Electrochimica Acta 318 (2019) 660e672

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

An intrinsically self-healing and biocompatible electroconductive

hydrogel based on nanostructured nanocellulose-polyaniline
complexes embedded in a viscoelastic polymer network towards
flexible conductors and electrodes
Jingquan Han a, *, Qinqin Ding a, Changtong Mei a, Qinglin Wu b, Yiying Yue c, **,
Xinwu Xu a, ***
a
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing, 210037, China
b
School of Renewable Natural Resources, Louisiana State University, Baton Rouge, LA, 70803, USA
c
College of Biology and Environment, Nanjing Forestry University, Nanjing, 210037, China

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

Article history: Electroconductive hydrogels (ECHs) that integrate gel features and electrochemical properties are
Received 18 December 2018 considered as promising tissue-like flexible materials important for broad applications. Nevertheless,
Received in revised form realizing the synergistic features of self-healing capability, conductivity, biocompatibility, stretchability
2 June 2019
and malleability is challenging. Herein, a novel kind of versatile ECHs built on a borax-crosslinked
Accepted 21 June 2019
Available online 24 June 2019
polyvinyl alcohol (PVA) hydrogel system and conducting PANI@CNF (polyaniline-cellulose nanofiber)
nanocomplexes which synergize the conductivity of PANI and the template feature of CNFs is reported.
The PANI@CNF nanocomplexes are firstly prepared via in situ polymerization of anilines on CNFs, which
Keywords:
Cellulose nanofibers
are then evenly distributed into borax-crosslinked PVA gel system to fabricate free-standing PANI@CNF-
Hydrogel PVA composite ECHs. Sustainable and renewable CNFs serve as flexible biotemplates and mediate the
Conductive development of PANI into integrated PANI@CNF with good dispersity, enabling the establishment of an
Self-healing integrated conducting and reinforcing network. The dynamic multi-complexation and chain entangle-
Flexible ments between PANI@CNF complexes, borax and PVA chains contribute to the development of a hier-
archical network structure. The maximum compression stress (~48.8 kPa) and storage modulus
(~31.5 kPa) of PANI@CNF-PVA hydrogel are about 3.5 and 400 times greater than those of pure PVA gel.
These hydrogels also demonstrate appealing biocompatibility, mouldability, pH sensitivity, thermo-
reversibility and fast self-healing ability within 15s. The hydrogel-based electrode with a conductivity
of ~5.2 S m
1 shows a maximum specific capacitance of 226.1 F g
1 and a capacitance retention of 74%
after 3000 cycles. The integration of such remarkable features enables the promising applications of the
as-prepared versatile ECHs in flexible, self-healing and implantable electronic devices.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction development of flexible electronics [2]. However, the synthesis of

intrinsically flexible and stretchable materials with desirable elec-
Nanostructured soft electronic materials have received exten- tronic performance remains a major challenge, especially for the
sive attention because of their novel features [1]. The progressive utilization of these soft materials in functional electronic devices
development of soft electronic components promotes the rapid [3]. Therefore, soft materials with versatile properties are urgently
needed to realize soft electronic devices with multifunctionality.
Electroconductive hydrogels (ECHs) are emerging as a promising
class of intelligent hydrogels that combine highly hydrated cross-
* Corresponding author.
linked hydrogels with inherently conductive polymers [4]. The
** Corresponding author.
*** Corresponding author. introduction of electronic conductivity into hydrogel network
E-mail addresses: hjq@njfu.edu.cn (J. Han), yue@njfu.edu.cn (Y. Yue), structure with little compromise of the physical-mechanical
xucarpenter@aliyun.com (X. Xu).

https://doi.org/10.1016/j.electacta.2019.06.132
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
 J. Han et al. / Electrochimica Acta 318 (2019) 660e672
properties makes ECHs intrinsic conducting yet mechanically tough
skeleton that can promote the charge transportation and diffusion
of ions and molecules [5,6]. By integrating some advantageous
properties such as mechanical flexibility, tissue-like softness, con-
ductivity and biocompatibility, ECHs are considered as a powerful
material platform for designing soft energy storage/conversion
devices, including flexible supercapacitor electrodes [7], biosensors
and wearable devices [8,9].
For a typical ECH structure, the insulating polymer provides the
3D aqueous gel matrix, while the conducting polymers impart
electrical conductivity to the hydrogel scaffold. Polyaniline (PANI)
with intrinsic electronic conductivities is one of the most widely
investigated conductive polymers due to its high environmental
and thermal stability, appropriate mechanical properties, inherent
biocompatibility, excellent electrical conductivity and simple
doping/dedoping chemistry [10]. Recently, some PANI-based ECHs
have been developed towards gel-based electrodes or super-
capacitors. For example, Li et al. [11] prepared a conductive PANI-
PVA hydrogel with good mechanical and electrochemical proper-
ties through a supramolecular strategy. The hydrogel-based solid-
state supercapacitor exhibited a high capacitance and energy
density. Huang et al. [12] demonstrated another type of conducting
PANI-PVA hydrogels by using in situ polymerization of aniline in
acidic aqueous solution of PVA and a cyclical freezing-thawing
method. The hydrogel-based electrode showed good responsive-
ness and rate capability, low resistance, high specific capacitance
and excellent cycling stability. Dou et al. [13] described a nano-
structured PANI hydrogel with excellent electrochemical properties
through the use of amino trimethylene phosphonic acid as the
gelator and dopant. The hydrogel-based supercapacitor electrodes
were used for 3D multilayer printing of micro-patterns.
However, rigid polymeric chains of PANI leads to its inadequate
dispersibility, small specific surface area, mechanical rigidity and
inaccessibility, and thus PANI tends to form aggregation in aqueous
hydrogel matrix [14]. Therefore, the mechanical inflexibility and
fragility of most previous PANI-based ECHs severely limited their
practical applications in flexible electronic devices [15]. Moreover,
the electrochemical properties of ECHs can be impaired by the
discontinuous conductive PANI network within hydrogel [16].
Consequently, fabricating homogeneous ECHs with ideal conduc-
tivity, strength and flexibility still remains a critical challenge.
Interestingly, nanostructured conductive polymers can provide
novel appealing features such as tailored conductivities, flexibility
and miscellaneous conductive mechanism [17]. Directly in situ
polymerizing aniline (ANI) onto nanostructured flexible templates
gradually becomes an essential approach to synthesizing ECHs with
stable, flexible and continuous conductive network, thus endowing
ECHs with improved electrochemical and mechanical properties.
Among diverse flexible templates, cellulose nanofibers (CNFs),
generally obtained from sustainable natural resources, are consid-
ered as desirable candidates due to their attractive characteristics
including nanoscale dimension, high toughness, low density, large
specific surface area, high aspect ratio, intrinsic biocompatibility
and flexibility [18]. Because of the negatively surface-charged
electrons, CNFs tend to form a stable colloidal dispersion in wa-
ter, thus making them ideal dispersant to carry PANI in water [19].
After coating of PANI layer on CNF templates, CNFs can easily unite
with PANI to assemble nanocomplexes that demonstrate an suc-
cessful integration of the electrochemical properties of PANI and
favorable characteristics of CNFs, making CNFs suitable bio-
templates to improve the dispersibility, flexibility and electro-
chemical properties of PANI in hydrogel matrix [20].
Given these background, we believe that CNFs carried PANI is
ideally suitable for synthesizing homogeneous, robust and elastic
ECHs with a combined reinforced and continuous conducting
661
network. Previously, we successfully incorporated various nano-
cellulose into a borax-crosslinked PVA gel system to prepare
composite hydrogels with improved mechanical toughness and
viscoelasticity [21,22]. Inspired by the attractive properties, we
expect that the borax-crosslinked PVA gel system can be applied as
an appropriate scaffold for the incorporation of another conducting
pathway, which can endow ECHs with continuous, flexible and
stable conductive pathways by integrating CNF-templated PANI
[23]. However, there have been relatively few reports available on
the versatile ECHs that integrate CNF-mediated PANI and PVA gel
matrix.
In this work, a new kind of multifunctional ECHs with syner-
gistic properties including intrinsic malleability, ideal mechanical
strength, high viscoelasticity, appropriate electroconductivity,
rapid self-healing capability and inherent biocompatibility was
developed. The nanostructured conductive PANI@CNF complexes
were homogeneously integrated into PVA hydrogel system to
prepare free-standing PANI@CNF-PVA composite hydrogels. By
integrating appealing characteristics of borax-crosslinked PVA gel
system and conducting PANI@CNF complexes, this type of ECHs
were considered as promising soft materials for assembling fast
self-healable, biocompatible and elastic implantable sensors or
electrodes with superb electrochemical properties.
2. Experimental
2.1. Materials
Wood pulp (KC-50 Flock, Japan) was dried at 55  C for
14 h. Sulfuric acid (98.0 wt%), sodium tetraborate decahydrate
(borax, Mw ¼ 381.37 g mol
1), polyvinyl alcohol (PVA,
Mw ¼ 146,000e186,000 g mol
1), aniline monomers (ANI, 99.5%)
and ammonium persulfate (APS, 98%) were purchased from
Aldrich Chemical Co.
2.2. Preparation of PANI@CNF complexes and PANI@CNF-PVA
composite hydrogels
CNFs were extracted from wood pulp as described in our pre-
vious work [24]. The obtained homogeneously dispersed CNF
aqueous colloid had a concentration of 0.86 ± 0.02 wt%. According
to our pre-experiments, the concentration of CNFs and feeding
compounding ratio of CNFs to ANI monomers are given in Table 1.
PANI@CNF nanocomplexes were synthesized via in situ chemi-
cally polymerizing ANI monomers employing CNFs as templates
and APS as initiator in a sulfuric acid environment. Initially, a ho-
mogeneous colloidal dispersion of CNFs was fabricated via a com-
bined acid hydrolysis and ultrasonication process. Nanostructured
PANI@CNF complexes were then prepared via in situ polymerizing
ANI monomers on CNFs by introducing APS in at 0  C. The well-
dispersed PANI@CNF were realized by the deposition of PANI
shell on the CNF templates via the hydrogen bonds between the
hydroxyls of CNFs and the amines of PANI. Typically, quantitative
purified ANI monomers were firstly added into 2.0 mol L
1 H2SO4
(solution-1). At once, CNF suspension was adjusted to desired
concentrations (dispersion-2). Subsequently, solution-1 and
dispersion-2 were continuously blended and stirred until a ho-
mogeneous suspension-3 was formed, followed by a 55 min
ultrasonication treatment. After suspension-3 was cooled down at
0  C, 20.0 mL of APS solution was dropwise incorporated into the
suspension-3 (one drop every 3s) under vigorous stirring to
accomplish the oxidative polymerization of ANI monomers. The
mole ratio of APS to ANI was fixed at 1.25 to 1.00. After 3 h,
suspension-3 was transferred a refrigerator at 0  C to continue the
in situ polymerization of ANI monomers. After 12 h, the obtained
662 J. Han et al. / Electrochimica Acta 318 (2019) 660e672
Table 1
Experimental formula of PANI@CNF complexes.
PANI@CNF designation CNF concentration/wt% ANI concentration/wt%
PANI@CNF 1 1.0 0.5
PANI@CNF 2 1.5 0.5
PANI@CNF 3 2.0 0.5
PANI@CNF 4 2.0 1.0
e 2.0 0.0
e 0.0 0.0
precipitates were washed and filtered with deionized water to
reach a neutral pH. The ultimate PANI@CNF nanocomplexes were
re-dispersed in deionized water to prepare an aqueous suspension
(97.6 g). As a reference, pure PANI was synthesized through a
similar oxidative polymerization method without CNFs.
In the second step, the uniformly-distributed PANI@CNF nano-
complexes were added into borax-crosslinked PVA system to
construct free-standing PANI@CNF-PVA composite hydrogels. More
importantly, the PANI coating layers on CNF templates were grown
into integrated PANI@CNF complexes with excellent conductivity,
flexibility and dispersity, thus allowing the establishment of
continuous conducting pathways in PVA hydrogel system. Specif-
ically, the composite hydrogels containing various PANI@CNF
nanocomplexes were synthesized as below. Firstly, 0.4 g of borax
was added into 97.6 g of PANI@CNF suspension with mechanical
stirring at 25  C for 25 min. After that, 2.0 g of PVA was added into
the suspension, and the solutions were heated at 90  C for 2 h with
constant stirring. After the uniform solutions with PANI@CNF
nanocomplexes were accomplished, they were cooled to 25  C and
the PANI@CNF-PVA hydrogels were obtained. As a reference, the
hydrogels without PANI and the hydrogels without PANI@CNF
complexes (designated as CNF-PVA and PVA, respectively) were
synthesized by incorporating PVA into CNF/borax water suspen-
sions and borax aqueous solutions, respectively.
2.3. Dynamic oscillation measurement
The rheological performances were analyzed with a Rheometer
(HAAKE, USA) using plate/plate geometry with a diameter of
35 mm. The plate and the distance between two plates was fixed at
100 mm. The detailed measurement processes are given in Sup-
porting information.
2.4. Mechanical measurements
Uniaxial compression measurements were performed with on a
Rheometer (HAAKE 600, Thermo Fisher, USA) at a 20 mm s
1
crosshead speed. Tensile measurements were performed with a
mechanical testing machine at 25 mm min
1 pulling rate. The
samples before and after self-healing in a size of 30  15  5 mm3
were fixed onto the tensile machine while testing.
2.5. Electrochemical measurements
Electrochemical tests were performed using an electrochemical
workstation (CHI760E, Shanghai). In a three-electrode system, a
saturated calomel electrode (SCE), a Pt wire and ~12 mg of the
composite hydrogel were applied as the reference, counter and
working electrode, respectively. The electrochemical tests were
conducted in a 1.0 mol L
1 H2SO4 electrolyte. The cyclic voltam-
metry (CV) tests were carried out in the potential range of
0e0.4 V at different scan rates of 10, 30, 50, 80 and 100 mV s
1.
Electrochemical impedance spectroscopy (EIS) tests were carried
out at open circuit potential with a frequency range from 0.01 Hz to
Mass ratio of ANI to CNFs Hydrogel designation
1:2 PANI@CNF-PVA1
1:3 PANI@CNF-PVA2
1:4 PANI@CNF-PVA3
2:4 PANI@CNF-PVA4
0:4 CNF-PVA
e PVA
100 kHz using a sine wave with alternate signal amplitude of 5 mV.
Galvanostatic charge/discharge (G-CD) tests were performed in the
potential ranging from 0 V to 0.4 V with current densities of 0.3, 0.5,
0.8, 1.0 and 2.0 A g
1. The capacitance (CS) values were calculated
from the charging and discharging curves using Eq. (1):
Cs ¼ I Dt=mDV (1)
where CS, Dt, I, DV and m were the specific capacitance (F g
1), the
discharge time (s), the discharge current (A), the potential reduc-
tion (V), and the weight of active materials in the electrodes (g),
respectively.
The conductivity of the composite hydrogels (1.0  1.0  10 cm3)
were tested with a twin electrode circuit. The sample resistance
was obtained using Eq. (2):
R ¼ U=I (2)
where R, U and I was the resistance in U, the open circuit potential
in V and the electric current in A, respectively. The electric con-
ductivity was obtained using Eq. (3):
s ¼ L=RS (3)
where s was electric conductivity in S m
1, R was resistance in U, L
was the distance of two electrodes in cm and S was the cross-
sectional area in cm2.
2.6. In vitro cell culture and cytotoxicity assays
L929 cells were cultured in High Glucose-Dulbecco  s Modified
Eagle's Medium (HG-DMEM) with 10% fetal bovine serum at 37  C
in 95% air and 5% carbon dioxide. Then the cells were washed
several times with phosphate buffer saline, and they were treated
by trypsin-EDTA solution at 37  C for 3.0 min for releasing. They
were subsequently re-suspended in culture media at a concentra-
tion of 1.5  105 cells mL
1. The cell cytotoxicity of hydrogels
was evaluated by the MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-
diphenyltetrazolium bromide] colorimetric assays. The optical
densities of the experimental group (ODe), control group (ODc) and
blank group (ODb) were tested at 490 nm by microplate reader. The
detailed processes of cytotoxicity assay, fluorescent staining and
cell adhesion and morphology were given in Supporting infor-
mation. The cell viability was obtained by Eq. (4):
ODe
ODb
Cell viability ½% ¼  100% (4)
ODc
ODb
3. Results and discussions
3.1. Preparation mechanism of composite hydrogels
The PANI@CNF-PVA hydrogels were prepared through a simple
 J. Han et al. / Electrochimica Acta 318 (2019) 660e672
two-step process as shown in Fig. 1a. The formation mechanism of
composite hydrogel was proposed as follows. After dissolved in
water, borax molecules were quickly transformed into tetrahedral
B(OH)


4 and trigonal planar B(OH)3. The B(OH)4 ions could revers-
ibly complex with PANI@CNF nanocomplexes and PVA chains [25].
In this manner, borate ions served as a cross-linking agent between
H2O molecules, PVA and PANI@CNF nanocomplexes, leading to the
formation of various complexes including PVA-B(OH)4-PVA, PVA-
B(OH)4-PANI@CNF and PANI@CNF-B(OH)4-CNF@PANI. Accordingly,
the concurrence of H2O interpenetration, multi-complexation,
polymer chain entanglements, inter- and intramolecular
hydrogen bonding system resulted in the creation of a robust hi-
erarchical structure within the PANI@CNF-PVA hydrogels. As ex-
pected, the resultant hydrogels showed a small density
(~1.17 g cm
3), high water content (~93.4%) and ideal conductivity
(~5.2 S m
1). Due to their homogeneity, stability and malleability,
these conductive hydrogels could be molded into diverse desired
shapes (Fig. 1b).
3.2. Chemical analysis of PANI@CNF nanocomplexes
The mean diameter and length of well-dispersed CNFs were
21 ± 7 nm and 732 ± 208 nm, respectively (Fig. 2a). Without CNFs,
ANI monomers were transformed into irregular PANI aggregations
during polymerization (Fig. 2b). These PANI particles further
gathered together to form large-scale aggregations with several
micrometers to reduce their surface energy [26]. Therefore, pure
PANI particles agglomerated together to form precipitation in
aqueous medium (Insert of Fig. 2b). After the introduction of CNFs,
the eOH groups of CNFs interacted with amines of ANI via many
hydrogen bonds, which ensured the absorption of ANI monomers
on the surfaces of CNF biotemplates [27]. Upon addition of the APS
oxidant, the polymerization reaction was initiated on the CNFs, and
the p-p stacking of benzene ring contributed to the development of
PANI chains and the successive deposition of PANI shell on the CNF
templates, resulting in the formation of well-distributed PANI@CNF
nanocomplexes with a core-shell structure in water (Fig. 2c)
[26,28]. The PANI@CNF complexes with dark green color formed a
stable aqueous suspension in water (Insert of Fig. 2c), indicating
Fig. 1. (a) Synthesis mechanism of homogeneous, free-standing, moldable and conductive PANI@CNF-PVA composite hydrogels and the dynamically reversible multi-complexation
between PANI@CNF and borate cross-linked PVA. (b) Demonstration of the mouldability and electro-conductivity of the hydrogels.
663
that CNFs served as suitable biotemplates for the stabilization and
dispersion of PANI@CNF complexes.
Fig. 2d shows the FTIR spectra of CNFs, PANI and PANI@CNF 4
complexes. In the case of CNFs, the characteristic absorption peaks
of 3336 and 2894 cm
1 were attributed to OeH and CeH stretching
vibration, respectively. The band at 1428 cm
1 was due to the eCH2
and eOCH in-plane bending. A sharp band observed at 1029 cm
1
was attributed to the CeOeC vibrations [27]. For neat PANI, the
band at 3270 cm
1 was due to NeH stretching. The peaks at 1535
and 1450 cm
1 arose from the C]C stretching vibration of the
benzenoid and quinoid rings, respectively. The bands of 1230, 1072
and 819 cm
1 corresponded to the CeN stretching vibration, CeH
in-plane bending and the CeH bending vibration at C1 and C4 of
benzene ring, respectively [14]. The entire spectrum of PANI@CNF
nanocomplexes was comparable to PANI. For PANI@CNF complexes,
all major peaks of PANI were altered to lower wavenumbers, indi-
cating the formation of hydrogen bonding between CNFs and PANI
[29]. The peaks of CNFs disappeared and the typical absorption
peaks that attributable to C]C stretching vibrations of quinone and
benzene rings in PANI were observed, indicating that the ANI
monomers were successfully polymerized onto the CNF templates.
Furthermore, the existence of the peaks which represented the
CeN stretching vibration and the CeH bending vibration at C1 and
C4 of benzene ring confirmed that the PANI was grafted on to CNFs.
The band at 3270 cm
1 arose from NeH stretching was larger than
that present in PANI, further proving the presence of PANI coating
layer on the CNFs surface. The interaction between PANI coating
and CNFs was further elucidated by XPS testes. Fig. S1a shows the
XPS results of CNFs, PANI and PANI@CNF. Both the PANI and PAN-
I@CNF mainly contained C (285.6 eV), O (532.6 eV) and N
(400.7 eV), while the N 1s peak was not found in CNFs. The XPS
spectra for the nitrogen of PANI and PANI@CNF were presented in
Fig. S1b and Fig. S1c. The binding energies of N 1s at 399.7, and
401.3 eV attributed to the benzenoid amine (eNHe) and positively
charged nitrogen (-Nþ-), respectively [30]. The percentage of eNHe
and eNþ- in PANI were of 5.6% and 3.8%, while the percentage of
eNHe and eNþ- in PANI@CNF were reduced to 2.8% and 1.7%
(Fig. S1d), respectively. The decrease of the percentage of eNþ-
suggested that the hydrogen bonding formed between nitrogen
664 J. Han et al. / Electrochimica Acta 318 (2019) 660e672

Fig. 2. TEM observation of (a) CNFs, (b) PANI and (c) PANI@CNF 4 complexes, the inserts of (a, b, c) illustrating the photographs of CNFs, PANI and PANI@CNF 4 aqueous suspensions
after a 24 h standing. (d) FTIR spectra of PANI, PANI@CNF 4 nanocomplexes and CNFs. (e) UV-Vis curves of PANI@CNF 4 and PANI aqueous suspensions. (f) Demonstration of the
construction mechanism of PANI@CNF nanocomplexes.

lone pairs of PANI and eOH groups CNFs [27,31]. The UV-Vis spectra
in Fig. 2e shows that the pure PANI aqueous solution had two ab-
sorption peaks at 335 and 680 nm, which represented the p-p*
transition of the benzenoid rings and n-p* transition of the
quinonoid rings, respectively. However, the p-p* and n-p* transi-
tion bands of PANI@CNF blue-shifted to 322 and 581 nm, respec-
tively [32]. The reason of blue-shifted might be due to the hydrogen
bonds between eNH groups of polyaniline and eOH groups of
nanocellulose, which leading to the perfect integration of PAN-
I@CNF nanocomplexes (Fig. 2f).
3.3. Dynamic rheological behavior of composite hydrogels
Fig. S2a shows the storage modulus (G’) versus applied strain (g)
for all gel samples. The curves of strain sweep confirmed the LVR of
these soft materials, where G’ and G00 were not dependent of the
strain values (g ¼ 0.1e100%). The critical strain (gc) was defined as
the point at which the G’ deviated by more than 5% from the
plateau value, and the gc values could reveal the departure degree
from linear viscoelastic behavior for the hydrogels. In Table 2, the gc
values of all hydrogels were ranging from 1.00% to 6.51%. For this
reason, the G’ values of these ECHs were basically constant at
g  1.0%, and g ¼ 1.0% was thus used for the following rheological
measurements. Obviously, among these hydrogels, PANI@CNF-PVA
4 showed the largest G'max (~32 kPa), and this value was nearly 2.6
times greater than the G'max value of CNF-PVA (~12 kPa) and 400-
fold larger than the G'max value of pure PVA gel (~0.08 kPa).
Fig. S2b shows the G’ and G00 of different hydrogels versus u ranging
from 0.1 to 100 rad s
1 within LVR. Due to the dynamically
reversible cross-linked network, these hydrogels exhibited
frequency-dependent rheological behavior. As u increased, an
initial regional monotonic increase was generated in G’ and G00
values. Subsequently, G’ reached up to a high-frequency plateau
value (G'∞), while G00 arrived at its peak value (G00 m) and then
started to gradually decline at high frequency range. In addition to
PVA hydrogel, the G00 for the other ECHs were constantly lower than
their counterpart G’ throughout the full u range, indicating that the
establishment of the hierarchical 3D hydrogel network were
accomplished by introducing CNFs or PANI@CNF complexes.
The plateau of G’ at large frequency (G'∞) and the maximum G00
value (G00 m) were two reliable indexes for reflecting the viscoelas-
ticity of hydrogels. Compared with pure PVA hydrogel, the addition
of 2.0 wt% CNFs led to an increase of almost 121-fold in G'∞ for CNF-
PVA, revealing the crosslinking and reinforcing effects of CNFs. In
 J. Han et al. / Electrochimica Acta 318 (2019) 660e672
Table 2
Rheological properties derived from moduli profiles.
Parameter PANI@CNF- PVA 1 PANI@CNF- PVA 2
Critical strains, gc/% 1.42 1.21
Maximum G’ within LVR, G'max/kPa 2.36 5.15
High-frequency plateau of G’, G'∞/kPa 3.09 9.61
Maximum G00 , G00 m/kPa 0.95 2.41
addition, the G'∞ value of PANI@CNF-PVA 4 was 574 times greater
than that of PVA gel and 4.8-fold larger than CNF-PVA, and the G00 m
value of PANI@CNF-PVA 4 was 328 times greater than that of PVA
gel and 4.3-fold higher than that of CNF-PVA gel, respectively,
revealing a better toughening performance of PANI@CNF nano-
complexes over CNFs at the same loading level of CNFs. Based on
the relationship between G'∞ (G'∞ ¼ rekBT) and entanglement
density (re) [33], the G'∞ value can be applied with rubber elasticity
theory to assess the crosslinking density of the hydrogels. There-
fore, re values and viscoelastic behavior of hydrogels followed the
order of PANI@CNF-PVA 4 > PANI@CNF-PVA 3 > CNF-PVA > PAN-
I@CNF-PVA 2 > PANI@CNF-PVA 1 > PVA. By introducing a moderate
amount of PANI@CNF, the linkages of PANI@CNF chains and the
denser polymer network with higher crosslinking density facili-
tated dissipation of energy, and the interactions between PAN-
I@CNF complexes and PVA chains contributed to the viscoelasticity
of composite hydrogels. Not surprisingly, PANI@CNF-PVA 4 showed
the greatest G* (complex modulus) and h* (complex viscosity)
among these hydrogels (Fig. S2c). To demonstrating its outstanding
elasticity, a piece of solid-like PANI@CNF-PVA 4 hydrogel could be
readily stretched more than 800% of its original length (Fig. S2d).
The flexibility of PANI@CNF complexes, chain entanglements of
PVA and dynamically interactions with borax contributed to the
elasticity of the hydrogel network. From this aspect, the PANI@CNF
complexes could be regarded as dual-functional reinforcing and
cross-linking nanoagents for the PVA gel system. The as-
synthesized hydrogels also exhibited intrinsic thermo-
reversibility confirmed by temperature sweep study (Fig. S3).
3.4. Self-healing ability of the composite hydrogels
The high-water-content hydrogels was operated with a large-
amplitude oscillatory collapse to study particular recovery of
their mechanical characteristics. In Fig. 3a, the hydrogel was first
deformed and exhibited a solid characteristic with a G’ of 11.1 kPa
and a G00 of 4.2 kPa at g ¼ 1.0%. However, the G’ value and the G00
value decreased to 0.2 and 0.6 kPa, respectively, at a large-
amplitude oscillatory force (g ¼ 100%). The G’ value was obviously
lower than the G00 value, revealing the quasi-liquid state of hydro-
gel. While applying the small-amplitude once more (g ¼ 1.0%), the
two moduli restored to the initial values immediately and the in-
ternal hydrogel network restored the initial quasi-solid status.
Because of the reversible crosslinks within hydrogel network, the
sample underwent the state alteration between quasi-solid (G'' < G’
at g ¼ 1.0%) and quasi-liquid (G'' > G’ at g ¼ 100%) under oscillatory
collapse. To assess their self-healing property, two white CNF-PVA
hydrogels and two blue CNF-PVA hydrogels colored with methyl-
thioninium chloride were contacted together. After 15s, they were
fully combined together to create one whole hydrogel (Fig. 3b). The
in situ self-healing behavior of PANI@CNF-PVA hydrogels was
further demonstrated in Fig. 3c. One fresh PANI@CNF-PVA hydrogel
was separated into two parts and then contacted together. After
about 15s, they were automatically merged together to create one
whole hydrogel, which could not be cracked under bending. In
Fig. 3d, two freshly synthesized CNF-PVA hydrogels and a block of
PANI@CNF-PVA were contacted together for about 15s. Then the
665
PANI@CNF- PVA 3 PANI@CNF- PVA 4 CNF-PVA PVA
1.15 1.00 6.51 n.a.
21.24 31.53 12.34 0.08
28.45 74.63 15.66 0.13
15.66 16.41 3.85 0.05
surface came to adhere to each other, leading to a fusion phe-
nomenon. They finally merged to form one single hydrogel
autonomously without any stimulus or external force and the self-
healed hydrogel could be stretched without any damage at the
interface. These results suggested that the self-healing behavior
was because of the mobility and the hydrophilic nature of polymer
chains, which could facilitate the reformation of hydrogen bonds
across the interface and reversible didiol-borax complex in the
network. The dynamically reversible crosslinks formed through
hydroxyl groups and borax complexation were especially quickly
damaged and re-established, making the PANI@CNF-PVA hydrogels
recover within a few seconds after mechanical deformation or
damage. In addition, the free hydroxyl groups and polymer chain
mobility inside hydrogel network could effectively facilitate the
autonomous self-healing behavior of PANI@CNF-PVA hydrogels.
Interestingly, all hybrid hydrogels exhibited pH-responsive per-
formance with the change of pH value, as shown in Fig. S4. The pH-
sensitive property of hydrogels was most likely because of the
reversible didiol complexation between eOH groups of PVA or
PANI@CNF and borax, the balance of which could be repeatedly
altered via altering pH.
3.5. Mechanical properties and microstructure of hydrogels
In Fig. 4a, the incorporation of PANI@CNF nanocomplexes
considerably increased the tensile strength of hydrogels. The
maximum value of tensile stress for PANI@CNF-PVA 4 (~31.6 kPa)
was about 5-fold greater than that of PVA (~6.3 kPa), and the
rupture strain value of PANI@CNF-PVA 4 was up to 635%. After a
cutting-healing process, the self-healed samples essentially main-
tained their initial mechanical properties (Fig. 4b). As to the
PANI@CNF-PVA 4, the initial maximum tensile strength was about
31.6 ± 1.2 kPa. After an in situ healing process (~15s), the fracture
stress value of the healed sample was 30.2 ± 0.9 kPa, indicating a
high self-healing efficiency of 96%.
Fig. 4c and d shows the typical compression profiles and the
corresponding energy absorption-strain profiles, respectively.
Obviously, all compressive parameters followed a similar trend:
PANI@CNF-PVA 4 > PANI@CNF-PVA 3 > CNF-PVA > PANI@CNF-PVA
2 > PANI@CNF-PVA 1 > PVA. This result suggested that the incor-
poration of CNFs and PANI@CNF nanocomplexes significantly
enhanced the mechanical property of pure PVA gel. Specially, the s
values of CNF-PVA (~33.8 kPa) and PANI@CNF-PVA 4 (~48.8 kPa) at
ε ¼ 90% were about 2.4 and 3.5 times greater than the s value of
PVA gel (~14.0 kPa) (Table 3), respectively.
Comparing PANI@CNF-PVA 1, 2 and 3, the mechanical strength
of hydrogels was gradually increased with the increasing amount of
CNFs when the content of PANI was fixed at 0.5 wt%, which was
mainly attributed to the denser crosslinking network between
PANI@CNF nanocomplexes and PVA gel system. Comparing CNF-
PVA with PANI@CNF-PVA 3 and 4, the mechanical strength was
gradually raised with the increased amount of PANI when CNFs
were fixed at 2.0 wt%, revealing that the efficient coating of PANI on
the CNF substrates made the PANI@CNF complexes ideal reinforc-
ing fillers for hydrogels. Noticeably, PANI@CNF-PVA 4 had the
largest compression strength compared with the other hydrogels.
666 J. Han et al. / Electrochimica Acta 318 (2019) 660e672
Fig. 3. (a) The G’ and G00 curves of PANI@CNF-PVA 4 as a function of time in continuous step strain tests. (b) Illustration of self-healing property for CNF-PVA and (c) PANI@CNF-PVA
hydrogels. (d) Illustration of self-healing process of PANI@CNF-PVA and CNF-PVA hydrogels, and the self-healing mechanism of composite hydrogels with reversible network.
The elastic modulus (Ee) (determined from the slopes of the initial
linear parts of s-ε curves) had a direct proportionality relationship
with crosslink density of hydrogel [34]. The Ee value of PANI@CNF-
PVA 4 (~18.0 kPa) was almost 1.6 and 15-fold greater than that of
CNF-PVA (~11.5 kPa) and PVA (~1.20 kPa). Therefore, the well-
distributed PANI@CNF nanocomplexes within PVA gel matrix
were able to efficiently improve the crosslink density and establish
the load-bearing percolating structures within the gel matrix. Not
surprisingly, PANI@CNF-PVA 4 exhibited the largest Ea value over
the entire ε range. In particular, its Ea value (~0.90 kJ m
3) was about
6.9 and 1.6-fold greater than that of PVA (~0.13 kJ m
3) and CNF-
PVA (~0.56 kJ m
3) gel at ε ¼ 90%, respectively (Table 3). The high-
water-content PANI@CNF-PVA 4 hydrogel cake (weight z 25.0 g,
Wc z 91.2%) could bear more than 12-fold of its own weight under
a 300 g loading (Inserts of Fig. 4a and b).
The SEM observation of CNF-PVA and PANI@CNF-PVA 4 hydro-
gels at the same magnification are shown in Fig. 4e and f. Both
hydrogels exhibited porous interconnected network structure. The
pore size of PANI@CNF-PVA 4 (650e800 nm) was smaller than that
of CNF-PVA (~1.11 mm), indicating a denser network structure of
PANI@CNF-PVA 4 hydrogel. The chain entanglement of PVA and
PANI@CNF complexes led to the establishment of the hierarchical
pore structure. The type of construction was capable of efficiently
promoting the transmission of ions, electrons and molecules within
the gel network. CNFs served as nanotemplates could promote the
establishment of continuous PANI conducting network. The stable
and continuous PANI network could contribute to the formation of
electrically conducting routes, thus undoubtedly increasing the
electrical conductivity because of the well-distributed PANI@CNF
nanocomplexes in PVA gel system [35].
3.6. Electrochemical properties of hydrogel-based conductors and
electrodes
Fig. 5a shows the electro-conductivity variation of PANI@CNF-
PVA composite hydrogels with different mass ratio of ANI to
CNFs. The hydrogel conductivity from 2.5 to 5.2 S m
1 showed a
nonlinear enhancement with the increasing PANI dosage. Inter-
estingly, the electro-conductibility increased with the increasing
amount of CNFs when the PANI content was fixed at 0.5 wt%. As
previously reported, CNFs were capable of enabling paths for
electron and ion transport after incorporated into electrochemical
composites [36]. Besides, CNFs with excellent dispersing ability
served as ideal biotemplates that could regulate the growth of PANI
and inhibit the aggregation of PANI. Therefore, as the content of
CNFs increased, PANI was expected to exhibit a more homoge-
neously dispersion state, and the CNF framework became denser
and more integrated, thus facilitating the construction of electri-
cally conductive pathways inside the hydrogels. The well-dispersed
PANI@CNF complexes constructed effective conductive paths in
PVA system, providing an ideal conducting ability to the hybrid
hydrogels. The conductive framework of the PANI@CNF-PVA
hydrogels provided ideal 3D interconnected paths for electron
transport, and the maximum electro-conductivity value for
PANI@CNF-PVA gels was up to 5.19 ± 0.07 S m
1.
In Fig. 5b, the conductive hydrogel could illumine a blue bulb in
a circuit. After the gel conductor was separated into two pieces, the
bulb was extinguished immediately because the circuit became
open. After a 15s self-healing, the two fractured hydrogel blocks
were merged together into an integral one. Due to the re-
establishment of circuit, the LED was illumined once more
without obvious electro-conductivity diminution, suggesting the
 J. Han et al. / Electrochimica Acta 318 (2019) 660e672 667

Fig. 4. (a) Tensile test profiles of hydrogels. (b) Stress histogram of original hydrogels and self-healed hydrogels after a 15s self-healing process. (c) Compression test and (d) energy
absorption profiles of hydrogels. The inserts demonstrating PANI@CNF-PVA 4 hydrogel under 300 g weight. SEM micrographs of (e) CNF-PVA and (f) PANI@CNF-PVA 4 showing their
porous morphology at high magnification (  12000).

Table 3
Physical-mechanical properties and Conductivity of hydrogels.

Sample s at ε ¼ 90%/kPa Ea at ε ¼ 90%/kJ m
3 Ee/kPa r/g cm
3 Wc/% Conductivity/S m
1

PANI@CNF-PVA 1 22.1 ± 0.5 0.217 ± 0.003 5.7 ± 0.3 1.13 ± 0.12 95.21 ± 0.05 2.5 ± 0.08
PANI@CNF-PVA 2 27.6 ± 0.5 0.424 ± 0.006 8.6 ± 0.3 1.15 ± 0.10 94.63 ± 0.12 3.46 ± 0.06
PANI@CNF-PVA 3 44.1 ± 0.7 0.670 ± 0.009 11.7 ± 0.4 1.18 ± 0.06 92.43 ± 0.07 4.61 ± 0.08
PANI@CNF-PVA 4 48.8 ± 0.8 0.903 ± 0.010 18.0 ± 0.5 1.20 ± 0.08 91.18 ± 0.11 5.19 ± 0.07
CNF-PVA 33.8 ± 0.6 0.559 ± 0.007 11.5 ± 0.4 1.16 ± 0.05 94.12 ± 0.09 0
PVA 14.0 ± 0.3 0.131 ± 0.003 1.2 ± 0.2 1.08 ± 0.07 96.97 ± 0.18 0
668 J. Han et al. / Electrochimica Acta 318 (2019) 660e672

Fig. 5. (a) Conductivity variation of PANI@CNF-PVA gels with changed mass ratio of ANI monomers to CNFs. (b) Luminance change of a bulb during a cyclic damaging, healing and
stretching process. (c) Current variation of PANI@CNF-PVA 4 gel under repeated damaging and healing processes. (d) Luminance change of a green LED and DR/R0 change of
PANI@CNF-PVA 4 under varying strains. (e) Schematic of the resistance change in the 3D conductive hydrogel network under stretching. (For interpretation of the references to
color in this figure legend, the reader is referred to the Web version of this article.)

self-healing ability of the conductive gel network. Moreover, the
hydrogel was able to circularly restore its original conducting
ability each time after damage. Even under stretching, the self-
healed hydrogel still maintained its integrity, and the circuit
remained closed. Because of their intrinsic self-healing ability,
PANI@CNF-PVA hydrogels could maintain their original conduc-
tivity, shape, strength after each damaging/healing process. Due to
dynamic union and separation of borate-induced complexation in
gel network, it was easy for these gels to achieve the self-restore
performance at atmospheric temperature without any applied
force. The healing behavior of PANI@CNF-PVA composite hydrogels
was also proved by current measurements (Fig. 5c). The circuit
turned to be open (current z 0 mA) after the first cutting. After the
two fractured surfaces contacted for about 15s, the circuit became
closed and the current recovered to its original value. After several
cutting-self-healing cycles, the hydrogel could still repeatedly self-
heal to its original state, indicating a comprehensive re-
establishment of the continuous conducting pathways of the
restored gel. The composite hydrogels composed of a self-healable
PVA network and a conducting PANI@CNF framework demon-
strated high elasticity and mechanical strength due to the distinc-
tive dynamically cross-linked polymer network, which was
extremely promising to fabricate intrinsic self-healable and soft
electronics [37].
The highly stable, elastic and conductive PANI@CNF-PVA
hydrogels were theoretically appropriate for making smart mate-
rials with sensing ability. To assess the sensing ability of these gels,
the relative resistance change (DR/R0 ¼ (R0-R)/R0, where R was the
electric resistance under stretching and R0 was the resistance
without stretching) versus strains was tested (Fig. 5d). The DR/R0
values displayed a monotonic increase with the increasing tensile
strain. The inserts of Fig. 5d shows the luminance change of a green
bulb during a stretching process. The electrical pathways inside the
hydrogel were still maintained even under a 200% strain, indicating
 J. Han et al. / Electrochimica Acta 318 (2019) 660e672 669

a high stability and stretchability of the conducting pathways of
hydrogels. The evolution mechanism of interconnected conductive
network of hydrogel under stretching is proposed in Fig. 5e. The
conducting gel paths were stable and compact in the original state.
The deformation of the hydrogel upon mechanical stretching
caused the disruption of PANI pathways, thus leading to an increase
in resistance. Because the average distance between PANI chains
increased with the change of the elongating length during the
stretching process, the electric resistance raised owing to tunneling
of charges transmitted between neighboring polyaniline molecules
in the conductive hydrogels [38].
The typical CV profiles of the gel-based electrode at 10, 30, 50,
80 and 100 mV s
1 scan rates with a potential window of 0e0.4 V
(vs. SCE) were presented in Fig. 6a. The characteristic redox
behavior of PANI was clearly observed, indicating the trans-
formation between different redox status of PANI and an ideal
pseudocapacitive feature. As the scan rate increased, the peak
anodic and cathodic current densities gradually increased, sug-
gesting an excellent electrochemical response. This behavior was
mainly attributed to the lack of redox reactions inside the hydrogel-
based electrode at high scan rates [39]. Due to the inherent resis-
tance of the electrode materials, the peaks of oxidation shifted to
more positive potentials and the reduction peaks shifted to nega-
tive potentials as the scan rate increased, respectively [2,40]. The

Fig. 6. Electrochemical properties of PANI@CNF-PVA 4 gel-based electrode. (a) CV profiles at 10e100 mV s
1; (b) EIS profiles and the enlarged insert at high frequency region; (c) G-
CD profiles at 0.2e2.0 A g
1; (d) specific capacitance versus different current density; (e) the first 15 cycles of G-CD profiles at 2.0 A g
1; (f) capacitance maintenance versus number
of cycles at a current density of 5.0 A g
1.
670 J. Han et al. / Electrochimica Acta 318 (2019) 660e672
electronic and ionic transport of the electrode in electrolyte was
studied by EIS (Fig. 6b). At lower frequencies, the linear part rep-
resented the diffusion-limited electron transfer process, and the
nearly vertical shape indicated an ideal capacitive behavior of the
hydrogel-based electrode [13,41]. The nonvisible semicircle in the
high frequency region showed the very low charge-transfer resis-
tance at the electrode/electrolyte interface [11,42]. The 3D contin-
uous nanostructured framework of hydrogel could maximize the
contact area of electrolyte at the electrolyte/electrode interface,
thus reducing the charge-transfer resistance [13].
To further investigate the potential ability of the hydrogel as
electrode materials, G-CD measurements were also carried out.
Fig. 6c illustrated the G-CD profiles at 0.2, 0.5, 0.8, 1.0 and 2.0 A g
1.
The symmetric shape of the G-CD curves indicated a relatively high
Coulombic efficiency and a highly reversible charge transfer in the
electrode [18]. However, the curves were not ideal straight lines,
indicating a faradaic reaction process [43]. As to the charging-
discharging process, the time required progressively decreased
with the increasing current density, in accordance with the previ-
ous supercapacitor electrodes [44,45]. The corresponding specific
capacitance (Cs) of the electrode could be estimated from the G-CD
profiles using Equation (1), and the values were plotted in Fig. 6d.
The Cs values were 226.1, 215.3, 205.8, 201.6 and 182.4 F g
1 at 0.2,
0.5, 0.8, 1.0 and 2.0 A g
1, respectively, analogous with previously
reported electrodes, including graphene hydrogels (~160 F g
1 at
1.0 A g
1) [46], PANI-SA hydrogels (~252 F g
1 at 0.5 A g
1) and
pectin/PANI aerogels (~184 F g
1 at 0.5 A g
1) [47,48]. The Cs value
was reduced with increasing scan rate, demonstrating the ideal ion
circulation behavior of the gel-based electrode. The enhanced Cs of
hydrogel-based electrode was ascribed to the synergistic effect of
PANI and CNFs that could considerably improve the electro-
chemical property of PANI itself [49]. Large surface area CNFs were
ideal biotemplates to carry PANI and could create a tough frame-
work to sustain the flexible PANI conducting pathways. This type of
Fig. 7. (a) Cell biocompatibility assays of PANI@CNF-PVA gel. (b) SEM observation of the cell adhered to the PANI@CNF-PVA after cultivation. (c, d) Fluorescent staining images
showing the live and dead L929 cells after incubation.
hierarchical network structure could achieve a short ion diffusion
length, thus providing the hydrogel-based electrode with an
excellent conductivity. Furthermore, the well-dispersed PANI@CNF
complexes within PVA system could help to increase the
electrolyte-accessible surface area to enhance utilization of PANI
for redox reactions [27]. Fig. 6e shows the first 15 cycles at 2.0 A g
1,
indicating an excellent cycling stability. After the following 3000
cycles at 5.0 A g
1, the Cs values remained almost 74% of its initial
value (Fig. 6f), which demonstrated a better cyclic stability than
previous reported pectin/PANI aerogel electrodes (a capacitance
drop of ~26% under 1000 cycles) [48]. The capacitance degradation
during charge-discharge cycling mainly resulted from the struc-
tural change of electroactive PANI during the cyclical doping/
dedoping process [50]. More importantly, the desired electro-
chemical stability of the gel-based electrodes was attributed to the
tight association of PANI@CNF nanocomplexes and the flexible
conductive pathways, which was able to efficiently stabilize PANI
and restrict the structural change of PANI during cyclical charge-
discharge process.
3.7. In vitro assay of cell attachment and biocompatibility for the
hydrogels
The biocompatibility was the most important criterion of bio-
materials in biomedical applications. Because of the intrinsic non-
toxicity of PANI, CNFs and PVA, PANI@CNF-PVA hydrogels should
be biocompatible. PANI@CNF-PVA 4 was selected to analyze the
cytotoxicity of composite hydrogels using L929 cells by MTT
colorimetric assays (Fig. 7). In Fig. 7a, the cell viability was ranging
from 90% to 96% for various concentrations of hydrogel extracts
after a 24 h incubation. Specifically, the cell viability of the group
with 100% concentration reached up to 96%, indicating the excel-
lent biocompatibility of PANI@CNF-PVA hydrogels. In Fig. 7b, the
extensively distributed L929 cells were obviously attached on the
 J. Han et al. / Electrochimica Acta 318 (2019) 660e672
surface of hydrogel. In addition, the wide-spread and confluent
behavior of cells seeded on the hydrogel indicated that the hy-
drophilic hydrogel surface was suitable for cell proliferation and
attachment [51]. Due to the similarity to extracellular matrix,
PANI@CNF-PVA hydrogel could serve as an excellent substrate to
cells adhesion and growth, thus making it possible to apply these
hydrogels to tissue engineering [52]. Fluorescent staining experi-
ments were employed to further demonstrate the non-cytotoxicity
of hydrogels. Hoechst 33342 live cell staining solution (100X) was a
solution suitable for living cell nuclear staining. The living cells
were dyed evenly blue, while the dead cells presented a bright blue.
In Fig. 7c, almost all cells were widely dispersed and arrived at high
confluence in 100 v/v% concentration of the extract liquid at 24 h
after seeding. In Fig. 7d, only few dead cells were observed, illus-
trating that cells maintained high viability and hydrogels were
essentially biocompatible. Therefore, the PANI@CNF-PVA hydrogels
with ideal biocompatibility and cell attachment were promising
flexible materials to create a human-device interface to fabricate
implantable tissue-like bioelectronic devices.
4. Conclusion
In conclusion, versatile conductive PANI@CNF-PVA hydrogels
were synthesized by incorporating conducting PANI@CNF com-
plexes into PVA gel matrix. CNFs worked as biotemplates during in
situ oxidatively polymerizing ANI monomers and assisted the for-
mation of well-dispersed PANI@CNF nanocomplexes, which not
only acted as reinforced nanofillers in the PVA matrix but also
served as nanocarriers in the construction of efficient conductive
network. The entanglements between PVA chains and/or PAN-
I@CNF via numerous hydrogen bonds and reversibly crosslinked
complexes with borate ions lead to the formation of a stable 3D
network structure within the hydrogels system. The obtained
PANI@CNF-PVA 4 hydrogel with high water content (~91%) pre-
sented the highest viscoelasticity (G'max up to 31.53 kPa) and me-
chanical strength (s up to 48.8 kPa at ε ¼ 90%). The PANI@CNF-PVA
4 hydrogel-based electrode (conductivity up to
5.19 ± 0.07 S m
1) had an ideal specific capacitance of 226.1 F g
1
and a capacitance retention of 74% after 3000 cycles. By virtue of
the dynamically reversible cross-links, the hydrogels showed pH
sensing property and fast self-healing capability. The hybrid
hydrogels also demonstrated good biocompatibility, mouldability
and thermo-reversibility. The design principle presented a bright
prospect in constructing next-generation multifunctional conduc-
tive hydrogels, and the integration of these distinctive features
enables many promising applications of as-prepared hybrid
hydrogels in soft, self-healable and implantable electronic devices.
Author contributions
H.J. and Q.D. contributed equally to this work. The manuscript
was written through contributions of all authors. All authors have
given approval to the final version of the manuscript.
Acknowledgements
This work was sponsored by National Natural Science Founda-
tion of China (31770609), Natural Science Foundation of Jiangsu
Province for Outstanding Young Scholars (BK20180090), Natural
Science Research Project of Jiangsu Province (17KJB220007), Qing
Lan Project of Jiangsu Province, 333 Project of Jiangsu Province
(BRA2018337), Priority Academic Program Development (PAPD),
and Analysis and Test Center of Nanjing Forestry University.
671
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.06.132.
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