Research Article

www.acsami.org

Preparation, Characterization, and Electrochromic Properties of

Nanocellulose-Based Polyaniline Nanocomposite Films
Sihang Zhang,† Gang Sun,‡ Yongfeng He,† Runfang Fu,† Yingchun Gu,† and Sheng Chen*,†
†
Functional Polymer Materials Laboratory, College of Light Industry, Textile and Food Engineering, Sichuan University, Chengdu
610065, China
‡
Fiber and Polymer Science, University of CaliforniaDavis, Davis, California 95616, United States
*
S Supporting Information

ABSTRACT: On the basis of nanocellulose obtained by

acidic swelling and ultrasonication, rodlike nanocellulose/
polyaniline nanocomposites with a core−shell structure have
been prepared via in situ polymerization. Compared to pure
polyaniline, the nanocomposites show superior film-forming
properties, and the prepared nanocomposite films demonstrate
excellent electrochemical and electrochromic properties in
electrolyte solution. Nanocomposite films, especially the one
prepared with 40% polyaniline coated nanocomposite,
exhibited faster response time (1.5 s for bleaching and 1.0 s
for coloring), higher optical contrast (62.9%), higher
coloration efficiency (206.2 cm2/C), and more remarkable
switching stability (over 500 cycles). These novel nanocellulose-based nanorod network films are promising novel electrochromic
materials with excellent properties.
KEYWORDS: polyaniline, nanocellulose, in situ polymerization, nanocomposite, electrochromism

1. INTRODUCTION by chemical polymerization processes,13 as pure PANI chains

Electrochromism is a reversible optical change in materials
upon redox reaction in the presence of an external potential.1
Electrochromic materials have attracted considerable attention
due to their potential applications in displays, electrochromic
windows, electronic books, antiglare rearview mirrors, etc.2,3
Inorganic oxides such as tungsten trioxide (WO3) and iridium
dioxide (IrO2) were first reported to be used as electrochromic
materials.4 After decades of research, inorganic electrochromic
materials have been widely developed for commercial
applications.5 However, inorganic electrochromic materials
suffer from many disadvantages, such as long response time,
high cost, high oxidative potential, and poor cycling stability.6
Recently, organic electrochromic materials have been exten-
sively studied for their electrochromic properties owing to their
low cost, short response time, long cycling stability, and low
operation potential.7−9
With the continuing development of organic electrochromic
materials, many conducting polymers, such as polyaniline
(PANI), polythiophene, polypyrrole, and their derivatives, have
been studied for electrochromic application.10 Among the
numerous conducting polymers, PANI has attracted the
extensive interest of researchers because of the relative low
cost of the monomer and its good environmental stability, ease
of synthesis, and tunable properties.11 PANI shows an obvious
color contrast between the bleached state and colored states in
the visible wavelength range (400−800 nm) at different applied
voltages.12 However, it is difficult to prepare a neat PANI film
are quite rigid and have a very low solubility in water solution
or other conventional organic solvents.14 In addition, the PANI
molecules in the neat film are closely packed, which hinders the
ionic transportation and thus greatly undermines the final
electrochromic response of the materials.15 To overcome these
limits, some approaches have been developed, such as
controlling the repeat-unit structure, adjusting electrodes,
electrospinning, formation of hybrid materials, and so on.16,17
Among these methods, hybridizing PANI with other materials
has been extensively exploited as an effective method to
improve the film-forming and electrochromic properties of
PANI. Silva et al.15 prepared hybrid materials based on
polyaniline, chitosan, and organically modified clay via in situ
polymerization, which showed good electrochromic properties
and good adhesion onto ITO glass electrodes as compared with
pristine PANI. Luo et al.18 reported a kind of graphene/PANI
hybrid hollow sphere which showed high specific capacitance
and good cycling stability. Shi et al.19 developed a new route to
construct a supramolecular complex of PANI/cellulose, and a
highly homogeneous structure and improved mechanical
properties of the resultant composite films were obtained. Xia
et al.20 had explored TiO2/PANI core/shell nanorod array
Received: February 25, 2017
Accepted: April 27, 2017
Published: April 27, 2017

© 2017 American Chemical Society 16426 DOI: 10.1021/acsami.7b02794

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ACS Applied Materials & Interfaces
Figure 1. Schematic illustration for preparation of NC/PANI nanocomposite films.
heterostructures as electrochromic materials, which showed
four color modes and fast optical switching speed.
Cellulose is one of the most important biomaterials and
chemical raw materials for human beings due to its low cost,
biodegradability, sustainability, and abundance.21 Currently,
intense research and development are focused on the isolation
and application of nanoscale cellulose fibers.22 Nanocellulose
(NC), which can be prepared from natural cellulose, with size
ranging from a few to tens of nanometers in one dimension, has
some unique properties, including its renewability, excellent
mechanical properties, high specific surface area, biodegrad-
ability, and biocompability,23 rendering it good reinforcement
for natural and synthetic polymer matrices.24−26 Moreover,
nanocellulose, rich in hydroxyl groups, has good affinity with a
wide variety of polymers, including conducting polymers.27,28
Therefore, combining cellulose nanowhiskers and PANI is a
promising strategy to develop novel functional PANI nano-
composite films and apply them in electrochromic devices.
In the present work, we report a facile process for preparing
nanocellulose/polyaniline (NC/PANI) nanocomposites in a
core−shell structure and their improved electrochromic
properties. The NC was prepared by a combination method
of mild acidic swelling and intensive ultrasonication. The NC/
PANI nanocomposites containing a variety PANI contents
ranging from 20% to 80% have been successfully developed
through in situ polymerization of aniline in a nanocellulose
suspension, and the electrochromic properties of the NC/PANI
nanocomposite films on ITO glass were measured. Compared
with the pure PANI film, the NC/PANI nanocomposite films
showed better film-forming properties and significantly
enhanced electrochromic behaviors.
2. EXPERIMENTAL SECTION
2.1. Materials. Cotton pulp was provided by Yibin Grace Group
Co. (NH4)2S2O8, H2SO4, HCl, aniline, and ammonium persulfate
(APS) were analytical reagents, purchased from Kelong Chemical
Reagent Co. Transparent indium tin oxide (ITO) coated glass was
used as a substrate with a sheet resistance of 15 Ω/□, provided by
Foshan Meijingyuan Glass Technology Co., Ltd. Deionized water was
used throughout the experiment.
2.2. Preparation of NC and NC/PANI Nanocomposites.
Cotton pulp board was first cut into small pieces that then were
added to 17 mL of 64 wt % sulfuric acid at 40 °C, stirred for 25 min,
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and then quenched by diluting with 200 mL of cold deionized water.
The suspension was washed by centrifuging (Jintan Medical
Instrument Factory) at 4000 rpm for 10 min several times, until the
pH of the supernatant was neutral. Then acid-swollen cellulose fibers
were obtained. About 150 mL of a suspension containing acid-swollen
cellulose fibers was placed in a JY98-III DN ultrasonic generator
(Ningbo Scientz Biotechnology Co., Ltd.) of 20−25 kHz frequency
and equipped with a cylindrical titanium alloy probe tip (1.5 cm). The
subsequent ultrasonication was conducted for 30 min at an output
power of 1000 W, resulting in a nanocellulose fiber suspension. The
suspension was filtered to remove large-scale cellulose fibers and
impurities. To prevent overheating, ultrasonic treatment was carried
out in an ice/water bath and stopped for 2 s every 2 s. The final
concentration of the suspension was 0.75 wt %, which was obtained by
rotary evaporation.
The NC/PANI nanocomposites were prepared according to our
reported procecdure with a modification.29 A typical example is
described as follows: An aniline (ANI) solution was first prepared by
dissolving aniline (0.08 g) in 6.314 g of concentrated HCl (37 wt %),
and then it was mixed with a certain amount of the freshly prepared
NC suspension to obtain 64 mL of a homogeneous reaction mixture
dispersion. The obtained aqueous dispersion was put in a vial in a low-
temperature water bath (10 °C). After stirring for 10 min, 0.132 g of
APS dissolved in 24 mL of HCl (1 mol/L) solution was added with
vigorous shaking to initiate polymerization of aniline. After polymer-
ization at 10 °C for 4 h, a dark green suspension was formed. Finally,
the suspension was washed several times by centrifugation with
deionized water. According to different contents of ANI, the NC/
PANI composites containing 20%, 40%, 60%, or 80% ANI were named
PN20, PN40, PN60, or PN80, respectively. As a reference, the pure
PANI was prepared by the same method, except that no nanocellulose
was introduced.
2.3. Preparation of NC/PANI Nanocomposite Film Electro-
des. The ITO substrate was rinsed with petroleum ether, acetone,
ethanol, and deionized water in sequence to remove contaminants
from the surface. The cleansed ITO substrate was dried and directly
used as the substrate for the NC/PANI nanocomposite films. The
NC/PANI thin film electrodes were prepared by dip-coating about 0.1
mL of NC/PANI aqueous dispersion (solid content of 0.2 wt %) onto
the ITO glass with an active area = 1.0 × 1.5 cm and dried at room
temperature. The thickness of all the film samples is about 5.2 ± 0.4
μm measured by micrometer. The area density of all film samples was
calculated to be about 1.33 ± 0.10 g/m2. The typical process for the
fabrication of a NC/PANI film electrode is illustrated in Figure 1.
2.4. Characterizations. The morphology of the nanocellulose and
nanocomposites was studied using field emission scanning electron
microscopy (FE-SEM) (JSM-5900LV, JEOL) and transmission
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Figure 2. SEM images of NC (a), PN20 (b), PN40 (c), PN60 (d), PN80 (e), and pure PANI (f) and TEM images of NC (g) and PN40 (h).
Figure 3. FTIR spectra of raw cellulose, NC, pure PANI, and PN40.
electron microscopy (TEM) (Tecnai G2 F20 S-TWIN, FEI). Fourier
transform infrared spectra (FTIR) were recorded on a Tracer100
spectrometer (Shimadzu Corp.). Thermal gravimetric analysis (TGA)
was measured under a nitrogen atmosphere with a DTA-60 thermal
analyzer (Shimadzu Corp.).
The electrochromic properties of the NC/PANI nanocomposite
film were measured by using a CS150 electrochemical workstation
(Wuhan Corrtest Instrument Co., Ltd., at room temperature in a
homemade colorimetric cell whose volume is 3 × 4 × 3 cm at room
temperature). A three-electrode system was used, consisting of the
NC/PANI-coated ITO glass as the working electrode (W-E), platinum
as the counter electrode (C-E), and a saturated calomel electrode as
the reference electrode (R-E), and 0.25 M HCl solution was used as
the electrolyte. Ultraviolet−visible (UV−vis) absorption spectra were
recorded on a TU-1900 UV−vis spectrometer (Beijing Purkinje
General Instrument Co., Ltd.).
3. RESULTS AND DISCUSSION
3.1. Morphology. The typical morphologies of nano-
cellulose are shown in Figure 2a,g. The pure nanocellulose film
is composed of randomly oriented rodlike cellulose nano-
whiskers. The diameters of rodlike nanocellulose range from 10
to 35 nm, and the average diameter is about 28.36 ± 4.03 nm,
measured by Nano Measurer software. Their lengths of them
are about 100−300 nm. The diameter distribution of obtained
nanocellulose is comparatively narrow. The results show that
the nanocellulose was successfully prepared by combining
swelling and ultrasonic treatments.
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Figure 2b−f show the morphologies of nanocellulose-based
composites containing (b) 20% PANI, (c) 40% PANI, (d) 60%
PANI, (e) 80% PANI, and (f) pure PANI (100% PANI). The
TEM image of PN40 is shown in Figure 2h. Figure 2h shows
the rodlike nanocellulose as the matrix materials and polyani-
line coating the surface of the nanocellulose to form the core−
shell structure. The lengths of nanocomposite particles range
from 100 to 300 nm. The average diameters of PN40
composites are about 38.82 nm, which are higher than that
of the pure cellulose nanowhiskers. It is further proved that the
PANI was coated on the surface of cellulose nanowhiskers to
form the core−shell structure of nanocomposites. Figure 2f
shows that the structure of pure PANI film prepared by
chemical oxidative polymerization without nanocellulose is
relatively uniform and compact. The particles of polyaniline are
small and stacked together compactly. From Figure 2b−e, the
average diameters of PN20, PN40, PN60, and PN80 are
measured to be about 32.92 ± 3.52, 38.82 ± 4.48, 54.14 ± 4.63,
and 55.11 ± 8.60 nm by Nano Measurer software. There are a
lot of small holes which can be found in the NC/PANI
composite film, which is probably due to the network structure
formed by rodlike nanocomposites. This should be good for the
injection and extraction of electrolyte ions during the
electrochemical redox process. Figure 2d,e shows that when
the content of PANI in the composites is higher, extra ANI
monomers were self-polymerized to form an increased amount
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Figure 4. (a) TGA curves of raw cellulose, NC, pure PANI, and PN40, respectively. (b) CV curves of pure PANI, PN80, PN60, and PN40,
respectively. Electrolytic solution was 0.25 M HCl and scan rate 100 mV/s. (c) CV curves of PN40 in 0.25 M HCl at different potential scan rates: 5,
10, 20, 50, 100, and 200 mV/s. (d) The relationships between the oxidation peak current density vs potential scan rate.
of polyaniline particles in solution rather than on the surface of
NC. In contrast, when the content of PANI in the composites
is low, almost all ANI monomers were polymerized on the
surface of NC to form rodlike nanocomposites with core−shell
structure, as shown in Figure 2b,c, which are beneficial to
improve the film-forming properties of the nanocomposites.
3.2. Chemical Structure. The FTIR spectra of raw
cellulose, NC, pure PANI, and PN40 nanocomposites are
shown in Figure 3. The obtained NC presents the usual
cellulose IR band, and the typical features of PANI have already
been described in the literature.30,31 For the FTIR spectra of
raw cellulose and NC, the characteristic broad band of the O−
H group in cellulose appears at 3341 cm−1. The peak around
2900 cm−1 is due to the asymmetrically stretching vibration of
C−H, and the band at 1649 cm−1 resulted from the H−O−H
bending of the absorbed water. The peak at 1371 cm−1 is
attributed to the O−H bending, and the characteristic peak at
1164 cm−1 corresponds to the C−O antisymmetric bridge
stretching. A strong band at 1061 cm−1 is due to the C−O−C
pyranose ring skeletal vibration. Comparing the FTIR spectra
of pure cellulose and NC, there is no new absorption peak that
appears for NC, which indicates that no new functional groups
were generated during the acid-swelling treatment and
ultrasonication process and that the original molecular structure
of cellulose is maintained.
For the FTIR spectra of PANI and NC/PANI nano-
composites, the peaks around 1484 and 1567 cm−1 originate
from the stretching vibration of N−A−N and NBN
structures, respectively (where A and B represent benzenoid
and quinoid moieties in the PANI chains). The peaks at 1126
and 1293 cm−1 have been observed because of the vibration of
C−H in the benzene ring and the stretching of the C−N band.
The peak corresponding to the out-of-plane bending vibration
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of the C−H band of the para-disubstituted benzene ring
appears at 793 cm−1.32 The characteristic peaks of NC (3341
cm−1) and PANI (1567, 1484, 1293, and 793 cm−1) are both
present in the spectrum of the NC/PANI nanocomposites. The
absorption peak at 3412 cm−1 in the spectrum of pure NC is
shifted to 3270 cm−1 in the spectrum of the NC/PANI
nanocomposite. These indicate that the nanocellulose is
successfully activated by acids and the intermolecular hydrogen
bands are broken.29 Thus, more hydroxyl groups in NC are
accessible and it helps to form the uniform dispersion of PANI
on the surfaces of NC. Combining SEM, TEM, and FTIR
analyses, it could be concluded that PANI was successfully
formed on the surface of NC upon in situ polymerization.
3.3. Thermal Stability. TGA curves of raw cellulose, NC,
pure PANI, and NC/PANI were recorded from 50 to 500 °C at
heating rate of 10 °C/min, as shown in Figure 4a. All the TGA
curves could be divided into three stages. During the initial
stage from 50 to 120 °C, the moisture present in the samples
containing cellulose vaporized, and the dopant HCl in PANI
was removed.33 The main weight losses of raw cellulose and
NC occur at the second stage from 120 to 400 °C. The onset
temperatures of thermal−oxidative degradation of NC and
PN40 were observed at 162 and 133 °C, respectively, lower
than that of raw cellulose (above 300 °C). The low degradation
temperature of NC means that the decomposition of
nanocellulose would require less thermal energy, which could
be caused by the smaller transverse dimension of nanofibers
and, consequently, more surface areas being exposing to heat as
compared to the raw cellulose. Additionally, surface carboxyl
groups and sulfate groups are expected to cause the lower
degradation temperature for NC by direct solid-to-gas phase
transitions from decarboxylation of surface carboxyl groups.34 A
massive weight loss of NC/PANI nanocomposite is observed at
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Figure 5. UV−vis absorption spectra of pure PANI (a), PN80 (b), PN60 (c), PN40 (d), and PN20 (e) films measured at different potentials (−0.2
to +1.0 V with a step size of 0.2 V) in 0.25 M HCl solution. (f) Photographic images of pure PANI and PN40 films at different applied potentials.
155 °C, but the decarboxylation of the NC should be at 180 °C.
Another possible reason is the weakened inter- and intra-
molecular hydrogen bonding of NC in the NC/PANI
nanocomposite.35 The final stage in weight loss is observed
in the region of 400−500 °C, where most samples have been
carbonized. Compared with raw cellulose (7.4%), PANI, NC/
PANI, and NC showed much higher char residues, which are
81.1, 47.2, and 37.2%, respectively. The result shows that the
thermal stability of PN40 is better than that of NC and weaker
than that of pure PANI.
3.4. Electrochromic Properties of Pure PANI and NC/
PANI Nanocomposite Films. 3.4.1. Cyclic Voltammetric
(CV) Analysis. Figure 4b displays CV curves of PN40, PN60,
and PN80 nanocomposite films and pure PANI film from −0.4
to +1.2 V, performed in 0.25 M HCl solution at a scan rate of
100 mV/s. As the content of PANI is low, PN20 film shows a
poor electrochromic response with very low current and an
irregular CV curve. This is due to nanocellulose being an
insulator, and the addition of a large amount of nanocellulose
might lead to the poor conductivity of the composite film and
the difficulty in ion transport during the electrochromic redox
process.36 So PN20 is not shown in Figure 4b. Comparing the
CV curves of pure PANI and NC/PANI, with the increase of
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NC contents, the first anodic peak potential (Epa1) decreases
initially and then increases. On the contrary, the second
cathodic peak potential (Epc2) increases initially and then
decreases. The results indicate that when the content of NC in
the nanocomposite (e.g., PN80) is low, the pores in the
nanocomposite film (as shown in Figure 2e) facilitate the
transmission of ions, and PANI formed on the surface of NC
can be oxidized at lower potential or reduced at higher
potential. However, with the increase of nonconductive NC
content (e.g., PN60 and PN40), films become more dense and
uniform and their resistance increases also, which results in
higher oxidation potential and lower reduction potential.
The current densities of NC/PANI films are larger than that
of pure PANI film. With the increase of NC content, the
current densities of NC/PANI nanocomposite films increase
obviously, the redox peaks become sharp and narrow, and a
larger area of closed CV curves appears, which exhibits the
higher specific capacitances of NC/PANI nanocomposite
electrodes. These may be due to the special structure of NC/
PANI nanocomposite films. The nanoscale architectures of the
NC/PANI composites with the network interwoven structures
significantly enhance the interface areas of electrode materials
and electrolyte, which makes the electrolyte ions easily pass
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through the films formed by loose fibrous NC/PANI. So with
the addition of NC in the composites, fluency conductive paths
are obtained, which results in the rapid transportation of the
electrolyte ions during charge/discharge processes and the
improved electrochemical properties of the NC/PANI nano-
composites.37−39
Figure 4c displays cyclic voltammograms of PN40 nano-
composite film, which were performed in 0.25 M HCl solution
at different potential scan rates (5−200 mV/s). The CV curves
were recorded from −0.4 to +1.2 V. There are two pairs of
redox peaks of PANI (A1/C1 and A2/C2) in all the CV curves,
typical redox characteristics of PANI, appearing in all the CV
curves. The peaks (A1/C1) around +0.2 and −0.1 V are
associated with the redox process between leucoemeraldine
base (LB) and emeraldine salt (ES) states of PANI, which
transform reversibly from yellow to green. The peaks (A2/C2)
around +0.7 and +0.5 V are associated with the redox process
between ES and pernigraniline base (PB) salt states of PANI,
which transform reversibly from green to blue or purple,40 and
the phenomenon is in accordance with the result in the
literature.41 From Figure 4d, it is clear that the current densities
of redox peaks increased with potential scan rates in the region
of 5−200 mV/s. For Figure 4d1, the current densities show a
linear relationship with potential scan rates in the region of 0−
50 mV/s, indicating that redox processes are controlled by
counterion insertion−deinsertion processes.42,43 However, the
current densities show a new linear relationship as the scan
rates are higher than 50 mV/s, and the redox processes tend to
be limited by ion diffusion from the electrolyte solutions to the
electrode surfaces.44
3.4.2. Spectroelectrochemistry. The UV−vis spectra of pure
PANI, PN80, PN60, PN40, and PN20 films in 0.25 M HCl
solution at different potentials is shown in Figure 5a−e. With
the increase of applied potentials, the absorption around 423
nm increases from −0.2 to +0.2 V and then drops from +0.2 to
+1.0 V. This can be explained by the formation of bipolaronic
species at higher potentials, which results in decreasing
polaronic population. A distinct blue-shift of the maximum
absorption wavelength at around 700 nm of the NC/PANI
occurs with increasing potentials from −0.2 to +1.0 V. At lower
potentials (−0.2 to 0 V), the absorbance band around 825 nm
makes the nanocomposite films exhibit pale yellow color, as
PANI is in a reduced state. At medium potentials (+0.2 to +0.6
V), two absorbance bands around 770 and 423 nm result in the
green color of the nanocomposite films, which is partially
oxidized in the intermediate state. At higher potentials (+0.8 to
+1.0 V), a characteristic absorbance band around 665 nm is
related to the π−π* transition in the quinoid ring of PANI,
which is totally oxidized as the pernigraniline structure form.
The phenomenon is in accordance with the results in the
literature.45−47 The nanocomposite film displays blue or dark
blue color. The results are consistent with the results of cyclic
voltammetry. The pure PANI film and the NC/PANI
nanocomposite films show similar properties in the UV−vis
spectra. In comparison with the UV−vis spectra of all of the
films, including pure PANI, PN80, PN60, PN40, and PN20, the
absorbance modulations (ΔA) of all the films at λ = 665 nm are
0.28, 0.37, 0.59, 0.64, and 0.09, respectively. Except for PN20,
all the NC/PANI composite films have larger ΔA than pure
PANI. PN40 film has the largest ΔA compared with all the
other films. The contrast ratio of the NC/PANI films increases
with the content of NC in the composite, except for PN20. It is
indicated that the electrochromic properties of PANI are
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improved by the combination of NC. However, the UV−vis
spectra of PN20 showed almost no change at different
potentials. This is because nanocellulose is an insulative
material, and the high cellulose content of PN20 may lead to
poor conductivity and a low electrochromic property.
Photographic images of pure PANI and PN40 films at a
bleaching state (−0.2 V), intermediate state (+0.4 V), and
coloring state (+0.8 V) are shown in Figure 5f. At −0.2 V, the
pure PANI and PN40 films are fully reduced and present
almost transparent color. At +0.4 V, the pure PANI and PN40
films change to partially oxidized and show light green color.
When increasing the applied potential to +0.8 V, the pure
PANI and PN40 films become fully oxidized and show very
dark blue and dark blue color, respectively. The color difference
is due to the partially excessive oxidation of the pure PANI film
at +0.8 V.43 However, for the nanocomposite film, the excessive
oxidation is avoided because of its excellent ion transport
efficiency, and nanocellulose shows a protective effect in NC/
PANI composite films that depresses the formation of the
highly oxidized PANI.36,48 From Figure 5f, it is obvious that the
film uniformity and color contrast of PN40 are better than that
of pure PANI, indicating that the combination of NC and
PANI improves the film-forming properties and electrochromic
behaviors of PANI.
3.4.3. Electrochromic Performance. Color-switching re-
sponse tests of pure PANI and NC/PANI nanocomposite films
in 0.25 M HCl solution were performed by the transmittance
change at 665 nm (the maximum absorption peak wavelength),
as shown in Figure 6. The optical transmittance spectra were
Figure 6. Kinetic optical transmittance curves at 665 nm of PN20,
PN40, PN60, PN80, and pure PANI films, switched between −0.2 and
+0.8 V for 4 s at each step in 0.25 M HCl solution.
measured with switched potentials between −0.2 and +0.8 V
for 4 s at each step. The optical contrast value (ΔT) is the
difference between colored states (Tc) and bleached states (Tb).
The response time is defined as the time required for 90%
transmittance change in the coloring process (τc) and bleaching
process (τb).49 The optical contrast and the response time
listed in Table 1 are important electrochromic parameters for
electrochromic materials. The response times of the samples
were all lower than 4 s, which meets the requirement of
electrochemic devices (0.1−10 s). It is evident that the
thickness of the shell increased as the content of PANI in the
composite films increased. For PN20 and PN40, with the
thickness of the shell increased, the electrochromic behaviors of
composite film increased. This is due to the conductivity of
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Table 1. Electrochromic Parameters of PN20, PN40, PN60, 3.4.4. Cycling Stability. The electrochemical stability of pure
PN80, and Pure PANI at 665 nm PANI and PN40 films was investigated by single-wavelength
spectrophotometry at λ = 665 nm for cycles 1−5 and 501−505,
sample PANI content (%) Tc/Tb ΔT (%) τc (s) τb (s)
as shown in Figure 7. The current−time curves and
PN20 20 53.5/56.6 3.1 3.5 3.4 corresponding transmittance-cycle number curves were ob-
PN40 40 19.2/82.1 62.9 1.0 1.5 tained with switched potentials between −0.2 and +0.8 V with a
PN60 60 21.5/78.8 57.3 1.2 1.0 4 s delay at each state. The electrochromic parameter values
PN80 80 32.8/78.5 45.7 1.1 1.6 were calculated from Figure 7 and are listed in Table 2. The
PANI 100 33.4/70.8 37.4 1.5 1.5 processes of coloration-switching response of pure PANI and
PN40 are different. Coloration efficiency (CE), which is also
called electrochromic efficiency, is defined as the change in
composite films gradually increasing. For PN40, PN60, PN80, optical density (ΔOD) induced by unit charge density (Q).51
and pure PANI, with the thickness of the shell increased, most The formulas for calculation are
of the PANI self-polymerized together instead of onto the
surfaces of nanocellulose, which is harmful to ion diffusion and CE = (ΔOD)/Q (1)
formation of a porous structure. The electrochromic perform-
ances of composite films gradually decreased. This result is ΔOD = log(Tb/Tc) (2)
consistent with the results of Figure 2. Table 1 shows that the
response times τc and τb of PN40 and PN60 are lower than that where Tb and Tc refer to the transmittance of the films in its
of pure PANI. The lower response time of the nanocomposite bleached and colored state, respectively. CE is an important
films is expected and is attributed to the porous film structures criterion to evaluate the electrochromic performance. The
formed by core−shell nanorods and the rapid ion trans- calculated CE values of PN40 films are 206.2 cm2/C (cycles 1−
portation performance,38 as shown in Figures 2 and 5. The 5) and 176.3 cm2/C (cycles 501−505), which are much higher
optical contrast (ΔT) of PN40 reached about 63%, while it is than those of pure PANI (28.4 cm2/C in cycles 1−5 and 22.2
only about 37% for pure PANI film. The contrast ratio and cm2/C in cycles 501−505). The higher CE values of NC/PANI
response speed of PN40 are significantly better than those of nanocomposite films indicate that a small amount of charges
PN20. This is due to the remarkably higher electrical injected per area is necessary to obtain an obvious change of
conductivity of PN40 than of PN20, which is in accordance color. These results demonstrated that, concerning energy
with the results in the literature.31 Except for PN20, the economy, NC/PANI nanocomposites are promising materials
transmittances at the bleached states of the NC/PANI for application in electrochromic devices. After 500 switched
nanocomposite films are larger than that of pure PANI. In cycles, the change of response times of pure PANI is larger than
addition, the electrochromic performances of NC/PANI those of PN40. And the ΔT and CE values of pure PANI
composite films are also better than many of PANI-based decrease by 39.8% and 21.8%, respectively, while those of PN40
composite films reported in the literature (Supporting decrease only by 21.3% and 14.5% respectively. The cycling
Information, Table S1). The improved contrast is due to the stability of PN40 film is also better than many reported results
improved film-forming properties of the composites and the in the literature (Supporting Information, Table S1). The above
porous space among the nanocomposites, which can make the results reveal that NC/PANI nanocomposite films exhibit
ion diffusion easier and provide larger surface area for redox better electrochromic properties and cycling stability, which
reactions.50 further proves the advantages of the novel core/shell

Figure 7. Potential, chronoamperometry, and transmittance curves of pure PANI film (a) and PN40 nanocomposite film (b) with applied potential
of −0.2 and +0.8 V for 500 cycles, respectively.

16432 DOI: 10.1021/acsami.7b02794

ACS Appl. Mater. Interfaces 2017, 9, 16426−16434
ACS Applied Materials & Interfaces
Table 2. Electrochromic Parameters of Pure PANI and PN40 Films at 665 nm for Cycles 1−5 and 501−505
sample PANI content (%) cycles Tc (%)
PANI 100 1−5 33.4
501−505 39.3
PN40 40 1−5 19.2
501−505 25.0
nanocomposites. The improved electrochromic properties are
mainly attributed to the core/shell structure, improvement of
the film-forming properties, and the porous space among the
nanorod composites, which can reduce the oxidation potential,
make ion diffusion easier, and provide larger surface area for
redox reactions.36,46,52 Besides, the presence of nanocellulose
might have retarded the formation of the highly oxidized PANI
and hence improved the durability.36,48
4. CONCLUSIONS
A series of NC/PANI nanocomposites containing different
contents of PANI have been prepared successfully via in situ
polymerization. The uniform porous films were constructed by
the interwoven core−shell NC/PANI nanorods with an average
diameter of over 30 nm and average length of about 200 nm.
The unique core−shell structure enhanced the transmission
rate of electrolyte ions and the redox reaction rate of the
electrochromic materials. The NC/PANI nanocomposite films
showed significant color changes (yellow, green, and blue) at
different electrical potentials. As compared with pure PANI
film, the NC/PANI nanocomposite films exhibited higher
optical contrast values, higher coloration efficiencies, lower
response times, and better electrochromic stabilities. The film
with a composition of PN40 demonstrated the highest
transmittance difference (ΔT 62.9%) and the fastest response
speed for coloring and bleaching (1.0 and 1.5 s) and was
preferred as an electrochromic material.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.7b02794.
A comparison of PANI-based electrochromic films
properties (Table S1) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +86 28 85401805. E-mail: chensheng@scu.edu.cn.
ORCID
Sheng Chen: 0000-0002-9428-3675
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (NSFC) (51003064) and Sichuan
Province Science and Technology Foundation (2014JY0146).
■
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DOI: 10.1021/acsami.7b02794
ACS Appl. Mater. Interfaces 2017, 9, 16426−16434