation but also easily leads to material
incompatibility, thus shortening the life of devices. It is
extremely pivotal to prepare materials with their own elastic
properties.
Here, we used DMAc/LiCl to dissolve freeze-dried BC22 to
fabricate high-strength BC macrofibers by the dry-wet spinning
process. The mechanical properties of BC macrofibers were
improved by adjusting BC concentration, dissolution time, air
section, and extrusion speed. Most importantly, we found that
the obtained BC macrofiber had unique rigidity,23,24 which can
boldly get rid of the preparation method that must rely on
elastic materials or complex twisting processes to endow the
fiber stretchability. Therefore, we coiled the macrofibers on
steel rods of different diameters to prepare superstretchable BC
helical fibers and explored their cycle recovery performance. In
addition, the knittability and washability of the helical fibers
have also been explored to increase their potential for wearable
applications. In addition, we added the active material carbon
nanotube (CNT) to the spinning solution and polymerization
poly(3,4-ethylenedioxythiophene) (PEDOT) on BC to obtain
a conductive fiber, which can be prepared to wearable devices
such as fiber supercapacitors. The scalable potential application
in the field of multifunctional wearable devices is indicated.
2. EXPERIMENTAL SECTION
2.1. Materials and Chemicals. BC was produced by incubating
gluconacetobacter xylinum in a static culture medium at 30 °C for 7
days in our laboratory (5 wt % glucose, 0.5 wt % peptone, 0.5 wt %
yeast extract, 0.2 wt % dibasic sodium phosphate, 0.1 wt % citric acid,
and 0.1 wt % potassium phosphate monobasic).2,25 The BC
membranes were boiled in NaOH (1 wt %) for 30 min, followed
by repeatedly rinsing with deionized water to remove the remaining
culture medium and microorganisms. Finally, BC membranes were
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fibrillated into the slurry by high-shear homogenization (T25 digital
ULTRA-TURRAX, IKA, Germany) at a speed of 72,000 rpm for 30
min. CNTs with a length less than 30 μm and a diameter range of
10−20 nm were purchased from Chengdu Organic Chemicals Co.,
Ltd. DMAc and NaOH were purchased from Sinopharm Chemical
Reagent Co., Ltd. Lithium chloride (LiCl) and 3,4-ethylenediox-
ythiophene were purchased from Shanghai Aladdin Bio-Chem
Technology Co., Ltd. Dyes were purchased from Zhejiang Jiabao
dyes Co., Ltd. All chemicals were used directly without any further
purification.
2.2. Dissolution of BC. The dissolution process of BC is as
follows: first, the homogeneous BC suspension was freeze-dried for 48
h and the dried BC (4 wt % and 6 wt %) was added into the mixed
solution of LiCl (8 wt %)/DMAc (88 and 86 wt %) and stirred by
mechanical agitation (1000 rpm) (MC-OS20, ART Miccra,
Germany) with different times (8, 10, 12, 14, 16 h) at room
temperature (20−25 °C). Then, the dissolved BC solutions were left
in a centrifuge for 30 min at 3000 rpm to remove the excess bubbles
and achieve the uniform spinning dopes.
2.3. Preparation of BC Macrofibers. The spinning dope was
filled into a syringe (2.5 mL) and spun using a syringe pump (Pump
11 ELITE, Harvard, USA). The injection speed is controlled in the
range of 2−8 mL/min (the corresponding spin speed is 10−40 m/
min), and the inner diameter of the needle is 0.5 mm. After the fiber
was extruded, it primarily passed through the air section (1, 3, 5, 7, 9
cm) and then entered the coagulation bath of DMAc/H2O (1:2 v/v)
to solvent-exchange, followed by washing with deionized water.
Meanwhile, to explore the influence of the air section on the
formation of fibers, the same fibers were extruded directly into the
coagulation bath for solvent exchange. The obtained fibers with
diameters of 120−160 μm were dried in a fume hood at room
temperature.
2.4. Preparation of BC-Based Helical Fibers. After taking out
the fibers from the coagulation bath, we connected one end of the
fiber to the motor and coiled on a steel rod with self-made equipment
and then soaked in deionized water to remove the unreacted
substances and solvents. After drying in a fume hood at room
temperature, the helical fibers with diameters of 350−400 μm were
obtained by removing the rod (Video S1).
2.5. Characterization. The mechanical properties, which
involved tensile strength and strain at break of straight macrofibers
and helical fibers, were tested using an electronic universal material
testing machine (Instron/5969, Bruker, USA) at a strain rate of 20
mm/min and gauge lengths of 20 mm (straight fiber) and 10 mm
(helical fiber). Before the tests, the diameter of the fibers was
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Figure 2. (a) X-ray diffractogram original BC and BC macrofibers. (b) Crystallinity of cellulose I and cellulose II in BC at different dissolution
times of original BC, 14 and 20 h. Surface FE-SEM images of BC macrofibers by wet spinning (c,d) and dry-wet spinning (e,f). (g,h) Stress−strain
curves of the macrofibers with different air sections and extrusion rates at a 4 wt % BC concentration. (i) Tensile strength and strain at break of our
BC macrofibers compared to those of other reported cellulose fibers.
observed using an optical microscope (CKX53, Olympus, China) and
the average diameter was determined by measuring ∼30 fibers. The
tensile cycle tests were performed at the tensile rates of 50, 100, and
200 mm/min and the gauge length of 10 mm, and the helical fiber
diameters are 0.7, 1.2, and 1.6 mm, respectively. All samples were
conditioned at the relative humidity for at least 24 h and tested at 23
± 1 °C and 55 ± 2% humidity. The X-ray diffraction (XRD; D2
Phaser X-ray diffractometer, Bruker, Germany) pattern was obtained
on a Rigaku D/max-2550VB+/PC X-ray diffractometer with Cu Kα
radiation at a scan rate of 1° s−1.25
Morphologies of fibers were observed by field emission scanning
electron microscopy (FE-SEM, S-4800, Japan). The spinning fibers
were fractured in liquid nitrogen to reveal the cross section and then
sputter-coated with a thin gold layer before observation. A JEM-2100
transmission electron microscope was used to characterize the
morphologies of the original BC and dissolved BC for 14 h. The
BC suspension (0.06 mg/mL) was deposited onto the glow-
discharged carbon-coated copper grid. The excess liquid was absorbed
by a piece of filter paper, and the remaining film of stain was allowed
to dry; the sample is observed at 100 kV.2 The cyclic voltammetry
(CV) curves of the solid-state supercapacitors were tested on an
electrochemical workstation (CHI 660E, Shanghai Chenhua, China).
3. RESULTS AND DISCUSSION
3.1. Dissolution and Spinning of BC. BC macrofibers
and helical fibers are prepared as shown in Figure 1. First, the
BC biofilm was homogenized and freeze-dried to obtain a
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relatively loose structure; thus, the DMAc/LiCl mixed solvent
can better penetrate into BC and obtain a homogeneous
spinning dope. It is worth mentioning that the degree of
dissolution varies with the time of dissolution and influences
the spinnability. It is reported that dry-wet spinning has been
used to spin high-stiffness cellulose macrofibers, in which the
air section presence significantly improved the orientation of
the fibers, resulting in highly aligned rigid cellulose fibers.26
Therefore, the dry-wet spinning method was used to spin BC
macrofibers. The dope was extruded from the injection needle
and then entered in air for a better stretching orientation,
which contributes to improve the mechanical properties of the
formed fibers. By adjusting the spinning dope concentration
and controlling the dissolution time of BC, we can obtain the
macrofibers and helical fibers with different structures and
properties by dry-wet spinning. For comparison, the same BC
macrofibers were prepared through wet spinning to analyze the
influence of the spinning method on the mechanical properties.
3.2. Morphology and the Mechanical Properties of
the Macrofibers. The dissolution degree of BC will influence
the spinnability of the dope and the mechanical properties of
the formed macrofiber. The polarizing microscope was
employed to monitor the dissolved status25 of 4 wt % BC at
different dissolution times. As shown in Figure S1, at the
beginning of dissolution (Figure S1a), BC shows many
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filamentous bright areas, indicating that BC has not yet begun
to dissolve. After 14 h, the filamentous areas turn into bright
spots, which implies that parts of the crystal area have been
destroyed and most of cellulose dissolved (Figure S1b). When
the dissolution time is 20 h, the bright spots almost completely
disappear, indicating that BC is almost completely dissolved
(Figure S1c). It is well known that natural cellulose is a type I
crystallite which will regenerate into cellulose II after
dissolution. Therefore, the dissolution of BC can be judged
by XRD of cellulose I and II. We tested the XRD of the
dissolved BC under different dissolved conditions. As shown in
Figure 2a, we can observe that the crystal form of the dissolved
BC changed at 14.3, 16.5, and 22.5° and the intensity of the
peaks weakens when dissolved for 14 h, which indicates the
cellulose I crystal decrease and the cellulose II crystal
regeneration.27,28 These regenerated cellulose II crystals and
the amorphous cellulose macromolecular chains as continuous
phases wrapped the undissolved cellulose I nanofiber to form a
“self-fiber-reinforced structure”, which contributes to rigidity of
the spinning macrofiber.10 When the dissolution time reaches
20 h, the overlapping peaks are assigned to cellulose II at
approximately 20.4 and 21.9°. It implies that the nanofibers are
almost completely dissolved to form an aggregation structure
dominated by cellulose II crystals.25 The ratio of cellulose I to
cellulose II (Figure 2b) can more clearly demonstrate the
above result. At the dissolution time of 14 h, most of cellulose I
changed to cellulose II and the ratio of cellulose I to cellulose
II is 0.17. After 20 h, there is only a little cellulose I, which
cannot make the fiber self-reinforced, thus resulting in the
decrease of the mechanical properties of the macrofibers.25,29
Transmission electron microscopy (TEM) images further
confirm the nanofiber existence after dissolution for 14 h. As
shown in Figure S2, compared with the clear nanofiber
network of original BC, the wormlike incompletely dissolved
network structure is still observed,30 demonstrating the
nanofiber-reinforced structure of the macrofibers.
The microstructure seriously affects the performance of the
macrofiber.4 We characterized the surface and cross-sectional
morphology of the wet spinning and dry-wet spinning
macrofibers by FE-SEM. As shown in Figure 2c,d, we can
observe the uniform cracks on the surface of the wet spinning
fiber, which is similar to the surface structure of the shark
skin.31,32 This may be due to the dramatic double diffusion of
the fibers when it is directly immersed in the coagulation bath,
and many pores can be observed from the cross-sectional SEM
image (Figure S3a),31 which proves the poor compactness of
the wet spinning macrofiber. However, when the fiber comes
out of the syringe, it first enters the air, accompanied by a slight
extrusion expansion. In the process, the gravity causes the fiber
to stretch in the downward flow process. Thus, the fibers
passing through the air section may show a denser structure
than that directly spun by wet spinning.33 As shown in Figures
2e,f and S3b, the surface and cross-sectional SEM images of the
fiber confirm the above result.34,35 Although there are relatively
obvious grooves on the surface of the dry-wet spinning fibers
(Figure 2f), which may be caused by the loss of exchange
moisture during the drying process,4,10,36 the denser structure
of the macrofibers would be beneficial to the improvement of
the mechanical properties. Table S1 lists the tensile mechanical
properties of BC macrofibers for different BC concentrations
(2, 4, 6 wt %) and different dissolution times (8, 10, 12, 14, 16
h) of BC. It can be seen that when the spinning solution
concentration is 4 wt % and the dissolution time is 14 h, the
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tensile strength of the macrofiber reaches the maximum value
of 649 MPa.10 Under these conditions, we can obtain the
homogeneous spinning dope for continuous spinning. When
the concentration is increased or the dissolution time is less
than 14 h, the degree of cellulose dissolution is not enough to
form uniform spinning.2 If the dissolution time is too long, the
spinning dope is easy to gelatinize so that it cannot be
successfully spun. By controlling the concentration and
dissolution time of BC, the dissolved macromolecular chain
can be used as the dissolving matrix for continuous spinning,
and rigid nanofibers (cellulose I) can be arranged in the matrix
under the action of shear force so as to achieve the self-fiber-
reinforced macrofibers. We also compared the effects of wet
spinning and dry-wet spinning on the mechanical properties of
the fibers at a 4 wt % BC concentration (Table S2). From the
data, we can observe that the tensile strength of dry-wet
spinning macrofibers was higher than that of wet spinning
macrofibers, especially at the dissolution time of 14 h. This is
due to the fact that when the content of nanofibers is
appropriate, the existence of the air section is conducive to the
improvement of the orientation of nanofibers.34 As shown in
Table S3, the birefringence and crystal orientation of dry-wet
spinning fibers are significantly better than those of wet
spinning fibers.37 The distance of the air section can affect the
mechanical properties. Figure 2g shows stress−strain curves of
the macrofibers with different air sections at a 4 wt % BC
concentration by dry-wet spinning compared with wet
spinning. It can be seen that the tensile strength and strain
at break of dry-wet spinning fibers are greater than those of wet
spinning.26 Meanwhile, with the increase of the air section,
both the stress and strain of the macrofiber show a trend of
first increase and then decrease (Figure 2g). This is mainly due
to the fact that the stretching and orientation of the fiber
mainly occur within 5 cm.38 When the air section is 5 cm, the
stress and strain reach the maximum value of 649 MPa and
17.2%, respectively. Compared with the values of other
reported cellulose fibers including cellulose/polyvinyl alcohol
(PVA) fibers,39 IL-dissolved cellulose fibers,40 DMSO-
dissolved cellulose fibers,26 TEMPO-oxidized BC fibers,2
interfacial fibers,41 BC/Alg fibers,5 and aligned nanofibers42
(Figure 2i), our fiber is one of the strongest and toughest
cellulose fibers. We believe that the fiber with such high
strength and toughness would be widely used in various fields
including biomedical engineering, geotextiles, smart textiles,
and even aerospace.4 Besides, the spinning speed affects
production efficiency and the mechanical properties of the
fiber. From Figure 2h, it is easily observed that when the
extrusion speed increases, the fiber t-stress and strain tend to
gradually increase. This is due to the fact that the moderate
increase of shear force is beneficial to the increase of nanofiber
orientation. However, when the extrusion speed is above 10
mL/min, the stress decreases sharply, which may be due to the
appearance of fiber defects by the insufficiency of spinning
pump pressure and pump supply.43,44 Therefore, unless
otherwise mentioned, the macrofibers were prepared under
the conditions of a BC concentration of 4%, a dissolution time
of 14 h, an air section of 5 cm, and an extrusion speed of 8
mL/min.
3.3. BC Helical Fibers. The wet macrofibers can be coiled
on a rod to obtain helical fibers.2 The diameter and shape can
be controlled by the rod diameter and shape. We coiled the BC
macrofiber on square steel rods with side lengths of 2, 3, and 4
mm, hexagonal steel rods with side lengths of 2.5, 3, and 3.5
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Figure 3. (a−c) Different helical fibers with different sizes (the inset is the image of one helix). The surface FE-SEM images of BC helical fibers
with helical diameters of 0.7 (d,g), 1.2 (e,h), and 1.6 mm (f,i). (j−l) Cross-sectional FE-SEM images of BC helical fibers.

Figure 4. Stretchability and stretch cycle performance of BC helical fibers. (a) Stress−strain curves of BC helical fibers under tension (inset: stress−
strain curve of the BC straight macrofiber). (b) Real shots with different stretching ratios. (c) Helical fiber cycled up to 100% strain 100 times.
Strain rate: 100 mm/min.

mm, and circle steel rods with different diameters of 2.1, 2.7,
and 3.5 mm. As shown in the inset of Figure 3a−c, all kinds of
fibers have good ability to maintain the original shape, which
will not change for a long time. Although the square helix with
a larger side length inclined to tilt, which will be improved with
the increase of the number of sides. The circular helix reveals
the best helical stability. It is believed that the stability of the
helical structure will be promoted gradually with the increase
of the side number. When it reaches the cycle, the stability is
maximized. Figure 3d−f shows the structure of helical fibers. It
can be observed that the fibers with different diameters have a
relatively smooth surface, and the magnification images (Figure
3g−i) show that they are composed of dense nanofibers, which
is why the helical fibers can maintain their shape well. From
the cross-sectional SEM images shown in Figure 3j−l, we can
observe a lot of rod-shaped nanofibers with a diameter of 20
nm embedded in the continuous matrix. In this structure,
nanofibers play an important role in supporting the matrix by
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forming the “self-fiber-reinforced structure” as previously
reported in the BC hydrogel by us.25 This unique and dense
multiscale structure is conducive to the excellent mechanical
properties of the fiber.
This unique helical spring structure endows the BC-based
fibers excellent stretchability, which lays a prominent
foundation for further research and development of the BC-
based fiber. As shown in Figure 4a, compared to the strength of
649 MPa of the straight fiber, the strength of the helical fiber
decreases to 238, 121, and 62 MPa with different helical
diameters, respectively. This is due to the fact that the helical
fiber is formed by coiling, which causes the fiber to bend, and
the coiling process causes the fibers to be unevenly stretched,
which affects the orientation of the fibers, thereby reducing the
strength of the fibers. However, the strength of helical fibers
can still reach a maximum of 238 MPa, which is much higher
than those of some reported stretchable wearable devices (such
as CNT/polymer nanofiber helical yarns,45 elastic 3D helical
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Figure 5. (a−d) Woven integration of the BC helical fibers. Real shot of the helical fiber before washing (e) and after ultrasonic washing for 40 min
(f). (g,h) FE-SEM images of the helical fiber before washing. (i,j) FE-SEM images of the helical fiber after ultrasonic washing for 40 min.
fibers,13 Ag-doped PEDOT:PSS/CNT composites for thin
films,46 or polyacrylamide/sodium alginate dual-network
hydrogels47) which can be used in wearable applications. In
addition, because of our unique “self-fiber-reinforced structure”
and the helical geometry effect caused by the open loop,45 the
fiber shows excellent superstretchability. The highest tensile
elongation of the helical diameters of 0.7, 1.2, and 1.6 mm
reaches 1140, 1209, and 1240%, respectively. It can be seen
that the elongation at break of the helical fibers increases as the
helical diameter increases, but it can be inferred from L = π ×
diameter (D) that the elongation at break does not increase in
proportion to the diameter of the circle. From the macroscopic
views in Figure 4b, the helical fiber with a diameter of 1.6 mm
is gradually elongated during the stretching process until it
becomes a straight fiber with a strain of 1240%, which is higher
than those of most of the reported stretchable helical
materials.12,20 Meanwhile, if we do not consider the distance
between the helixes and the strain of the fiber itself, we choose
a helical fiber with a diameter (d) of about 400 μm, a helical
diameter (D) of 1.6 mm, and a coiled number of 23 to explore
the stretchability. Therefore, the initial length L0 = d × coiled
number = 0.4 mm × 23 = 9.2 mm and the stretched length L1
= πD × coiled number = 3.14 × 1.6 × 23 = 115.6 mm.
Therefore, the elongation of the helical fiber we prepared is L =
(L1 − L0)/L0 = (11.56 − 0.92)/0.92 × 100% = 1156%. This
theoretical result is basically consistent with our experimental
results. Moreover, when the BC helical fiber is stretched for
100 cycles under 100% tensile elongation, the helical structure
in the first cycle occur loop opening relaxation and the weak
hydrogen bond is damaged between the nanofiber network and
the matrix inside the helical fiber, caused the strain recovery
drop to 88%. It can be observed that in the subsequent 2−100
cycles, because of the helical geometry effect and the reformed
hydrogen bonds at the new position, the tensile recovery rate
remains basically constant, which indicates the tensile cycle
stability of the helical fiber (Figure 4c).25,45 In daily life, the
elongation of the human skin can be about 55%.48,49 The good
recovery of the helical fibers under 100% deformation and
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cyclic stability fully meet the deformation requirements of daily
wearable devices. It should be pointed out that these fibers
have no elastic material added or loading on the elastic matrix,
which not only increases the complexity of preparation but also
easily causes material incompatibility, thereby shortening the
life of the devices. In addition, their preparation is completely
controllable, convenient, and continuous. Therefore, this
makes up for the lack of elasticity, structural instability, and
irreversibility of existing reports under relative tensile
strain,20,50,51 which greatly encourages our confidence as
wearable devices.
Because of the excellent deformability and recoverability,52
the helical fibers can be bent arbitrarily with the fingers (Figure
5). After bending 50 times, there is no visible change in the
shape and size of the helical fiber (Figure 5d). It is indicated
that the helical fibers can be woven or integrated into
commercial clothing or fabrics to further study their
application in wearable devices.53 The washability is a key
parameter in the practical application for the helical fibers.54
Ultrasonic washing, a washing method that is more powerful
than ordinary household laundry washing,13 is used to test the
washability of the helical fibers. From the real shots (Figure
5e,f), we can observe that the fiber maintains even and smooth
after ultrasonic washing for 40 min. Compared with the
enlarged FE-SEM images before (Figure 5g,h) and after
washing (Figure 5i,j), no obvious cracks or cavities are
observed, indicating the structural stability and washability of
our fibers during the washing process.13
3.4. Scalability of BC-Based Fibers. At present, BC can
be produced in several tons per day in a large number of
companies in China,4 and the cultivation methods of BC are
also diverse, such as food processing wastewater,55 molasses,56
and wheat straw.57 These raw materials are abundant and
relatively inexpensive, which not only reduce the environ-
mental burden but also achieve the purpose of low-cost, large-
scale production. Using the dry-wet spinning method of
industrialized lyocell fibers for spinning,26 by continuously
dissolving and extruding, BC macrofibers and BC helical fibers
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Figure 6. (a) Original helical fiber of a helical diameter of 1.6 mm. (b) Colored helical fibers after dyeing. (c) Colored helical fibers after washing.
(d) Hole gloves. (e) The macrofiber is inserted through a needle and can be sewed in gloves like a common thread. (f) The holed gloves are sewn
and knotted like ordinary fibers.

Figure 7. (a) Schematic diagram of the preparation process of BC/CNT and BC/PEDOT helical fibers. (b) FE-SEM images of BC/CNT and BC/
PEDOT helical fibers. (c) Mechanical properties of BC/CNT and BC/PEDOT helical fibers and the inset shows the straight macrofibers. (d)
Schematic diagram of a solid supercapacitor. (e) CV curves of BC/CNT helical fibers under different scan rates. (f) CV curves of BC/PEDOT
helical fibers under different scan rates.

can be continuously produced, indicating the industrially
scalable prospects. Besides, the BC dissolution process does
not require heat supply, so it will not cause any thermal
runaway reactions and does not require any additives and
special equipment. Hence, the process is relatively energy-
saving, which further reduces the production cost.58
The prepared BC macrofibers are easy to dye, which further
proves their potential application in the textile industry.3,59 By
immersing the representative BC helical fiber with a helical
diameter of 1.6 mm in household dyes of different colors at
room temperature (25°) for 30 min, washing it with water
until the water becomes clear, and putting it in a fume hood to
1551
air dry, the original white helical fiber (Figure 6a) was dyed
with different colors (red, orange, yellow, green, blue, indigo,
and purple) (Figure 6b). By putting the dyed helical fiber into
the water and ultrasonic washing at room temperature for 60
min, the fiber color shows no particularly visible change
(Figure 6c). Although there is a slight almost invisible color
change in the water, this kind of floating color is normal and
may also be related to the type of dye,60 proving the fine color
retention of the BC helical fiber. After all, the household dyes
we used are different from the professional dyes used in the
industry. As is known, aramid fibers are representative of high-
performance fibers, especially aramid 1313 and aramid 1414,
https://dx.doi.org/10.1021/acsami.0c19149
ACS Appl. Mater. Interfaces 2021, 13, 1545−1554
ACS Applied Materials & Interfaces
which have very high strength and rigidity.61 However, it is
difficult to dye because of their high crystallinity. It is necessary
to add dye assistants before dyeing, which greatly limit its
potential application in the direction of materials with color
requirements.61 However, the BC-based fiber is not only high-
strength and superstretchable but also easy to dye into a variety
of colors. Further, although the fibers are very rigid, the fibers
also have a good braidability, which can also be used to sew
clothes and textiles such as ordinary threads. We first threaded
the needle extremely easily and then sewed holes in the gloves
(Figure 6d,e). The sewing effect is no different from that of
ordinary commercial fibers, and the knotting operation after
sewing is easy to complete (Figure 6f).62 This further shows
that the BC macrofibers have potential in practical textiles.
Besides, by adding carbon materials in the spinning solution
and polymerizing conductive polymers on BC, high-strength
BC/CNT and BC/PEDOT conductive composite fibers were
prepared. Figure 7a shows the schematic diagram of the
preparation process. As shown in Figures 7b and S4, CNTs are
well dispersed in the BC matrix, and PEDOT is successfully
polymerized on the inside and surface of BC to form nanoscale
particles.63 Although the tensile strengths of BC/CNT and
BC/PEDOT conductive fibers decrease (Figure 7c) after
adding an appropriate addition amount of CNTs and PEDOT.
The presence of the undissolved BC network and CNTs
(PEDOT) plays an excellent support and reinforcement role,
which still exhibit remarkable rigidity of the composite
fiber.64,65 Because of the necking effect caused by stress
concentration, BC/CNT and BC/PEDOT helical fibers have
only 11.1 and 152.6 MPa breaking strengths.45 However,
compared with the BC macrofiber, the tensile deformation
ability of BC/CNT has not changed and the BC/PEDOT
helical fiber increases the maximum elongation to 1628%. This
is due to intrinsic mechanical flexibility caused by the
amorphous and tangled conductive polymer.66 Simultaneously,
the weaving experiments and ultrasonic washing experiments
were performed. The results also show that the addition of
CNTs did not change the wearability (Figure S5) and
washability (Figure S6) of the helical fibers.
Consequently, as a proof of concept, we used BC/CNT
helical fibers and BC/PEDOT helical fibers as electrodes to
fabricate solid supercapacitors. As shown in Figure 7d, we used
two parallel BC/CNT or BC/PEDOT superstretchable fibers
to prepare a symmetrical electrochemical supercapacitor and
used the water-based PVA/H3PO4 gel electrolyte for coating,
which can maintain a quasi-solid of high viscosity even when
exposed in air.67,68 The rectangular CV curve shows that our
ultrastretchable supercapacitor has no Faraday redox reaction
(Figure 7e,f),68 and these curves are consistent with the energy
storage of CNT and PEDOT electrochemical double-layer
capacitors.69,70 In addition, the superstretchable BC/CNT
fibers can still apply 600% strain even if they are coated with
the PVA/H3PO4 gel electrolyte (Figure S7), which indicates
that the presence of the transparent gel electrolyte does not
reduce the stretchability of the electrodes.68 This fully
indicated that the high-strength superstretchable macrofibers
with helical properties have a broad prospect in the application
of smart textiles and wearable electronic products.
4. CONCLUSIONS
In summary, we prepared superstrong BC macrofibers by dry-
wet spinning with a tensile strength of 649 MPa and a strain of
17.2%. It is precisely due to the self-fiber-reinforced structure
1552
www.acsami.org Research Article
that the fiber has excellent rigidity and can be made into a
stable helical fiber. When the helical diameter is 1.6 mm, the
elongation at break can reach 1240%, and the fiber has
excellent stability, washability, dyeability, and weavability. In
the meantime, CNTs can also be added to the spinning dope
or the polymerized conductive polymer on the surface, which
does not affect its rigidity and helicity under the condition of
an appropriate amount. This conductive fiber can be used to
prepare supercapacitors, sensors, etc., which has wide
application prospects in the manufacture of wearable electronic
devices with superstrength, superscalability, and excellent
electrical properties.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.0c19149.
Fabrication process of the macrofibers and helical fibers
(AVI)
Polarizing microscopy images, TEM images, FE-SEM
images, sewing ability and washability, and mechanical
properties (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Peng Ji − Co-Innovation Center for Textile Industry, Donghua
University, Shanghai 201620, PR China; Email: jipeng@
dhu.edu.cn
Shiyan Chen − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai
201620, PR China; orcid.org/0000-0002-4195-3014;
Email: chensy@dhu.edu.cn
Authors
Qianqian Liang − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai
201620, PR China
Dong Zhang − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai
201620, PR China
Nan Sheng − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai
201620, PR China
Minghao Zhang − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai
201620, PR China
Zhuotong Wu − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai
201620, PR China
Huaping Wang − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai
201620, PR China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.0c19149
https://dx.doi.org/10.1021/acsami.0c19149
ACS Appl. Mater. Interfaces 2021, 13, 1545−1554
ACS Applied Materials & Interfaces
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (52073050), the Fundamental Research
Funds for the Central Universities, and the Graduate Student
Innovation Fund of Donghua University (CUSF-DH-D-
2020041).
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