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org Research Article

Polyvinylpyrrolidone Assisted Preparation of Highly Conductive,

Antioxidation, and Durable Nanofiber Composite with an Extremely
High Electromagnetic Interference Shielding Effectiveness
Shu Zhang, Xuewu Huang, Wei Xiao, Lulu Zhang, Hang Yao,* Ling Wang, Junchen Luo,
and Jiefeng Gao*
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sı Supporting Information

ABSTRACT: With booming development of electronics, electro-

magnetic interference (EMI) shielding materials based on conductive
Downloaded via SICHUAN UNIV on June 15, 2021 at 01:43:02 (UTC).

polymer composites (CPCs) have received increasing attention.

However, it remains challenging to develop flexible and lightweight
CPCs with excellent stretchability, breathability, durability, and high
EMI shielding effectiveness (EMI SE). Here, we propose a facile
polyvinylpyrrolidone (PVP) assisted preparation of highly electrically
conductive and durable nanofiber composites for high performance
EMI shielding. The PVP layer could not only greatly enhance the
interfacial interaction between the Ag nanoparticles (AgNPs) and
hence the mechanical properties (both tensile strength, Young’s
modulus and elongation at break) of the polymer nanofiber
membrane but also forms a protection layer preventing the AgNPs
from oxidizing. The electrical conductivity of the nanofiber composite can reach up to 245.7 ± 30.6 S/cm, which is, to a large degree,
maintained after cyclic stretching, abrasion, and ultrasonic washing. In addition, the nanofiber composite exhibits excellent
breathability, antibacterial, and Joule heating performance. When used as the EMI shielding material, the nanofiber composite shows
an extremely high SE and SSE of ∼96.9 dB and 169.7 dB cm3/g, respectively, and EMI shielding performance possesses outstanding
stability and durability. This multifunctional nanofibrous composite membrane exhibits promising applications in wearable
electronics.
KEYWORDS: PVP, Ag nanoparticles, nanofiber composite, electromagnetic interference shielding, Joule heating

1. INTRODUCTION the hydrogen bonding between the hydroxyl or carboxyl groups

Stretchable and wearable electronics have become the frontier
and hot research field in material science and technology, owing
to their potential and promising applications in artificial skin,
disease surveillance, etc.1 Electrically conductive nanofiber
composites (CNCs), possessing unique porous structure,
excellent breathability, large aspect ratio of the nanofibers, and
controllable conductivity, have been good candidates for the
wearable electronics.2,3 A composite is usually a combination of
two or more components that possess significantly different
physical and chemical characteristics. Recently, decorating
conductive nanofillers onto the nanofiber surface is an effective
and versatile strategy for fabrication of CNCs, because the
unique polymer nanofiber core/nanofiller shell imparts to the
nanofibrous membrane electrical conductivity while maintain-
ing the material flexibility.4−6 Interfacial hydrogen bonding is
widely used as the driving force for the adsorption of the
nanofiller onto the polymer nanofiber surface.7,8 For example,
graphene oxide and Mxene were successfully assembled onto the
fiber surface through the dip coating method, which is based on
of GO and Mxene and the amino groups of polymers or the
modification layer on fiber surface. We proposed ultrasonication
induced carbon nanofillers decoration onto the surface of
electrospun polymer nanofibers.9,10 Under ultrasonication, the
nanofillers were pushed, at a high speed, toward the polymer
nanofiber surface, where interfacial sintering occurred, leading
to the softening or even partially melting of the polymers. As a
consequence, the nanofillers including the reduced graphene
oxide and carbon nanotubes were finally anchored onto the fiber
surface. For the CNCs prepared by either hydrogen bonding or
ultrasonication, only a thin nanofiller layer was formed on the
Received: March 22, 2021
Accepted: April 23, 2021
Published: April 29, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsami.1c05319

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fiber surface, corresponding to a relatively low electrical
conductivity (usually less than 2.0 × 10−2 S/m).11
To enhance the membrane conductivity and hence extend
material applications such as in the field of the electromagnetic
interference (EMI) shielding, Bhawal and his co-workers
incorporated high amount graphene in polymer matrix, and
the obtained polymer composite possessed the EMI shielding
effectiveness of around 30 dB.12,13 In our previous work, the Ag
precursor was first adsorbed onto the fiber surface, and after the
precursor was reduced, a high density of Ag nanoparticles
(AgNPs) were finally generated, wrapping the nanofiber surface.
However, it remains a major challenge to improve the Ag
precursor adsorption and hence the electrical conductivity. In
addition, the interparticles interaction was generally weak, and
the adhesion agent (e.g., PDMS) was used to improve the
interfacial interaction between the AgNPs and the fibers as well
as between the individual AgNPs. Nevertheless, the introduction
of adhesion agent could not only require multistep manipulation
and thus make the preparation more complicated but also bring
about the decrease in conductivity due to the thick insulation
layer surrounding the AgNPs.14−16 As the wearable devices, it is
also desirable that the performance of the CNCs is stable and
durable even when the material undergoes mechanical
deformation, abrasion, washing, etc. Since the CNCs may
contact the people’s skin during the practical use, the nanofiber
composite should be antibacterial. However, it is still challenging
to develop a facile method for fabrication of CNCs with high
conductivity, strong interfacial interaction, good antibacterial,
and excellent surface stability and durability.
In this work, a facial polyvinylpyrrolidone (PVP) assisted
method was used to prepare flexible, highly conductive,
antibacterial and durable CNCs. PVP can not only promote
Ag precursor adsorption onto the polymer nanofiber surface but
also greatly enhance the interfacial interaction and antioxidation
of the finally formed AgNPs. The conductivity of the obtained
CNCs can reach 245.7 S/cm with the EMI shielding
effectiveness (SE) and SSE as high as 96.9 and 169.7 dB cm3/
g, respectively. Furthermore, the conductivity can keep stable
when the CNCs experience cyclic stretching, abrasion and
ultrasonic washing. Also, the AgNPs based CNCs exhibit
excellent antibacterial properties. The PVP assisted preparation
strategy opens a new avenue for producing multifunctional and
high performance nanofibrous composite membranes with great
potential application prospects in flexible and wearable
electronics.
2. EXPERIMENTAL SECTION
2.1. Materials. Polyurethane (PU) was supplied from BASF,
Germany. The anhydrous ethanol, N,N-dimethylformamide (DMF)
and hydrazine hydrate (N2H4·H2O) were provided by Sinopharm
Chemical Reagent Co. Ltd., Shanghai, China. Silver trifluoroacetate
(STA) was obtained from Meryer Chemical Technology Co., Ltd.
Polyvinylpyrrolidone (PVP) of various molecular weights were brought
from Sigma-aldrich Co. Ltd., Shanghai, China. All the reagents were
used as is without any further treatment.
2.2. Preparation of PVP/Ag@PU Nanofibrous Composite. An
electrospinning technique was employed to fabricate the pristine PU
nanofibrous mat, which was mentioned in our previous work.17 The
PVP/Ag@PU nanofiber membrane was fabricated via a simple two-step
dipping method. Typically, the PVP and STA mixture was dissolved
into the ethanol, deriving homogeneous PVP/STA solution with
different PVP concentration of 0, 0.2, 1, 2, 5, 7, and 10 wt %, and the
STA concentration was controlled at 10 wt %. Subsequently, the PU
nanofiber membrane was immersed into the as-prepared PVP/STA
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solution for 40 min at the room temperature (∼25 °C). Then the
membrane adsorbing the PVP and STA (STAP) was migrated to the
N2H4·H2O solution for 1 h, during which the STA was completely
reduced to Ag nanoparticles. After being washed by deionized water,
the final PVP/Ag@PU nanofiber membrane was dried at 60 °C. The
resultant composite membrane was denoted as PVP-X/Ag@PU (X: the
concentration of PVP in the PVP/STA solution). It is worth noting that
the composite membrane without special explanation was prepared
under the PVP (Mw = 10 000) concentration of 5 wt % in this article,
and the PVP-5/Ag@PU composite membrane was called APP in the
characterization part.
2.3. Characterization. The microstructures and surface morphol-
ogies of the nanofibrous membranes were observed by a field emission
scanning electron microscopy (FE-SEM, Zeiss Supra55, Germany),
and a Transmission electron microscopy (TEM, Philips FEG -CM200).
The acceleration voltage of SEM and TEM characterization was 5 and
20 kV, respectively. The chemical composition of the nanofiber
composite was examined by X-ray photoelectron spectroscope (XPS)
analysis (ESCALAB 250Xi). An attenuated total reflection (ATR)
mode on a Cary 610/670 instrument was applied for the Fourier
transform infrared spectroscopy (FT-IR) measurement. The Raman
spectra of the samples were obtained via a Raman confocal microscope.
The conductivity of the membranes was measured by a Four-Probe
Resistance Meter (RTS-9, Guangzhou, China). The surface repellence
of the nanofiber composites was reflected by the water contact angles
(CAs). The thermal property of the nanofiber composites was
characterized using a thermogravimetric analysis system (TGA/Pyris
1 TGA, PerkinElmer Co. Ltd., U.S.) with the temperature ranging from
30 to 800 °C at a heating rate of 10 °C min−1 in a nitrogen atmosphere.
A Universal Testing Machine (Instron Co. Ltd., U.S.) was used to
analyze the mechanical property of PU nanofibrous membrane and its
composites. The samples were cut into a dumbbell-shape (20 × 4 × 0.2
mm3) for the test, and the corresponding crosshead speed was fixed at
100 mm min−1. The stability of the conductivity was examined by
exposure in air, sand abrasion, ultrasonication washing, and stretching
tests.
2.4. EMI Shielding Measurements. A vector network analyzer
(Agilent N5230) was used to measure scattering parameters (S11 and
S21) which can reflect the EMI shielding property by calculating the
effectiveness (SE) in the frequency of 8.2−12.4 GHz (X-band). The
electromagnetic interference (EMI) shielding properties of the
composite membranes with a size of 25 × 13 mm were evaluated
according to the following detailed equations:18
R = |S11|2
T = |S21|2
A+R+T=1
SET (dB) = − 10log T
SER (dB) = − 10log(1 − R )
SET (dB) = SEA + SER + SEM
In the equations, R represents the power coefficients of reflectivity, T
stands for transmissivity, and A is absorptivity, and SET, SER, SEA refers
to the total EMI shielding effectiveness, reflection shielding
effectiveness, absorption shielding effectiveness, respectively.
2.5. Antibacterial Assessments. To measure the antibacterial
performance, the nanofiber membranes were cut into small round
pieces and was assessed by an inhibition method against Escherichia coli
and Staphylococcus aureus bacteria. The above two bacteria suspensions
were incubated at 37 °C for 12 h in the centrifuge tubes. And then the
activated bacteria (E. coli and S. aureus) were diluted with the
concentration of 10−7 cfu/mL. The composite membranes were placed
on a Luria−Bertani (LB) agar solid medium which was coated with 100
μL diluted bacterial solution and incubated in a constant temperature
incubator at 37 °C for 24 h. All the samples and equipment were
sterilized in the UV light for 15 min before the test.
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Figure 1. Schematic demonstration for the preparation of the PVP/Ag @PU.
Figure 2. (a) The photograph of the PVP/Ag@PU with an ultralow resistance. SEM images of the nanofiber composite (b) Top-view and (c) cross-
sectional view. TEM image of (d) the nanofiber composites, (e) PVP/Ag nanoparticles, and (f) the magnified TEM image of the nanoparticles.
3. RESULTS AND DISCUSSION
3.1. Morphology and Structure Characterization. The
PVP assisted preparation of the PVP/Ag@PU is schematically
described in Figure 1, which mainly includes two steps, that is,
the dip coating and ion reduction. In the first dipping process,
Ag+ is chelated with the nitrogen in PVP through electrostatic
interaction, forming the PVP@STA nanoclusters.19,20 Then, the
Ag complex in the solvent is adsorbed onto the PU nanofibers by
the ion−dipole interaction between trifluoroacetate anions
(CF3COO−) and the hydroxyl groups (−OH) of the alcohol
that facilitates the interaction between the Ag precursor and the
urethane of PU.21 Furthermore, the PVP that can be considered
as a surfactant further promotes the Ag+ adsorption.22 Then, the
STAP membrane is immersed into the solution of hydrazine
hydrate (N2H4·H2O) to reduce Ag+, forming the PVP/Ag core−
shell nanoparticles decorated onto the surface of PU nanofibers.
SI Figure S1 displays the XRD pattern of the composite
membranes. The diffraction peaks with the 2θ of 38.2°, 44.3°,
64.5°, and 77.4° correspond to [111], [200], [220], and [311]
crystal faces of sliver (JCPDS No. 04-0783),23 indicating that the
crystal structure of Ag nanoparticles is face-centered cubic
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(fcc).24 However, the characteristic peaks were not present in
the STAP membrane, which indicates the Ag precursor rather
than AgNPs is uniformly coated on the surface of the nanofibers
under the assistance of PVP.
Figure 2a shows a piece of composite membrane with metallic
luster whose surface resistance is as low as 2.44 Ω. The Ag
particles are uniformly and tightly anchored onto the PU
nanofibers (Figure 2b), forming a continuous conductive shell.
The thickness of PVP/Ag shell layer is approximately 200 nm
(see the cross- section SEM image in Figure 2c and the TEM
image in Figure 2d). It is also found from Figure 2b,c that the
interface between AgNPs (or Ag aggregates) and between
AgNPs and PU nanofibers is vague, indicating a strong
interfacial adhesion. It can be found from SI Figure S2 that
the size for the AgNPs ranges from a few tens of nanometers to
300 nm, and the average size is around 149.8 nm. The detailed
information about the interface between AgNPs is shown in
Figure 2e,f. Clearly, the AgNPs are wrapped by a thin layer of
PVP with the thickness of a few tens of nanometers (see the blue
dotted line in Figure 2f), and the electrons can transmit by
tunneling effect.25,26 In fact, the molecular weight (Mw) of PVP
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Figure 3. (a) Typical stress−strain curves of the composite membrane. (b) Mechanical performance of pure PU nanofiber and its composite
membranes.
strongly affects the size of the generated Ag nanoparticles and
the interfacial interaction between AgNPs and PU nanofibers.
As shown in SI Figure S3, the higher the molecular weight, the
smaller the Ag nanoparticle size, because the PVP with a higher
molecular weight has stronger encapsulation to Ag particles due
to its longer molecular chain and was able to hinder the
nucleation and growth and further aggregation.27,28 The long
molecular chain is adverse to the electron transfer. Furthermore,
when the Mw of PVP reaches a critical value, the long molecule
chain can, to a certain degree, obstruct both the STA adsorption
and the interfacial interaction between the generated nano-
particles and the PU nanofibers. As shown in SI Figure S3c,
microcracks appear on the PVP/AgNPs shell when the PVP with
the Mw of 58 000 is used. However, more and bigger cracks are
found on the surface of the nanofiber composite prepared by
using a very high Mw PVP (130 0000) (SI Figure S3e), which
can severely damage the conductive network. In addition, the
PVP with a lower Mw is dissolved in water more easily and thus
water can wet the PVP/AgNPs surface more quickly. As a result,
the increase of Mw leads to the decline of both the conductivity
and wetting time, as is summarized in SI Table S1. It is found
that the PVP (Mw = 10 000)/Ag@PU nanofiber composite
exhibits an extremely high conductivity of 245.7 ± 30.6 S/cm
and a very short wetting time of 3 s. However, the conductivity
largely decreases to 30.9 ± 10.9 S/cm while the wetting time
increases to 14 s for PVP (Mw = 1 300 000)/Ag@PU nanofiber
composite. Apart from the molecule weight, the PVP
concentration in the precursor solution can influence the
conductivity and wettability of the membrane. As shown in SI
Figure S4a, the conductivity of the nanofiber composite
increases with the concentration of PVP (Mw = 10 000) and
reaches the maximum value at 5 wt %. At the concentration of 10
wt %, the conductivity drops to even lower than that of the
composite prepared without use of the PVP, due to the thick
insulating PVP layer wrapping the AgNPs. On the other hand,
the wetting time first drops and then rises with increasing the
PVP concentration, and also reaches the minimum value at 5 wt
% (SI Figure S4b).
The XPS spectrum including survey, C 1s, O 1s, and Ag 3d is
shown in SI Figure S5. In SI Figure S5a, there are five
characteristic peaks in the total survey, corresponding to the
elements of C, N, O, Ag, and F. It can be found in SI Figure S5b
that the CC, CO, CO, and CH2CH2 are located
at 284.3, 285.58, 288.53, and 291.28 eV, respectively. Also, the
corresponding peaks of CO and CO are at 532.78 and
531.88 eV in O 1s spectra (SI Figure S5c). SI Figure S5d
presents Ag 3d spectra, and the peaks at 367.78 and 373.78 eV
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are attributed to 3d5/2 and 3d3/2 bands of Ag, respectively.29
Compared with the XPS spectrum of the PU nanofiber mat, the
new peak of −CH2−CH2− at 291.28 eV reveals that the PVP is
successfully introduced to the surface of the AgNPs. The
functional groups of the PU nanofiber membrane and its
composites are characterized by the ATR-FTIR and Raman
spectra. For the FTIR spectra of pristine PU nanofiber, there are
several prominent peaks ascribed to the vibration of N−H
stretching (3332 cm−1), hydrogen-bonded CO (1724 and
1597 cm−1), NH in-plane bending (1529 cm−1), CO band
(1170 cm−1) and COC (1070 cm−1) showing in SI Figure
S6a.30 By comparison, some new peaks appear while some
original peaks of TPU were absent after adsorption of STA and
PVP. For instance, the original peak at 1597 cm−1 shifts to 1633
cm−1 due to the reaction between Ag particles and the CO
group. The peaks at 1425, 841, and 725 cm−1 belong to the
stretching vibration of CF3, OH band, and the out-plane
bending vibration of C−H group of the trifluoroacetate anions
(CF3COO−), respectively.21 However, all these characteristic
peaks such as the peaks at around 1425, 841, and 725 cm−1,
become less evident and even disappear for the PVP/Ag@PU
indicating the complete reduction of STA to AgNPs. In the
Raman spectra (SI Figure S6b), the peaks associated with the
stretching vibration of CH2, CO, CC, and CH for the
PU spectra are at around 2923, 1725, 1614, and 1436 cm−1,
respectively.10,31 After introducing the STA and PVP, the peak
belonging to the CH2 shifts to 2942 cm−1, and the new peaks at
1438 and 849 cm−1 are corresponding to the shear vibration of
CH2 in the PVP long chain and stretching vibration of CC in
the heterocycle, respectively. Nonetheless, the peak at around
1438 cm−1 in STAP transforms into two intense broad bands at
1595 and 1397 cm−1 which relates to the Ag nanoparticles in the
APP.32 Meanwhile the peak at 849 cm−1 shifts to 853 cm−1 with
a weaker intensity, indicating some interaction may exist
between the heterocycle of the PVP molecules and AgNPs.
The thermal decomposition behavior of three nanofiber
composite membranes (PU, STAP and APP) is presented in SI
Figure S6c,d. It is clear that PU and APP membrane begin to
decompose when the temperature is higher than 320 °C and has
one major weight loss process, while the STAP membrane
begins to thermally degrade over 100 °C and exhibits three
weight loss process (see the corresponding peaks in the STG
curve in SI Figure S6d). The three weight loss of the STAP (0−
100 °C, 220−320 °C, over 320 °C) refer to the evaporation of
absorbed water, precursor decomposition and thermal degra-
dation of PU and PVP, respectively. After the composites
completely decomposes, the weight percentages of the residue
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Figure 4. Photographs of the inhibition ring of the composite membranes after 12 h of incubation against (a) E. coli and (b) S. aureus.
for PU, STAP and APP at the temperature of 800 °C are
approximately 3.28, 30.73, and 35.05 wt %, respectively.17,33
3.2. Mechanical, Antibacterial and Permeability
Property. In practical applications, the wearable material is
usually subject to mechanical deformations (e.g., stretching).
Figure 3a shows the stress−strain curves of the PU nanofiber
membrane and its composites and the detailed mechanical
properties is summarized in Figure 3b. The Young’s modulus,
tensile strength and elongation at break of the PU nanofiber
membrane are 1.47 MPa, 7.57 MPa, and 451.68%, respectively.
The Young’s modulus and tensile strength are not improved for
PVP-0/Ag@PU despite the introduction of the rigid AgNPs.
The reason is that the interfacial bonding between Ag NPs and
PU nanofiber is relatively weak and thus the stress during
stretching cannot be effectively transferred to AgNPs. Never-
theless, both the Young’s modulus, tensile strength, and
elongation of PVP-5/Ag@PU greatly increase to 2.54 MPa,
12.27 MPa, and 552.16%, respectively. The PVP served as an
“interfacial binder” can enhance the interfacial bonding between
Ag particles and matrix and hence achieve efficient stress transfer
from PU nanofibers to rigid Ag particles. Since the nanofiber
composite possesses a multiple core−shell structure, the rigid
AgNPs do not hinder the macromolecular movement and thus
the material’s stretchability. Benefiting from the good interfacial
interaction, the interface debonding between the nanofiber and
the PVP-Ag core−shell particles can absorb large fracture
energy, leading to the enhancement of the fracture toughness.
As well-known, Ag (0) nanoparticles maybe ionized into Ag
(1) with the existence of any fluid (e.g., wound fluid) and react
with bacteria in binding to protein and cell membranes,
inhibited bacteria growth and even resulted in cell death
which is desirable for wearable materials.34 Here, the inhibition
ring test was carried out to evaluate the antibacterial properties
of the composite membrane. The experiment results are shown
in Figure 4a,b and in Table 1. It is found that there’s no clear
inhibition ring around the outer edge of the PU nanofiber
membrane against both E. coli and S. aureus, suggesting the poor
antibacterial performance. Whereas, both the PVP-0/Ag@PU
and the PVP-5/Ag@PU have clear inhibition rings against two
kinds of bacteria, demonstrating the excellent antibacterial
performance. Surprisingly, the PVP-5/Ag@PU has a larger
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Table 1. Outer Size of Bacteriostatic Belt of the Two
Composite Membranes
bacterial species PVP-0/Ag@PU PVP-5/Ag@PU
E. coli 1.7 cm 1.8 cm
S. aureus 1.8 cm 2 cm
inhibition ring radius, compared with PVP-0/Ag@PU, which
indicates that the PVP can also play a positive role in inhibition
of the two bacteria growth. Moreover, it is found that the
composite membranes show similar kind of zone of inhibition
for E. coli and S. aureus which may be ascribed to the high
concentration and even distribution of Ag particles in the
membrane.34,35 Accordingly, the synergistic effect of PVP and
Ag is conducive to antibacterial performance.
As well-known, breathability is quite important for the
wearable fabric composite. The PU nanofibrous membrane
possesses unique porous structure formed during the electro-
spinning. Fortunately, these pores between the polymer
nanofibers are preserved after the introduction of the PVP/Ag
on the nanofiber surface. These pores are served as the
transmission channels for the gas diffusion, and the water
vapor permeates from a relatively high humidity to low humidity
environment through these pores. Additionally, the super-
hydrophilicity of the membrane is conducive to the breath-
ability. The quantitative evaluation for the gas permeability is
shown in SI Figure S7a by recording the mass change of the
water (∼45 °C) in a small bottle sealed with the composite
membrane. An infrared lamp was used to maintain a stable
temperature of the water (see the inset of SI Figure S7a). It is
found the water evaporation rate for the pristine PU and PVP/
Ag@PU nanofiber membrane is 0.21 kg m−2 h−1 and 0.23 kg
m−2 h−1, respectively. Interestingly, the breathability of the
composite membrane is even better than that of the pristine
polymer nanofiber membrane although the conductive Ag shell
can, to a certain degree, reduce the pore size inside the
membrane. The PVP decorated AgNPs contributes to the
superhydrophilicity and hence improve the breathability of the
membrane. In order to visually show the permeability of the
membrane, the following two experiments were carried out (SI
Figure S7b,c). An opening vial filled with hot water with the
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Figure 5. Normalized relative conductivity variation of PVP-0/Ag @PU and PVP-5/Ag @PU with (a) storage days in air, (b) sand abrasion cycles, (c)
ultrasonication washing time, and (d) stretching cycles. The insets in each figure are the photographs showing the durability tests.

Figure 6. (a) I−V curve of the PVP/Ag @PU with a low resistance. (b) Temperature−time curve of the sample under different voltages and (c) the
corresponding IR images of the equilibrium temperature under different applied voltages, (d) Cyclic electro-thermal performance of the nanofiber
composite under 0.6 V.

temperature of about 80 °C is placed in a beaker, and the vial is
covered with the composite membrane. As seen in SI Figure S7b,
the water vapor can pass through the composite membrane and
condense into small droplets after meeting the wall of the cold
beaker. SI Figure S7c reflects that not only water but also the
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HCl gas can penetrate through the PVP/Ag@PU and generate
the white smoke of the ammonium chloride after the reaction
with the ammonia evaporated from another opening vial.
The stability and durability of material performance is quite
important during the long-term use. Figure 5 shows the
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Figure 7. (a) The Scheme showing the EMI shielding mechanism of the PVP/Ag@PU membrane. (b) The influence of PVP concentration on EMI SE
of the composite membrane in the X band. (c) The average SET, SEA, and SER of the PVP-X/Ag@PU. (d) Comparison of the EMI shielding
effectiveness (SE) and specific SE (SSE) of different composite fabrics. (e,f) EMI shielding performance of the PVP/Ag@PU before and after the
ultrasonic washing for 10 min, stretching for 500 cycles, respectively.
normalized relative conductivity variation (σ/σ0) of the
nanofiber composites undergoing different durability tests, and
σ0 and σ refer to the initial conductivity and the conductivity
after the test. As known, Ag is easily oxidized in air. As shown in
Figure 5a, PVP-0/Ag @PU exhibits a continuous decrease in
electrical conductivity when exposed in air, and the conductivity
drops more than 60% after 10 days exposure in air. However, the
conductivity can maintain ∼85% of its initial value for PVP-5/Ag
@PU, because the PVP layer wrapping the AgNPs can, to a large
extent, prevent the oxidization of AgNPs. Therefore, the
presence of PVP can improve the service life of the membrane.
Afterward, the conductivity changes of the nanofiber mem-
branes were recorded during the sand abrasion test which can
simulate the actual wear condition (Figure 5b). It is clear that the
conductivity of the PVP-5/Ag@PU shows excellent stability,
and the σ/σ0 shows slight decrease during the first test and then
is stabilized to approximately 0.8 during the following cyclic
abrasion test. On the contrary, the conductivity of the PVP-0/
Ag@PU dramatically declines and σ/σ0 is only around 0.1 after
ten tests, because large number of AgNPs may fall off the
nanofibers during the abrasion, due to the poor interfacial
adhesion. Figure 5c displays the σ/σ0 of the nanofiber
composites during the ultrasonic washing. The conductivity of
the PVP-5/Ag@PU slightly decreases with the ultrasonic time,
and the water remains clear after ultrasonic treatment for 10 min,
indicating that the AgNPs have strong bonding with the
nanofibers. On the other hand, the σ/σ0 of the controlled sample
greatly drops to below 0.6. Figure 5d shows the σ/σ0 of the
samples under different stretching-releasing cycles. It is found
that PVP-5/Ag@PU still maintains more than 85% of the
original conductivity after 500 cycles and fluctuates at this value
(σ/σ0 = 0.83) in the next 300 cycles, suggesting that the
conductive network of the PVP-5/Ag@PU is maintained during
the multiple stretching tests. While, on the other hand, the
conductive network of the PVP-0/Ag@PU is gradually damaged
during the cyclic stretching test with the σ/σ0 of ∼0.2. All the
above tests verify that the PVP can be served as an antioxidant
layer and also enhance the interfacial bonding between the Ag
particles and substrate and thus guarantees the excellent
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durability and reliability of the nanofiber composite during the
practical applications.
3.3. Electro-Thermal Conversion and EMI Shielding
Property. Thermal management and electromagnetic shielding
properties can greatly expand the application of wearable fabrics
in addition to the basic properties such as flexibility and
breathability. The self-heating performance of the wearable
electronic is important and desirable especially in an extremely
cold environment. Here, the flexible PVP/Ag@PU nanofiber
composite membrane has excellent Joule heating performance
because of its high conductivity. The detailed information about
the electro-thermal conversion behavior can be found from
Figure 6. The linear I−V curve (Figure 6a) demonstrates that
the membrane obeys the Ohm’s law with a low resistance.
Generally, the higher the applied voltage, the larger the
generated Joule heat. When the voltage is on, the material
temperature increases quickly, reaches an equilibrium value and
then levels off (Figure 6b). The equilibrium temperature of the
PVP/Ag@PU raises up from the room temperature to 32.8 °C
under a very low voltage of 0.4 V, while the temperature can
arrive at 46.6 and 55 °C at 0.6 and 0.8 V, respectively. The
equilibrium temperature can even reach 76.1 °C under the
relatively low voltage of 1 V. The corresponding IR images of the
equilibrium temperatures of the nanofiber composite at the four
voltages can be observed in Figure 6c. Hence, the high
conductivity endows the material with excellent electro-thermal
conversion performance at a low voltage, which can not only
ensure the safety during the practical use but also significantly
reduce the energy consumption.36,37 The recyclability of the
Joule heating performance is shown in Figure 6d. In this first
cycle, the temperature rises to 47 °C in 120 s when the voltage is
on, and it can return to the room temperature within 120 s after
the voltage is off, indicating outstanding recoverability. More-
over, the curve of the tenth heating and cooling cycle is almost
same as the first one, verifying the excellent recyclability.
With the advent of 5G era, the shielding of high-frequency
electromagnetic wave becomes more and more important for
the human health and normal working of the electronic
equipment. The flexible PVP/Ag@PU possesses a very high
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ACS Applied Materials & Interfaces
electrical conductivity and hence exhibits excellent EMI
shielding performance. The EMI shielding mechanism of the
nanofiber composite is schematically illustrated in Figure 7a, and
mainly includes the reflection, absorption, and multireflection.
When the high-frequency electromagnetic wave passes through
the conductive material, a changing magnetic field will be
generated inside the conductor, thus affecting the electro-
magnetic interference shielding effect. Therefore, the “skin
depth” (δ) of conductive materials is an important index in the
field of electromagnetic shielding which refers to the thickness
from material surface to where the surface current density is 1/e.
As is known to all, when the conductivity, σ ≫ 2πfε0, the δ can be
evaluated by the following equation:
δ = (πfμσ )−1/2
Where ε0 represents the vacuum permittivity, f refers to the
frequency, σ and μ are the electrical conductivity and magnetic
permeability of the material. (μ = μ0μr, μ0 = 4π × 10−7 H m−1 and
the nanofiber membrane is nonmagnetic, so the value of μr is
1).38,39 In our experiment, the highest frequency of electro-
magnetic wave is 12.4 GHz. Hence the value of 2πfε0 can reach
up to approximately 0.667 Hz F/m (equal to 0.667 S/m), which
is far smaller than the electrical conductivity of our nanofiber
membrane (24570 S/m). Therefore, the above formula for skin
depth applies to our materials.
As well-known, the shielding effectiveness of the reflectivity
(SER) and absorptivity (SEA) can be expressed as38,40
Z0 σμ0
SER = 20log = 20log
4Z1 4 2πfμε0
d d
SEA = 20 log e = 8.686 = 8.686d πfμσ
δ δ
Where d represents the thickness of EMI shielding material, Z0 (
Z0 = σμ0 ) and Z1 (Z1 = 2πfμε0 ) are the impedances of free
space and the composite membrane. According to the
theoretical formula, reflection relates to the free electrons in
material surface which means high conductivity may cause the
reflection of most the incident electromagnetic wave. On the
other hand, absorption is relevant to electric dipoles and
electron transport, and porous architectures are beneficial to the
multireflection.41,42 Herein, PVP/Ag@PU membrane possesses
an extremely high conductivity and a large number of microsized
pores between nanofibers. The abundant Ag nanoparticles can
provide plenty of mobile charge carriers, which results in a very
high EMI reflection. When the residual electromagnetic wave
enters inside the composite membrane, the large conductivity
mismatch between conductive AgNPs and insulating PVP or PU
contributes to the polarization and charge accumulation that are
beneficial to the wave absorption. Meanwhile the porous
structure of membrane provides sufficient multireflection
venues which can enhance the continuous reflection. It can be
seen from Figure 7b,c that the values of SEA, SER, and SET all
increase with the increase of the PVP concentration, which
accords with the evolution of the conductivity. It is worth noting
that PVP-5/Ag@PU shows the highest EMI shielding
effectiveness (EMI SE) of 96.9 dB, resulting from its high
conductivity of 245.7 S/cm. The higher SEA with increased PVP
content is ascribed to more electron transport which relates to
the EM wave depleting and transforming into thermal energy.
Composite fabrics with a high electrical conductivity have been
extensively studied in the EMI shielding field, including the
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metal, carbon, and MXene-based shields. Figure 7d summarizes
the EMI shielding performance including the SE and SSE of the
conductive fibric composites from our study and some recently
published work.43−55 And the detailed information is shown in
SI Table S2. For example, Hong and his co-workers fabricated a
carbon nanofiber mat with an ultrahigh SSE value of 394.9 dB
cm3/g, while the composite mat with 3−4 mm thickness only
exhibits a moderate SE of 52.2 dB. 51Recently, Zeng and his
colleagues designed an ultrathin cellular membrane by electro-
spinning, thermal lamination and PDA assisted copper
deposition. 44The as-prepared metal-wrapped polymer nano-
fiber membrane exhibits excellent EMI shielding performance
(with the SE and SSE of 48 and 76.8 dB cm3/g, respectively)
with the thickness of only 5 μm. Nevertheless, the hot-pressing
process led to significant decrease of the pores between the fibers
and hence the air permeability (i.e., breathability) of the fiber
membrane, although it greatly reduced the contact resistance
between the fibers and hence enhance the electrical con-
ductivity. Also, the density of the copper decorated fiber
composite was 1.6 g cm−3, indicating a high mental content.
Improving the EMI SE by increasing the metal content is not
only costly but also sacrifices, to a certain degree, the mechanical
properties. In this study, the thickness and density of PVP/Ag@
PU membrane is approximately 100 μm and 0.56 g/cm3 with an
extremely high EMI SE of 96.9 dB that can satisfy the
requirement in most commercial applications. By calculation,
the SE/d and the SSE (SE divided by density) of our membrane
is 959.7 dB/mm and 169.7 dB cm3/g. As shown in Figure 7d, the
SSE of the PVP/Ag@PU is the second highest among the listed
samples and the EMI SE is far beyond that of other shielding
materials. In summary, the PVP/Ag@PU in this work exhibits
excellent EMI shielding performance with a low thickness and
density while at the same time maintain the outstanding
breathability.
As known, good durability in complex conditions is required
for wearable electronics in practical use. Figure 7e shows the
EMI shielding performance of the nanofiber composite before
and after the durability test. The EMI SE after the ultra-
sonication washing and multiple stretching tests is 85.4 and 82.8
dB, respectively, exhibiting slight decline compared with that of
the pristine sample. The detailed SEA and SER are summarized in
Figure 7f. It is found there is only a small drop for the SEA after
the ultrasonic treatment for 10 min and stretching for 500 cycles
(75.6 and 73.1 dB, respectively), although the SER drops to a half
of its original value (9.8 and 9.7 dB, respectively). The excellent
surface stability and durability for the EMI shielding perform-
ance are ascribed to the good interfacial bonding between the
AgNPs and the substrate. In order to proof, the excellent EMI
shielding of the nanofiber composite is examined by a
homemade wireless power transmission system composed of a
DC power, a transistor, a transmitter coil, a receiver coil and
light-emitting diode (LED) lights (SI Figure S8a). The direct
current is transformed into alternating current by a transistor,
forming an alternating magnetic field by the aid of the
transmitter coil. Magnetism generates electricity, turning on
the LED on the receiver end when the circuit is closed (SI Figure
S8b). Due to the dissipation of the EM waves by the versatile
membrane, the LED is turned off when the nanofiber composite
is inserted between the two coils (SI Figure S8c and SI Video
S1). The test shows promising applications of the nanofiber
composite in antijamming electronics.
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ACS Appl. Mater. Interfaces 2021, 13, 21865−21875
ACS Applied Materials & Interfaces
4. CONCLUSIONS
Herein, a highly electrically conductive, anti- oxidant,
antibacterial, and durable nanofiber composite is prepared by
PVP assisted adsorption of Ag precursor and then reduction of
Ag+. PVP serves as “interfacial adhesion agent” and significantly
improves the interfacial bonding between Ag particles and
matrix and also protects AgNPs from being oxidized. The
Young’s modulus, tensile strength and elongation of the
composite membrane reaches up to 2.5 MPa, 12.2 MPa, and
552.2%, respectively, which are 1.1 MPa, 4.7 MPa, and 100.48%
higher than those of the PU nanofiber membrane. AgNPs shell
on the nanofiber surface construct the conductive network,
which can endow the nanofibrous membrane with not only high
electrical conductivity (as high as 245.7 ± 30.6 S/cm) and hence
excellent Joule heating performance but also the antibacterial
property. In addition, the core−shell structure does not damage
the porous structure of the polymer nanofibrous membrane and
hence the outstanding breathability is preserved after
introduction of the AgNPs. The conductivity is, to a large
degree, maintained when the material is exposed to air, sand
abrasion, ultrasonication washing, and multiple stretching tests,
exhibiting excellent surface stability and durability. The
multifunctional membrane exhibits an extremely high EMI SE
and SSE of 96.9 dB and 169.7 dB cm3/g, respectively, which can
almost be maintained after ultrasonication washing and cyclic
stretching test. This multifunctional composite membrane has
great potential application prospects in flexible and wearable
electronics.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c05319.
XRD pattern; size distribution of the AgNPs; SEM image;
conductivity and wetting time of membrane with PVP of
different molecular weight and concentration; XPS, FTIR,
and Raman spectra; TGA curves; evaporation test results;
comparison of EMI shielding performance; visual experi-
ment of EMI shielding performance (PDF)
Video showing the excellent EMI shielding of the
nanofiber composite examined by a homemade wireless
power transmission system (MP4)
■
AUTHOR INFORMATION
Corresponding Authors
Jiefeng Gao − School of Chemistry and Chemical Engineering,
Yangzhou University, Yangzhou, Jiangsu 225002, China;
State Key Laboratory of Polymer Materials Engineering,
Sichuan University, Chengdu, Sichuan 610065, P. R. China;
Key Laboratory of Organosilicon Chemistry and Material
Technology of Ministry of Education, Hangzhou Normal
University, Hangzhou 311121, People’s Republic of China;
Email: jfgao@yzu.edu.cn
Hang Yao − School of Chemistry and Chemical Engineering,
Yangzhou University, Yangzhou, Jiangsu 225002, China;
Email: yaohang@yzu.edu.cn
Authors
Shu Zhang − School of Chemistry and Chemical Engineering,
Yangzhou University, Yangzhou, Jiangsu 225002, China
21873
www.acsami.org Research Article
Xuewu Huang − School of Chemistry and Chemical
Engineering, Yangzhou University, Yangzhou, Jiangsu 225002,
China
Wei Xiao − School of Chemistry and Chemical Engineering,
Yangzhou University, Yangzhou, Jiangsu 225002, China
Lulu Zhang − School of Chemistry and Chemical Engineering,
Yangzhou University, Yangzhou, Jiangsu 225002, China
Ling Wang − School of Chemistry and Chemical Engineering,
Yangzhou University, Yangzhou, Jiangsu 225002, China
Junchen Luo − School of Chemistry and Chemical Engineering,
Yangzhou University, Yangzhou, Jiangsu 225002, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c05319
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by Natural Science
Foundation of China (Nos. 51873178, 21673203), the Opening
Project of State Key Laboratory of Polymer Materials Engineer-
ing (Sichuan University) (No. sklpme2020-4-03), Qing Lan
Project of Yangzhou University and Jiangsu Province, High-end
Talent Project of Yangzhou University, the Priority Academic
Program Development of Jiangsu Higher Education Institu-
tions, Postgraduate Research & Practice Innovation Program of
Jiangsu province (No. KYCX18_2364, No. KYCX20_2977)
and Outstanding Doctoral Dissertation Fund of Yangzhou
University.
■
REFERENCES
(1) Yang, T.; Xie, D.; Li, Z.; Zhu, H. Recent Advances in Wearable
Tactile Sensors: Materials, Sensing Mechanisms, and Device Perform-
ance. Mater. Sci. Eng., R 2017, 115, 1−37.
(2) Zeng, W.; Shu, L.; Li, Q.; Chen, S.; Wang, F.; Tao, X.-M. Fiber-
Based Wearable Electronics: A Review of Materials, Fabrication,
Devices, and Applications. Adv. Mater. 2014, 26 (31), 5310−5336.
(3) Pan, Q.; Shim, E.; Pourdeyhimi, B.; Gao, W. Nylon-Graphene
Composite Nonwovens as Monolithic Conductive or Capacitive
Fabrics. ACS Appl. Mater. Interfaces 2017, 9 (9), 8308−8316.
(4) Nezakati, T.; Seifalian, A.; Tan, A.; Seifalian, A. M. Conductive
Polymers: Opportunities and Challenges in Biomedical Applications.
Chem. Rev. 2018, 118 (14), 6766−6843.
(5) Das, T. K.; Ghosh, P.; Das, N. C. Preparation, Development,
Outcomes, and Application Versatility of Carbon Fiber-Based Polymer
Composites: a Review. Adv. Compos. Hybrid Mater. 2019, 2, 1−20.
(6) Mondal, S.; Ravindren, R.; Bhawal, P.; Shin, B.; Ganguly, S.; Nah,
C.; Das, N. C. Combination Effect of Carbon Nanofiber and Ketjen
Carbon Black Hybrid Nanofillers on Mechanical, Electrical, and
Electromagnetic Interference Shielding Properties of Chlorinated
Polyethylene Nanocomposites. Composites, Part B 2020, 197, 108071.
(7) Huang, X.; Zhang, S.; Xiao, W.; Luo, J.; Li, B.; Wang, L.; Xue, H.;
Gao, J. Flexible PDA@ACNTs Decorated Polymer Nanofiber
Composite with Superhydrophilicity and Underwater Superoleopho-
bicity for Efficient Separation of Oil-in-Water Emulsion. J. Membr. Sci.
2020, 614, 118500.
(8) Song, Y.; Zheng, N.; Dong, X.; Gao, J. Flexible Carboxylated
CNT/PA66 Nanofibrous Mat Interleaved Carbon Fiber/Epoxy
Laminates with Improved Interlaminar Fracture Toughness and
Flexural Properties. Ind. Eng. Chem. Res. 2020, 59 (3), 1151−1158.
(9) Zheng, N.; Song, Y.; Wang, L.; Gao, J.-f.; Wang, Y.; Dong, X.
Improved Electrical and Mechanical Properties for the Reduced
Graphene Oxide-Decorated Polymer Nanofiber Composite with a
Core−Shell Structure. Ind. Eng. Chem. Res. 2019, 58 (34), 15470−
15478.
https://doi.org/10.1021/acsami.1c05319
ACS Appl. Mater. Interfaces 2021, 13, 21865−21875
ACS Applied Materials & Interfaces
(10) Wang, L.; Chen, Y.; Lin, L.; Wang, H.; Huang, X.; Xue, H.; Gao, J.
Highly Stretchable, Anti-Corrosive and Wearable Strain Sensors Based
on the PDMS/CNTs Decorated Elastomer Nanofiber Composite.
Chem. Eng. J. 2019, 362, 89−98.
(11) Huang, X.; Li, B.; Song, X.; Wang, L.; Shi, Y.; Hu, M.; Gao, J.;
Xue, H. Stretchable, Electrically Conductive and Superhydrophobic/
Superoleophilic Nanofibrous Membrane with a Hierarchical Structure
for Efficient Oil/Water Separation. J. Ind. Eng. Chem. 2019, 70, 243−
252.
(12) Bhawal, P.; Ganguly, S.; Das, T. K.; Mondal, S.; Das, N. C.
Mechanically Robust Conductive Carbon Clusters Confined Ethylene
Methyl Acrylate−Based Flexible Composites for Superior Shielding
Effectiveness. Polym. Adv. Technol. 2018, 29 (1), 95−110.
(13) Bhawal, P.; Ganguly, S.; Das, T. K.; Mondal, S.; Choudhury, S.;
Das, N. C. Superior Electromagnetic Interference Shielding Effective-
ness and Electro-Mechanical Properties of EMA-IRGO Nano-
composites through the in-Situ Reduction of GO from Melt Blended
EMA-GO Composites. Composites, Part B 2018, 134, 46−60.
(14) Huo, L.; Luo, J.; Huang, X.; Zhang, S.; Gao, S.; Long, B.; Gao, J.
Superhydrophobic and Anti-Ultraviolet Polymer Nanofiber Composite
with Excellent Stretchability and Durability for Efficient Oil/Water
Separation. Colloids Surf., A 2020, 603, 125224.
(15) Luo, J.; Gao, S.; Luo, H.; Wang, L.; Huang, X.; Guo, Z.; Lai, X.;
Lin, L.; Li, R. K. Y.; Gao, J. Superhydrophobic and Breathable Smart
MXene-based Textile for Multifunctional Wearable Sensing Elec-
tronics. Chem. Eng. J. 2021, 406, 126898.
(16) Luo, J.; Huo, L.; Wang, L.; Huang, X.; Li, J.; Guo, Z.; Gao, Q.;
Hu, M.; Xue, H.; Gao, J. Superhydrophobic and Multi-Responsive
Fabric Composite with Excellent Electro-photo-thermal Effect and
Electromagnetic Interference Shielding Performance. Chem. Eng. J.
2020, 391, 123537.
(17) Lin, L.; Wang, L.; Li, B.; Luo, J.; Huang, X.; Gao, Q.; Xue, H.;
Gao, J. Dual Conductive Network Enabled Superhydrophobic and
High Performance Strain Sensors with Outstanding Electro-thermal
Performance and Extremely High Gauge Factors. Chem. Eng. J. 2020,
385, 123391.
(18) Bhawal, P.; Ganguly, S.; Das, T. K.; Mondal, S.; Nayak, L.; Das,
N. C. A Comparative Study of Physico-Mechanical and Electrical
Properties of Polymer-Carbon Nanofiber in Wet and Melt Mixing
Methods. Mater. Sci. Eng., B 2019, 245, 95−106.
(19) Jiang, C.; Nie, J.; Ma, G. A Polymer/Metal Core−Shell Nanofiber
Membrane by Electrospinning with an Electric Field, and its
Application for Catalyst Support. RSC Adv. 2016, 6 (27), 22996−
23007.
(20) Koczkur, K. M.; Mourdikoudis, S.; Polavarapu, L.; Skrabalak, S.
E. Polyvinylpyrrolidone (PVP) in Nanoparticle Synthesis. Dalton
Trans. 2015, 44 (41), 17883−17905.
(21) Park, M.; Im, J.; Shin, M.; Min, Y.; Park, J.; Cho, H.; Park, S.;
Shim, M.-B.; Jeon, S.; Chung, D.-Y.; Bae, J.; Park, J.; Jeong, U.; Kim, K.
Highly Stretchable Electric Circuits from a Composite Material of
Silver Nanoparticles and Elastomeric Fibres. Nat. Nanotechnol. 2012, 7
(12), 803−809.
(22) Kan, C.; Wang, C.; Zhu, J.; Li, H. Formation of Gold and Silver
Nanostructures within Polyvinylpyrollidone (PVP) Gel. J. Solid State
Chem. 2010, 183 (4), 858−865.
(23) Das, T. K.; Ganguly, S.; Remanan, S.; Ghosh, S.; Das, N. C.
Mussel-Inspired Ag/Poly(norepinephrine)/MnO2 Heterogeneous
Nanocatalyst for Efficient Reduction of 4-nitrophenol and 4-nitroani-
line: an Alternative Approach. Res. Chem. Intermed. 2020, 46 (7),
3629−3650.
(24) Wang, Y.; Li, Y.; Yang, S.; Zhang, G.; An, D.; Wang, C.; Yang, Q.;
Chen, X.; Jing, X.; Wei, Y. A Convenient Route to Polyvinyl
Pyrrolidone/Silver Nanocomposite by Electrospinning. Nanotechnol-
ogy 2006, 17 (13), 3304−3307.
(25) Wang, L.; Wang, H.; Huang, X.-W.; Song, X.; Hu, M.; Tang, L.;
Xue, H.; Gao, J. Superhydrophobic and Superelastic Conductive
Rubber Composite for Wearable Strain Sensors with Ultrahigh
Sensitivity and Excellent Anti-Corrosion Property. J. Mater. Chem. A
2018, 6 (47), 24523−24533.
21874
www.acsami.org Research Article
(26) Lin, Y.; Liu, S.; Chen, S.; Wei, Y.; Dong, X.; Liu, L. A Highly
Stretchable and Sensitive Strain Sensor Based on Graphene−Elastomer
Composites with a Novel Double-Interconnected Network. J. Mater.
Chem. C 2016, 4 (26), 6345−6352.
(27) Sun, Y.; Xia, Y. Shape-Controlled Synthesis of Gold and Silver
Nanoparticles. Science 2002, 298 (5601), 2176.
(28) Miao, Z.; Wang, P.; Zhong, A.; Yang, M.; Xu, Q.; Hao, S.; Hu, X.
Development of a Glucose Biosensor Based on Electrodeposited Gold
Nanoparticles−Polyvinylpyrrolidone−Polyaniline Nanocomposites. J.
Electroanal. Chem. 2015, 756, 153−160.
(29) Xie, K.; Sun, L.; Wang, C.; Lai, Y.; Wang, M.; Chen, H.; Lin, C.
Photoelectrocatalytic Properties of Ag Nanoparticles Loaded TiO2
Nanotube Arrays Prepared by Pulse Current Deposition. Electrochim.
Acta 2010, 55 (24), 7211−7218.
(30) Menes, O.; Cano, M.; Benedito, A.; Giménez, E.; Castell, P.;
Maser, W. K.; Benito, A. M. The Effect of Ultra-Thin Graphite on the
Morphology and Physical Properties of Thermoplastic Polyurethane
Elastomer Composites. Compos. Sci. Technol. 2012, 72 (13), 1595−
1601.
(31) Li, Y.; Zhou, B.; Zheng, G.; Liu, X.; Li, T.; Yan, C.; Cheng, C.;
Dai, K.; Liu, C.; Shen, C.; Guo, Z. Continuously Prepared Highly
Conductive and Stretchable SWNT/MWNT Synergistically Compos-
ited Electrospun Thermoplastic Polyurethane Yarns for Wearable
Sensing. J. Mater. Chem. C 2018, 6 (9), 2258−2269.
(32) Kendouli, S.; khalfallah, O.; Sobti, N.; Bensouissi, A.; Avci, A.;
Eskizeybek, V.; Achour, S. Modification of Cellulose Acetate Nano-
fibers with PVP/Ag Addition. Mater. Sci. Semicond. Process. 2014, 28,
13−19.
(33) Farjas, J.; Camps, J.; Roura, P.; Ricart, S.; Puig, T.; Obradors, X.
The Thermal Decomposition of Barium Trifluoroacetate. Thermochim.
Acta 2012, 544, 77−83.
(34) Basri, H.; Ismail, A. F.; Aziz, M. Polyethersulfone (PES)−Silver
Composite UF Membrane: Effect of Silver Loading and PVP Molecular
Weight on Membrane Morphology and Antibacterial Activity.
Desalination 2011, 273 (1), 72−80.
(35) Jung, W. K.; Koo, H. C.; Kim, K. W.; Shin, S.; Kim, S. H.; Park, Y.
H. Antibacterial Activity and Mechanism of Action of the Silver Ion in
Staphylococcus aureus and Escherichia coli. Appl. Environ. Microbiol.
2008, 74 (7), 2171.
(36) Luong, D. X.; Yang, K.; Yoon, J.; Singh, S. P.; Wang, T.; Arnusch,
C. J.; Tour, J. M. Laser-Induced Graphene Composites as Multifunc-
tional Surfaces. ACS Nano 2019, 13 (2), 2579−2586.
(37) Wang, Q.-W.; Zhang, H.-B.; Liu, J.; Zhao, S.; Xie, X.; Liu, L.;
Yang, R.; Koratkar, N.; Yu, Z.-Z. Multifunctional and Water-Resistant
MXene-Decorated Polyester Textiles with Outstanding Electro-
magnetic Interference Shielding and Joule Heating Performances.
Adv. Funct. Mater. 2019, 29 (7), 1806819.
(38) Wan, Y.-J.; Zhu, P.-L.; Yu, S.-H.; Sun, R.; Wong, C.-P.; Liao, W.-
H. Anticorrosive, Ultralight, and Flexible Carbon-Wrapped Metallic
Nanowire Hybrid Sponges for Highly Efficient Electromagnetic
Interference Shielding. Small 2018, 14 (27), 1800534.
(39) Zhang, K.; Li, G.-H.; Feng, L.-M.; Wang, N.; Guo, J.; Sun, K.; Yu,
K.-X.; Zeng, J.-B.; Li, T.; Guo, Z. Ultralow Percolation Threshold and
Enhanced Electromagnetic Interference Shielding in Poly (L-lactide)/
Multi-Walled Carbon Nanotube Nanocomposites with Electrically
Conductive Segregated Networks. J. Mater. Chem. C 2017, 5 (36),
9359−9369.
(40) Song, W.-L.; Cao, M.-S.; Lu, M.-M.; Bi, S.; Wang, C.-Y.; Liu, J.;
Yuan, J.; Fan, L.-Z. Flexible Graphene/Polymer Composite Films in
Sandwich Structures for Effective Electromagnetic Interference
Shielding. Carbon 2014, 66, 67−76.
(41) Ma, Z.; Kang, S.; Ma, J.; Shao, L.; Zhang, Y.; Liu, C.; Wei, A.;
Xiang, X.; Wei, L.; Gu, J. Ultraflexible and Mechanically Strong Double-
Layered Aramid Nanofiber−Ti3C2Tx MXene/Silver Nanowire Nano-
composite Papers for High-Performance Electromagnetic Interference
Shielding. ACS Nano 2020, 14 (7), 8368−8382.
(42) Li, L.; Ma, Z.; Xu, P.; Zhou, B.; Li, Q.; Ma, J.; He, C.; Feng, Y.;
Liu, C. Flexible and Alternant-Layered Cellulose Nanofiber/Graphene
https://doi.org/10.1021/acsami.1c05319
ACS Appl. Mater. Interfaces 2021, 13, 21865−21875
ACS Applied Materials & Interfaces www.acsami.org Research Article

Film with Superior Thermal Conductivity and Efficient Electro-

magnetic Interference Shielding. Composites, Part A 2020, 139, 106134.
(43) Lee, T.-W.; Lee, S.-E.; Jeong, Y. G. Highly Effective Electro-
magnetic Interference Shielding Materials based on Silver Nanowire/
Cellulose Papers. ACS Appl. Mater. Interfaces 2016, 8 (20), 13123−
13132.
(44) Zeng, Z.; Jiang, F.; Yue, Y.; Han, D.; Lin, L.; Zhao, S.; Zhao, Y.-B.;
Pan, Z.; Li, C.; Nyström, G.; Wang, J. Flexible and Ultrathin Waterproof
Cellular Membranes Based on High-Conjunction Metal-Wrapped
Polymer Nanofibers for Electromagnetic Interference Shielding. Adv.
Mater. 2020, 32 (19), 1908496.
(45) Wang, Y.; Gu, F.-q.; Ni, L.-j.; Liang, K.; Marcus, K.; Liu, S.-l.;
Yang, F.; Chen, J.-j.; Feng, Z.-s. Easily Fabricated and Lightweight PPy/
PDA/AgNW Composites for Excellent Electromagnetic Interference
Shielding. Nanoscale 2017, 9 (46), 18318−18325.
(46) Lim, G.-H.; Kwon, N.; Han, E.; Bok, S.; Lee, S.-E.; Lim, B.
Flexible Nanoporous Silver Membranes with Unprecedented High
Effectiveness for Electromagnetic Interference Shielding. J. Ind. Eng.
Chem. 2021, 93, 245−252.
(47) Wang, Y.; Peng, H.-K.; Li, T.-T.; Shiu, B.-C.; Zhang, X.; Lou, C.-
W.; Lin, J.-H. Layer-by-layer Assembly of Low-Temperature in-Situ
Polymerized Pyrrole Coated Nanofiber Membrane for High-Efficiency
Electromagnetic Interference Shielding. Prog. Org. Coat. 2020, 147,
105861.
(48) Yu, Y.-H.; Ma, C.-C. M.; Teng, C.-C.; Huang, Y.-L.; Lee, S.-H.;
Wang, I.; Wei, M.-H. Electrical, Morphological, and Electromagnetic
Interference Shielding Properties of Silver Nanowires and Nano-
particles Conductive Composites. Mater. Chem. Phys. 2012, 136 (2),
334−340.
(49) Fang, F.; Li, Y.-Q.; Xiao, H.-M.; Hu, N.; Fu, S.-Y. Layer-
Structured Silver Nanowire/Polyaniline Composite Film as a High
Performance X-Band EMI Shielding Material. J. Mater. Chem. C 2016, 4
(19), 4193−4203.
(50) Arjmand, M.; Moud, A. A.; Li, Y.; Sundararaj, U. Outstanding
Electromagnetic Interference Shielding of Silver Nanowires: Compar-
ison with Carbon Nanotubes. RSC Adv. 2015, 5 (70), 56590−56598.
(51) Hong, X.; Chung, D. D. L. Carbon Nanofiber Mats for
Electromagnetic Interference Shielding. Carbon 2017, 111, 529−537.
(52) Al-Saleh, M. H.; Saadeh, W. H.; Sundararaj, U. EMI Shielding
Effectiveness of Carbon Based Nanostructured Polymeric Materials: A
Comparative Study. Carbon 2013, 60, 146−156.
(53) Zeng, Z.; Chen, M.; Jin, H.; Li, W.; Xue, X.; Zhou, L.; Pei, Y.;
Zhang, H.; Zhang, Z. Thin and Flexible Multi-Walled Carbon
Nanotube/Waterborne Polyurethane Composites with High-Perform-
ance Electromagnetic Interference Shielding. Carbon 2016, 96, 768−
777.
(54) Arjmand, M.; Apperley, T.; Okoniewski, M.; Sundararaj, U.
Comparative Study of Electromagnetic Interference Shielding Proper-
ties of Injection Molded versus Compression Molded Multi-Walled
Carbon Nanotube/Polystyrene Composites. Carbon 2012, 50 (14),
5126−5134.
(55) Hou, Y.; Cheng, L.; Zhang, Y.; Du, X.; Zhao, Y.; Yang, Z. High
Temperature Electromagnetic Interference Shielding of Lightweight
and Flexible ZrC/SiC Nanofiber Mats. Chem. Eng. J. 2021, 404,
126521.

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ACS Appl. Mater. Interfaces 2021, 13, 21865−21875